JPH01170636A - Impact-resistant highly rigid material - Google Patents

Abstract

PURPOSE:To obtain the title material having excellent impact resistance, heat- resistance, rigidity and moldability, by compounding a specific rubber-reinforced styrene copolymer resin with one or more components selected from polyamide resin, etc., and other additive. CONSTITUTION:The objective material is produced by compounding (A) 5-90wt.%, preferably 10-80wt.% of a rubber-reinforced styrene copolymer resin copolymerized with 0.1-8wt.% of an unsaturated compound having carboxyl group with (B) 5-90wt.%, preferably 10-80wt.% of one or more resins selected from polyamide resin, polyester resin and polycarbonate resin and (C) 3-55wt.%, preferably 5-45wt.% of an inorganic filler and/or organic filler. The content of the rubber component in the whole composition is 3-40wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Application The present invention relates to an impact-resistant, high-rigidity material that has excellent impact resistance, heat resistance, rigidity (modulus of elasticity), and moldability.

b. Prior Art In recent years, materials with high rigidity have been required as substitute materials for metals in various fields. In order to meet this demand,
BACKGROUND ART Materials are provided in which thermoplastic resin is composited with inorganic or organic fillers (eg, glass fibers, carbon fibers, Kepler, etc.). According to these materials, not only rigidity but also heat resistance can be improved by combining fillers.
In particular, when a crystalline polymer is used, heat resistance can be significantly improved.

However, as the amount of filler increases, the impact resistance of these filler composite resins decreases, and depending on the application, they may not be able to exhibit sufficient functionality.

In order to improve the impact resistance of such filler composite resins, various methods have been studied, such as making the surface of the filler more easily wetted by the resin, or increasing the impact resistance of the polymer to compensate for the decrease caused by the filler. However, the reality is that there are not necessarily satisfactory products available for use in automobile parts and parts for electrical and electronic devices.

Problems to be Solved by the C0 Invention As mentioned above, although it was possible to obtain a highly rigid and heat-resistant resin using conventional methods, it was not possible to obtain a filler composite resin that had both impact resistance and moldability. There wasn't.

Therefore, as a result of intensive studies, the present inventors found that (A) a rubber-reinforced styrene copolymer resin copolymerized with a carboxyl group-containing unsaturated compound, (B) a polyamide resin, a polyester resin, and a polycarbonate resin. A resin with excellent impact resistance, heat resistance, rigidity, and moldability can be obtained by a specific composition comprising at least one resin and (C) an inorganic and/or organic filler. This is the heading that led to the present invention.

Means for solving the d0 problem, that is, the present invention provides (A) a rubber-reinforced styrenic copolymer resin 5 copolymerized with a carboxyl group-containing unsaturated compound.
~90% by weight, (B) 5 to 90% by weight of at least one resin selected from polyamide resin, polyester resin, and polycarbonate resin, and (C) 3 to 55% by weight of inorganic filler and/or organic filler. %, wherein (i) the bond content of the carboxyl group-containing unsaturated compound in component (A) is 0.1 to 8% by weight, and (ii) the rubber in the entire composition The present invention provides an impact-resistant and highly rigid material characterized in that the content of the components is 3 to 40% by weight.

The rubber-reinforced styrenic copolymer resin (A) copolymerized with a carboxyl group-containing unsaturated compound used in the present invention is a rubber-reinforced styrenic copolymer resin copolymerized with a carboxyl group-containing unsaturated compound,
It is a resin formed by polymerizing a resin component consisting of an aromatic vinyl compound and, if necessary, another vinyl monomer copolymerizable with these.

As rubbery polymers, copolymers of ethylene and α-olefin such as ethylene-propylene random copolymers or block copolymers, ethylene-butene random copolymers or block copolymers; ethylene-methacrylate , copolymers of ethylene and unsaturated carboxylic acid esters such as ethylene-butyl acrylate; copolymers of ethylene and fatty acid vinyl such as ethylene-vinyl acetate; ethylene-propylene-ethylidene norbornene copolymers, ethylene-propylene- Ethylene-propylene-nonconjugated polymers such as hexadiene copolymers; diene systems such as polybutadiene, isoprene, styrene-butadiene random or block copolymers, acrylonitrile-butadiene copolymers, butadiene-isoprene copolymers, etc. Rubber; butylene-isoprene copolymer, etc. can be used, and these may be used alone, but two or more types can also be used in combination. Among these, preferred rubbery polymers in terms of impact resistance and the like are ethylene-propylene rubber, ethylene-propylene-nonconjugated genter polymer, and diene rubber. More preferred are polybutadiene and styrene-butadiene copolymers, and preferred styrene-butadiene copolymers are those in which the styrene content in the copolymer is 50% by weight or less.

The content of the rubbery polymer, i.e., the rubber component, is 3 to 4 in the total composition.
It is preferably 0% by weight, more preferably 5 to 5% by weight.
35% by weight, particularly preferably 5 to 33% by weight. 3
If it is less than 40% by weight, the impact resistance will be poor, and if it exceeds 40% by weight, the moldability will be poor, which is not preferable.

Examples of the carboxyl group-containing unsaturated compound to be copolymerized with the rubbery polymer include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, and maleic acid, with acrylic acid and methacrylic acid being preferred. These may be used alone or in combination.

The bond content of these carboxyl group-containing unsaturated compounds in component (A) is 0.1 to 8% by weight.

Preferably 0.2 to 7% by weight, more preferably 0.2%
~6% by weight. If it is less than 0.1% by weight, the impact resistance will be poor, and if it exceeds 8% by weight, the impact resistance and moldability will be poor.

Aromatic vinyl compounds used in component (A) include styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, p-tert-butylstyrene, and ethylstyrene. , vinylnaphthalene, 0
-Methylstyrene, p-methylstyrene, dimethylstyrene, etc., and these can be used alone or in combination of two or more. Among these, the aromatic vinyl compound that is preferably used is styrene, and even when two or more aromatic vinyl compounds are used in combination, it is highly preferable to use styrene in a proportion of 50% by weight or more.

Other copolymerizable monomers include vinyl cyanide monomers such as acrylonitrile and methacrylate, maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and N-o-chlorophenyl. Maleimide compounds such as maleimide and N-cyclohexylmaleimide; other vinyl compounds that can be copolymerized with these include methyl acrylate, ethyl acrylate, propylene acrylate, butyl acrylate,
Alkyl esters of acrylic acid such as amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, phenyl acrylate, benzyl acrylate; methacrylic acid such as methyl methacrylate, butyl methacrylate, hexyl methacrylate, phenyl methacrylate Alkyl ester;
These can be used alone or in combination of two or more.

Specific examples of component (A) include the following.

1) In the presence of a rubbery polymer copolymerized with a carboxyl group-containing unsaturated compound, a monomer having an aromatic vinyl monomer as an essential component or a monomer having an aromatic vinyl and a carboxyl group-containing unsaturated compound as essential components is added. A graft copolymer obtained by polymerizing polymers.

2) A graft copolymer obtained by copolymerizing a monomer containing an aromatic vinyl and a carboxyl group-containing unsaturated compound as essential components in the presence of a rubbery polymer.

3) A mixture of a rubber-reinforced styrene resin in which a carboxyl group-containing unsaturated compound is not copolymerized and a monomer copolymer containing a carboxyl group-containing unsaturated compound and an aromatic vinyl as essential components.

4) A mixture of the above copolymer 1) or 2) and a copolymer containing a carboxyl group-containing unsaturated compound and an aromatic vinyl compound as essential components.

5) A mixture of the above copolymer or mixture of 1), 2), 3) or 4) and a copolymer containing aromatic vinyl as an essential component.

The aromatic vinyl used in the above copolymers or mixtures 1) to 5) is preferably styrene, and the monomer copolymerizable with the aromatic vinyl is preferably acrylonitrile.

Among the above, preferred are 1), 2), 4) or 5), and more preferred are 2), 4) or 5).

The proportion of the rubber-reinforced styrene copolymer resin copolymerized with the carboxyl group-containing unsaturated compound (A) described above in the total composition is 5 to 90% by weight, preferably 10 to 85% by weight.
% by weight, more preferably 10 to 80% by weight. 5
If it is less than 90% by weight, the impact resistance will be poor; if it exceeds 90% by weight, the heat resistance will be poor.

The method for producing the rubber-reinforced styrenic copolymer resin copolymerized with the carboxyl group-containing unsaturated compound (A) includes emulsion polymerization of the monomers in the presence of the rubbery polymer;
Examples include polymerization methods such as solution polymerization, bulk polymerization, and suspension polymerization. The polymerization initiator used at this time,
As the molecular weight regulator, emulsifier, dispersant, solvent, etc., conventionally known ones can be used as they are. 30-1 using monomers, an additional emulsifier and a polymerization initiator in the presence of a rubbery polymer preferably obtained by emulsion polymerization.
This is a method in which a graft obtained by polymerization at 50° C. for 1 to 15 hours at -1.0 to 5 kg/cd is mixed with a styrene copolymer resin obtained by emulsion polymerization or solution polymerization.

The polyamide resin (B) that can be used in the present invention is not particularly limited, and examples thereof include ethylene diamine, hexamethylene diamine, decamethylene diamine,
dodecamethylene diamine, 2.2.4- or 2,4.
4-)limethylhexamethylenediamine, 1.3- or 1.4-bis(aminomethyl)cyclohexane, bis(
aliphatic, alicyclic, aromatic diamines such as p-aminocyclohexyl)methane, m-xylylenediamine 1, p-xylylenediamine and adipic acid, superric acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid Polyamides derived from aliphatic, alicyclic, and aromatic dicarboxylic acids such as ε-caprolactam, ω-
Polyamides obtained by ring-opening polymerization of lactams such as dodecalactam, polyamides derived from 6-aminocaproic acid, 1,1-amitsudecanoic acid, 1,2-aminododecanoic acid, etc., copolymerized polyamides of these, mixed polyamides, etc. can be mentioned. Among these, nylon is industrially produced at low cost and in large quantities.
6 (polycaproamide), nylon-66 (polyhexamethylene adipamide), nylon-12, nylon-1
Particularly useful are Nylon-1, Nylon-10, Nylon-4,6, or copolymers or mixtures thereof.

The degree of polymerization of the polyamide resin is not particularly limited, but it usually has a relative viscosity (98% for 1 g of polymer) of 1zS.
Dissolved in 100 μl of Oa and measured at 25℃) is 1.8 ~
Polyamide resins in the range of 6 can be preferably used, and in particular, polyamide resins in the range of 2 to 5 can be used to obtain an excellent balance between impact resistance and moldability.

Furthermore, the molecular structure of the polyamide resin is not limited either, and both linear polyamide and branched polyamide are preferably used.

The polyester resin that can be used in the present invention is not particularly limited, but is preferably one obtained from a polycondensate of a dicarboxylic acid or a derivative such as an atV kill ester of a dicarboxylic acid and a diol. .

Among the constituent components of the polyester resin, 70 to 100 mol% of the portion composed of dicarboxylic acid is introduced by terephthalic acid, and 30 to 0 mol% is comprised of isophthalic acid, terephthalene dicarboxylic acid, and adipine. It is introduced by acids such as sebacic acid. Parts composed of glycol include ethanediol, propanediol, butanediol, bentanediol,
It is introduced by hexanediol, and may be composed of two or more of these polyesters. It may also include a portion introduced by oxybenzoic acid or bisphenol A, and furthermore, it may contain one or more of these polyesters. Mixed blended polyesters are also included within the scope of the present invention. Such polyesters include polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, and copolymers and mixtures thereof.

The polycarbonate resin that can be used in the present invention is obtained, for example, by reacting bisphenols with a carbonate precursor such as phosgene or diaryl carbonate. As the bisphenols, bis(hydroxyaryl)alkanes are preferred, such as 2,2'-bis(4-hydroxyphenyl)propane,
2. Examples include 2'-bis(4-hydroxy-3,5-dibromophenyl)propane and 2,2'-bis(4-hydroxy-3,5-dichlorophenyl)propane. These bisphenols can be used alone or in combination.

The degree of polymerization of the polycarbonate resin is not particularly limited (usually, the intrinsic viscosity (solvent, methylene chloride, 20
Measurement) of 0.3 to 1.0 can be preferably used, and in particular, if one of 0.35 to 0.75 is used, a product with a high level of balance between impact resistance and moldability can be obtained. .

The amount of component (B) in the composition is 5 to 90% by weight, preferably 10 to 85% by weight, and more preferably 10 to 80% by weight. If it is less than 5% by weight, the impact resistance and heat resistance will be low, and if it exceeds 90% by weight, the impact resistance will be poor.

Component (C) of the present invention is an inorganic and/or organic filler, such as a fibrous reinforcing agent such as glass fiber, carbon fiber, or aromatic polyamide fiber, calcium carbonate, talc, zinc oxide, wallasnite, or glass. Examples include inorganic fillers such as peas, silica, mica, silicates, feldspar, quartz, talc, titanium dioxide, and wollastonite. Among these fillers, in order to improve rigidity and heat resistance, those with large directionality (It/1HIl: filler length, t: diameter) are preferable.

From the viewpoint of cost and performance balance, glass fiber is most preferable. Among commonly used glass fibers, glass roving, glass chopped strand, glass thread or Glass wool with a diameter of about 0.3 to 30 μm and an average length of 0.5 m or more is preferable for high rigidity.

In order to improve the wetting of the inorganic material with the resin, it is preferable to treat the inorganic material in advance with a chromium-based, silane-based, or titanium-based surface treatment agent, but it exhibits sufficiently favorable physical properties even without such treatment.

The amount of component (C) used in the present invention is 3 to 55% by weight.
The content is preferably 5 to 50% by weight, more preferably 5 to 45% by weight. If it is less than 3% by weight, heat resistance and rigidity will be low, and if it exceeds 55% by weight, impact resistance and moldability will be poor.

Other thermoplastic resins can also be added to the compositions of the present invention. In particular, styrenic resins are preferred in order to improve the objective performance of the present invention.

The composition of the present invention may also include antioxidants such as 2.6-di-t-butyl-4-methylphenol, 2-(1-methylcyclohexyl)-4,6-dimethylphenol,
．． 2-methylene-bis-(4-ethyl-6-t-butylphenol), tris(di-nonylphenyl)phosphite; ultraviolet absorbers such as pt-butylphenyl salicylate, 2. 2'-dihydroxy-4-methoxybenzophenone, 2-(2'-hydroxy-41,
-octoxyphenyl)benzotriazole; lubricants such as paraffin wax, stearic acid, hydrogenated oils, stearamide, methylene bisstearamide, n-butyl stearate, ketone wax, octyl alcohol, hydroxystearic acid triglyceride; flame retardants such as antimony oxide, Aluminum hydroxide, zinc oxalate, tricresyl phosphate, tris(dichloropropyl) phosphate, chlorinated paraffin, tetrabromobutane,
Hexabromobenzene, tetrabromobisphenol A
; Antistatic agents such as stearamidopropyl, dimethyl-β-hydroxyethylammonium nitrate; Colorants such as titanium oxide, carbon black, pigments, etc. may be added as necessary.

The components (A) to (C) of the present invention and other additives can be mixed by a conventional method. For example, after mixing each component in a mixer, an extruder is used to
It can be melt-kneaded and granulated at 0°C. It is also possible to adopt a simple method of directly melting and kneading each component in a molding machine and molding it.

e. EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

In the examples, parts mean parts by weight unless otherwise specified.

In this example, a rubber-reinforced styrenic copolymer copolymerized with a carboxyl group-containing unsaturated compound as component (^) is produced, for example, as follows.

+11 Production of rubbery polymer: A polymerization reaction was carried out according to the recipe shown in Table 1 using a stainless steel polymerization reactor with an internal volume of 1,001 cm equipped with four-stage paddle blades. The temperature is raised while stirring at a rotation speed of a paddle blade of 9 Orpm, and when the temperature reaches 50°C, potassium persulfate is added, and thereafter the polymerization reaction is carried out while controlling the reaction temperature to be kept constant at 50°C. When the polymerization rate reached 90%, 0.1 part by weight of diethylhydroxyamine was added to stop the reaction, and unreacted monomers were substantially distilled off by steam distillation to obtain a rubbery latex.

Table 1 (2) Production of carboxyl group-containing unsaturated compound copolymerized graft copolymer (A-2) using the above rubbery polymer: In a 71 glass flask equipped with a stirring blade, 100 parts of ion-exchanged water was added. , sodium dodecylbenzenesulfonate 0.
5 parts of potassium hydroxide, 0.01 part of t-dodecyl mercaptan, and a batch polymerization component consisting of the rubbery polymer latex shown in Table 1 and various monomers in the proportions shown in Table 2, The temperature was raised while stirring.

When the temperature reached 45°C, add 0.1 part of ethylenediaminetetraacetic acid sodium salt, 0.003 part of ferrous sulfate, sodium formaldehyde, and 0.0% of sulfoxylate trihydrate.
An aqueous solution of an active agent consisting of 2 parts and 15 parts of ion-exchanged water and 0.0 parts of diisopropylbenzene hydroperoxide.
1 part was added and the reaction continued for 1 hour.

Thereafter, 50 parts of ion-exchanged water, 1 part of sodium dodecylbenzenesulfonate, 0.02 part of potassium hydroxide, t-
A mixture of incremental polymerization components consisting of 0.1 part of dodecyl mercaptan, 0.2 part of diisopropylbenzene hydroperoxide, and various monomers in the proportions shown in Table 2 was continuously added over 3 hours to continue the reaction. .

After the addition was completed, the reaction was continued for 1 hour with further stirring, and then 2,2-methylene-bis-(4-ethyl-6-t-
0.2 parts by weight (butylphenol) was added, and the reaction product was taken out from the flask.

coagulate and dehydrate the product using 2 parts by weight of potassium chloride;
After washing with water and drying, the title copolymer was recovered as a powdery graft resin.

Table 2 shows the monomer polymerization conversion rate and the graft rate intrinsic viscosity [η] measured by the method described above.

Component (A) produced in the same manner (A-1, ^-2', A-4
-8-10) are shown in Table-3.

Table 2 Examples 1 to 20, Comparative Examples 1 to 4 Component (A) and components (B) and (C) described below were mixed according to the formulation shown in Table 4, and heated in a 40 m extruder at a temperature of 2.
Pellets were produced by melt-kneading at 60°C.

Using these pellets, the melt flow index (MFR: measurement condition: 260°C) was determined in accordance with JIS K7210.
, 10 kg). In addition, 5oz of the above pellets
Test specimens were prepared by molding at a molding temperature of 260°C using an injection molding machine (Toshiba ■ 1S-8OA), and were evaluated for eye shift impact strength (ASTMD256.2″/7 inch, 23°C), flexural modulus (ASTM 0790, thickness 1) 8") and heat distortion temperature (thickness 2", 66 psi).Furthermore, the falling weight strength was measured by placing a sheet-like test piece with a thickness of 2.4 fi on the lower plate with a diameter of 43.5 m. A 500 g striking rod (diameter 13.5 m) was dropped from a height of 50 cs, and the energy at the time of breaking the test piece was determined.

As the component (B), the following was used.

Nylon-6: Amilan CM1017PC (polycarbonate) manufactured by Toshi: A-2200 manufactured by Idemitsu Sekika (C) The following was used as the component.

Glass fiber: Asahi Fiber 03MA414 diameter 1
3μ Length 311m Glass beads; GB731 Diameter 30 manufactured by Toshiba Balloteiny
μ Carbon fiber: Toho Rayon side type) ITA-C
3-S diameter 7μ The results shown in Table 4 reveal the following.

The compositions of Examples 1 to 20 all have excellent elastic modulus and excellent heat resistance, and also have excellent impact resistance and good moldability.

On the other hand, the composition of Comparative Example 1 has poor impact resistance because the component (A) is a rubber-reinforced styrene resin that does not contain a carboxyl group-containing unsaturated compound.

The composition of Comparative Example 2 has poor impact resistance because component (A) is a rubber-reinforced styrenic resin containing a carboxyl group-containing unsaturated compound in an amount exceeding the range of the present invention.

The composition of Comparative Example 3 has a high content of glass fiber as component (C), and therefore has poor impact resistance and poor moldability.

The composition of Comparative Example 4 does not contain component (C), and therefore has poor rigidity.

10 Effects of the Invention Metal parts are made into resin, that is, high-rigidity thermoplastic resins are used for the purpose of reducing the weight of automobile parts, electric/electronic equipment, and improving productivity. Highly rigid thermoplastic resins are made by combining thermoplastic resins with inorganic and organic fillers such as glass fibers, carbon fibers, and Kepler, but these compositions have extremely low impact resistance.

Therefore, since it does not have sufficient strength as a substitute for metals, it feels like it is time to expand its uses.

However, the impact resistant and highly rigid material of the present invention has impact resistance,
It is a composition with excellent heat resistance, rigidity and moldability,
Its industrial value as an alternative material to metals is great.

Patent applicant: Japan Synthetic Rubber Co., Ltd. Agent: Hisao Okuyama (and 2 others)

Claims (1)

[Claims] (1) (A) 5 to 90% by weight of a rubber-reinforced styrene copolymer resin copolymerized with a carboxyl group-containing unsaturated compound;
(B) 5 to 90% by weight of at least one resin selected from polyamide resin, polyester resin, and polycarbonate resin; (C) 3 to 5% of inorganic filler and/or organic filler
5% by weight, (i) the bond content of the carboxyl group-containing unsaturated compound in component (A) is 0.1 to 8% by weight, and (ii) the content of the rubber component in the entire composition is An impact-resistant and highly rigid material having a content of 3 to 40% by weight.