JP2022155550A - Epoxy group-containing vinyl-based copolymer, method for producing the same, thermoplastic resin composition and molded article - Google Patents

Abstract

To provide an epoxy group-containing vinyl-based copolymer from which a thermoplastic resin composition that improves moldability and releasability of a thermoplastic resin such as a thermoplastic polyester resin, and has a good balance between flowability and impact resistance can be provided.SOLUTION: An epoxy group-containing vinyl-based copolymer (A) is a copolymer composed of at least 60 to 79.9 pts.wt. of an aromatic vinyl-based monomer (a1), 20 to 39.9 pts.wt. of a vinyl cyanide-based monomer (a2) and 0.1 to 5 pts.wt. of an epoxy group-containing vinyl-based monomer (a3) (total of (a1), (a2) and (a3) is 100 pts.wt.), and has a weight average molecular weight Mw in terms of polystyrene determined by GPC of 100,000 to 300,000, and a ratio Mw/Mn of the weight average molecular weight Mw to a number average molecular weight Mn of 2.5 to 3.5.SELECTED DRAWING: None

Description

In the present invention, by blending an epoxy group-containing vinyl copolymer with a thermoplastic resin such as a thermoplastic polyester resin, the balance between fluidity and impact resistance is good, and moldability and mold release are obtained. The present invention relates to a thermoplastic resin composition having excellent properties and molded articles thereof.

Styrene-based resins, represented by acrylonitrile-butadiene-styrene (ABS) resin, have excellent mechanical properties, molding processability, and electrical insulation properties. It is used in a wide range of fields. On the other hand, polyester resins such as polybutylene terephthalate (PBT) resin are excellent in electrical properties, chemical resistance, heat resistance, dimensional stability, etc. It is widely used as a material for manufacturing interior and exterior parts for vehicles and other general industrial products. Many of these parts require the resins used to have good moldability.

In recent years, polymer alloy technology, in which a plurality of different types of polymers are mixed, has been studied as a means of improving physical properties of polymer compounds. The purpose of the polymer alloy is to obtain a polymer having the characteristics of each constituent polymer by mixing a plurality of different polymers.

In Patent Document 1, one or more selected from glycidyl methacrylate and an aromatic vinyl monomer/vinyl cyanide monomer is used for the purpose of improving the molding processability, heat resistance, and hydrolysis resistance of a thermoplastic polyester resin. A thermoplastic resin comprising an epoxy-modified vinyl copolymer having a weight average molecular weight of 50,000 to 300,000 and a molecular weight distribution Mw/Mn of 1.9 to 2.4, which is obtained by copolymerizing a monomer of A composition is proposed. However, releasability has not been studied, and a problem remains in releasability.

In Patent Document 2, a structural unit based on an aromatic vinyl-based monomer and a vinyl cyanide-based monomer are used for the purpose of achieving both mechanical properties, thermal properties, and dimensional stability of a molded article made of a fiber-reinforced resin composition. or consisting of a structural unit based on an aromatic vinyl-based monomer, a structural unit based on a vinyl cyanide-based monomer, and a structural unit based on another vinyl-based monomer. proposed the formulation of modifiers consisting of However, its compatibility with polyester is insufficient, and there remain concerns about moldability and impact resistance of molded articles.

International Publication No. 2018/043334 JP 2019-210489 A

INDUSTRIAL APPLICABILITY The present invention provides a thermoplastic resin composition having improved moldability and releasability of thermoplastic resins such as thermoplastic polyester resins and having a good balance between fluidity and impact resistance. An object of the present invention is to provide a vinyl copolymer. The present invention also provides a thermoplastic resin composition containing this epoxy group-containing vinyl copolymer and a thermoplastic resin such as a thermoplastic polyester resin, and a molded article obtained by molding this thermoplastic resin composition. With the goal.

The present inventors obtained by copolymerizing an epoxy group-containing vinyl-based monomer, an aromatic vinyl-based monomer, and a vinyl cyanide-based monomer in a predetermined ratio, It has been found that an epoxy group-containing vinyl copolymer having a distribution Mw/Mn within a predetermined range solves the above problems. The present invention has the following configurations.
(1) At least 60 to 79.9 parts by weight of an aromatic vinyl monomer (a1), 20 to 39.9 parts by weight of a vinyl cyanide monomer (a2), and an epoxy group-containing vinyl monomer ( a3) A copolymer comprising a vinyl monomer mixture (a) containing 0.1 to 5 parts by weight (where the total of (a1), (a2) and (a3) is 100 parts by weight) The polystyrene equivalent weight average molecular weight Mw obtained by GPC is 100,000 to 300,000, and the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn is 2.5 to 3.5. An epoxy group-containing vinyl copolymer (A) characterized by:
(2) In the cumulative elution weight obtained by GPC/FT-IR measurement of the epoxy group-containing vinyl copolymer (A), the epoxy group in an integrated value of less than 30% integrated from the low molecular weight side of the copolymer Let (I) be the average concentration of the containing vinyl monomer unit, and the average concentration of the epoxy group-containing vinyl monomer unit in the integrated value of 30% or more and less than 70% integrated from the low molecular weight side of the copolymer is ( Assuming that II) is the average concentration of the epoxy group-containing vinyl monomer units at an integrated value of 70% or more integrated from the low molecular weight side of the copolymer, the average concentration of the epoxy group-containing vinyl monomer units is (III). The epoxy group-containing vinyl copolymer according to (1), wherein the composition distribution is (I)<(II) and (III)<(II).
(3) The epoxy group-containing vinyl according to (1) or (2), wherein the vinyl-based monomer mixture (a) is subjected to suspension polymerization using two or more mercaptan-based chain transfer agents. A method for producing a system copolymer.
(4) The method for producing an epoxy group-containing vinyl copolymer according to (3), wherein at least one of the mercaptan chain transfer agents is n-octylmercaptan.
(5) A thermoplastic resin composition comprising the epoxy group-containing vinyl copolymer (A) according to any one of (1) and (2) and a thermoplastic resin (B).
(6) The thermoplastic resin composition of (5) in which the thermoplastic resin (B) contains a thermoplastic polyester resin (C).
(7) The thermoplastic resin according to (5) or (6), which contains 0.1 to 50 parts by weight of the epoxy group-containing vinyl copolymer (A) with respect to 100 parts by weight of the thermoplastic resin (B). Composition.
(8) A molded article made of the thermoplastic resin composition according to any one of (5) to (7).

The use of the epoxy group-containing vinyl copolymer of the present invention improves the moldability and releasability of thermoplastic resins such as thermoplastic polyester resins, and provides thermoplastic resins with a good balance between fluidity and impact resistance. A composition can be provided.

1 shows the external appearance of box-shaped molded articles used for moldability evaluation in Examples and Comparative Examples. 2 is a schematic side view (1) and a schematic plan view (2) of FIG. 1; FIG.

Embodiments of the present invention are described in detail below.

<Epoxy Group-Containing Vinyl Copolymer (A)>
The epoxy group-containing vinyl copolymer (A) of the present invention comprises an aromatic vinyl monomer (a1), a vinyl cyanide monomer (a2) and an epoxy group-containing vinyl monomer (a3). It is obtained by copolymerizing the vinyl-based monomer mixture (a) containing Such a copolymer can be preferably used as a compatibilizer with a thermoplastic polyester resin, improves the moldability and releasability of thermoplastic resins including thermoplastic polyester resins, and improves fluidity and impact resistance. It is possible to provide a thermoplastic resin composition having a good balance of properties.

Examples of the aromatic vinyl monomer (a1) include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, ethylstyrene, vinyltoluene, vinylxylene, methyl-α-methylstyrene, t- Butylstyrene, divinylbenzene, 1,1-diphenylstyrene, N,N-diethyl-p-aminomethylstyrene, N,N-diethyl-p-aminoethylstyrene, vinylnaphthalene, vinylpyridine, monochlorostyrene, dichlorostyrene, etc. chlorinated styrene; brominated styrene such as monobromostyrene and dibromostyrene; and monofluorostyrene. Of these, styrene and α-methylstyrene are preferred. These aromatic vinyl-based monomers can be used singly or in combination of two or more.

Examples of the vinyl cyanide monomer (a2) include acrylonitrile, methacrylonitrile, ethacrylonitrile, and fumaronitrile. Among them, acrylonitrile is preferred. These vinyl cyanide monomers can be used singly or in combination of two or more.

As the epoxy group-containing vinyl monomer (a3), a (meth)acrylic ester monomer having an epoxy group is preferable, and examples thereof include epoxy group-containing methacrylates such as glycidyl methacrylate and epoxy group-containing acrylates such as glycidyl acrylate. . You may use 2 or more types of these. Among them, glycidyl methacrylate is preferred.

In addition, the vinyl-based monomer mixture (a) contains the aromatic vinyl-based monomer (a1), the vinyl cyanide-based monomer (a2), and the epoxy group-containing vinyl within a range that does not impair the effects of the present invention. A vinyl monomer other than the monomer (a3) may also be included. Vinyl-based monomers other than (a1) to (a3) include, for example, unsaturated carboxylic acid alkyl ester-based monomers and acrylamide-based monomers. You may use 2 or more types of these.

The unsaturated carboxylic acid alkyl ester-based monomer is not particularly limited, but esters of alcohols having 1 to 6 carbon atoms and acrylic acid or methacrylic acid are preferred. Esters of alcohols having 1 to 6 carbon atoms and acrylic acid or methacrylic acid include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and n-(meth)acrylate. -butyl, t-butyl (meth)acrylate, n-hexyl (meth)acrylate and cyclohexyl (meth)acrylate, and methyl (meth)acrylate is preferred. In addition, "(meth)acrylic acid" indicates acrylic acid or methacrylic acid.

Examples of acrylamide-based monomers include acrylamide, methacrylamide, and N-methylacrylamide.

The content of the epoxy group-containing vinyl monomer in the epoxy group-containing vinyl copolymer (A) is 0.1 to 5 parts by weight, preferably 0.2 to 4 parts by weight, particularly 0.3. ~3 parts by weight is preferred. If the content of the epoxy group-containing vinyl monomer in the epoxy group-containing vinyl copolymer (A) is less than 0.1 parts by weight, the compatibility with the polyester resin is reduced, and the polyester resin is included. The impact resistance of the molded article made of the thermoplastic resin composition is lowered. When the content of the epoxy group-containing vinyl monomer in the epoxy group-containing vinyl copolymer (A) exceeds 5 parts by weight, the epoxy group content increases. Crosslinked products are likely to form due to excessive reaction with polyester resin, flowability of thermoplastic resin compositions containing styrene resins and polyester resins, and impact resistance and surface glossiness of molded articles made of thermoplastic resin compositions. decreases.

The vinyl monomer components other than the epoxy group-containing vinyl monomer in the epoxy group-containing vinyl copolymer (A) are aromatic vinyl monomers and vinyl cyanide monomers. The total content of vinyl monomer components excluding the epoxy group-containing vinyl monomer in the epoxy group-containing vinyl copolymer (A) is 95 to 99.9 parts by weight, and further 70 to 99.9 parts by weight. 9 parts by weight is preferred, and 85 to 99.9 parts by weight is particularly preferred. When the content of these vinyl-based monomers exceeds 99.9 parts by weight, the compatibility with the polyester-based resin is lowered, and the impact resistance of the molded article made of the thermoplastic resin composition containing the polyester-based resin is lowered. do. If the content of these vinyl monomers is less than 95 parts by weight, the fluidity of the resulting thermoplastic resin composition and the impact resistance and surface glossiness of molded articles made from the thermoplastic resin composition are lowered.

In the present invention, the content of each vinyl monomer in the epoxy group-containing vinyl copolymer (A) means the epoxy group-containing vinyl monomer, the aromatic vinyl monomer, and the vinyl cyanide. It is the content when the total with the system monomer is 100 parts by weight. The content of the vinyl-based monomer in the epoxy-group-containing vinyl-based copolymer (A) refers to the number of structural units derived from the vinyl-based monomer that constitutes the epoxy-group-containing vinyl-based copolymer (A). is the content, and is usually an epoxy group-containing vinyl monomer, which is a raw material for copolymerization when producing the epoxy group-containing vinyl copolymer (A), an aromatic vinyl monomer, and a vinyl cyanide It corresponds to the content of each vinyl monomer in 100 parts by weight of the mixture with the monomer.

The content of the aromatic vinyl monomer (a1) in the epoxy group-containing vinyl copolymer (A) is preferably 60 to 79.9 parts by weight, more preferably 65 to 79 parts by weight, particularly preferably 70 to 78 parts by weight. . If the content of the aromatic vinyl-based monomer is less than 60 parts by weight, the compatibility when mixed with the polyester-based resin is lowered, and the impact resistance of the molded article made of the thermoplastic resin composition containing the polyester-based resin is lowered. do. When the content of the aromatic vinyl-based monomer exceeds 80 parts by weight, the compatibility with the polyester-based resin also decreases, and the impact resistance of the molded article made of the thermoplastic resin composition containing the polyester-based resin decreases. .

The content of the vinyl cyanide monomer (a2) in the epoxy group-containing vinyl copolymer (A) is preferably 20 to 39.9 parts by weight, more preferably 21 to 35 parts by weight, particularly preferably 22 to 30 parts by weight. . If the content of the vinyl cyanide monomer is less than 20 parts by weight, the compatibility with the polyester resin is lowered, and the impact resistance of the molded article made of the thermoplastic resin composition containing the polyester resin is lowered. When the content of the vinyl cyanide-based monomer exceeds 39.9 parts by weight, the compatibility with the polyester-based resin is lowered, and the impact resistance of the molded article made of the thermoplastic resin composition containing the polyester-based resin is lowered. In addition, the yellowness of the molded product becomes stronger.

The epoxy-modified vinyl copolymer (A) of the present invention has a weight average molecular weight Mw of 100,000 to 300,000, preferably 120,000 to 270,000. When the weight average molecular weight Mw is within this range, the thermoplastic resin composition containing the epoxy group-containing vinyl copolymer (A) is improved in moldability and releasability, and has fluidity and resistance. A thermoplastic resin composition having a good balance of impact properties can be provided. Here, the weight average molecular weight Mw is the polystyrene equivalent molecular weight determined by gel permeation chromatography.

The molecular weight distribution Mw/Mn of the epoxy group-containing vinyl copolymer (A) of the present invention is preferably 2.5 to 3.5, more preferably 2.5 to 3.4. When the molecular weight distribution Mw/Mn is in this range, the thermoplastic resin composition containing the epoxy group-containing vinyl copolymer (A) is improved in moldability and releasability, and also has fluidity and A thermoplastic resin composition having a good balance of impact resistance can be provided.

The weight average molecular weight Mw and the molecular weight distribution Mw/Mn of the epoxy group-containing vinyl copolymer (A) are measured by the methods described in Examples below.

Means for adjusting the weight-average molecular weight Mw and the molecular weight distribution Mw/Mn of the epoxy group-containing vinyl copolymer (A) within the above ranges include a method of adjusting the amount of the chain transfer agent and the polymerization initiator to be within the preferred ranges described later. is mentioned.

In the cumulative eluted weight of the epoxy group-containing vinyl copolymer (A) of the present invention obtained by GPC/FT-IR, the epoxy group-containing vinyl at an integrated value of less than 30% integrated from the low molecular weight side of the copolymer Let (I) be the average concentration of the system monomer unit, and (II) be the average concentration of the epoxy group-containing vinyl monomer unit at an integrated value of 30% or more and less than 70% integrated from the low molecular weight side of the copolymer. Let (III) be the average concentration of the epoxy group-containing vinyl monomer unit at an integrated value of 70% or more integrated from the low molecular weight side of the copolymer, and the composition distribution of the epoxy group-containing vinyl monomer unit is (I)<(II) and (III)<(II). Here, the average concentration of epoxy group-containing vinyl monomer units refers to the arithmetic mean of the concentrations of the epoxy group-containing vinyl monomer units in each molecular weight region. Further, from the viewpoint of improving the accuracy of the average concentration of the epoxy group-containing vinyl monomer unit, the number of points for measuring the concentration of the epoxy group-containing vinyl monomer unit in each molecular weight range is preferably 30 points or more. A score of 35 or more is more preferable. In addition, M1 is the molecular weight at which the concentration of the epoxy group-containing vinyl monomer unit reaches a peak value, M2 is the molecular weight at which the integrated value is 30% by mass integrated from the low molecular weight side, and M2 is the integrated value integrated from the low molecular weight side. Assuming that the molecular weight at which the value becomes 70% by mass is M3, M2<M1<M3. The term "peak value" as used herein refers to the peak of a regression analysis of a plot of the concentration of the epoxy group-containing vinyl-based monomer unit against the polystyrene-equivalent molecular weight using a quadratic function. In the epoxy group-containing vinyl copolymer (A), the epoxy group reacts with the functional group remaining in the thermoplastic polyester resin to bond, and the vinyl monomer unit is introduced into the thermoplastic polyester resin. to give compatibility. Therefore, in the region below the molecular weight where the integrated value is 30 mass% integrated from the low molecular weight side, the number of vinyl monomer units is relatively small, so the compatibility with the thermoplastic polyester resin is poor. In the region where the integrated value is 70% by mass or more, the molecular weight after bonding to the thermoplastic polyester resin is relatively large and the fluidity is poor. Therefore, by satisfying M2<M1<M3, both compatibility and fluidity with respect to the thermoplastic polyester resin can be achieved at a high level.

The composition distribution described above can be measured by the following method. 0.1 g of epoxy group-containing vinyl copolymer (A) was dissolved in 50 g of chloroform to prepare a solution of about 0.2% by weight. From the GPC chromatogram obtained by eluent evaporation type GPC/FT-IR under the following conditions, the molecular weight distribution and weight average molecular weight were calculated using polystyrene as a standard substance. At the same time, the concentration derived from the epoxy group-containing vinyl monomer at each molecular weight was calculated from each absorption peak height obtained by FT-IR measurement.
Column: TSKgelGMHHR-M (2 pieces) (manufactured by Tosoh)
Solvent: chloroform Flow rate: 1.0 mL/min
Measurement interval: 30 times/min
Column temperature: 23°C
Differential refractive index detector: RI8020 type (manufactured by Tosoh)
Infrared absorption spectroscopic detector: Nicoleti S50 (manufactured by Thermo Fisher)
Resolution: 4 cm ^-1
Accumulation times: 16 times.

As a means for adjusting the concentration of the epoxy group-containing vinyl monomer unit relative to the molecular weight distribution of the epoxy group-containing vinyl copolymer (A) to the above range, the amount of the chain transfer agent and the polymerization initiator to be added is within the preferred range described later. and the like.

The epoxy group-containing vinyl-based copolymer (A) of the present invention can be prepared by subjecting the vinyl-based monomer mixture (a) to known polymerization methods such as bulk polymerization, solution polymerization, emulsion polymerization and suspension polymerization. It can be obtained by copolymerizing by the polymerization method of. Among them, the suspension polymerization method is preferable because it facilitates polymerization control and does not require a step of removing unreacted components, a reaction solvent, an emulsifier, and the like.

A polymerization initiator may be used in the method for producing the epoxy group-containing vinyl copolymer (A). Polymerization initiators include peroxides, azo compounds, persulfates and the like. You may use 2 or more types of these. The polymerization initiator can also be used in redox systems.

Specific examples of peroxides include benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, diisopropylbenzene hydroperoxide, t-butyl hydroperoxide, t-butyl peroxyacetate and t-butyl peroxybenzoate. , t-butyl isopropyl carbonate, di-t-butyl peroxide, t-butyl peroctate, 1,1-bis(t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1- bis(t-butylperoxy)cyclohexane, t-butylperoxy-2-ethylhexanoate and the like.

Specific examples of azo compounds include 2,2′-azobisisobutyronitrile, azobis(2,4-dimethylvaleronitrile), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2- Cyano-2-propylazoformamide, 1,1'-azobiscyclohexane-1-carbonitrile, azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, 1 -t-butylazo-2-cyanobutane, 2-t-butylazo-2-cyano-4-methoxy-4-methylpentane and the like.

Specific examples of persulfates include potassium persulfate, sodium persulfate and ammonium persulfate.

Among these, 2,2'-azobisisobutyronitrile, azobis(2,4-dimethylvaleronitrile) and the like are preferably used.

The amount of the polymerization initiator to be added is preferably 0.1 to 0.5 parts by weight per 100 parts by weight of the total amount of the vinyl monomer mixture (a).

In the method for producing the epoxy group-containing vinyl copolymer (A), it is preferable to use a chain transfer agent, and the weight average molecular weight of the epoxy group-containing vinyl copolymer can be adjusted within a desired range. As the chain transfer agent, mercaptans are preferred, and specific examples thereof include n-octylmercaptan, t-dodecylmercaptan, n-dodecylmercaptan, n-tetradecylmercaptan, n-octadecylmercaptan and the like. It is preferable to use two or more of these. Among them, n-octylmercaptan and t-dodecylmercaptan are preferably used.

The amount of the chain transfer agent to be added is preferably 0.01 to 1.0 parts by weight per 100 parts by weight of the total amount of the vinyl monomer mixture (a). By using 0.01 parts by weight or more of the chain transfer agent, the weight average molecular weight of the epoxy group-containing vinyl copolymer can be easily adjusted to 300,000 or less. On the other hand, by using 1.0 parts by weight or less of the chain transfer agent, the weight average molecular weight of the epoxy group-containing vinyl copolymer can be easily adjusted to 100,000 or more.

When the epoxy group-containing vinyl copolymer (A) is produced by suspension polymerization, it is preferred to use a suspension stabilizer. Examples of suspension stabilizers include inorganic suspension stabilizers such as clay, barium sulfate, and magnesium hydroxide, and organic suspension stabilizers such as polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, polyacrylamide, and methyl methacrylate/acrylamide copolymers. turbidity stabilizers and the like. You may use 2 or more types of these. Among them, organic suspension stabilizers are preferably used in terms of color tone stability.

Generally, the suspension polymerization method disperses a monomer in which a polymerization initiator is dissolved in an aqueous medium containing a suspension stabilizer to generate radicals to carry out polymerization. The monomer components may be initially charged all at once, or part or all of the monomer components may be charged continuously or intermittently.

A slurry of the epoxy group-containing vinyl copolymer (A) is obtained by suspension polymerization, followed by dehydration and drying to obtain a bead-like epoxy group-containing vinyl copolymer.

The thermoplastic resin (B) contained in the thermoplastic resin composition of the present invention includes thermoplastic polyester resin (C), ABS resin, ASA resin, AES resin, polycarbonate, polyvinyl chloride, polystyrene, polyacetal, and modified polyphenylene ether. (modified PPE), ethylene-vinyl acetate copolymer, polyarylate, liquid crystal polyester, polyethylene, polypropylene, fluororesin, polyamide and the like. The thermoplastic resin composition of the present invention may contain one of these thermoplastic resins (C), or may contain two or more thereof.

Among these thermoplastic resins (B), the thermoplastic resin composition of the present invention preferably contains a thermoplastic polyester resin (C) described below as the thermoplastic resin (B).

If, for example, an ABS resin is mixed with the thermoplastic polyester resin (C) as the thermoplastic resin (B) other than the thermoplastic polyester resin (C), mechanical strength such as impact resistance can be improved. can.

When the thermoplastic resin composition of the present invention contains a thermoplastic polyester resin (C) and a thermoplastic resin (B) other than the thermoplastic polyester resin (C), by using the thermoplastic polyester resin (C) In order to reliably obtain the effect, the content of the thermoplastic resin (B) other than the thermoplastic polyester resin (C) is preferably 150 parts by weight or less with respect to 100 parts by weight of the thermoplastic polyester resin (C). .

The thermoplastic polyester resin (C) in the present invention refers to a resin having an ester bond in the main chain. Polymers of monomers and the like can be mentioned. Examples thereof include polybutylene terephthalate (PBT) resin, polyethylene terephthalate (PET) resin, polylactic acid (PLA) resin, and the like. By containing the thermoplastic polyester resin (C) in the epoxy group-containing vinyl copolymer of the present invention, the release property and moldability of the thermoplastic resin composition are improved, and fluidity and impact resistance are improved. A well-balanced thermoplastic resin composition can be provided.

The thermoplastic resin composition of the present invention comprises the epoxy group-containing vinyl copolymer (A) of the present invention and a thermoplastic resin (B) such as the thermoplastic polyester resin (C) described above.

The thermoplastic resin composition of the present invention may contain only one type of the epoxy group-containing vinyl copolymer (A) of the present invention. may contain two or more different ones. In addition, the thermoplastic resin composition of the present invention may contain only one type of the thermoplastic resin (B) such as the thermoplastic polyester resin (C) described above, or may contain two or more types. good too.

The content of the epoxy group-containing vinyl copolymer (A) in the thermoplastic resin composition of the present invention is 0.1 to 50 parts by weight, particularly 1 to 45 parts by weight, per 100 parts by weight of the thermoplastic resin (B). It is preferable that it is a part. If the content of the epoxy group-containing vinyl copolymer (A) relative to 100 parts by weight of the thermoplastic resin (B) is less than 0.1 parts by weight, the thermoplastic polyester resin (C) based on the epoxy-modified vinyl copolymer (A) The compatibility of the thermoplastic resin (B) with the polyester-based resin is lowered, and the impact resistance of the molded article made of the thermoplastic resin composition containing the polyester-based resin is lowered. If the content of the epoxy-modified vinyl copolymer (A) exceeds 50 parts by weight with respect to 100 parts by weight of the thermoplastic resin (C), the epoxy group content increases. A cross-linked product is likely to form due to excessive reaction with the resin, and the fluidity of the thermoplastic resin composition containing the styrene resin and the polyester resin, and the impact resistance and surface glossiness of the molded article made of the thermoplastic resin composition. descend.

The thermoplastic resin composition of the present invention contains resins other than the epoxy group-containing vinyl copolymer (A) and the thermoplastic resin (B), elastomers, etc., within a range that does not impair the effects of the present invention. can do.

In addition, the thermoplastic resin composition of the present invention may further contain glass fibers, glass powder, glass beads, glass flakes, alumina, alumina fibers, carbon fibers, graphite fibers, as long as the objects of the present invention are not impaired. Inorganic fillers such as stainless steel fibers, whiskers such as silicon carbide, potassium titanate fibers, wollastonite, asbestos, hard clay, calcined clay, talc, kaolin, mica, calcium carbonate, magnesium carbonate, aluminum oxide and minerals, and hinders Antioxidants such as dophenols, sulfur-containing compounds, and phosphorus-containing organic compounds; heat stabilizers such as phenols and acrylates; UV absorbers such as benzotriazoles, benzophenones, and salicylates; and hindered amine light stabilizers. Lubricants and plasticizers such as higher fatty acids, acid esters, acid amides, and higher alcohols Mold release agents such as montanic acid and its salts, its esters, its half esters, stearyl alcohol, stearamide and ethylene wax, flame retardant aids agents, anti-coloring agents such as phosphites and hypophosphites, neutralizing agents such as phosphoric acid, monosodium phosphate, maleic anhydride, and succinic anhydride, nucleating agents, amines, sulfonic acids, poly It may contain one or more additives such as an antistatic agent such as an ether-based agent, a coloring agent such as carbon black, a pigment, and a dye.

Next, the method for producing the thermoplastic resin composition of the present invention will be described. The thermoplastic resin composition of the present invention can be prepared, for example, by mixing the epoxy group-containing vinyl copolymer (A), the thermoplastic polyester resin (C) and, if necessary, other components using a mixer. , a method of melt-kneading using a melt-kneader, or the like. Mixers include, for example, V-type blenders, super mixers, super floaters and Henschel mixers. Melt-kneaders include, for example, kneaders, single-screw and twin-screw extruders, and the like. In general, a method of pre-mixing each component using a mixer and uniformly melt-kneading the pre-mixture using a melt-kneader is preferably used. The melt-kneading temperature is preferably about 230 to 300°C, more preferably about 250 to 285°C. A method of pelletizing with a pelletizer after melt-kneading is common.

The thermoplastic resin composition of the present invention can be molded by any molding method used for molding thermoplastic resin compositions, and can be used as molded articles of any shape. Molding methods include, for example, injection molding, extrusion molding, blow molding, vacuum molding, compression molding, and gas-assisted molding. Examples of the shape of the molded product include injection molded products such as automobile parts, electrical and electronic equipment parts, films, sheets, TV frames, pedestals, cosmetic containers, and the like.

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited thereto. First, methods for measuring and evaluating various characteristics in Examples and Comparative Examples will be described. Hereinafter, "%" and "parts" are by weight unless otherwise specified.

(1) Weight average molecular weight Mw, Mw/Mn
About 0.03 g of each sample of the epoxy group-containing vinyl copolymer (A) obtained in each example and comparative example was dissolved in about 15 g of tetrahydrofuran to prepare a solution of about 0.2% by weight. From the GPC chromatogram measured under the following conditions, polystyrene was converted as a standard substance to calculate the weight average molecular weight Mw and Mw/Mn.
Equipment: Waters 2695
Column temperature: 40°C
Detector: RI2414 (differential refractometer)
Carrier eluent flow rate: 0.3 ml/min (solvent: tetrahydrofuran)
Columns: TSKgel SuperHZM-M (6.0 mm ID×15 cm), TSKgel SuperHZM-N (6.0 mm ID×15 cm) in series (both from Tosoh).

(2) MFR (melt flow rate)
The epoxy group-containing vinyl copolymer (A) obtained in each example and comparative example and the thermoplastic resin composition were pre-dried in a hot air dryer at 80 ° C. for 5 hours, and dried according to ISO 1133 (2005). The melt flow rate was measured under the conditions of 220° C. or 240° C. and a load of 10000 g.

(3) Weight-average particle size of rubbery polymer (R) The polybutadiene latex used in the production of the ABS graft copolymer (D) described below was diluted and dispersed in an aqueous medium, and the particle size distribution was measured by laser scattering diffraction method. The particle size distribution was measured with an apparatus LS 13 320 (manufactured by Beckman Coulter, Inc.). From the particle size distribution, the weight average particle size of the rubbery polymer (R) was calculated.

(4) Graft ratio of ABS graft copolymer (D) About 1 g (m: sample weight) of ABS graft copolymer (D) described later was added with acetone, refluxed for 3 hours, and the solution was stirred at 8800 rpm (10000 G). ) for 40 minutes, the insoluble matter was collected by filtration. The insoluble matter was dried under reduced pressure at 60° C. for 5 hours, and its weight (n) was measured. The graft ratio was calculated from the following formula. However, in the following formula, L represents the rubbery polymer content (% by weight) of the ABS graft copolymer. Graft rate (%)={[(n)-[(m)×L/100]]/[(m)×L/100]}×100.

(5) Reduced viscosity [ηsp/c] of ABS graft copolymer (D)
For the ABS graft copolymer (D) described later, 200 ml of acetone was added to 1 g of the sample, and the solution was refluxed for 3 hours. The solution was centrifuged at 8800 rpm (10000 G) for 40 minutes, and the insoluble matter was filtered. The filtrate was concentrated using a rotary evaporator, and the precipitate (acetone-soluble matter) was dried under reduced pressure at 60°C for 5 hours. ηsp/c] was measured.

(6) Charpy impact strength The pellets obtained in each example and comparative example were pre-dried in a hot air dryer at 105 ° C. for 5 hours, and a cylinder using an electric injection molding machine SE50 manufactured by Sumitomo Heavy Industries, Ltd. A multi-purpose test piece A type (total length 150 mm, test part width 10 mm, thickness 4 mm) specified in ISO 3167 (2002) was injection molded under the conditions of temperature: 260°C and mold temperature: 60°C. Using the obtained multi-purpose test piece A type, impact strength was measured under the conditions of V notch (remaining width 8.0 mm), 23° C., 50% RH in accordance with ISO 179 (2000). Charpy impact strength (kJ/m ² ) was measured for each of 10 test pieces, and the number average value was calculated.

(7) Moldability The pellets obtained in each example and comparative example were pre-dried in a hot air dryer at 105 ° C. for 5 hours, and using a Nissei Plastic Industry injection molding machine "PS60", the cylinder temperature was 260 ° C., gold Under the molding conditions of a mold temperature of 80 ° C. and a cooling time of 10 seconds, a box-shaped molded product (width 30 mm × depth 30 mm × height 30 mm, thickness 1.5 mm) having the opening shown in FIGS. Molded. Poor moldability is marked with an "X" in the table if it is impossible to fill due to poor fluidity during molding, or if the test piece deforms when the molded product is ejected after filling, or if the protrusion is greatly buckled. Indicated. "O" indicates that deformation did not occur when the molded product was ejected after filling.

(8) Retention Stability Using a melt indexer (manufactured by Toyo Seiki Co., Ltd.), pellets dried in advance at 130° C. for 3 hours were measured according to ISO 1133 under conditions of a test temperature of 250° C. and a load of 2160 g. At that time, the MFR when staying for 5 minutes and the MFR when staying for 20 minutes were measured, and the staying stability was evaluated as follows.
Change in retention MFR (g/10 min) = MFR at retention for 20 minutes - MFR at retention for 5 minutes
If the above calculation result is 0 or more, it can be judged that the retention stability is good.

(9) Mold Releasing Force Using the pellets obtained in each example and comparative example, the mold releasing force was measured using a mold having the shape of the molded article shown in FIG. The molding conditions were a cylinder temperature of 260°C, a mold temperature of 80°C, and an injection molding machine "SGE75DU" manufactured by Sumitomo Heavy Industries, Ltd. was used as the molding machine. To measure the release force, a Technoplus "load cell 1C-1B" is inserted into the mold, a strain amplifier is Toyo Baldwin's "MD-1031", and a recording device is Hioki Denki's "memory A high coder 8840″ was used to measure the release force when ejecting the bottom surface of the molded product of FIG. 1 with four φ10 ejector pins. A release force of 500 MPa or less can be judged to have good release properties.
450 MPa or less is more preferable.

(10) Bar flow length Using a Nissei Plastic Industry injection molding machine "PS40", the pellets obtained in each example and comparative example were injected into a strip shape with a thickness of 1 mm and a width of 10 mm for 8 seconds. The length of the molded product (bar flow length) was measured. The injection conditions were a cylinder temperature of 260°C, a mold temperature of 80°C, and an injection pressure of 63 MPa. If the flow length was 100 mm or more, it was determined that the fluidity was good.

[Production of epoxy group-containing vinyl copolymer (A)]
The method for producing the epoxy group-containing vinyl copolymer (A) used in Examples and Comparative Examples is as follows.

<Preparation of suspension stabilizer>
80 parts by weight of acrylamide, 20 parts by weight of methyl methacrylate, 0.3 parts by weight of potassium persulfate, and 1,800 parts by weight of ion-exchanged water were charged into a reactor, the gas phase in the reactor was replaced with nitrogen gas, and the mixture was stirred to 70 parts by weight. °C. The reaction was continued until the monomer was completely converted into the polymer to obtain an aqueous solution of acrylamide-methyl methacrylate copolymer. 20 parts by weight of sodium hydroxide and 2000 parts by weight of ion-exchanged water are added to the resulting aqueous solution, stirred at 70° C. for 2 hours, and then cooled to room temperature to obtain methyl methacrylate as a medium for suspension polymerization. - An aqueous acrylamide copolymer solution was obtained.

<Production of epoxy group-containing vinyl copolymer (A-1)>
A solution obtained by dissolving 0.05 parts by weight of the aqueous methyl methacrylate-acrylamide copolymer solution in 150 parts by weight of ion-exchanged water was placed in a stainless steel autoclave having a capacity of 20 L and equipped with a baffle and a Faudler-type stirring blade, and the mixture was stirred at 400 rpm. After stirring, the inside of the system was replaced with nitrogen gas. Next, 24 parts by weight of acrylonitrile, 75 parts by weight of styrene, 1 part by weight of glycidyl methacrylate, 0.32 parts by weight of 2,2'-azobisisobutyronitrile, 0.09 parts by weight of t-dodecyl mercaptan, and n-octyl A monomer mixture of 0.10 parts by weight of mercaptan was initially added over 30 minutes while stirring the reaction system, the temperature was raised to 70°C to initiate the copolymerization reaction, and the temperature was raised to 100°C over 180 minutes. did. After reaching 100° C., the temperature was kept at 100° C. for 30 minutes, and then the polymer was separated, washed and dried to obtain an epoxy group-containing vinyl copolymer (A-1). Here, in the integrated eluted weight obtained by GPC/FT-IR, the average concentration (I) of the epoxy group-containing vinyl monomer units in the integrated value of less than 30% integrated from the low molecular weight side of the copolymer, Average concentration (II) of the epoxy group-containing vinyl-based monomer units at an integrated value of 30% or more and less than 70% integrated from the low molecular weight side of the copolymer, and an integrated value of 70 or more integrated from the low molecular weight side of the copolymer. The average concentration (III) of the epoxy group-containing vinyl monomer unit in % was (I) = 0.94%, (II) = 1.05%, and (III) = 0.93%, respectively. . Further, the molecular weight M1 at which the concentration of the epoxy group-containing vinyl monomer unit reaches a peak value, the molecular weight M2 at which the integrated value integrated from the low molecular weight side is 30% by mass, and the integrated value integrated from the low molecular weight side is 70% by mass. The resulting molecular weights M3 were M1=134,400, M2=75,500, and M3=238,900, respectively.

<Production of Epoxy Group-Containing Vinyl Copolymers (A-2 to A-8) Epoxy Group-Containing Vinyl Copolymer A-2 was produced by changing the formulation as shown in Table 1 according to the production method of A-1. ~A-8 was obtained.

<Production of epoxy group-containing vinyl copolymer (A-9)>
Using a continuous mass polymerization apparatus consisting of a 2 m3 complete mixing type polymerization tank having a condenser for evaporating and refluxing monomer vapor and double helical ribbon blades, and a twin-screw extruder type demonomer, co-polymerization was carried out as follows. Polymerization and mixing of the resin components was carried out. First, then from 24 parts by weight of acrylonitrile, 75 parts by weight of styrene, 1 part by weight of glycidyl methacrylate, 0.015 parts by weight of 1,1-di(t-butylperoxy)cyclohexane, and 0.16 parts by weight of n-octyl mercaptan. The monomer mixture was continuously supplied to a polymerization tank at a rate of 150 kg/hour, and was continuously bulk-polymerized while maintaining a polymerization temperature of 130° C. and an internal tank pressure of 0.08 MPa. The rate of polymerization of the polymerization reaction mixture at the outlet of the polymerization tank was controlled between 74 and 76%. Unreacted monomers are recovered from the vent port of the resulting polymerization reaction product by distillation under reduced pressure using a twin-screw extruder type demonomer, and the apparent polymerization rate is 99% or more. Epoxy group-containing vinyl copolymer (A-9) was obtained.

The following were used as the thermoplastic polyester resin (C) and the ABS graft resin (D).

<Thermoplastic polyester resin (C)>
Polybutylene terephthalate (PBT) resin "PBT1100S" manufactured by Toray Industries, Inc.
<ABS graft resin (D)>
120 parts by weight of pure water, 0.5 parts by weight of glucose, 0.5 parts by weight of sodium pyrophosphate, 0.005 parts by weight of ferrous sulfate and polybutadiene latex (weight average particle diameter of 0.3 μm, 60 parts by weight (in terms of solid content) of 85% gel content was charged, and the temperature in the reactor was raised to 65° C. while stirring. A mixture of 30 parts by weight of styrene, 10 parts by weight of acrylonitrile and 0.3 parts by weight of t-dodecylmercaptan was continuously added dropwise over 5 hours to initiate polymerization when the internal temperature reached 65°C. At the same time, an aqueous solution consisting of 0.25 parts by weight of cumene hydroperoxide, 2.5 parts by weight of potassium oleate and 25 parts by weight of pure water was continuously added dropwise over 7 hours to complete the reaction. The obtained styrenic copolymer latex was coagulated in a dilute aqueous sulfuric acid solution at a temperature of 90° C., neutralized with an aqueous sodium hydroxide solution, washed, filtered and dried to obtain an ABS graft copolymer (D). . The graft ratio of this ABS graft copolymer (D) was 35%, and the reduced viscosity ηsp/c of the acetone-soluble portion was 0.35 dl/g.

The thermoplastic polyester resin (C), the ABS graft resin (D) and the epoxy group-containing vinyl copolymer (A--1 to A-9) were mixed at the compounding ratio shown in Table 2, and a 30 mm biaxial with vent was prepared. A pellet-shaped thermoplastic resin composition was produced by melt-kneading at a cylinder setting temperature of 260° C. using an extruder. Table 2 shows the results of evaluating the MFR, Charpy impact strength and moldability of the obtained thermoplastic resin composition.

As is clear from Table 2, Examples 1 to 4 in which the epoxy group-containing vinyl copolymer (A) of the present invention was blended with the thermoplastic resin (C) and the ABS graft resin (D) meet the requirements of the present invention. Moldability is improved while maintaining MFR and Charpy impact strength from Comparative Examples 1 to 5 in which epoxy group-containing vinyl copolymers that do not satisfy are blended.

The following was used as the reinforcing fiber (E).

<Reinforcing fiber (E)>
"T-120H" manufactured by Nippon Electric Glass Co., Ltd. (chopped strand 3 mm length,
Average fiber diameter 10.5 μm)

The thermoplastic polyester resin (C), the reinforcing fiber (E) and the epoxy group-containing vinyl copolymer (A) are mixed at the compounding ratio shown in Table 3, and the cylinder is set using a vented 30 mm twin screw extruder. A pellet-shaped thermoplastic resin composition was produced by melt-kneading at a temperature of 260°C. Table 3 shows the results of evaluating the retention stability, Charpy impact strength, mold release force and bar flow length of the obtained thermoplastic resin composition.

As is clear from Table 3, Examples 5 and 6, in which the epoxy group-containing vinyl copolymer (A) of the present invention was blended with the thermoplastic resin (C) and the reinforcing fiber (E), satisfied the requirements of the present invention. From Comparative Examples 6 to 9 in which unsatisfactory epoxy group-containing vinyl copolymers were blended, releasability and fluidity were improved while maintaining retention stability and Charpy impact strength.

a: Spool/runner b: Box molded product for formability evaluation

Claims (8)

At least 60 to 79.9 parts by weight of an aromatic vinyl monomer (a1), 20 to 39.9 parts by weight of a vinyl cyanide monomer (a2), and 0 epoxy group-containing vinyl monomer (a3) .A copolymer consisting of a vinyl monomer mixture (a) containing 1 to 5 parts by weight (where the total of (a1), (a2) and (a3) is 100 parts by weight), and is obtained by GPC The weight average molecular weight Mw in terms of polystyrene obtained by is 100,000 to 300,000, and the ratio Mw/Mn between the weight average molecular weight Mw and the number average molecular weight Mn is 2.5 to 3.5. , an epoxy group-containing vinyl copolymer (A). In the cumulative elution weight obtained by GPC/FT-IR measurement of the epoxy group-containing vinyl copolymer (A), the epoxy group-containing vinyl system at an integrated value of less than 30% integrated from the low molecular weight side of the copolymer Let (I) be the average concentration of the monomer unit, and (II) be the average concentration of the epoxy group-containing vinyl monomer unit in the integrated value of 30% or more and less than 70% integrated from the low molecular weight side of the copolymer. Let (III) be the average concentration of the epoxy group-containing vinyl monomer unit at an integrated value of 70% or more integrated from the low molecular weight side of the copolymer, and the composition distribution of the epoxy group-containing vinyl monomer unit is: , (I)<(II) and (III)<(II). 3. The epoxy group-containing vinyl copolymer according to claim 1 or 2, wherein the vinyl monomer mixture (a) is subjected to suspension polymerization using two or more mercaptan chain transfer agents. Production method. 4. The method for producing an epoxy group-containing vinyl copolymer according to claim 3, wherein at least one of the mercaptan chain transfer agents is n-octylmercaptan. A thermoplastic resin composition comprising the epoxy group-containing vinyl copolymer (A) according to any one of claims 1 and 2 and a thermoplastic resin (B). The thermoplastic resin composition according to claim 5, wherein the thermoplastic resin (B) contains a thermoplastic polyester resin (C). 7. The thermoplastic resin composition according to claim 5, wherein the epoxy group-containing vinyl copolymer (A) is contained in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the thermoplastic resin (B). A molded article made of the thermoplastic resin composition according to any one of claims 5 to 7.

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