WO2012036173A1 - Thermoplastic resin processing aid, and thermoplastic resin composition containing same - Google Patents

Abstract

[Problem] To provide a thermoplastic resin processing aid that can effectively increase molding/processing properties of a thermoplastic resin or a composition containing same without detracting from the intrinsic properties of the thermoplastic resin. [Solution] The processing aid for being combined with a thermoplastic resin is characterized by (1) the processing aid containing a copolymer (A) obtained by copolymerizing a) 50-95 wt% of an aromatic vinyl monomer, b) 5-50 wt% of a vinyl cyanide monomer, and d) 0-45 wt% of another vinyl monomer that can copolymerize with the aromatic vinyl monomer and the vinyl cyanide monomer (however, the total of the monomers used in the copolymer (A) is 100 wt%), (2) the peak molecular weight (Mp) of the copolymer (A) being at least one million, and (3) the copolymer being a particulate, wherein 1-50 wt% of particles with a particle size of at least 355 µm are contained in every 100 wt% of the copolymer (A).

Description

Processing aid for thermoplastic resin and thermoplastic resin composition containing the same

The present invention relates to a thermoplastic resin as a processing aid for thermoplastic resin that is suitable as a processing aid for improving the molding processability of a thermoplastic resin. Furthermore, the present invention relates to a thermoplastic resin composition containing the processing aid.

For example, thermoplastic resins such as styrene-based resins and vinyl chloride resins are widely used as molding materials for, for example, vehicle products, household products, and electrical appliances because they are excellent in molding processability and rigidity.

In general, molding methods such as extrusion molding, foam molding, vacuum molding, pressure molding, blow molding, and the like require molding materials that can maintain good viscoelasticity over a wide temperature range. More specifically, when the molding material (resin component) is melted, if a high melt elasticity can be exhibited, excellent molding processability can be obtained. As a result, a molded product having excellent quality and appearance can be obtained. It can be manufactured.

Therefore, in particular, increasing the melt elasticity of the thermoplastic resin is an important factor in obtaining an excellent molded product. For example, even in the case of producing a resin molded product such as a foam sheet, it is necessary to appropriately increase the melt elasticity of a thermoplastic resin that is a molding material (raw material). In this case, it is conceivable to increase the melt elasticity by increasing the molecular weight of the thermoplastic resin itself, but there is a drawback in that the fluidity of the molten resin significantly decreases as the molecular weight increases. For this reason, in order to improve the balance between fluidity and impact strength, a method in which a thermoplastic resin contains both a component having a high molecular weight and a component having a low molecular weight, a method for adjusting the molecular weight distribution of the thermoplastic resin, etc. have been proposed. However, there is room for further improvement in order to obtain a molding material suitable for various molding methods such as extrusion molding, foam molding, vacuum molding, pressure molding, and blow molding.

On the other hand, even when the same thermoplastic resin is used as the molding material, the desired melt elasticity is required depending on the molding method to be applied, molding conditions, etc., so that the inherent properties of the thermoplastic resin are not impaired. The development of a processing aid that can arbitrarily adjust the melt elasticity is eagerly desired.

On the other hand, a method of using a styrene copolymer having a relatively high molecular weight as an aid for improving the processability of a thermoplastic resin has been proposed (Patent Documents 1 to 3). However, these prior art processing aids still have room for further improvement from the viewpoint of moldability when blended with a thermoplastic resin or a composition containing the same.

JP-A-10-168131 JP 02-302412 JP-A-11-92528

Therefore, the main object of the present invention is to provide a thermoplastic resin processing aid that can effectively improve the molding processability of a thermoplastic resin or a composition containing the thermoplastic resin without impairing the original properties of the thermoplastic resin. It is to provide. A further object of the present invention is to provide a thermoplastic resin composition containing the processing aid.

As a result of intensive studies in view of the above-mentioned problems of the prior art, the present inventors have achieved the above object by using a specific copolymer as a processing aid for a thermoplastic resin. The headline, the present invention has been reached.

That is, the present invention relates to the following processing aid for thermoplastic resin and a thermoplastic resin composition containing the same.
1. A processing aid for blending with a thermoplastic resin,
(1) The processing aid is a) an aromatic vinyl monomer of 50 to 95% by weight, b) a vinyl cyanide monomer of 5 to 50% by weight, and d) another vinyl copolymerizable therewith. A copolymer (A) obtained by copolymerizing 0 to 45% by weight of a system monomer (provided that the total amount of monomers used in the copolymer (A) is 100% by weight);
(2) The peak apex molecular weight (Mp) of the copolymer (A) is 1 million or more,
(3) The copolymer is in the form of particles and contains 1 to 50% by weight of particles having a particle diameter of 355 μm or more in 100% by weight of the copolymer (A).
A processing aid for thermoplastic resins.
2. The copolymer comprises a) an aromatic vinyl monomer 50 to 70% by weight, b) a vinyl cyanide monomer 9 to 40% by weight, c) a (meth) acrylic acid ester monomer 21 to 35% by weight and d) a copolymer (A) obtained by copolymerizing 0 to 20% by weight of other vinyl monomers copolymerizable with these (monomers used in the copolymer (A)) The total amount of the polymer is 100% by weight.), The processing aid for thermoplastic resin according to Item 1.
3. Item 3. The thermoplastic resin processing aid according to Item 1 or 2, wherein the copolymer (A) has a peak peak molecular weight (Mp) of 2 million or more.
4). Item 4. The processing aid for a thermoplastic resin according to any one of Items 1 to 3, wherein the crushing strength of particles of 850 μm or more contained in the copolymer (A) is 250 to 900 g / mm ² .
5. Item 2. The processing aid for a thermoplastic resin according to Item 1, wherein the copolymer (A) is recovered from latex that is a reaction product of emulsion polymerization of the monomer.
6). Item 6. The processing aid for a thermoplastic resin according to Item 5, wherein the latex particles of the copolymer (A) have a weight average particle size of 160 nm or less.
7. Item 6. The thermoplastic resin processing aid according to Item 5, wherein the total amount of unreacted components remaining in the latex is 2.0% by weight or less.
8). A thermoplastic resin composition comprising 100 parts by weight of a thermoplastic resin and 0.1 to 15 parts by weight of the processing aid according to any one of Items 1 to 7.
9. A resin molded product obtained by molding the thermoplastic resin composition according to Item 8.

Since the processing aid of the present invention contains a specific copolymer and is a powder having a specific particle size, by blending it with a thermoplastic resin, excellent molding processability is obtained during melt molding. be able to. As a result, it is possible to more reliably provide a molded product having quality, appearance and the like superior to those of the prior art.

Hereinafter, the present invention will be described in detail.

1. The processing aid for thermoplastic resin of the present invention The processing aid for thermoplastic resin of the present invention (the processing aid of the present invention) is a processing aid for blending into a thermoplastic resin,
(1) The processing aid is a) an aromatic vinyl monomer of 50 to 95% by weight, b) a vinyl cyanide monomer of 5 to 50% by weight, and d) another vinyl copolymerizable therewith. A copolymer (A) obtained by copolymerizing 0 to 45% by weight of a system monomer (provided that the total amount of monomers used in the copolymer (A) is 100% by weight);
(2) The peak apex molecular weight (Mp) of the copolymer (A) is 1 million or more,
(3) The copolymer is in the form of particles and contains 1 to 50% by weight of particles having a particle diameter of 355 μm or more in 100% by weight of the copolymer (A).
It is characterized by that.

(1) Copolymer (A)
The processing aid of the present invention is mainly composed of the copolymer (A). The content of the copolymer (A) in the processing aid of the present invention is usually 90 to 100% by weight, preferably 95 to 100% by weight. Accordingly, for example, a processing aid having a copolymer (A) content of 100% by weight is also included in the present invention. The third component (additive) contained when the content of the copolymer (A) is less than 100% by weight will be described in detail in (1-4) below.

(1-1) Monomer constituting copolymer (A) The processing aid of the present invention essentially comprises a) an aromatic vinyl-based monomer and b) a vinyl cyanide-based monomer. Other vinyl monomers can also be used.

a) Aromatic vinyl monomer The aromatic vinyl monomer used in the present invention is not particularly limited, and examples thereof include styrene, t-butyl styrene, α-methyl styrene, p-methyl styrene, divinyl benzene. 1,1-diphenylstyrene, N, N-diethyl-p-aminoethylstyrene, N, N-diethyl-p-aminomethylstyrene, vinylpyridine, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, fluorostyrene , Ethyl styrene, vinyl naphthalene and the like. These aromatic vinyl monomers can be used alone or in combination of two or more. Among these, in the present invention, at least one of styrene and α-methylstyrene is particularly preferable.

The content of the aromatic vinyl monomer used in the present invention needs to be 50 to 95% by weight in a total of 100% by weight of the monomers used in the copolymer (A). When the aromatic vinyl monomer is less than 50% by weight, the thermal stability of the thermoplastic resin composition after blending the processing aid is lowered, and yellowing tends to occur. On the other hand, when it exceeds 95% by weight, the polymerization reaction rate is lowered during the polymerization of the copolymer (A), and the productivity is deteriorated. Therefore, from the viewpoint of productivity and colorability, it is preferably 50 to 70% by weight, and more preferably 55 to 65% by weight.

b) Vinyl cyanide monomer The vinyl cyanide monomer used in the present invention is not limited, and examples thereof include acrylonitrile, methacrylonitrile, ethacrylonitrile, fumaronitrile, and acrylonitrile is preferable. . These vinyl cyanide monomers can be used alone or in combination of two or more. The vinyl cyanide monomer used in the present invention excludes the monomer a) used as the aromatic vinyl monomer.

The content of the vinyl cyanide monomer used in the present invention needs to be 5 to 50% by weight in a total of 100% by weight of the monomers used in the copolymer (A). If the vinyl cyanide monomer is less than 5% by weight, the polymerization reaction rate is lowered during the polymerization of the copolymer (A), and the productivity is deteriorated. On the other hand, if it exceeds 50% by weight, it is not preferable because heat control during polymerization becomes difficult and the yellowness of the final product increases. Therefore, it is preferably 9 to 40% by weight, more preferably 10 to 30% by weight, particularly from the viewpoint of productivity and the color tone (appearance) of the final product.

d) Other monomer Other vinyl copolymerizable with the aromatic vinyl monomer and vinyl cyanide monomer used in the copolymerization of the copolymer (A) used in the present invention. Examples of the monomer include (meth) acrylic acid ester monomer, maleimide monomer, unsaturated acid, acid anhydride-containing unsaturated monomer, epoxy group-containing unsaturated monomer, hydroxyl group Examples thereof include an unsaturated monomer containing an amide group, an unsaturated monomer containing an amide group, an unsaturated monomer containing an amino group, and an unsaturated monomer containing an oxazoline group. These monomers can be used alone or in combination of two or more. Among these monomers, it is preferable to use a (meth) acrylic acid ester monomer from the viewpoints of compoundability and thermal stability. In addition, as for the other monomer used by this invention, all the monomers used by said a) and b) are remove | excluded.

Examples of the (meth) acrylic acid ester monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl acrylate, ( (Meth) acrylic acid phenyl, (meth) acrylic acid 4-t-butylphenyl, (meth) acrylic acid bromophenyl, (meth) acrylic acid dibromophenyl, (meth) acrylic acid 2,4,6-tribromophenyl, ( Examples thereof include monochlorophenyl methacrylate, dichlorophenyl (meth) acrylate, and trichlorophenyl (meth) acrylate, and at least one of methyl methacrylate and butyl acrylate is preferred.

Examples of the maleimide monomer include at least one of maleimide, N-methylmaleimide, N-butylmaleimide, N- (p-methylphenyl) maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and the like. Preferably, at least one of N-phenylmaleimide and N-cyclohexylmaleimide is used.

Examples of the unsaturated acid include at least one of acrylic acid and methacrylic acid.

Examples of the acid anhydride group-containing unsaturated monomer include at least one of maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. Preferred is maleic anhydride.

Examples of the epoxy group-containing unsaturated monomer include at least one kind such as glycidyl methacrylate and allyl glycidyl ether. Glycidyl methacrylate is preferred.

Examples of the hydroxyl group-containing unsaturated monomer include 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3- There may be mentioned at least one of hydroxy-2-methyl-1-propene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, etc., and 2-hydroxyethyl methacrylate is preferred.

Examples of the amide group-containing unsaturated monomer include at least one of acrylamide, methacrylamide and the like, and preferably acrylamide.

Examples of the amino group-containing unsaturated monomer include at least one of acrylic amine, dimethylamino methacrylate, diethylamino methacrylate, dimethylamino acrylate, and the like.

Examples of the oxazoline group-containing unsaturated monomer include vinyl oxazoline.

Other monomers (especially when a (meth) acrylic acid ester monomer is used) are used in the total 100% by weight of the monomers used in the copolymer (A) from the viewpoint of polymerization stability. The content is preferably 21 to 35% by weight.

(1-2) Synthesis of copolymer (A) The polymerization method of the copolymer (A) of the present invention is not particularly limited, and any known polymerization method can be applied, but production of a polymer having a particularly high degree of polymerization is possible. It is preferable to be produced by emulsion polymerization in terms of good properties. The emulsion polymerization method itself may be in accordance with a known method, for example, a step of preparing a latex (suspension) as a reaction product by polymerizing a monomer in a liquid phase containing water and an emulsifier. It can manufacture suitably with a manufacturing method. Thereafter, if necessary, the copolymer particles may be recovered from the obtained latex according to a known solid-liquid separation method or the like.

In the case of emulsion polymerization, examples of the emulsifier used include alkali metal salts of rosin acid, alkali metal salts of fatty acids, alkali metal salts of aliphatic alcohol sulfates, alkali metal salts of alkylallyl sulfonic acids, and dialkyl sulfosuccinic acid esters. At least one of an alkali metal salt, a polyoxyethylene alkyl (phenyl) ether sulfate alkali metal salt, a polyoxyethylene alkyl (ether) phosphate alkali metal salt, and the like can be suitably used. The amount of the emulsifier used is 1 to 5% by weight based on 100% by weight of the total amount of monomers used in the copolymer (A), the polymerization reaction rate and reaction stability, the appropriate latex viscosity, salt This is preferable from the standpoint of eutectability.

In addition, it is preferable to use a polymerization initiator in the emulsion polymerization. As a polymerization initiator, well-known things, such as a persulfate and organic hydroperoxide, can be used suitably, for example. In particular, it is preferable to use a persulfate from the viewpoint of the stability of the latex. The amount of the polymerization initiator used is usually 0.01 to 0.00% with respect to 100% by weight of the total amount of monomers used in the copolymer (A) from the viewpoint of adjusting the polymerization reaction initiation behavior and the peak peak molecular weight. 5 wt%, preferably 0.03 to 0.3 wt%, more preferably 0.05 to 0.2 wt%.

The amount of water used in the emulsion polymerization is usually in the range of 100 to 200% by weight with respect to 100% by weight of the total amount of monomers used in the copolymer (A). From the viewpoint of productivity.

The polymerization temperature for polymerizing the copolymer (A) is not limited, but is preferably 50 to 75 ° C, and more preferably 55 to 70 ° C. During the polymerization, it is preferable to keep the internal temperature constant within this polymerization temperature range as long as the exotherm accompanying the reaction can be confirmed. When the polymerization temperature is less than 50 ° C., the polymerization initiator is not easily decomposed, so that the polymerization start tends to be unstable. On the other hand, when it exceeds 75 ° C., the molecular weight cannot be increased because the radical generation rate becomes too fast.

The method for adding the monomer during the production of the copolymer (A) is not limited. For example, generally known methods such as batch addition, continuous addition, and multistage addition in which the composition of each stage is changed. Can be adopted. Of these, methods such as batch addition and continuous addition are preferred. Moreover, when performing superposition | polymerization by continuous addition, it is preferable that continuous addition time shall be 3 hours or more. When the polymerization time is less than 3 hours, the heat generated by the polymerization heat is large, so that it is difficult to control the polymerization temperature, and as a result, the molecular weight of the copolymer tends to decrease. Furthermore, the total polymerization time including the continuous addition time and the polymerization time after the continuous addition is preferably 7 to 11 hours.

When the copolymer (A) of the present invention is polymerized, the polymerization activity is reduced due to the influence of dissolved oxygen in the polymerization solution. The oxygen concentration before polymerization is preferably 6.5 mg / L or less, and more preferably 5.0 mg / L or less. More preferably, the dissolved oxygen is substantially completely removed by an oxygen removing agent such as hydrosulfite.

In the case of emulsion polymerization or the like, the weight average particle size of the copolymer (A) latex is not particularly limited, but the weight average particle size of the copolymer (A) latex is preferably 160 nm or less. When the weight average particle diameter is 160 nm or less, not only the polymerization time can be reduced, but also the molding processability when used as a processing aid is improved. The particle size of the latex of the copolymer (A) can be appropriately controlled by adjusting the type of emulsifier used in the polymerization, the amount of the emulsifier, the method of adding the monomer, and the like. The weight average particle diameter of the copolymer (A) latex can be measured by observing the particles using a transmission electron microscope.

The amount of the unreacted monomer component remaining in the latex of the copolymer (A) of the present invention is not particularly limited, but is preferably 2.0% by weight or less based on the copolymer (A). . The residual unreacted monomer component of the latex of the copolymer (A) is the monomer or monomer used for polymerizing the copolymer remaining in the latex of the copolymer (A). It is composed of oligomers having a weight average molecular weight of 200 to 1000 such as dimers, trimers and the like. Usually, since the unreacted monomer component is removed in the step of salting out the copolymer latex, there is almost no need to manage the residual unreacted monomer in the copolymer latex. However, when the amount of residual unreacted monomer component in the copolymer latex is not more than 2.0% by weight instead of the amount of residual unreacted monomer component contained in the copolymer powder, When salting out the latex of A), excessive fusion of the particles of the copolymer (A) can be suppressed, so that the powder of the copolymer (A) having excellent dispersibility becomes a final product. As a result, the molding processability of the is improved. The amount of the residual unreacted monomer component can be controlled by adjusting the polymerization temperature and the like. The amount of the residual unreacted monomer component in the latex of the copolymer (A) can be measured by using a gas chromatography analyzer.

After the reaction by emulsion polymerization, the copolymer (A) can be obtained by salting out and drying the latex. The coagulant used in salting out is not limited, and for example, at least one of sulfuric acid, magnesium sulfate, calcium chloride, aluminum sulfate and the like can be suitably used. The drying method is not particularly limited, and either natural drying or forced drying can be employed. Moreover, the obtained copolymer (A) can also perform classification etc. as needed.

(1-3) Physical properties of copolymer (A) The peak apex molecular weight (Mp) of the copolymer (A) of the present invention needs to be 1 million or more. When the peak vertex molecular weight is less than 1,000,000, it is impossible to impart desired melt elasticity to the thermoplastic resin as a processing aid. From the viewpoint of moldability, it is preferably 2 million or more, more preferably 3.5 million or more. The upper limit of the molecular weight (Mp) is not particularly limited, and can be set to 8 million or even 6 million, for example. The peak apex molecular weight is a value measured by gel permeation chromatography (GPC), and indicates the value of the apex portion having the highest detection frequency on the detected molecular weight distribution. In addition, molecular weight distribution of the copolymer (A) obtained by this invention, Mw / Mn by a gel permeation chromatography (GPC) (Mw shows a weight average molecular weight, Mn shows a number average molecular weight.) Here. From the viewpoint of thermal stability and the like, it is preferably 5.0 or more.

The peak apex molecular weight of the copolymer (A) of the present invention can be adjusted by adding a chain transfer agent, for example. However, when a chain transfer agent is used, the reaction rate may be lowered. Therefore, for example, it is preferable to adjust by a use amount of a polymerization initiator, a monomer addition method, and the like.

The copolymer (A) of the processing aid of the present invention is usually in the form of particles (powder). The particles having a size of 355 μm or more contained in the powder are contained in 1 to 50% by weight in 100% by weight of the copolymer (A). When particles with a particle diameter of 355 μm or more are less than 1% by weight, aggregation of salting out particles is insufficient, so that the biting into the screw is inferior at the time of kneading and the dispersibility is deteriorated. Inferior in workability. Moreover, when the particle diameter exceeds 355 μm, the proportion of coarse particles is too large, resulting in poor dispersibility and inferior moldability of the final product. The proportion of the particles is preferably in the range of 2 to 45% by weight, more preferably in the range of 5 to 35% by weight. Further, among the particles having a particle size of 850 μm or more among the particles having a particle size of 355 μm or more, it is preferably less than 18% by weight, more preferably less than 10% by weight from the viewpoint of the size of the final product or moldability. Furthermore, it is most preferable that particles having a size of 850 μm or more are not present.

When particles of 850 μm or more are present as the powder of the copolymer (A) of the present invention, the crushing strength of the particles of 850 μm or more is not particularly limited, but is 250 to 900 g / mm ^2. preferable. If the crushing strength is in the range of 250 to 900 g / mm ² , the copolymer (A) powder becomes fine particles during transportation and storage, and the ease of handling as a powder is reduced, so that moderate ease of loosening is achieved. Therefore, the dispersibility when kneaded with other thermoplastic resins is improved, and the moldability is improved. From this point of view, 300 to 850 g / mm ² is more preferable, and 350 to 800 g / mm ² is most preferable.

The particle size of the powder in the copolymer (A) of the present invention can be adjusted, for example, by changing the salting-out temperature, the slurry concentration, the concentration of the salting-out agent, etc. during salting-out. The salting out temperature is preferably a temperature that is 10 ° C. to 40 ° C. lower than the glass transition temperature (° C.) of the copolymer (A) from the viewpoint of preferable particle size and excessive fusion suppression.

(1-4) Other components of the processing aid of the present invention The processing aid of the present invention includes the copolymer (A) and, if necessary, the following as long as the effects of the present invention are not impaired. Additives may be included. For example, 1) 2,6-di-t-butyl-4-methylphenol, 2- (1-methylcyclohexyl) -4,6-dimethylphenol, 2,2′-methylene-bis- (4-ethyl-6) -T-butylphenol), 4,4'-thiobis- (6-t-butyl-3-methylphenol), dilaurylthiodipropionate, tris (di-nonylphenyl) phosphite, etc .; 2) UV absorbers such as pt-butylphenyl succinate, 2,2'-dihydroxy-4-methoxybenzophenone, 2- (2'-hydroxy-4'-n-octoxyphenyl) benzotriazole; 3) For example, wax, paraffin wax, stearic acid, hydrogenated oil, stearylamide, methylenebisstearylamide, ethylenebisstearylamide lubricants such as n-butyl stearate, ketone wax, octyl alcohol, lauryl alcohol, hydroxystearic acid triglyceride; 4) for example antimony trioxide, aluminum hydroxide, zinc borate, tricresyl phosphate, tris (dichloropropyl) phosphate, Flame retardant such as chlorinated paraffin, tetrabromobisphenol A, condensate of tetrabromobisphenol A and epichlorohydrin; 5) antistatic agent such as stearylamidopropyldimethyl-β-hydroxyethylammonium nitrate; 6) such as titanium oxide, Coloring agents such as carbon black; 7) Fillers such as calcium carbonate, clay, silica, glass fiber, glass sphere and carbon fiber; 8) Lower carbon such as propane, butane, pentane and hexane. Examples thereof include halogenated hydrocarbons such as hydrogen fluoride, methyl chloride, dichloromethane, trichloromonofluoromethane, and dichlorodifluoromethane, and blowing agents such as carbon dioxide and nitrogen.

2. Use of the processing aid of the present invention The processing aid of the present invention can be blended with a thermoplastic resin or a resin composition containing the same in order to improve or improve the molding processability and the like. More specifically, the processing aid of the present invention can be added to the thermoplastic resin in order to improve the physical properties (particularly melt elasticity) of the molten thermoplastic resin. In other words, the processing aid of the present invention can be suitably used for a method for improving the melt elasticity (and molding processability) of a thermoplastic resin. Then, by adding the processing aid of the present invention to the thermoplastic resin, a resin molded product excellent in quality, appearance and the like can be obtained.

The thermoplastic resin (B) to which the processing aid of the present invention can be applied is not particularly limited. For example, (rubber reinforced) styrene such as ABS resin, AES resin, ASA resin, SAS resin, PS resin, HIPS resin, and AS resin. Resin, vinyl chloride resin, chlorinated polyethylene resin, ethylene-vinyl acetate resin, polypropylene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyacetal, polyamide, polyamide elastomer, epoxy resin, polyvinylidene fluoride, polysulfone, polyisoprene, natural rubber In addition to chlorinated butyl rubber, PPE resin, PPS resin, polyether ether ketone, styrene-maleic anhydride copolymer, a mixture containing two or more of these resins, alloy resin, and the like can be given. In particular, at least one of (rubber reinforced) styrene-based resin such as ABS resin, AES resin, ASA resin, SAS resin, PS resin, HIPS resin, AS resin, vinyl chloride resin, chlorinated polyethylene resin, ethylene-vinyl acetate resin, etc. Species are preferred.

The addition amount of the processing aid of the present invention can be appropriately set according to the type of thermoplastic resin to be applied, etc., but generally 0.1 to 15 parts by weight per 100 parts by weight of the thermoplastic resin In particular, it is more preferable to add 0.5 to 12 parts by weight.

3. Thermoplastic resin composition and molded article thereof The present invention includes a thermoplastic resin composition containing 100 parts by weight of a thermoplastic resin and 0.1 to 15 parts by weight of the processing aid of the present invention. The present invention also includes a resin molded product obtained by molding the thermoplastic resin composition.

As the above-mentioned thermoplastic resin, 2. Can be used. Further, as the processing aid of the present invention, the above-mentioned 1. Can be used.

In addition, the thermoplastic resin composition of the present invention may contain other additives as necessary. That is, the same additives as those that can be used in the processing aid of the present invention can be used. For example, 1) 2,6-di-t-butyl-4-methylphenol, 2- (1-methylcyclohexyl) -4,6-dimethylphenol, 2,2′-methylene-bis- (4-ethyl-6) -T-butylphenol), 4,4'-thiobis- (6-t-butyl-3-methylphenol), dilaurylthiodipropionate, tris (di-nonylphenyl) phosphite, etc .; 2) UV absorbers such as pt-butylphenyl succinate, 2,2'-dihydroxy-4-methoxybenzophenone, 2- (2'-hydroxy-4'-n-octoxyphenyl) benzotriazole; 3) For example, wax, paraffin wax, stearic acid, hydrogenated oil, stearylamide, methylenebisstearylamide, ethylenebisstearylamide lubricants such as n-butyl stearate, ketone wax, octyl alcohol, lauryl alcohol, hydroxystearic acid triglyceride; 4) for example antimony trioxide, aluminum hydroxide, zinc borate, tricresyl phosphate, tris (dichloropropyl) phosphate, Flame retardant such as chlorinated paraffin, tetrabromobisphenol A, condensate of tetrabromobisphenol A and epichlorohydrin; 5) antistatic agent such as stearylamidopropyldimethyl-β-hydroxyethylammonium nitrate; 6) titanium oxide, Coloring agents such as carbon black; 7) Fillers such as calcium carbonate, clay, silica, glass fiber, glass sphere and carbon fiber; 8) Lower carbons such as propane, butane, pentane and hexane Examples thereof include halogenated hydrocarbons such as hydrogen fluoride, methyl chloride, dichloromethane, trichloromonofluoromethane, and dichlorodifluoromethane, and blowing agents such as carbon dioxide and nitrogen.

The thermoplastic resin composition of the present invention or a molded product thereof can also be obtained according to a known method for producing a thermoplastic resin or a resin molded product. For example, the processing aid of the present invention (copolymer (A)) and thermoplastic resin (B) (or a resin composition containing the same) are mixed in advance by a mixer or the like without being melted and heated in advance. A resin molded product can be obtained by directly feeding into an extrusion molding machine, injection molding machine, sheet molding machine, vacuum molding machine, profile forming machine, foam molding machine, blow molding machine, and the like. In addition, for example, using various extruders, Banbury mixers, kneaders, rolls, etc., the present processing aid and the thermoplastic resin (B) (or a resin composition containing the same) are melt-heated and mixed, for example, an extruder, A resin molded product can be obtained by molding using an injection molding machine, a sheet molding machine, a vacuum molding machine, a profile forming machine, a foam molding machine, a blow molding machine, or the like. Preferably, it is a method in which each component is directly fed into a molding machine without being previously melted and mixed. Various molded articles obtained by the molding method can be used for various parts such as home appliances and automobile parts by utilizing their excellent properties.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited to the examples. In addition, unless otherwise indicated, the part and% in an Example are a weight part and weight%. In addition, various measurement items in the examples were according to the following measurement methods.

A gel permeation chromatograph (LC-10A vp) manufactured by Shimadzu Corporation was used as a measuring and analyzing apparatus for peak apex molecular weight (Mp), number average molecular weight (Mn), and weight average molecular weight (Mw) , and the column was manufactured by Tosoh Corporation GMH HR. -H (30) was used. Calibration was performed based on polystyrene standards, and tetrahydrofuran was used as the solvent, and measurement was performed at a flow rate of 0.5 ml / min and a temperature of 50 ° C.
The measurement sample was prepared by placing 0.01 g of a measurement object and 25 ml of tetrahydrofuran in a 50 ml glass flask, sealing it, soaking it at 25 ° C. for 12 hours, and then filtering with a polytetrafluoroethylene membrane filter having a pore size of 3.0 μm. .
The peak vertex molecular weight (Mp) is a numerical value obtained by quantifying the value of the vertex portion having the highest detection frequency on the detected molecular weight distribution. The number average molecular weight (Mn) and the weight average molecular weight (Mw) were quantitatively calculated from the detected values according to the following formulas. The results are shown in Table 1.

The definitions of symbols in the formula are as follows.
W = total weight of polymer Wi = weight of i-th polymer Mi = molecular weight at the i-th elution time Ni = number of molecular weights Mi = height at the i-th elution time

Measurement of particle size distribution After weighing about 50 g of the copolymer (A) powder, 20 mesh (mesh size 850 μm) using a dry sonic sieving measuring machine Sonic Shifter L-200P (manufactured by Seishin Enterprise Co., Ltd.) The particle size distribution was measured under the condition of using each sieve and a 42 mesh (aperture 355 μm) sieve. The particle content with a particle size of 850 μm or more and 355 μm or more and less than 850 μm was calculated by the following formula. The results are shown in Table 1.
Content of particles having a particle diameter of 850 μm or more = weight of particles remaining on a 20 mesh sieve / weight of powder before measurement × 100 (%)
Content of particles having a particle size of 355 μm or more and less than 850 μm = weight of particles remaining on 42 mesh sieve / powder weight before measurement × 100 (%)

Measurement of weight average particle size of latex of copolymer (A) Copolymer latex is dyed with osmium tetroxide (OsO ₄ ), dried, and photographed with a transmission electron microscope (JEOL Ltd., JEM-1400) Did. The area of 100 particles was measured using an image analysis processor (apparatus name: IP-1000PC manufactured by Asahi Kasei Co., Ltd.), the equivalent circle diameter (diameter) was obtained, and the weight average particle diameter of the copolymer latex was determined. Calculated. The results are shown in Table 1.

Measurement of Residual Unreacted Monomer Component Amount of Latex of Copolymer (A) About 1.0 g of copolymer latex was diluted with about 20 ml of dimethylformamide, and 0.06% with dimethylformamide as an internal standard in the diluted solution. A sample for measurement was prepared by adding 5.0 ml of a diluted hexylbenzene solution.
Using a gas chromatography analyzer (GC apparatus: [Shimadzu Corporation GC2010 Capillary column: Agilent J & W DB-5]), measurement was performed under the following conditions, and from the obtained chart, the area with hexylbenzene as a standard substance was measured. The amount of unreacted monomer components remaining in the copolymer latex was determined by calculating the ratio. The results are shown in Table 1.
Injection volume: 1.0 μl
(Sample vaporization chamber)
Sample vaporization chamber temperature 230 ° C Carrier gas: Helium Control mode: Linear velocity
Pressure: 90.6 kPa Total flow rate: 44.2 mL / min
Column flow rate: 1.00 mL / min Linear velocity: 26.4 cm / sec
(Column oven)
Column temperature 70 ° C Equilibrium time: 3.0min
(Detector FID)
Detector temperature 330 ° C Sampling rate: 40 msec
Makeup gas: Nitrogen / Air Makeup flow rate: 30.0 mL / min
Hydrogen flow rate: 40.0 mL / min Air flow rate: 400.0 mL / min

Measurement of Crushing Strength Using a sonic sifter L-200P (Seishin Enterprise Co., Ltd.), a dry sonic sieving measuring machine, a powder of copolymer (A) exceeding 20 mesh (aperture 850 μm) was obtained. The crushing strength of this powder was measured using a particle hardness measuring device (BHT-500 manufactured by Seishin Enterprise Co., Ltd.) (load cell: 500 g environment: 23 ° C.). At the time of measurement, 20 points were randomly selected and measured, and an average value was obtained. The results are shown in Table 1.
Crushing strength within the range of 250 to 900 g / mm ² : ○
Out of range of crushing strength of 250 to 900 g / mm ² : ×

(1) Synthesis of copolymer (A) The copolymer (A) of the processing aid of the present invention was synthesized by the following methods.

Production of copolymer A-1 In a reactor purged with nitrogen, 150 parts of pure water, 4 parts of a monomer mixture in the proportions shown in Table 1, 1.5 parts of a 20% aqueous solution of sodium dodecylbenzenesulfonate were placed at 50 ° C. Heated. After heating, 0.1 part of potassium persulfate was added, the temperature was raised to 60 ° C. at a rate of 0.5 ° C./min, and the mixture was aged for 10 minutes after reaching 60 ° C. After aging, 96 parts of the monomer mixture and 8.5 parts of 20% aqueous solution of sodium dodecylbenzenesulfonate were continuously added over 6 hours. After completion of the addition, polymerization was further performed at 60 ° C. for 4 hours to obtain a copolymer latex A-1.
4 parts of magnesium sulfate is put into the salting-out tank with respect to 100 parts of the solid content of the copolymer latex A-1 and water under the condition that the solid content in the salting-out tank after dropping is 15%. The bath was heated to 85 ° C. After the temperature elevation, the obtained copolymer latex A-1 was added dropwise. After completion of the dropwise addition, the salting-out tank was heated to 95 ° C, and the salting-out was terminated when the temperature reached 95 ° C. After salting out, dehydration and washing were performed using a centrifugal dehydrator, and the mixture was dried at 90 ° C. for 12 hours using a hot air drier to obtain a copolymer A-1.

Production of copolymer A-2 Using the monomer mixture in the proportions shown in Table 1, the aqueous emulsifier solution added initially is 1.0 part, and the amount of potassium persulfate used is 0.09 part. The copolymer latex was polymerized under the same conditions as for the copolymer A-1, except that the emulsifier aqueous solution used in the above was changed to 8.0 parts and the continuous addition time of the monomer mixture and the emulsifier aqueous solution was changed to 4 hours. A-2 was obtained. Salting-out and drying conditions were performed in the same manner as for copolymer A-1, and copolymer A-2 was obtained.

Production of copolymer A-3 Using the monomer mixture in the proportions shown in Table 1, the amount of potassium persulfate was 0.04 parts, and the aging time after the reactor reached 60 ° C. was 40 minutes. Polymerization was carried out under the same conditions as for copolymer A-2 except that the continuous addition time of the monomer mixture and the aqueous emulsifier solution was changed to 3.5 hours to obtain copolymer latex A-3. The salting-out and drying conditions were the same as those for copolymer A-1, except that the temperature of the salting-out tank was changed to 80 ° C., and copolymer A-3 was obtained.

Production of copolymer A-4 The copolymer latex A-2 was used, and the salting-out and drying conditions were the same except that the temperature of the salting-out tank was changed to 83 ° C and the temperature raised after dropping was changed to 90 ° C. The same process as for polymer A-2 was carried out to obtain copolymer A-4.

Production of copolymer A-5: A reactor purged with nitrogen was charged with 130 parts of pure water, 3 parts of a monomer mixture in the ratio shown in Table 1, and 1.5 parts of a 20% aqueous solution of potassium stearate, and the mixture was heated to 50 ° C. Heated. After heating, 0.08 part of potassium persulfate was added, the temperature was raised to 60 ° C. at a rate of 0.5 ° C./min, and the mixture was aged for 40 minutes after reaching 60 ° C. After aging, 97 parts of the monomer mixture and 8.5 parts of a 20% aqueous solution of potassium stearate were continuously added over 4.25 hours. After completion of the addition, polymerization was further performed at 60 ° C. for 4 hours to obtain a copolymer latex A-5.
3 parts of magnesium sulfate and 3 parts of 10% sulfuric acid aqueous solution are salted with respect to water with a solid content of 15% in the salting-out tank after completion of dropping and 100 parts of solid content of copolymer latex A-5. The salting-out tank was heated up to 80 degreeC in the precipitation tank. After the temperature elevation, the obtained copolymer latex A-5 was added dropwise. After completion of the dropwise addition, the salting-out tank was heated to 95 ° C, and the salting-out was terminated when the temperature reached 95 ° C. After salting out, the mixture was dehydrated and washed using a centrifugal dehydrator, and dried at 90 ° C. for 12 hours using a hot air drier to obtain a copolymer A-5.

Production of copolymer A-6 In a reactor purged with nitrogen, 140 parts of pure water, 4 parts of a monomer mixture in the proportions shown in Table 1, 1.5 parts of 20% aqueous solution of dipotassium alkenyl succinate were placed at 50 ° C. Heated. After heating, 0.06 part of potassium persulfate was added, the temperature was raised to 60 ° C. at a rate of 0.5 ° C./min, and the mixture was aged for 10 minutes after reaching 60 ° C. After aging, 96 parts of the monomer mixture and 8.5 parts of 20% aqueous solution of dipotassium alkenyl succinate were continuously added over 3.5 hours. After completion of the addition, polymerization was further performed at 60 ° C. for 4 hours to obtain a copolymer latex A-6.
3 parts of magnesium sulfate and 1.5 parts of 10% aqueous sulfuric acid solution for 100 parts of solid content of copolymer latex A-6 and water under conditions where the solid content concentration in the salting-out tank after dropping is 15% Was put in a salting-out tank, and the salting-out tank was heated to 75 ° C. After the temperature elevation, the obtained copolymer latex A-6 was added dropwise. After completion of dropping, the salting-out tank was heated to 90 ° C., and salting-out was terminated when the temperature reached 90 ° C. After salting out, dehydration and washing were performed using a centrifugal dehydrator, and the mixture was dried at 85 ° C. for 12 hours using a hot air drier to obtain a copolymer A-6.

Production of copolymer A-7 Polymerization was carried out under the same conditions as for copolymer A-6, except that the monomer mixture was used in the proportions shown in Table 1, to obtain copolymer latex A-7. Salting out and drying conditions were performed in the same manner as for copolymer A-6 to obtain copolymer A-7.

Production of copolymer A-8 Using the monomer mixture in the proportions shown in Table 1, the potassium persulfate amount was changed to 0.04 parts, and the aging time after the reactor reached 60 ° C. was changed to 40 minutes. Except for the above, polymerization was performed under the same conditions as for copolymer A-7, to obtain copolymer latex A-8. Salting-out and drying conditions were performed in the same manner as for copolymer A-7 to obtain copolymer A-8.

Production of copolymer A-9 Using copolymer latex A-7, the salting out and drying conditions were the same as those for copolymer A-6 except that the temperature raised after dropping was changed to 85 ° C. And copolymer A-9 was obtained.

Production of copolymer A-10 The monomer mixture was used in the proportion described in Table 1, the monomer mixture initially added was used as 2 parts, and the monomer used during continuous addition was used as 98 parts initially. A copolymer latex A-10 was obtained using the same conditions as for the copolymer A-7, except that the aqueous emulsifier solution was changed to 2.0 parts and the aqueous emulsifier solution used during continuous addition was changed to 8.0 parts. . Salting-out and drying conditions were performed in the same manner as for copolymer A-6 to obtain copolymer A-10.

Production of copolymer A-11 Polymerization was carried out under the same conditions as for copolymer A-6, except that the monomer mixture was used at the ratio shown in Table 1 and the polymerization temperature after continuous addition was changed to 73 ° C. To obtain a copolymer latex A-11. Salting-out and drying conditions were performed in the same manner as for copolymer A-6 to obtain copolymer A-11.

Preparation of copolymer A-12 The monomer mixture was used in the proportions shown in Table 1, the monomer mixture initially added was 3 parts, and the monomer used during continuous addition was 97 parts initially. Polymerization was carried out under the same conditions as for the copolymer A-11, except that the aqueous emulsifier solution was changed to 3.0 parts and the aqueous emulsifier solution used for continuous addition was changed to 7.0 parts, to obtain a copolymer latex A-12. It was. Salting-out and drying conditions were performed in the same manner as for copolymer A-6 to obtain copolymer A-12.

Production of copolymer a-1 In a reactor purged with nitrogen, 150 parts of pure water, 3 parts of a mixture of the monomer shown in Table 1 and 0.05 part of tertiary decyl mercaptan, Na20 dodecylbenzenesulfonate A 1.0% aqueous solution was added and heated to 50 ° C. After heating, 0.1 part of potassium persulfate was added, the temperature was raised to 60 ° C. at a rate of 0.5 ° C./min, and the mixture was aged for 10 minutes after reaching 60 ° C. After aging, 97 parts of the monomer mixture and 9.0 parts of a 20% aqueous solution of sodium dodecylbenzenesulfonate were continuously added over 6 hours. After completion of the addition, polymerization was further carried out at 60 ° C. for 4 hours to obtain a copolymer latex a-1. Salting-out and drying conditions were performed in the same manner as for copolymer A-1, and copolymer a-1 was obtained.

After the completion of the production of the copolymer a-2 , the magnesium sulfate was added to water in a condition that the solid content concentration in the salting-out tank becomes 7.5% and 100 parts of the solid content of the copolymer latex A-2. 0.5 part was put into a salting-out tank, and the salting-out tank was heated to 65 ° C. After the temperature elevation, the obtained copolymer latex A-2 was added dropwise. Salting out was terminated when the dropping was completed. After salting out, the mixture was dehydrated and washed using a centrifugal dehydrator, and dried at 90 ° C. for 12 hours using a hot air drier to obtain a copolymer a-2.

After the completion of the production of the copolymer a-3, the water under the condition that the solid content in the salting-out tank is 20% and the solid content of 100 parts of the copolymer latex A-7 are 3 parts of magnesium sulfate and 3 parts of 10% sulfuric acid aqueous solution was put into a salting-out tank, and the salting-out tank was heated to 85 ° C. After the temperature elevation, the obtained copolymer latex A-7 was added dropwise. After completion of the dropwise addition, the salting-out tank was heated to 95 ° C, and the salting-out was terminated when the temperature reached 95 ° C. After salting-out, dehydration and washing were performed using a centrifugal dehydrator, and the mixture was dried for 12 hours at 85 ° C. using a hot air drier to obtain a copolymer A-5.

(2) Physical properties of the copolymer or latex About the copolymer or latex, peak peak molecular weight, number average molecular weight, weight average molecular weight, molecular weight distribution, weight average particle diameter of latex, content of residual unreacted monomer and compression The strength was examined. The results are shown in Table 1.

(3) Manufacture of the resin molded product which consists of a thermoplastic resin composition After using each copolymer, a thermoplastic resin (B), and an additive so that it may become a composition shown in Table 2, after mixing these uniformly Then, the sheet was put into a 40 mm sheet extruder set at 160 ° C., and a sheet was formed using a die having a thickness of 2 mm and a width of 200 mm. The thermoplastic resin (B) and additives used in Table 2 are as shown below.
Thermoplastic resin (B)
-Vinyl chloride resin: Product name "TH-1000" (Tayo PVC Co., Ltd., degree of polymerization 1000)
ABS resin: ABS resin obtained by known emulsion polymerization using 60% polybutadiene, 30% styrene and 10% acrylonitrile. AS resin: Obtained by known emulsion polymerization using 75% styrene and 25% acrylonitrile. AS resin additive / stabilizer: Alkyl tin mercapto compound Product name “TM-181FSJ” (manufactured by Katsuta Chemical Co., Ltd.)
・ Lubricant: Stearic acid compound Product name “L-27” (manufactured by Katsuta Chemical Co., Ltd.)

(4) Evaluation of molding processability of resin molded product In the above (3), a sample having a length of 2 m was cut out 30 minutes after the start of sheet molding, and the width of this sample was measured at intervals of 5 cm to obtain the maximum of the sample. The difference between the large and minimum widths and the average width were calculated. The evaluation results are shown in Table 2. The magnitude | size of an average width | variety shows the magnitude | size of the modification effect to the thermoplastic resin (B) by a copolymer (A), and shows that the modification effect is so large that a numerical value is large.

Evaluation in Table 2 was performed as follows.
Average width is less than 170 mm = E
Average width is 170mm or more and less than 174mm
Average width is 174 mm or more and less than 178 mm = C
Average width is 178mm or more and less than 182mm = B
Average width is 182mm or more = A

In addition, the difference between the maximum width and the minimum width is a measure of the molding processability of the thermoplastic resin composition in which the copolymer (A) is blended with the thermoplastic resin (B). Indicates high.
Evaluation in the table was performed as follows.
The difference between the maximum width and the minimum width is 7mm or more = ×
Difference between maximum width and minimum width is 5mm or more and less than 7mm = △
Difference between maximum width and minimum width is 3mm or more and less than 5mm = ○
Difference between maximum width and minimum width is less than 3mm = ◎

As shown in Table 2, Examples 1 to 19 are thermoplastic resin compositions according to the present invention, and it can be seen that all are excellent in moldability. When the peak apex molecular weight is 3.5 million or more, when the weight average particle diameter of the copolymer latex is 160 nm or less and / or when the amount of volatile matter remaining in the copolymer latex is 0.2 wt% or less, In particular, the results show that the moldability is excellent.

On the other hand, Comparative Example 1 in which the copolymer of the present invention was not used was inferior in the moldability of the vinyl chloride resin. Comparative Example 2 using a copolymer having a peak peak molecular weight of less than 1 million, and Comparative Example 3 using a copolymer having a particle size of 355 μm or more of less than 1% by weight or more than 50% by weight In 5 to 5, no effect of improving the molding processability with respect to vinyl chloride resin or ABS resin was observed.

By blending the processing aid of the present invention, the molding processability of the thermoplastic resin composition can be improved, and as a result, a product with high commercial value can be produced. Therefore, the present invention has great industrial value.

Claims (9)

1. A processing aid for blending with a thermoplastic resin,
   (1) The processing aid is a) an aromatic vinyl monomer of 50 to 95% by weight, b) a vinyl cyanide monomer of 5 to 50% by weight, and d) another vinyl copolymerizable therewith. A copolymer (A) obtained by copolymerizing 0 to 45% by weight of a system monomer (provided that the total amount of monomers used in the copolymer (A) is 100% by weight);
   (2) The peak apex molecular weight (Mp) of the copolymer (A) is 1 million or more,
   (3) The copolymer is in the form of particles and contains 1 to 50% by weight of particles having a particle diameter of 355 μm or more in 100% by weight of the copolymer (A).
   A processing aid for thermoplastic resins.
2. The copolymer comprises a) an aromatic vinyl monomer 50 to 70% by weight, b) a vinyl cyanide monomer 9 to 40% by weight, c) a (meth) acrylic acid ester monomer 21 to 35% by weight and d) a copolymer (A) obtained by copolymerizing 0 to 20% by weight of other vinyl monomers copolymerizable with these (monomers used in the copolymer (A)) 2. The processing aid for thermoplastic resin according to claim 1, wherein the total amount of the polymer is 100% by weight.
3. The processing aid for a thermoplastic resin according to claim 1 or 2, wherein the peak apex molecular weight (Mp) of the copolymer (A) is 2 million or more.
4. The processing aid for a thermoplastic resin according to any one of claims 1 to 3, wherein the crushing strength of the particles of 850 µm or more contained in the copolymer (A) is 250 to 900 g / mm ² .
5. The processing aid for a thermoplastic resin according to claim 1, wherein the copolymer (A) is recovered from a latex which is a reaction product obtained by emulsion polymerization of the monomer.
6. The processing aid for a thermoplastic resin according to claim 5, wherein the latex particles of the copolymer (A) have a weight average particle diameter of 160 nm or less.
7. The processing aid for a thermoplastic resin according to claim 5, wherein the total amount of unreacted components remaining in the latex is 2.0% by weight or less.
8. A thermoplastic resin composition comprising 100 parts by weight of a thermoplastic resin and 0.1 to 15 parts by weight of the processing aid according to any one of claims 1 to 7.
9. A resin molded product obtained by molding the thermoplastic resin composition according to claim 8.