JPH10237296A - Thermoplastic resin composition and compatibilizing agent used therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the impact resistance, flowability in processing, and the appearance and weld strength of a molded article by using as the constituents resin(s) selected from polycarbonate resins, polyamide resins and polyester resins, a styrene resin, a polyphenylene ether resin and copolymers of two kinds of monomers. SOLUTION: This composition contains a component (A) comprising at least one resin selected from among polycarbonate resins, polyamide resins and polyester resins, a component (B) comprising at least one of a styrene resin and a polyphenylene ether resin, the weight ratio of component A to component B being (50 to 90):(10 to 50), a copolymer (C) of monomers comprising essentially an aromatic vinyl monomer and a monomer containing formaldehyde groups and represented by the formula (wherein R1 to R6 are each H, a 1-8C alkyl, a 6-10C cycloalkyl, a 6-10C alkylaryl, or a 6-10C arylalkyl), and a copolymer (D) of monomers comprising essentially a (meth)acrylic ester monomer and a monomer containing formaldehyde groups and represented by the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel thermoplastic resin composition which can be formed into various molded articles, sheets, films and the like by various molding methods such as injection molding and extrusion molding, and a novel phase used therein. It relates to a solubilizer.

[0002]

2. Description of the Related Art Engineering plastics such as polycarbonate, polyamide, polyacetal, polybutylene terephthalate, polyphenylene ether and polyphenylene sulfide generally have excellent mechanical properties such as impact resistance and thermal properties such as heat resistance. On the other hand, there is a problem that high manufacturing costs are required due to poor molding workability. Furthermore, the required properties other than the above-mentioned mechanical properties and thermal properties, for example, properties such as chemical resistance and low water absorption cannot be satisfied by a single engineering plastic as described above. Among these engineering plastics, polycarbonate resins are used in a wide range of fields such as electric / electronic / automobile / medical fields because of their excellent heat resistance and dimensional stability. However, while having excellent impact resistance, the thickness dependency of the impact strength is large, and the notch sensitivity is also high. Furthermore, there has been a demand for improvement in processing fluidity in recent years for the purpose of producing lighter and thinner molded products and shortening the molding cycle.

[0003] Attempts have been made to develop new functional characteristics while blending or alloying a polycarbonate resin with another resin to complement the disadvantages of both. As a technique for processing fluidity, a technique of blending and adding an ABS resin (acrylonitrile-butadiene-styrene copolymer) to a polycarbonate resin is known (JP-B-38-15225).
No.). Recently, a technique of blending a polystyrene resin with a polycarbonate resin has been known (Japanese Patent Application Laid-Open No. 8-34915).

[0004]

However, usually,
Simply blending two or more resins does not mix well, and the resulting thermoplastic resin composition generally has reduced impact resistance. Also,
When molded into a desired shape using such a thermoplastic resin composition, there has been a problem in that the appearance itself is poor and delamination is caused. Further, the technique of adding and adding the ABS resin improves the impact strength, but is insufficient in processing fluidity and processing temperature. Furthermore, the technique of adding the polystyrene resin uses a compatibilizer having a limited SP value (solubility parameter), and thus has a narrow application range. Further, in recent years, while the shape of a molded article has become more complicated, importance has been placed on the weld adhesive surface strength at the time of injection molding. However, the thermoplastic resin composition also lacked strength in that respect.

The present invention has been made in view of such circumstances, and is excellent in impact resistance and processing fluidity, and has good appearance and no delamination when formed, and has an improved weld adhesion strength. It is an object of the present invention to provide a thermoplastic resin composition to be subjected to the following and a compatibilizer used for the composition.

[0006]

Means for Solving the Problems In order to achieve the above object, the present invention provides, as a first gist, a thermoplastic resin composition containing the following components (A) to (D). (A) at least one resin selected from the group consisting of polycarbonate resins, polyamide resins and polyester resins. (B) at least one of a styrene resin and a polyphenylene ether resin. (C) A copolymer comprising a formamide group-containing monomer represented by the following general formula (1) and a monomer having an aromatic vinyl monomer as an essential component. (D) a copolymer comprising a formamide group-containing monomer represented by the following general formula (1) and a monomer containing at least one of an acrylate monomer and a methacrylate monomer as an essential component Coalescing.

[0007]

Embedded image

A copolymer of a formamide group-containing monomer represented by the above general formula (1) and a monomer containing at least one of an acrylate monomer and a methacrylate monomer as an essential component The second compatibilizer is referred to as a second gist.

The present inventors have conducted a series of studies to solve the above problems, and as a result, first, in order to uniformly mix and dissolve the above components (A) and (B), When a copolymer [component (C)] containing a formamide group-containing monomer represented by the formula (1) and an aromatic vinyl monomer as essential components is used as a compatibilizer, both components are compatible with each other. It has been found that a thermoplastic resin composition which can be accommodated, has excellent impact resistance and processing fluidity, and has a good appearance when molded is obtained. However, in view of the present situation that in addition to the improvement and improvement of the above-mentioned problems and improvement in weld adhesion strength is required, further intensive studies have been made. As a result, together with the component (C), a formamide group-containing monomer represented by the above general formula (1), an acrylic acid ester monomer and a methacrylic acid ester monomer are newly added as compatibilizers. When a copolymer (component (D)) comprising a monomer having at least one of the following as an essential component is used, the above (A)
It has been found that a component in which the affinity between the component and the component (B) is further optimized can be obtained, and a thermoplastic resin composition having more excellent properties due to the above-mentioned various properties can be obtained.
The present invention has been reached.

In the above component (C), the proportion of the constituent part derived from the formamide group-containing monomer is 0.05 to 20% by weight, and the proportion of the constituent part derived from the aromatic vinyl monomer is The proportion is set to 60% by weight or more, and the proportion of the component derived from the formamide group-containing monomer in the component (D) is set to 0.05 to 20%.
By setting the proportion of the component derived from at least one of an acrylate monomer and a methacrylate monomer to 50% by weight or more by weight,
In addition to the effect of further improving the miscibility of the component (A) and the component (B), a sufficient effect of improving impact resistance and weld strength can be obtained.

[0011]

Next, an embodiment of the present invention will be described.

The thermoplastic resin composition of the present invention is obtained using the following components (A), (B), (C) and (D).

(A) at least one resin selected from the group consisting of polycarbonate resins, polyamide resins and polyester resins. (B) at least one of a styrene resin and a polyphenylene ether resin. (C) A copolymer comprising a monomer containing a formamide group-containing monomer represented by the general formula (1) and an aromatic vinyl monomer as essential components. (D) a copolymer comprising a formamide group-containing monomer represented by the general formula (1) and a monomer containing at least one of an acrylate monomer and a methacrylate monomer as an essential component .

The polycarbonate resin in the component (A) may be either an aliphatic or aromatic polycarbonate resin, such as a 2,2'-bis (4-hydroxyphenyl) alkane-based polycarbonate resin. , 2-bis (4-hydroxy-3,5-dimethylphenyl) alkane-based,
Polymers or copolymers of bisphenols such as 2,2-bis (4-hydroxy-3,5-dipropylphenyl) alkane sulfone, sulfide and sulfoxide are exemplified.

As the polycarbonate resin used as the component (A), a commercially available polycarbonate resin can be used in addition to the above components. Commercially available polycarbonate resins include Toughlon series (manufactured by Idemitsu Petrochemical), Iupilon series (manufactured by Mitsubishi Engineering Plastics), Panlite series (manufactured by Teijin Chemicals), Lexan series (manufactured by Nippon GE Plastics), Sumitomo Dow) and Macrolon (Bayer).

The polyamide resin in the component (A) includes nylon 6, nylon 6,6, nylon 6,12,
Examples thereof include aliphatic polyamides such as nylon 11, nylon 12, nylon 6,12, and nylon 4,6, and aromatic polyamides such as polyhexamethylene diamine terephthalamide, polyhexamethylene diamine isophthalamide, and xylene group-containing polyamide. Further, polyester amide, polyester ether amide and the like can be mentioned.

Further, examples of the polyester resin in the component (A) include polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethyl phthalate, and polyarylate.

These components (A) can be used alone or in combination of two or more. However, it is preferable to use a polycarbonate resin in view of particularly high impact strength.

The styrene resin in the component (B) of the present invention includes an impact-resistant polystyrene resin which is a composition of a styrene homopolymer, a styrene homopolymer or a copolymer and a rubber component, an ABS resin, and an AS resin. Resin (acrylonitrile-styrene copolymer), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), AES resin (acrylonitrile-ethyl acrylate-styrene copolymer), and SEBS which is a styrene-based thermoplastic elastomer. Resin (hydrogenated styrene-butadiene-styrene copolymer), SEPS resin (styrene-
Hydrogenated product of isoprene-styrene copolymer), SEP
Resin (hydrogenated product of styrene-isoprene copolymer).

Examples of the rubber component include polybutadiene rubber, polyisoprene rubber, polyurethane elastomer, ethylene-acrylate copolymer, ethylene-methacrylate copolymer, and styrene-based thermoplastic elastomer. Can be

Among such polystyrene resins,
In particular, an impact-resistant polystyrene resin, and a composition of a styrene homopolymer or copolymer and a rubber component are preferable.
Commercially available resins can be used as the impact-resistant polystyrene resin. As a commercially available impact-resistant polystyrene resin,
Sumibrite series (Sumitomo Chemical Co., Ltd.), Estyrene series (Nippon Steel Chemical Co., Ltd.), Idemitsu Styrol HT series (Idemitsu Petrochemical Co., Ltd.), Diaflex series (Mitsubishi Chemical Corp.), Denka Styrol HI series ( Dick Styrene GH Series (Dai Nippon Ink and Chemicals), Asahi Kasei Polystyrene Series (Asahi Kasei), Esbrite Series (Showa Denko), Toporex Series (Mitsui Toatsu Chemical) Manufactured).

The polyphenylene ether resin in the component (B) includes, for example, 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dipropylphenol, 2-methyl-6-ethylphenol, −
Methyl-6-propylphenol, 2-ethyl-6-propylphenol, m-cresol, 2,3-dimethylphenol, 2,3-diethylphenol, 2,3-dipropylphenol, 2-methyl-3-ethylphenol , 2-methyl-3-propylphenol, 2-ethyl-3-methylphenol, 2-ethyl-3-propylphenol, 2-propyl-3-methylphenol, 2-
Propyl-3-ethylphenol, 2,3,6-trimethylphenol, 2,3,6-triethylphenol,
Examples include homopolymers of 2,3,6-tripropylphenol, 2,6-dimethyl-3-ethylphenol, and 2,6-dimethyl-3-propylphenol, and copolymers thereof.

Next, the component (C) used together with the components (A) and (B) can function as a compatibilizer, and is a formamide group represented by the following general formula (1). It is a copolymer comprising a monomer containing a monomer and an aromatic vinyl monomer as an essential component.

[0024]

Embedded image

In the above general formula (1), preferably,
R ₁ , R ₂ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom or a methyl group. Particularly preferably, R ₁ ,
R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are hydrogen atoms.

The formamide group-containing monomer represented by the general formula (1) is described in more detail below.
N, N-diallylformamide, N, N-di- (1-methyl-2-propenyl) formamide, N, N-di-
(1-ethyl-2-propenyl) formamide, N, N
-Di- (1-n-propyl-2-propenyl) formamide, N, N-di- (1-n-butyl-2-propenyl) formamide, N, N-di- (n-hexyl-2-
Propenyl) formamide, N, N-di- (1-benzyl-2-propenyl) formamide, N, N-di- (2
-Methyl-2-propenyl), N-allyl-N- (1-
Methyl-2-propenyl) formamide, N-allyl-
N- (1-ethyl-2-propenyl) formamide, N
-Allyl-N- (2-methyl-2-propenyl) and the like.

The aromatic vinyl monomers include styrene, p-methylstyrene, α-methylstyrene, p-tert-butylstyrene, p-chlorostyrene, p-bromostyrene, 2,4,5 -Tribromostyrene and the like, which may be used alone or in combination of two or more.

As such an aromatic vinyl-based monomer, it is also possible to use a monomer composition in which at least one monomer copolymerizable with the above-mentioned aromatic vinyl-based monomer is used in combination. Among such aromatic vinyl monomers, a composition containing styrene as an essential component is preferred, and styrene alone is particularly preferred.

The monomers copolymerizable with the above-mentioned aromatic vinyl monomer include acrylic acid ester monomers, methacrylic acid esters, unsaturated nitrile monomers, acrylic acid monomers and methacrylic acid monomers. , An α, β-unsaturated carboxylic anhydride and a maleimide-based monomer.

The acrylic acid ester monomer includes:
Methyl acrylate having 1 to 18 carbon atoms in the alkyl group, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, stearyl acrylate, and the like.Examples of the methacrylate monomer include:
Examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, octyl methacrylate, and stearyl methacrylate in which the alkyl group has 1 to 18 carbon atoms. Preferable examples include ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, butyl methacrylate, octyl methacrylate, and lauryl methacrylate. And the above-mentioned acrylate monomer, methacrylate monomer is an acrylate monomer, as a monomer composition with one or more monomers copolymerizable with the methacrylate monomer. It is also possible to use.

Examples of the α, β-unsaturated carboxylic anhydride include maleic anhydride and itaconic anhydride.

Among the monomers copolymerizable with these aromatic vinyl monomers, acrylate monomers,
Methacrylic acid ester monomers and unsaturated nitrile monomers are preferred.

The monomer which can be copolymerized with the aromatic vinyl monomer in the copolymer which is the component (C) used in the present invention is preferably contained in the monomer composition in an amount of from 0 to 40% by weight. %
And more preferably 0 to 25% by weight.

The proportion of the component derived from the formamide group-containing monomer in the copolymer (C) is preferably in the range of 0.05 to 20% by weight, more preferably 0.2 to 20% by weight. 10% by weight. Further, the proportion of the component derived from the aromatic vinyl monomer in the copolymer of the component (C) is preferably in a range of 60% by weight or more, more preferably 75% by weight or more. That is, when the proportion of the component derived from the formamide group-containing monomer in the copolymer as the component (C) is less than 0.05% by weight, the copolymer is further derived from an aromatic vinyl monomer. When the proportion of the constituent components is less than 60% by weight, the miscibility of the components (A) and (B) in the obtained thermoplastic resin composition tends to be poor. Further, the ratio of the constituent part derived from the formamide group-containing monomer is 2%.
If the amount exceeds 0% by weight, it is not economical to produce a copolymer (component (C)) containing a formamide group-containing monomer and an aromatic vinyl monomer as essential components, and therefore, a thermoplastic resin The production of the composition is also not economical.

The proportion (addition amount) of the component derived from the formamide group-containing monomer in the copolymer as the component (C) is determined by the content of the formyl group in the infrared absorption spectrum (IR spectrum). Can be determined. That is, the absorption at 1590 to 1610 cm ^-1 specific to the component derived from the aromatic vinyl monomer, and the 165 specific to the component derived from the formamide group-containing monomer.
It can be determined using the absorbance ratio of the absorption between ⁰ and 1700 cm ^-1 .

The weight average molecular weight of the component (C) is preferably from 5.0 × 10 ^{3 to} 2.0 × 10 ⁶ , more preferably from 1.0 × 10 ^{4 to} 1.0 × 10 ⁶ .

The component (C) is used for bulk polymerization, solution polymerization,
It is an addition polymer produced by a known polymerization method such as suspension polymerization, emulsion polymerization, and precipitation polymerization. Preferably, it is produced by solution polymerization or emulsion polymerization, and particularly preferably, it is produced by emulsion polymerization.

For such a copolymerization reaction of monomers, a radical-forming catalyst such as a peroxide or an azo compound is used. The radical-forming catalyst includes benzoyl peroxide, t-butylbenzate, cyclohexane peroxide, azobisisobutyronitrile and the like, and mixtures thereof.

Among the above polymerization methods, a specific method for producing the component (C) by solution polymerization includes, for example, dissolving a predetermined amount of a monomer and the above radical-forming catalyst in a solvent,
The radical generating catalyst is heated to a temperature at which radicals are generated. After reacting at the same temperature for a predetermined time, washing with a non-solvent such as methanol is repeated several times, and dried under reduced pressure,
There is a method for producing a copolymer as the component (C).

The solvent used in the production by the solution polymerization is not particularly limited as long as it dissolves each monomer and a radical-forming catalyst and shows a liquid at the reaction use temperature. Aromatic solvents such as xylene, chlorobenzene, dichlorobenzene, and trichlorobenzene; ethyl acetate, dioxane, N, N
-Aliphatic solvents such as dimethylformamide and dimethylsulfoxide can be used.

Among the above polymerization methods, as a specific method for producing the component (C) by emulsion polymerization, for example, a predetermined amount of a monomer, distilled water and a dispersion stabilizer are stirred, and the monomer is added to water. Disperse. Further, a predetermined amount of a radical generation catalyst is added, and the mixture is heated to a temperature at which radicals are generated. After a predetermined amount of reaction at the same temperature, the reaction solution is poured into a non-solvent such as methanol to precipitate a copolymer. After washing the copolymer several times with water and a non-solvent, by drying under reduced pressure,
A method for producing a copolymer serving as the component (C) is exemplified.

In the above emulsion polymerization, among the radical forming catalysts, water-soluble radical forming catalysts are preferable, and 2,2-azobis (N, N'-dimethyleneisobutylamidine) hydrochloride, 2,2-azobis (2- Amidino-propane) hydrochloride, 2- (carbamoylazo) -isobutyronitrile hydrochloride, and peroxosulfate. The amount of such a radical-forming catalyst to be added is the same as in known radical polymerization, and a particularly useful addition amount is from 0.05 to 5.0% by weight based on the monomer composition. Further, the reaction temperature needs to be sufficiently high for the radical generation catalyst to generate radicals.

As the dispersion stabilizer used in the above-mentioned production by emulsion polymerization, general surfactants are used, and particularly preferred are anionic and nonionic surfactants.

Examples of the anionic activator include fatty acid soap, rosin soap, alkylbenzene sulfonate, alkyl sulfate, alkane sulfonate, alkyl ether sulfonate, dialkyl sulfosuccinic acid, and naphthalene sulfonate formalin condensate. Examples of the nonionic activator include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, and polyvinyl alcohol. The dispersion stabilizer is used alone or in combination of two or more of these surfactants.

The reaction medium used in the above-mentioned production by emulsion polymerization may be water alone or a mixture of water and one or more organic solvents. As the organic solvent,
A solvent that dissolves an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer and separates them completely without mixing when mixed with water at a volume ratio of 1: 1. If there is, it is not particularly limited. Specific examples of such an organic solvent include benzene, toluene, ethylbenzene, xylene, monochlorobenzene, dichlorobenzene, chloroform, cumene, cyclohexane, hexane, heptane, and butyl alcohol.

The component (D) used together with the components (A) to (C) can function as a compatibilizer similarly to the component (C), and can be represented by the general formula (1). Formamide group-containing monomer to be, a copolymer consisting of a monomer having at least one of an acrylic acid ester monomer and a methacrylic acid ester monomer as an essential component,
It is an addition polymer produced by a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and precipitation polymerization.
Preferably, it is produced by solution polymerization or emulsion polymerization, and particularly preferably, it is produced by emulsion polymerization. The method for polymerizing the component (D) is as described in the above (C).
It is the same as the method for the components.

The formamide group-containing monomer represented by the general formula (1) is the same as that used in the component (C).

The acrylic acid ester monomer includes:
Examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, stearyl acrylate and the like in which the alkyl group has 1 to 18 carbon atoms. Further, as the methacrylate monomer, methyl methacrylate having an alkyl group having 1 to 18 carbon atoms, ethyl methacrylate, propyl methacrylate, butyl methacrylate, octyl methacrylate,
And stearyl methacrylate. Preferably,
Ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, butyl methacrylate, octyl methacrylate, and lauryl methacrylate.

At least one of the above-mentioned acrylate monomer and methacrylate monomer can be used as a monomer composition using one or more monomers copolymerizable with these ester copolymers. It is. The monomers copolymerizable with the ester copolymer include aromatic vinyl monomers, unsaturated nitrile monomers, acrylic acid monomers, methacrylic acid monomers, α, β-unsaturated carboxylic acids. Acid anhydrides and maleimide monomers are exemplified. The monomer copolymerizable with at least one of the acrylic acid ester monomer and the methacrylic acid ester monomer is preferably used in the monomer composition in an amount of 0 to 50% by weight, more preferably 0 to 50% by weight. It is used in the range of ３０30% by weight.

Then, in the copolymer as the component (D),
The proportion of the constituent part derived from at least one of the acrylate monomer and the methacrylate monomer is preferably in a range of 50% by weight or more, more preferably 70% by weight or more. The proportion of the component derived from the formamide group-containing monomer in the copolymer as the component (D) is preferably 0.05 to 20% by weight, more preferably 0.2 to 10% by weight. is there. That is, in the copolymer as the component (D), when the proportion of the component derived from the formamide group-containing monomer is less than 0.05% by weight, or when the acrylate monomer and the methacrylate ester are used. When at least one of the monomers is less than 50% by weight in the monomer composition, the resulting thermoplastic resin composition has an insufficient effect of improving impact resistance, and has an improved weld adhesive strength. This is because the effect becomes insufficient.

Form in Component (D) Copolymer
Percentage of components derived from amide group-containing monomers (Appendix
Addition) is based on the infrared absorption spectrum (IR spectrum).
Can be determined. That is, acrylic ester
And methacrylic acid ester monomers
Also 1720cm unique to the components derived from one side ^-1
Derived from near-absorption and formamide group-containing monomers
1650cm unique to components^-1Absorbance ratio of nearby absorption
Can be determined.

The component (D) preferably has a weight average molecular weight of 5,000 to 2,000,000, more preferably 10,000 to 1,000,000.

In the above-mentioned components (C) and (D), for example, the component (C) comprises a formamide group-containing monomer represented by the general formula (1) and an aromatic vinyl monomer. And a copolymer comprising at least one of an acrylate monomer and a methacrylate monomer, wherein the component (D) is a formamide group-containing monomer represented by the general formula (1). In the case where the copolymer is a copolymer obtained by using an aromatic vinyl monomer together with the copolymer and at least one of an acrylic acid ester monomer and a methacrylic acid ester monomer, both have the same monomer component. However, the component (C) essentially comprises a formamide group-containing monomer and an aromatic vinyl monomer, and the component (D) comprises a formamide group-containing monomer, an acrylate monomer and a methacrylate ester. Since at least one of the monomers is an essential component, the component having a higher proportion of the aromatic vinyl monomer becomes the component (C) except for the formamide group-containing monomer which is a common essential component. The proportion of at least one of the acrylic acid ester monomer and the methacrylic acid ester monomer is higher, which is the component (D).

Among the components (A) to (D) constituting the thermoplastic resin composition of the present invention, the mutual mixing ratios of the components (A) and (B) are as follows. The component (A) is preferably 50 to 90 parts by weight, more preferably 50 parts by weight, based on 100 parts by weight of the total [(A) + (B)].
Ｂ85 parts by weight, and the component (B) is preferably 50-1
0 parts by weight, more preferably 50 to 15 parts by weight.
That is, if the mutual ratio of the component (A) and the component (B) is out of the above range, the obtained thermoplastic resin composition tends to have low mechanical strength such as impact strength.

Next, the component (C) is preferably used in an amount of 0.1 part by weight based on a total of 100 parts by weight of the components (A) and (B).
0 to 20 parts by weight, more preferably 0.5 to 15 parts by weight. That is, if the component (C) is less than 0.05 parts by weight, the miscibility of the component (A) and the component (B) is inferior, the mechanical strength such as the impact strength of the thermoplastic resin composition is reduced, and the physical properties are improved. The effect may not be obtained. Further, even if it is added in an amount exceeding 20 parts by weight, no further effect corresponding to the amount added in excess of the above-mentioned amount can be recognized, which is economically disadvantageous in producing a thermoplastic resin composition. Because.

The component (D) is preferably used in an amount of 0.1 to 100 parts by weight in total of the components (A) and (B).
0 to 20 parts by weight, more preferably 0.5 to 15 parts by weight. That is, when the component (D) is less than 0.05 parts by weight, a certain improvement in impact strength is observed due to the compatibilizing effect of the component (C), but the impact value of the polystyrene resin used as the component (B) varies depending on the type. There is a large difference in the degree of improvement, and further, it is difficult to obtain the effect of improving the weld adhesive strength. Further, even if it is added in an amount exceeding 20 parts by weight, no further effect corresponding to the amount added in excess of the above-mentioned amount can be recognized, which is economically disadvantageous in producing a thermoplastic resin composition. Because.

The thermoplastic resin composition of the present invention is constituted by using the components (A) to (D).
Further other additives as needed, for example, glass fiber,
A reinforcing material such as carbon fiber, an inorganic filler, a heat stabilizer, an antistatic agent, an antioxidant, and an ultraviolet absorber may be appropriately added.

As a method of mixing the components (A) to (D) in the production of the thermoplastic resin composition of the present invention, for example, a melt mixing method is used. As for the method of adding each component, for example, the components (A), (B)
A method in which the components, components (C) and (D) are premixed in the form of pellets or powder and heated and melt-mixed,
Alternatively, a similar thermoplastic resin composition can be obtained by adding and melt-mixing the component (B) to a composition in which the components (A), (C) and (D) are previously melt-mixed.

A more specific method for producing the thermoplastic resin composition of the present invention will be described. That is, the components (A) to (D) and other additives are heated and melted using a kneader such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneading roll, or a mixer such as a Henschel mixer. What is necessary is just to mix in a state. The heating and melting temperature varies depending on the type and amount of each component and the physical properties of the thermoplastic resin composition, but is usually from 180 to 340 ° C.

In the present invention, the component (C), which is a copolymer of a formamide group-containing monomer and an aromatic vinyl monomer, enhances the miscibility of the components (A) and (B), The component (D), which is a copolymer of the containing monomer and at least one of an acrylate monomer and a methacrylate monomer, appropriately adjusts the affinity between the components (A) and (B). However, the mechanism of the action is presumed as follows.

First, the formamide group portion of the formamide group-containing monomer in the component (C) is decomposed by heat during melt mixing to be converted to an amino group. Then, the amino group reacts with a partial bond of the polycarbonate, polyamide and polyester in the component (A) to form a compatibilizer in which the components (C) and (A) are bonded. Further, the formamide group portion of the formamide group-containing monomer in the component (D) is also decomposed by heat at the time of melt mixing and converted into an amino group. The amino group reacts with the partial bond of the polycarbonate, polyamide and polyester in the component (A) to form a composition in which the components (D) and (A) are bonded. Thereby, the miscibility of each resin of the component (A) and the component (B) is enhanced, and the affinity of both the resin of the component (A) and the resin of the component (B) is appropriately adjusted, so that various physical properties are greatly improved. It is thought to be done.

The compatibilizer in the present invention acts on the dispersion interface of the resins (A) and (B) to reduce the interfacial tension between the dispersed phase and the matrix phase, and to reduce the interfacial tension. It has a stabilizing effect.

Next, examples will be described together with comparative examples.

First, the components (C) and (D) are produced according to the following production method.

[Production Example 1a of Copolymer as Component (C) by Emulsion Polymerization] 1000 ml equipped with a stirring device, a heating device, a dropping funnel, a thermometer, a reflux cooling device, and a nitrogen inlet tube.
94 g of styrene, 6 g of N, N-diallylformamide, sodium alkylbenzenesulfonate 3
g and water (397 g) were stirred at a high speed to disperse the monomer composition. Then, 30 g of a 3% aqueous solution of ammonium persulfate was added, and the mixture was reacted at 70 ° C. for 6 hours. Then, after cooling the reaction solution to 30 ° C., the reaction solution is stirred for 5 minutes.
It was poured into 000 ml of methanol to precipitate a copolymer. After repeating filtration and washing with methanol using the copolymer, drying was performed under reduced pressure to obtain a copolymer 1a. This copolymer 1a was 1 according to IR spectrum measurement.
The formyl group content was 1.5% by weight based on the peak intensities at 660 cm ⁻¹ and 1600 cm ⁻¹ , and the weight average molecular weight was determined to be 5.1 × 10 ⁵ by gel permeation chromatography.

[Production Example 1b of Copolymer as Component (C) by Emulsion Polymerization] 1000 ml equipped with a stirring device, a heating device, a dropping funnel, a thermometer, a reflux cooling device, and a nitrogen inlet tube.
Was charged with 98 g of styrene, 2 g of N, N-diallylformamide, 60 g of ethylbenzene, 3 g of sodium alkylbenzenesulfonate and 397 g of water, and the mixture was stirred at high speed to disperse the monomer composition. Thereafter, a copolymer 1b was obtained in the same manner as in Production Example 1a. The copolymer 1b is 0.15% by weight formyl group content than the peak intensity of 1660 cm ^-1 and 1600 cm ^-1 by IR spectroscopy, gel permeation chromatography weight average molecular weight of 6.5 × 10 than the measurement ^Four
It was measured.

[Production Example 1c of Copolymer as Component (C) by Emulsion Polymerization] 1000 ml equipped with a stirring device, a heating device, a dropping funnel, a thermometer, a reflux cooling device, and a nitrogen inlet tube.
Was charged with 75 g of styrene, 25 g of N, N-diallylformamide, 3 g of sodium alkylbenzenesulfonate, and 397 g of water, and stirred at high speed to disperse the monomer composition. Thereafter, a copolymer 1c was obtained in the same manner as in Production Example 1a. The copolymer 1c is 14.3% by weight formyl group content than the peak intensity of 1660 cm ^-1 and 1600 cm ^-1 by IR spectroscopy, gel permeation chromatography weight average molecular weight of 8.1 × 10 than the measurement Measured as ⁴ .

[Production Example 2 of Component (D) Copolymer by Emulsion Polymerization] 94 g of ethyl acrylate was placed in a 1000 ml flask equipped with a stirrer, a heating device, a dropping funnel, a thermometer, a reflux cooling device, and a nitrogen inlet tube. , N, N-diallylformamide, 6 g of rosin acid soap and 397 g of water were stirred at high speed to disperse the monomer composition, and 30 g of a 3% aqueous solution of ammonium persulfate was added. Allowed to react for hours. Then, the reaction solution was poured into a 5% magnesium sulfate solution to precipitate a copolymer. After repeating filtration and water washing using this copolymer, drying was performed under reduced pressure to obtain Copolymer 2. This copolymer 2 was found to have 1660 cm ^-1 and 1720 cm
^The formyl group content was 1.8% by weight based on the peak intensity of ^-1 , and the weight average molecular weight was determined to be 8.1 × 10 ⁵ by gel permeation chromatography.

[Production Examples 3 to 11 of Component (D) Copolymer by Emulsion Polymerization] The monomers, dispersion stabilizers, and polymerization initiators shown in Tables 1 and 2 below were used in the amounts shown in the tables. Using.
Otherwise, copolymers 3 to 11 shown in Tables 1 and 2 below were obtained in the same manner as in Production Example 2 above. In addition, the formamide group-containing monomer addition amount and the weight average molecular weight of the copolymers 3 to 11 were measured by the same measurement method as described above,
The results are shown in Tables 1 and 2 below.

[0070]

[Table 1]

[0071]

[Table 2]

[Production Example 12 of Component (D) Copolymer by Solution Polymerization] In a 1000 ml flask equipped with a stirring device, a heating device, a thermometer, a reflux cooling device, and a nitrogen inlet tube, 100 g of butyl acrylate, N , N-diallylformamide (6 g), benzene (400 g), and benzoyl peroxide (1 g) were charged, heated to 70 ° C., and reacted for 5 hours. Further, the reaction solution was dried under reduced pressure at 40 ° C. to recover a copolymer. This copolymer was repeatedly washed with hexane, and dried under reduced pressure to obtain a copolymer 12. This copolymer 12 had 1660 cm ^-1 and 1720 cm
^From the peak intensity of ^-1 , the content of the formyl group was 1.5% by weight, and the weight average molecular weight was determined to be 7.5 × 10 ⁴ .

[Production Example 1 for Comparative Example of Component (C) Copolymer by Solution Polymerization] In a 1000 ml flask equipped with a stirring device, a heating device, a thermometer, a reflux cooling device, and a nitrogen introducing tube, 40 g of styrene was added. , Methyl acrylate 60 g, N,
6 g of N-diallylformamide, 400 g of benzene, and 1 g of benzoyl peroxide were charged, heated to 70 ° C., and reacted for 5 hours. Further, the reaction solution was dried under reduced pressure at 40 ° C. to recover a copolymer. After repeating washing of this copolymer with hexane, the copolymer was dried under reduced pressure to obtain Comparative Copolymer 1. This comparative copolymer 1 was 1 according to IR spectrum measurement.
From the peak intensities at 660 cm ^-1 and 1600 cm ^-1 ,
The formyl group content was 1.6% by weight and the weight average molecular weight was measured to be 3.6 × 10 ⁴ .

[Production Example 2 for Comparative Example of Component (D) Copolymer by Solution Polymerization] Acrylic acid was placed in a 1000 ml flask equipped with a stirring device, a heating device, a thermometer, a reflux cooling device, and a nitrogen inlet tube. Butyl 40 g, styrene 60 g, N,
6 g of N-diallylformamide, 400 g of benzene, and 1 g of benzoyl peroxide were charged, heated to 70 ° C., and reacted for 5 hours. Further, the reaction solution was dried under reduced pressure at 40 ° C. to recover a copolymer. After repeating washing of this copolymer with hexane, drying was performed under reduced pressure to obtain Comparative Copolymer 2. This comparative copolymer 2 was 1 according to IR spectrum measurement.
From the peak intensities at 660 cm ^-1 and 1720 cm ^-1 ,
The formyl group content was 1.8% by weight, and the weight average molecular weight was measured to be 6.5 × 10 ⁴ .

[0075]

Examples 1 to 17, Comparative Examples 1 and 2, Comparative Examples 1 to 1
8. First, as shown below, a resin used as the component (A) and a resin used as the component (B) were prepared.

[Resin used as component (A)] PC: Polycarbonate (Panlite L1250, manufactured by Teijin Chemicals Ltd.) PA: Polyamide (Leona 1300S, manufactured by Asahi Kasei Corporation) PBT: Polybutylene terephthalate (Toray PBT resin 1401-X06, Toray) Company)

[Resin Used as Component (B)] HIPS1: Impact-resistant polystyrene (Sumibright DJ)
-7000, manufactured by Sumitomo Chemical Co., Ltd.) HIPS2: Impact-resistant polystyrene (Idemitsu Styrol H)
HIPS3: impact-resistant polystyrene (Idemitsu Styrol H)
HIPS4: Impact-resistant polystyrene (Stylon H86)
52, manufactured by Asahi Kasei Kogyo Co., Ltd.) ABS: ABS resin (Toyolac 500, manufactured by Toray Co., Ltd.) SEBS: SEBS resin (Tuftec H1041, manufactured by Asahi Kasei Kogyo Co., Ltd.)
GPPS: polystyrene resin (Estyrene G-20, manufactured by Nippon Steel Chemical Co., Ltd.)

The components (A) to (D) shown in Tables 3 to 6 described below were mixed in the proportions shown in the same table, and a thermoplastic resin composition was obtained by the following method. That is, after the components (A) to (D) shown in Tables 3 to 6 described below are dry-blended in advance at a ratio shown in the same table and dried, a twin-screw extruder (KRC kneader,
(Kurimoto Iron Works). Then, it was taken out and pelletized to obtain a thermoplastic resin composition.

The thermoplastic resin composition thus obtained was processed using an injection molding machine (Hipershot 3000, manufactured by Niigata Iron Works) to obtain a molded product. The Izod impact strength, weld strength, appearance and peelability of this molded product were measured and evaluated according to the following evaluation methods, and the results are shown in Tables 3 to 6 below.

[Izod impact strength] JIS-K671
The Izod impact value was measured at 23 ° C. according to No. 9. In addition, in order to check the notch sensitivity, Examples 1 to 8, 13 and Comparative Examples 1 and 2 and Comparative Examples 1 to 12, 17, and 18 have JI.
The measurement value of the No. 2 A test piece (12.7 mm in thickness) in S-7110 is also described.

[Weld adhesive strength] JIS-K7113
A test piece having the same shape as the No. 2 test piece in the above, injection molded using a mold prepared so that the molten resin is injected from both ends at the time of injection molding and the tip of the molten resin is adhered at the center, and JIS A tensile test was performed according to -K7113.

[Appearance] With respect to the appearance and hue of the obtained molded product, flow marks, fluffing, generation of silver, and coloring degree were visually determined. Good appearance is ○,
Somewhat poor were rated as △, and some poor were rated as ×.

[Presence or absence of laminar peeling] The peelability was evaluated by a cross-cut test. That is, a cut is made on the surface of the test piece using a knife, and a 1 mm × 1 mm square 100
The pieces were formed in a grid pattern. Then, the cellophane tape was pressed and then peeled off with a strong force to count the number of squares that did not adhere to the cellophane tape and did not peel off from the test piece.

[0084]

[Table 3]

[0085]

[Table 4]

[0086]

[Table 5]

[0087]

[Table 6]

From the results in Tables 3 to 6, (A) to
Examples in which the four components (D) are used as constituents are all
The Izod impact value and the weld strength were high, and there was no problem in appearance, and good results were obtained in terms of peelability. On the other hand, Comparative Examples 1, 3, in which the three components of the component (A), the component (B), and the component (C) were used as constituent components
Nos. 5, 7, 10, and 17 had no problem with respect to appearance and peelability, but had low Izod impact value and inferior weld strength as compared with the examples. Comparative Example 8, which has three components of component (A), component (B) and component (D), has a low evaluation of appearance and releasability, a low Izod impact value, and a weld strength test. Also did not adhere. Then, Comparative Examples 2, 4, 6, 9, and 2 comprising two components (A) and (B)
Nos. 11, 12, 13 to 16, 18 had remarkably low Izod impact values, low or no weld adhesion, poor appearance, and poor peelability evaluation test results. In addition, in Comparative Examples 1 and 2, each evaluation result was lower than in all Examples, but was better than the evaluation result of Comparative Example.

Further, in Example 1, a thermoplastic resin composition was prepared by using PC and PA in combination instead of PC alone as the component (A), and using HIPS1 and PPE in place of HIPS1 alone as the component (B). A product was made. The same evaluation as above was performed using this thermoplastic resin composition.
As a result, as in all the above Examples, the Izod impact value and the weld adhesive strength were high, and there was no problem in appearance, and good results were obtained in terms of peelability.

[0090]

As described above, according to the present invention, the resin represented by the general formula (1) is added to both the resin components (A) and (B).
A copolymer (component (C)) containing a formamide group-containing monomer and an aromatic vinyl monomer as essential components represented by the following formula (I) as an compatibilizer, and further represented by the above general formula (1). A copolymer (component (D)) comprising a formamide group-containing monomer and a monomer having at least one of an acrylate monomer and a methacrylate monomer as an essential component is newly compatible. This is a thermoplastic resin composition used as an agent. Therefore, by using the component (C) and the component (D), which is a novel compatibilizer, a component in which the affinity between the component (A) and the component (B) is further optimized can be obtained. An excellent thermoplastic resin composition which is excellent in impact resistance and processing fluidity, has a good appearance when molded, does not cause delamination, and has improved weld adhesion strength can be obtained.

In the component (C), the proportion of the constituent derived from the formamide group-containing monomer is 0.05 to 20% by weight, and the proportion of the constituent derived from the aromatic vinyl monomer is 0.05 to 20% by weight. The proportion is set to 60% by weight or more, and the proportion of the component derived from the formamide group-containing monomer in the component (D) is 0.05 to 20%.
By setting the proportion of the component derived from at least one of the acrylate monomer and the methacrylate monomer to 50% by weight or more by weight,
In addition to the effect of further improving the miscibility of the component (A) and the component (B), a sufficient effect of improving impact resistance and weld strength can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 71/12 C08L 71/12 77/00 77/00

Claims (6)

[Claims] 1. A thermoplastic resin composition comprising the following components (A) to (D). (A) at least one resin selected from the group consisting of polycarbonate resins, polyamide resins and polyester resins. (B) at least one of a styrene resin and a polyphenylene ether resin. (C) A copolymer comprising a formamide group-containing monomer represented by the following general formula (1) and a monomer having an aromatic vinyl monomer as an essential component. (D) a copolymer comprising a formamide group-containing monomer represented by the following general formula (1) and a monomer containing at least one of an acrylate monomer and a methacrylate monomer as an essential component Coalescing. Embedded image 2. In the component (C), the ratio of the constituent part derived from the formamide group-containing monomer is from 0.05 to 0.05.
20% by weight, the proportion of the component derived from the aromatic vinyl monomer is set to 60% by weight or more, and the component derived from the formamide group-containing monomer in the component (D). Is 0.05-20% by weight
The thermoplastic resin composition according to claim 1, wherein the proportion of the constituent component derived from at least one of an acrylate monomer and a methacrylate monomer is set to 50% by weight or more. 3. The mixing ratio of the component (A) and the component (B) [(A) / (B)] is expressed by a weight ratio of (A) / (B) =
The thermoplastic resin composition according to claim 1 or 2, wherein the ratio is set to (50 to 90) / (10 to 50). 4. The method according to claim 1, wherein the content of the component (C) is less than the content of the component (A).
0.0 with respect to 100 parts by weight of the total amount of the component and the component (B).
The thermoplastic resin composition according to any one of claims 1 to 3, which is set to 5 to 20 parts by weight. 5. The method according to claim 1, wherein the content of said component (D) is
0.0 with respect to 100 parts by weight of the total amount of the component and the component (B)
The thermoplastic resin composition according to any one of claims 1 to 4, which is set to 5 to 20 parts by weight. 6. A copolymer of a formamide group-containing monomer represented by the following general formula (1) and a monomer containing at least one of an acrylate monomer and a methacrylate monomer as an essential component: Compatibilizer consisting of a polymer. Embedded image