JPS6047045A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having high rigidity and excellent resistance to heat, impact and hot water, consisting of a specified thermoplastic resin, glass fiber and a carbon fiber and/or Aramid fiber. CONSTITUTION:2-60pts.wt of the combined quantity of a carbon fiber and glass fiber and/or Aramid fiber is mixed with 40-98pts.wt thermoplastic resin contg. 10-90wt% imidated copolymer obtd. by reacting NH3 and/or a prim. amine with a copolymer of 100-60wt% monomer mixture consisting of 0-40wt% rubbery polymer (A), 40-80wt% arom. vinyl monomer (B), 25-80wt% unsaturated dicarboxylic acid anhydride (C) and 0-30wt% copolymerizable vinyl monomer (D) to convert 60-100% of acid anhydride groups to imide groups; 10- 90wt% graft copolymer obtd. by grafting 95-20wt% monomer mixture consisting of 40-80wt% component B, 40-80wt% vinyl cyanide monomer (E) and 0- 40wt% component D onto 5-80wt% component A; and 0-80wt% copolymer obtd. from 40-80wt% component B, 0-40wt% component E and 0-40wt% component D.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to thermoplastic resin compositions containing imidized copolymers reinforced with fibrous materials. More specifically, ammonia and/or a primary amine is added to a copolymer prepared by polymerizing a monomer mixture containing an aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride in the presence of a rubbery polymer if necessary. A thermoplastic resin whose essential component is a mixture of a reacted imidized copolymer and a rubber-modified aromatic vinyl copolymer, reinforced with a fibrous material selected from glass fibers, carbon fibers, and aramid fibers. Misaki regarding resin compositions Conventionally, in the case of glass fiber reinforcement, aromatic vinyl monomers,
Compositions of unsaturated dicarboxylic acid anhydrides and copolymers of other vinyl monomers are known (Japanese Patent Application Laid-open No. 4-1131)
8-881891゜A composition of a copolymer obtained by copolymerizing unsaturated socarboxylic acid anhydride with glass fiber has an acid anhydride group originating from the unsaturated nocarboxylic acid anhydride in the copolymer chain. Because of this, there are significant restrictions when using injection or extrusion processing, which is not only sensitive to water at high temperatures but also easily decomposes due to heat, and there are also significant restrictions on processing processed products when exposed to water or steam. When exposed to high pressure, the mechanical properties, especially the impact strength, deteriorate.

Further, US Pat. No. 3,632,791 discloses that a combination of 40 to 95% by weight of an aromatic vinyl monomer, 5 to 25% by weight of maleimide, and θ to 35% by weight of other monomers, and glass fibers. compositions are disclosed. However, in such compositions, the maleimide content is low, so the affinity with the copolymer on the glass fiber surface is insufficient, and there are substances such as rubber-modified copolymers that increase impact strength. This has the disadvantage of lacking impact resistance.

The present invention was developed as a result of intensive research to improve the above-mentioned drawbacks when using not only glass fibers but also carbon fibers and/or aramid fibers. A rubber-modified aromatic vinyl copolymer and an imidized copolymer prepared by reacting the copolymer with ammonia and/or a primary amine, if necessary in the presence of a rubbery polymer, and a rubber-modified aromatic vinyl copolymer. By mixing one or more selected fibers such as glass fiber, carbon fiber and aramid fiber with a thermoplastic resin whose essential component is a mixture of This was the first success in obtaining a thermoplastic resin composition with excellent aqueous properties.

That is, the present invention consists of component A: 40 to 80% by weight of an aromatic vinyl monomer, 25 to 50% by weight of an unsaturated dicarboxylic acid anhydride, and 40 to 80% by weight of a rubbery polymer θ to 40% by weight, and a component copolymerizable with these. Monomer mixture 60-10 consisting of 0-30% by weight of vinyl monomer
By reacting ammonia and/or primary amine with a polymer obtained by copolymerizing 0 polymers, 80 to 100 of acid anhydride groups are
Imidized copolymer 10 in which molti is converted to imide group
90% by weight, component B: 5 to 80% by weight of rubbery polymer, 40 to 80% by weight of aromatic vinyl monomer, 0 to 40% by weight of vinyl cyanide monomer, and copolymerizable with these. Monomer mixture 2 consisting of 0 to 40 vinyl monomers by weight
Graft copolymer 10 to 95% by weight copolymerized
90% by weight, component C: a copolymer consisting of 40 to 80% by weight of aromatic vinyl monomer, 0 to 40% by weight of vinyl cyanide monomer, and 0 to 40% by weight of vinyl monomer copolymerizable with these. Polymer 0~
80% by weight of a thermoplastic resin containing 40 to 98 parts by weight and 2 to 60 parts by weight of one or more types of fibers selected from glass fibers, carbon fibers, and aramid fibers. Composition.

The composition of the present invention is used in applications requiring the above-mentioned properties, such as automobile interiors, exteriors, engine compartment parts,
It is suitable for electrical/electronic equipment parts, industrial machine parts, and even kitchen utensils that use hot water.

The thermoplastic resin of the present invention may consist only of component A and B, but even if it is further mixed with the aromatic vinyl copolymer of component C in an amount of 80% by weight or less, the thermoplastic resin of the present invention Since the excellent properties of the thermoplastic resin do not deteriorate, it has the advantage that a large amount of an inexpensive aromatic vinyl copolymer can be blended.

First, the A component polymer and its manufacturing method will be explained. The monomer mixture used consists of 40-8-0% by weight of aromatic vinyl monomers, 25-50% by weight of unsaturated dicarboxylic acid anhydrides, and 0-30% by weight of vinyl monomers copolymerizable with these. . If necessary, add rubbery polymer to the monomer mixture at 40%
Weight - can be used below.

If the content of the aromatic vinyl monomer in the monomer mixture is less than 40 parts, moldability and dimensional stability, which are characteristics of the aromatic vinyl compound, will be impaired. Furthermore, if the unsaturated dicarboxylic acid anhydride is less than 25% by weight, the compatibility with glass fibers, carbon fibers and aramid fibers will not be sufficient, and the heat resistance will also decrease. On the other hand, if the annual salary of dicargonic acid anhydride exceeds 50 parts per year, the copolymer composition will become brittle and its moldability will deteriorate significantly.

The aromatic vinyl monomers constituting component A include styrene monomers and their substituted monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene, among which styrene is particularly preferred.

Examples of unsaturated dicarboxylic acid anhydrides include maleic acid, itaconic acid, and cyto. Examples include anhydrides such as laconic acid and aconitic acid, with maleic anhydride being particularly preferred.

Vinyl monomers that can be copolymerized with these include vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile; acrylic acid ester monomers such as methyl acrylate and ethyl acrylate; Methacrylate monomers such as methyl methacrylate and ethyl methacrylate,
There are vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylamide, methacrylic acid amide, etc. Among these, acrylonitrile, methacrylic ester,
Monomers such as acrylic acid and methacrylic acid are preferred.

Examples of rubbery polymers include butadiene polymers, copolymers of butadiene and copolymerizable vinyl monomers, ethylene-propylene copolymers, ethylene-nolopylene i-diene copolymers, and blocks of butadiene and aromatic vinyl. Copolymers, acrylic ester polymers, copolymers of acrylic esters and vinyl monomers copolymerizable therewith, and the like are used. If the rubber component in the A-component polymer exceeds 40 H, it is unfavorable in terms of heat resistance and moldability.

Ammonia and primary amines used in the imidization reaction may be in either anhydrous or hydroxyl solution, and examples of primary amines include alkyl amines such as methylamine, ethylamine, butylamine, and cyclohegycylamine. , and aromatic amines such as chloro- or bromo-substituted alkyl amines, aniline, tolylamine, naphthylamine, and no-rogne-substituted aromatic amines such as chloro- or bromo-substituted aniline.

When the imidization reaction is carried out in a solution or suspension state, it is preferable to use a normal reaction vessel, such as an autoclave.If the imidization reaction is carried out in a bulk molten state, an extruder equipped with a devolatilization device may be used. . Further, a catalyst may be present during imidization, and for example, a tertiary amine or the like is preferably used.

The temperature of the imidization reaction is about 80-350°C, preferably 100-300°C.

If the temperature is lower than 80°C, the reaction rate is slow and the reaction takes a long time, which is not practical. On the other hand, if the temperature exceeds 350°C, the physical properties will deteriorate due to thermal decomposition of the polymer.

The amount of ammonia and/or primary amine used is preferably 0.8 to 1.05 molar equivalents based on the unsaturated dicarboxylic anhydride. If it is less than 0.8 molar equivalent, the imidized copolymer will have a large amount of acid anhydride groups, resulting in poor thermal stability and hot water resistance, which is not preferable.

Next, component B and its manufacturing method will be explained. The rubbery polymer used for component B is a polymer consisting of a vinyl monomer copolymerizable with getadiene alone or with it, an ethylene-propylene copolymer, an ethylene-propylene-diene copolymer, or an acrylic ester alone or There are polymers other than vinyl monomers that can be copolymerized with this.

Aromatic vinyl monomers used in component B, styrene monomers such as styrene, α-methylstyrene, vinyltoluene, t-ditylstyrene, chlorostyrene, and their substituted monomers, among which styrene and α−
Monomers such as methylstyrene are particularly preferred.

Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, with acrylonitrile being particularly preferred. Vinyl monomers that can be copolymerized with these include acrylic esters such as Nisder methyl acrylate, ethyl acrylate, butyl acrylate, and methacrylic esters such as methyl methacrylate and ethyl methacrylate. Examples include vinylcarboxylic acid monomers such as acrylic acid and methacrylic acid, acrylamide, and methacrylic acid amide. Among these, methyl methacrylate, acrylic acid, and methacrylic acid are particularly preferred.

The method for producing the graft copolymer of component B is to prepare rubber-like polymers 5 to 8.
0 weight - 40-80% by weight of aromatic vinyl monomer in the presence
is obtained by graft copolymerizing 20 to 95% by weight of a monomer mixture consisting of 0 to 40% by weight of vinyl cyanide monomers and 0 to 40% by weight of vinyl monomers copolymerizable with these monomers. Any known polymerization technique can be employed for the polymerization, including suspension polymerization, aqueous heterogeneous polymerization such as emulsion polymerization, bulk polymerization, solution polymerization, and precipitation polymerization of the resulting polymer in a nonsolvent.

Next, component C and its manufacturing method will be explained. The aromatic vinyl monomer used as component C is styrene, α-
Among styrene monomers such as methylstyrene, vinyltoluene, t-ditylstyrene, and chlorostyrene and substituted monomers thereof, styrene and α-methylstyrene are particularly preferred.

Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, with acrylonitrile being particularly preferred.

Vinyl monomers that can be copolymerized with these include acrylic ester monomers such as methyl acrylate, ethyl acrylate, and butyl acrylate, and methacrylic ester monomers such as methyl methacrylate and ethyl methacrylate. Examples include vinylcarboxylic acid monomers such as acrylic acid and methacrylic acid, acrylic acid amide, methacrylic acid amide, acenaphthylene, N-vinyl carbazole, N-alkyl substituted maleimide, N-aromatic substituted maleimide, and the like.

In the resin composition of the present invention, the content of one or more fibers selected from glass fibers, carbon fibers and aramid fibers is 2 to 60% by weight, more preferably 5 to 40% by weight. If the content of these fibers is less than 2% by weight, the rigidity and dimensional stability of the resulting molded article will not be sufficiently improved, and if it exceeds 60% by weight, molding, especially injection molding, etc. will become extremely difficult.

Aramid fibers are polyamide fibers with aromatics introduced into the molecular chain. Examples of polymers with aramid fibers include poly-m-xylylene azideamide, poly-p-benzamide, poly-p-phenylene terephthalamide, and yf! Lee-m
- Phenylene isophthalamide, etc.

The physical properties of the fiber composition vary greatly depending on the shape of the fibers and the state of surface treatment, similar to the known woodcutter fiber reinforced compositions. Even in the fiber reinforced composition of the present invention, the fiber length is 0.
．． A thickness of 3 mm or more is preferable, and silane coupling agents such as Matamifushin 2, epoxy silane, titanium coupling agents, etc. can be used.

The composition of the present invention comprises a thermoplastic resin containing a mixture of an imidized copolymer and a rubber-modified aromatic vinyl copolymer as an essential component, and one or more fibers selected from glass fiber, carbine fiber, and aramid fiber. However, there are no particular restrictions on the mixing method, and known means can be used. Examples of the means include a Banbury mixer, tumbler mixer, Henschel mixer, mixing roll, 1
Examples include a screw or twin screw extruder. As for the mixing form, there are methods for obtaining the cylindrical acid by conventional melt mixing, multi-stage melt mixing using master pellets, solution blending, mixing in a reaction solution, etc.

The composition of the present invention may further include stabilizers, flame retardants, plasticizers,
It is also possible to add lubricants, ultraviolet absorbers, colorants, and fillers such as talc, silica, clay, mica, calcium carbonate, and the like.

The present invention will be further explained below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. In addition, all parts and parts in the examples are expressed on a weight basis.

Experimental Example (1) Production of Component A 60 parts of styrene and 50 parts of methyl ethyl ketone were placed in an autoclave equipped with a stirrer, and after purging the system with nitrogen gas, the temperature was raised to 85°C, and 40 parts of maleic anhydride and 50 parts of methyl ethyl ketone were charged. A solution of 0.15 parts of penzoylno-9-oxide dissolved in 250 parts of methyl ethyl ketone was added continuously over 8 hours. Vorticity was maintained at 85° C. for an additional 3 hours after addition. A portion of the viscous reaction solution was sampled and determined by gas chromatography to determine the amount of unreacted monomer. As a result, the polymerization rate was 98% for styrene and 98% for maleic anhydride. To the copolymer solution obtained here were added 36.1 parts of aniline and 0.3 parts of triethylamine in an amount of 0.95 equivalent to maleic anhydride, and the mixture was reacted at 140° C. for 7 hours. 200 parts of methyl ethyl ketone was added to the reaction solution, cooled to room temperature, poured into 1500 parts of vigorously stirred methanol, precipitated, separated, and dried to obtain an imidized polymer.

C--C-13 part analysis showed that 100% of aniline had reacted in the reaction of the sialic acid anhydride group to the imide group. This was designated as Polymer A.

Experimental example (2) Production of component A Styrene 60 was placed in the same autoclave as in experimental example (1).
1 part, 100 parts of methyl ethyl ketone, and 10 parts of polybutatsuene cut into small pieces were charged, stirred all day and night in Murogata to dissolve the rubber, then purged the system with nitrogen gas, and lowered the temperature to 85.
The temperature was raised to ℃. Solution 5 in which 40 parts of maleic anhydride and 0.15 parts of azobisinbutyronitrile were dissolved in 200 parts of methyl ethyl ketone was continuously added over 8 hours. From this point on, exactly the same operations as in Experimental Example (1) were performed. The polymerization rate was 98% for styrene and 99% for maleic anhydride. In the reaction of acid anhydride groups to imide groups, the reaction rate of aniline was 100- as in Experimental Example (1).

This was designated as Polymer B.

Experimental example (3) Production of component A Styrene 60 was placed in the same autoclave as in experimental example (1).
parts, 10 parts of acrylonitrile, 50 parts of methyl ethyl ketone
The experiment was conducted except that a solution of 30 parts of maleic anhydride and 0.15 parts of azobisisobutyronitrile dissolved in 250 parts of methyl ethyl ketone was added continuously over 9 hours, and 27.0 parts of aniline was used. I did exactly the same operation as in example (1). The polymerization rate was 99% for styrene, 92% for acrylonitrile, and 96% for maleic anhydride. As in Experimental Example (1), aniline reacted with 'xioos.

This was designated as Polymer C.

Experimental Example (4) Production of component B 143 parts of polybutadiene latex (solid content 35%, weight average particle size 0.35μ, glue content 90%), potassium stearate 1 part, sodium form aldehyde sulfoxylate 0 .1 part, tetrasodium ethylenesoamine tetraacetic acid 0.03 part, ferrous sulfate 000
3 parts and 150 parts of water were heated to 50°C, and to this were added 50 parts of a monomer mixture of 70% styrene and 30% acrylonitrile, 0.2 parts of t-dodecylmercaptan, and 0.15 parts of cumene hydroperoxide. The addition was continued for 6 hours, and after the addition, the temperature was raised to 65°C and polymerization was carried out for 2 hours. The polymerization rate reached 97% as determined by gastalomadography analysis. After adding antioxidant to the obtained latex,
After coagulating with calcium chloride, washing with water, and drying, a graft copolymer was obtained as a white powder. This was made into a polymer.

Experimental example (5) Production of component C 60 parts of α-methylstyrene, 1 part of styrene, 30 parts of acrylonitrile, 2.5 parts of potassium stearate, t-
70 parts of dodecyl mercaptan and 250 parts of water
0.05 parts of potassium persulfate was added thereto, and the temperature was raised to 75°C and maintained for 3 hours to complete the polymerization.

The polymerization rate reached 97%. The resulting latex was coagulated with calcium chloride and washed with water.

After drying, a white powder copolymer was obtained. This was designated as Polymer E.

Examples 1 to 7 Polymers A-E obtained in Experimental Examples (1) to (5), glass fibers of 5 lengths, PAN carbon fibers of 6 lengths, and aramid fibers of 6 lengths (du Kevlar (manufactured by Pont Co., Ltd.) (-49) was mixed in a Henschel mixer at the ratio shown in Table 1, and then extruded in an extruder equipped with a Henschel to form pellets. The pellets were molded using an injection molding machine and subjected to physical property tests, and the results are shown in Table 1. The composition contains 2 parts of l-distearylphosphite, 0 parts of octadecyl 3-(3,5-ditertiarybutyl-4-hydroxyphenyl)-zolobionate,
5 parts were added.

Comparative Example 1 Styrene 90 was placed in the same autoclave as in Experimental Example (1).
150 parts of methyl ethyl ketone were charged, a solution of 10 parts of maleic anhydride and 0.15 parts of azobisin butyronitrile dissolved in 100 parts of methyl ethyl ketone was added continuously over 10 hours, and 9.49 parts of aniline was used. The operation was exactly the same as in Experimental Example (1) except for the following. The polymerization rate was 95% for styrene and 99% for maleic anhydride. As in experimental example (1), aniline reacted at 100%. This is called polymer P, and 5 uI! Long glass fibers were mixed in the proportions shown in Table 1 in the same manner as in Example 1, molded, and measured for physical properties.
Shown in the table.

Ratios shown in Table 1 The composition of the present invention has high rigidity, and significant improvements in impact resistance and heat resistance are observed.

The physical properties were measured by the following method.

(1) Tensile strength: Measured according to ASTM-D 651.

(2) Impact strength: Izot strength with marks and marks.

Measured according to ASTM-D 256.

(3) Vicat softening point...Load 5#.

According to ASTM-D 1525 measurement.

Patent applicant Denki Kagaku Kogyo Co., Ltd. 307-

Claims (1)

[Claims] Component A: 40 to 80% by weight of aromatic vinyl monomer, 25 to 50% by weight of unsaturated dicarboxylic acid anhydride, and copolymerizable with these, based on 0 to 40% by weight of the rubbery polymer. A monomer mixture consisting of 0 to 30 weight φ of vinyl monomers 60 to 10
By reacting ammonia and/or primary amine with a polymer copolymerized with 0 weight i%, 80 to 100 of the acid anhydride groups are
Imidized copolymer 10 in which molti is converted to imide group
90% by weight, component B: 5 to 80% by weight of rubbery polymer, 40 to 80% by weight of aromatic vinyl monomer, 0 to 40% by weight of vinyl cyanide monomer, and copolymerizable with these. Monomer mixture 2 consisting of 0 to 40% by weight of vinyl monomer
Graft copolymer 10 to 95% by weight copolymerized
Component C: 40 to 80% by weight of aromatic vinyl monomer, 0 to 40% by weight of vinyl cyanide monomer, and 0 to 40% by weight of vinyl monomer copolymerizable with these. Copolymer 0
Thermoplastic resin 40-98 containing ~80% by weight
1. A thermoplastic resin composition comprising 2 to 60 parts by weight of one or more fibers selected from glass fibers, carbon fibers and aramid fibers.