JP3308686B2 - Fiber reinforced thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fiber-reinforced thermoplastic resin composition having excellent heat resistance, impact resistance, rigidity, and excellent moldability.

[0002]

2. Description of the Related Art Aromatic polyester is a thermoplastic material having excellent properties such as chemical resistance and moldability, and is used in the fields of electric and electronic parts, automobile parts and the like. However, due to its high crystallinity, it has disadvantages such as low notched impact strength and poor dimensional stability. It is also known that the addition of glass fiber to aromatic polyester not only gives rigidity but also has properties such as heat resistance and creep resistance, but also has the disadvantage of low notched impact strength. ing.

[0003] In order to improve these disadvantages, a method of blending an aromatic polyester and an ABS resin (Japanese Patent Publication No.
-25261) has been proposed, but sufficient mechanical properties cannot be obtained due to poor compatibility between the aromatic polyester and the ABS resin.

Therefore, a method of adding a copolymer mainly composed of a glycidyl ester of an α-olefin and an α, β-unsaturated acid as a compatibilizer (JP-A-1-138261, JP-A-3-2674)
No. 8) has been proposed, but the resin composition obtained by this method, particularly with a fiber reinforced resin composition, has an insufficient effect of improving the impact resistance or has a large decrease in moldability. There was a problem.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to improve the impact resistance of a fiber-reinforced resin composition and prevent a reduction in molding processability in a system using a copolymer as a compatibilizer as described above. And so on.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, by blending a specific copolymer with a specific aromatic polyester and an ABS resin in a specific amount, The inventors have found that impact resistance can be improved while maintaining moldability, and the present invention has been achieved.

That is, the present invention relates to 100 parts by weight of a thermoplastic resin composition comprising 5 to 95% by weight of the following A component, 95 to 5% by weight of the B component and 0 to 30% by weight of the C component. .
A fiber-reinforced thermoplastic resin composition comprising 5 to 10 parts by weight and 5 to 50 parts by weight of an E component. A component: carboxyl terminal (-COOH) and hydroxyl terminal (-O
Aromatic polyesters wherein the ratio -COOH / -OH of H) is 0/100 to 50/50. Component B: 50 to 80% by weight of an aromatic vinyl monomer and 20 to 20 parts by weight of a vinyl cyanide monomer based on 10 to 60 parts by weight of a diene rubber polymer.
A monomer mixture 40 to 50% by weight and 0 to 20% by weight of a vinyl monomer copolymerizable with these monomers if necessary.
Graft copolymer obtained by graft polymerization of 90 parts by weight
(However, the total amount of the diene rubber polymer and the monomer mixture is
100 parts by weight) . Component C: 50 to 80 parts by weight of an aromatic vinyl monomer, 20 to 50 parts by weight of a vinyl cyanide monomer and, if necessary, 0 to 20 parts by weight of a vinyl monomer copolymerizable with these monomers. Styrene copolymer obtained by copolymerization (however, the total amount of monomers is 1
00 parts by weight) . Component D: 50 to 79.5 parts by weight of an aromatic vinyl monomer, 20 to 45 parts by weight of a vinyl cyanide monomer, 0.5 to 5 parts by weight of an epoxy group-containing vinyl monomer and, if necessary, a copolymer with these monomers. A copolymer obtained by copolymerizing 0 to 20 parts by weight of a polymerizable vinyl monomer (provided that the total amount of monomers is 100 parts by weight.
) . E component: fibrous reinforcement. Further, the present invention is the above fiber-reinforced thermoplastic resin composition, wherein the aromatic polyester is polybutylene terephthalate. The fiber reinforced thermoplastic resin composition is an A component.
Temperature from 50 ° C below melting point to 100 ° C above melting point
And heat-treat for a time range from 10 minutes to 100 hours
Fiber-reinforced thermoplastic resin composition obtained by
Good.

Hereinafter, the present invention will be described in detail. The aromatic polyester as the component A of the present invention is a resin obtained by subjecting an aromatic dicarboxylic acid or an ester-forming derivative thereof to a diol or an ester-forming derivative thereof through a polycondensation reaction.

Examples of the above aromatic dicarboxylic acids include:
Terephthalic acid, isophthalic acid, orthophthalic acid, 2,6
-Naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, adipic acid, azelaic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-bicyclo [2,2,2 Octanedicarboxylic acid and the like, and terephthalic acid is most preferred.

Examples of the above diols include ethylene glycol, 1,4-butanediol, 1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, Examples include bisphenol A, with 1,4-butanediol being most preferred.

The aromatic polyester used in the present invention has a terminal group ratio -COOH / -OH of 0/100 to 50/50. -COOH
If the number of groups is larger than the number of —OH groups, molding processability is undesirably reduced.

[0012] In the thermoplastic resin composition of the present invention, A
The content of the components is 5-95% by weight, preferably 30-70% by weight. If the content of the component A is less than 5% by weight, the chemical resistance, heat resistance and moldability are insufficient, and if it exceeds 95% by weight, the notched impact strength is insufficient.

The graft copolymer which is the component B of the present invention refers to an aromatic vinyl monomer, a vinyl cyanide monomer and, if necessary, these monomers in the presence of a diene rubber polymer. It is obtained by graft copolymerizing a monomer mixture composed of a copolymerizable vinyl monomer.

Examples of the diene rubber polymer include:
Examples include polybutadiene, acrylonitrile-butadiene copolymer, and styrene-butadiene copolymer.

Examples of the aromatic vinyl monomer include:
Styrene, α-methylstyrene, t-butylstyrene,
Examples include vinyl toluene and chlorostyrene.

Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile, and acrylonitrile is most preferred.

Examples of the vinyl monomers copolymerizable therewith include acrylic esters such as methyl acrylate, ethyl acrylate and propyl acrylate, and methacrylic acids such as methyl methacrylate, methyl ethyl acrylate and methyl butyl acrylate. Esters, acrylic acid, methacrylic acid and the like can be mentioned.

In the thermoplastic resin composition of the present invention, B
The content of the components is 95-5% by weight, preferably 70-30% by weight. When the content of the component B exceeds 95% by weight, the chemical resistance, heat resistance, and moldability are insufficient.
If it is less than weight%, the notched impact strength is insufficient.

The styrene copolymer as the component C of the present invention includes aromatic vinyl monomers, vinyl cyanide monomers, and, if necessary, vinyl monomers copolymerizable with these monomers. Is a copolymer obtained by copolymerizing

Examples of the above-mentioned aromatic vinyl monomer, vinyl cyanide monomer and vinyl monomer copolymerizable therewith are the same as those of the aforementioned component B.

In the thermoplastic resin composition of the present invention, C
The content of the components is 0-30% by weight. If the content of the component C is more than 30% by weight, the impact strength is undesirably low.

The copolymer which is the component D of the present invention includes aromatic vinyl monomers, vinyl cyanide monomers, epoxy group-containing vinyl monomers and, if necessary, copolymerizable with these monomers. It is a copolymer obtained by copolymerizing various vinyl monomers.

Examples of the above-mentioned aromatic vinyl monomer, vinyl cyanide monomer and vinyl monomer copolymerizable therewith are the same as those of the above-mentioned component B.

Examples of the epoxy group-containing vinyl monomer include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate and glycidyl itaconate, and glycidyl methacrylate is most preferred.

The D component of the present invention comprises an aromatic vinyl monomer 50
-79.5 parts by weight, vinyl cyanide monomer 20-45 parts by weight, epoxy group-containing vinyl monomer 0.5-5 parts by weight, and vinyl monomers 0-20 copolymerizable with these monomers as required. It is a copolymer obtained by copolymerizing parts by weight. If the amount of the aromatic vinyl monomer or vinyl cyanide monomer exceeds this range, the impact resistance decreases, which is not preferable. The epoxy group-containing vinyl monomer is 0.5 to 5 parts by weight, preferably
1 to 3 parts by weight. Epoxy group-containing vinyl monomer is 0.
If the amount is less than 5 parts by weight, the impact resistance is insufficient. If the amount is more than 5 parts by weight, the moldability deteriorates and the impact resistance is also insufficient.

In the present invention, the content of the component D is determined by the thermoplastic resin composition 10 comprising the components A, B and C.
0.5 to 10 parts by weight with respect to 0 parts by weight, preferably 2 to 10 parts by weight.
~ 8 parts by weight. If the content of the component D is less than 0.5 part by weight, the impact resistance becomes insufficient, and if it exceeds 10 parts by weight, the moldability decreases.

The fibrous reinforcing agent which is the E component of the present invention includes:
For example, glass fibers, carbon fibers, asbestos, aramid fibers, whiskers, potassium titanate and the like are preferred, and among them, chopped strand type glass fibers whose surfaces are surface-treated with a silane coupling agent or the like are most preferable.

In the present invention, the content of the component E is determined by the thermoplastic resin composition 10 comprising the components A, B and C.
0 is 5 to 50 wt parts relative to weight parts, the heat resistance is less than 5 parts by weight, the effect of improving the rigidity is insufficient, unfavorably remarkably reduced moldability exceeds 50 parts by weight.

The fiber-reinforced thermoplastic resin composition of the present invention comprises:
It can be manufactured by using various known mixing methods.For example, each raw material is uniformly mixed in advance by a mixer such as a tumbler or a Henschel mixer, and supplied to a single-screw or twin-screw extruder to melt-knead. After that, there is a method of preparing as pellets.

[0030] The fiber-reinforced thermoplastic resin composition of the present invention may optionally contain a flame retardant, a coloring agent, a heat stabilizer, an antioxidant, an antistatic agent, a lubricant and other auxiliaries. .

The fiber-reinforced thermoplastic resin composition of the present invention comprises:
For example, a desired molded product can be formed by a molding method such as injection molding, compression molding, or extrusion molding.

[0032]

The present invention will be described in more detail with reference to examples.

Examples 1 to 5 and Comparative Examples 1 to 11 The following components A to E were blended, pelletized by an extruder, and the pellets were molded by an extruder to prepare test pieces to evaluate various physical properties. . Tables 1 to 3 show the mixing ratio (parts by weight) of each component and the evaluation results.

Component A: Aromatic polyester A-1: Ratio of terminal groups -COOH / Polybutylene terephthalate having -OH of 20/80 (NOVADUR5114ZS: manufactured by Mitsubishi Chemical Corporation) A-2: Ratio of terminal groups -COOH / Polybutylene terephthalate with -OH of 95/5 (NOVADUR 5020: manufactured by Mitsubishi Kasei)

Component B: Production of graft copolymer B-1: 100 parts by weight of polybutadiene latex (solid content: 50% by weight, average particle size: 0.3 in an autoclave equipped with a stirrer)
5 μ, gel content 90%), 1 part by weight of sodium stearate, 0.1 part by weight of sodium formaldehyde sulfoxylate, 0.03 part by weight of tetrasodium ethylenediaminetetraacetic acid, 0.003 part by weight of ferrous sulfate and water
Heat 200 parts by weight to 65 ° C and add acrylonitrile 30
50 parts by weight of a monomer mixture consisting of 100% by weight and 70% by weight of styrene, 0.3 parts by weight of t-dodecyl mercaptan, and 0.2 parts by weight of cumene hydroperoxide were continuously added over 4 hours, and after the addition was completed, polymerization was carried out at 65 ° C. for 2 hours. did. The polymerization rate is
96%. After adding an antioxidant to the obtained latex, it was coagulated with calcium chloride, washed with water and dried to obtain a white powdery graft copolymer.

Component C: Production of styrene-based copolymer C-1: 100 parts by weight of pure water and 0.6 parts by weight of tribasic calcium phosphate were added to an autoclave equipped with a stirrer, and then 44 parts by weight of styrene were stirred. Acrylonitrile, 24 parts by weight, tert-butyl peroxy 3.5.5 trimethylhexanoate 0.05 parts by weight, tert-butyl peroxy acetate 0.05 parts by weight, tertiary decyl mercaptan 0.35 parts by weight, and publishing with nitrogen gas for 15 minutes Stir and then seal. From the point when the temperature was raised to 100 ° C. for the first time, 32 parts by weight of styrene monomer was added at a constant rate over 5 hours. After the addition of styrene, the temperature rose to 120 ° C 2.
After holding for 5 hours, the mixture was cooled, neutralized, dehydrated and dried according to a conventional method to obtain a copolymer.

Component D: Production of copolymers (D-1 to D-5) D-1: 100 parts by weight of pure water and 0.25 parts by weight of tribasic calcium phosphate were added into an autoclave equipped with a stirrer, and then Under stirring, 74 parts by weight of styrene, 1 part by weight of glycidyl methacrylate (hereinafter abbreviated as GMA), 25 parts of acrylonitrile
0.5 parts by weight of 2,2′-azobisisobutyronitrile having a decomposition temperature of 82 ° C. to obtain 1 part by weight and a half life of 1 hour were added, and the inside of the autoclave was replaced with nitrogen gas and then sealed. Next, after polymerization was carried out at a polymerization temperature of 80 ° C. for 7 hours, the mixture was cooled, neutralized, dehydrated and dried in a conventional manner to obtain a copolymer.

D-2: In an autoclave equipped with a stirrer,
100 parts by weight of pure water and 0.25 parts by weight of tricalcium phosphate are added, followed by stirring with 73 parts by weight of styrene, 2 parts by weight of GMA, 25 parts by weight of acrylonitrile, and a decomposition temperature of 82 ° C. to obtain a half-life of 1 hour. 0.5 parts by weight of 2,2'-azobisisobutyronitrile were added, the inside of the autoclave was replaced with nitrogen gas, and the autoclave was sealed. Then the polymerization temperature was increased to 80
After polymerization for 7 hours, the mixture was cooled and neutralized according to a conventional method.
Dehydration and drying gave a copolymer.

D-3: In an autoclave equipped with a stirrer,
100 parts by weight of pure water and 0.25 parts by weight of tricalcium phosphate were added, and then, with stirring, 74.7 parts by weight of styrene and 0.
3 parts by weight, 25 parts by weight of acrylonitrile, and 0.5 parts by weight of 2,2′-azobisisobutyronitrile having a decomposition temperature of 82 ° C. to obtain a half-life of 1 hour were added, and the inside of the autoclave was replaced with nitrogen gas. And then sealed. Next, polymerization was carried out at a polymerization temperature of 80 ° C. for 7 hours, followed by cooling, neutralization, dehydration and drying according to a conventional method to obtain a copolymer.

D-4: In an autoclave equipped with a stirrer,
100 parts by weight of pure water and 0.25 parts by weight of tricalcium phosphate are added, and then 70 parts by weight of styrene, 7 parts by weight of GMA, 23 parts by weight of acrylonitrile, and a decomposition temperature of 82 ° C. to obtain a half-life of 1 hour 2 0.5 parts by weight of 2,2'-azobisisobutyronitrile were added, the inside of the autoclave was replaced with nitrogen gas, and the autoclave was sealed. Then the polymerization temperature was increased to 80
After polymerization for 7 hours, the mixture was cooled and neutralized according to a conventional method.
Dehydration and drying gave a copolymer.

D-5: A graft copolymer obtained by graft-polymerizing an ethylene-GMA copolymer with a styrene-acrylonitrile copolymer (Morihapa A4400 manufactured by NOF Corporation) was used.

E component: fibrous reinforcing material Chopped strand RES-03-TP72K (manufactured by Nippon Sheet Glass) having a fiber diameter of 13 μφ and a fiber length of 3 mm as glass fiber, and HTA-C6-SR (Toho rayon) as carbon fiber Was used.

Each physical property was determined in accordance with the following measuring method. Notched Izod impact strength: ASTM D256 (thickness 1 /
4 ", measurement temperature 23 ° C) Flexural modulus: ASTM D-790 Heat deformation temperature: ASTM D-648 (thickness 1/4", load 18.6kg / c)
m ² , annealing 105 ° C) Flow length (moldability): Injection molding machine (TOSHIBA MACHINE IS-
30 EPN), molding temperature 260 ° C, mold temperature 90
A spiral molded article was formed at a temperature of 70 ° C. and an injection pressure of 70 kgf / cm ² , and the flow length at this time was measured.

[0044]

[Table 1]

[0045]

[Table 2]

[0046]

[Table 3]

[0047]

The fiber-reinforced thermoplastic resin composition of the present invention has excellent impact resistance, rigidity, heat resistance and moldability, and is an excellent resin. It is useful in a wide range of fields such as electric and electronic parts, and has an extremely large industrial utility value.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 55/02 C08L 25/12 C08L 67/02

Claims (2)

(57) [Claims] 1. The following component A component 5 to 95% by weight, component B 95 to 5%
% To 100 parts by weight of the thermoplastic resin composition comprising 0 to 30% by weight of the C component and 0.5 to 10 parts by weight of the D component,
A fiber-reinforced thermoplastic resin composition comprising 5 to 50 parts by weight of a component. A component: carboxyl terminal (-COOH) and hydroxyl terminal (-O
A) An aromatic polyester having a ratio of -COOH / -OH of 0/100 to 50/50 B component: 50 to 80% by weight of an aromatic vinyl monomer with respect to 10 to 60 parts by weight of a diene rubber polymer. , Vinyl cyanide monomer
A monomer mixture 40 comprising 20 to 50% by weight and, if necessary, 0 to 20% by weight of a vinyl monomer copolymerizable with these monomers.
Graft copolymer obtained by graft polymerization of up to 90 parts by weight (provided that the total amount of the diene rubber polymer and the monomer mixture is
Is 100 parts by weight) Component C: 50 to 80 parts by weight of an aromatic vinyl monomer, 20 to 50 parts by weight of a vinyl cyanide monomer and, if necessary, a vinyl monomer copolymerizable with these monomers Styrene copolymer obtained by copolymerizing 0 to 20 parts by weight of a copolymer ( provided that the total amount of monomers is 1
00 and parts) D component: aromatic vinyl monomer 50 to 79.5 parts by weight of vinyl cyanide monomer 20 to 45 parts by weight, epoxy group-containing vinyl monomer 0.5 to 5 parts by weight and optionally A copolymer obtained by copolymerizing 0 to 20 parts by weight of a vinyl monomer copolymerizable with these monomers (provided that the total amount of monomers is 100 parts by weight.
That) E component: fibrous reinforcing material, however, the fiber-reinforced thermoplastic resin composition of the A component of a melting point
10 minutes at a temperature between 50 ° C below and 100 ° C above the melting point
From 100 to 100 hours.
Excluding the fiber reinforced thermoplastic resin composition. 2. The fiber-reinforced thermoplastic resin composition according to claim 1, wherein the aromatic polyester is polybutylene terephthalate.