KR930001994B1 - Thermoplastic resin composition - Google Patents

Abstract

The thermoplastic resin compsn. comprises (A) 10-90 wt.% of a thermoplastic polyester resin, (B) 10-90 wt.% of a polycarbonate resin, (C) 1-25 wt.% of a butadiene core-shell type copolymer resin w.r.t. (A)+(B), (D) 0.1-15 wt.% of an epoxy-contg. olefin copolymer w.r.t. (A)+(B), (E) 0.01-2 wt.% of a phosphorus cpd. of formula (I) and/or (II) [R1=R2=R3=C1-30 aliphatic alkyl w.r.t. (A)+ (B)+(C)+(D), and (E) 0.01-5 wt.% of a polyfunctional cpd. w.r.t. (A)+(B)+(C) +(D). The resin (A) is pref. polybutylene terephthalate having 0.4 dl/g limit viscosity, and the resin (B) is pref. poly (bisphenol A carbonate) having 10000-200000 ave. molecular weight.

Description

Thermoplastic resin composition

The present invention relates to a thermoplastic resin composition, and more particularly to a thermoplastic resin composition excellent in impact resistance and hydrothermal stability.

Aromatic thermoplastic polyester resins, which are typically represented by polyethylene terephthalate or polybutylene terephthalate, are mainly used for injection molding because of their fast crystallization rate, and have been used in various applications such as electric, electronic parts and automobile parts.

These polyesters are used in the form of reinforcement or non-reinforcement and have excellent electrical properties, wear resistance, surface strength and surface condition compared to other thermoplastic resins, while their stiffness, heat resistance and impact strength are particularly low in the unreinforced state. A method of adding an impact modifier while mixing with polycarbonate has been proposed due to a limited or difficult difficulty in handling.

For example, the addition of polyalkylacrylates and aromatic polycarbonates has been proposed in US Pat. No. 4,425,373, while in US Pat. No. 3,444,28, methacrylate monomers have been grafted to polybutyrene terephthalate alone or in mixtures with other polyesters. The addition of conjugated diene vinyl aromatic copolymers and aromatic polycarbonates has been limited.

In addition, US Pat. No. 4,804,944 proposes the addition of core-shell resins and aromatic polycarbonates having butadiene cores to polybutylene terephthalate, and in No. 4280948, dienes conjugated to polybutylene terephthalate copolymers are used alone. Or with a polycarbonate grafted with a vinyl aromatic mixture, an acrylic or methacryl monomer.

However, the above-described prior arts have a problem in that impact strength is improved only at a specific temperature and a certain thickness, and particularly, hydrothermal stability is not satisfactory.

As a specific example, in the case of the above-mentioned US Patent No. 4257937 to which acrylate is added as an impact reinforcing material, the impact strength at room temperature is excellent, but the impact strength drops sharply at low temperature, and the hydrothermal stability is insufficient.

In the case of US Pat. Nos. 3,442,281,4180494, and 4280948, the impact strength at room temperature and low temperature is excellent, but the thickness dependence, which is the disadvantage of polycarbonate resin, is high. Value, when thick (1/4 inch), the strength was lowered and the hydrothermal stability was also poor.

Accordingly, an object of the present invention is to provide a thermoplastic resin composition which can improve the hydrothermal stability by eliminating the thickness dependency of impact strength by improving the above problems.

Hereinafter will be described in detail the configuration of the present invention.

The thermoplastic resin composition of the present invention is characterized by being composed of the following (A) to (F).

(A) thermoplastic polyester resin; 10 to 90 wt%

(B) polycarbonate resin; 90 to 10% by weight

(C) butadiene type core-shell type copolymer resin; 1-25 weight% with respect to (A) + (B)

(D) an epoxy-containing olefin copolymer; 0.1-15 weight% with respect to (A) + (B)

(E) phosphorus compounds of the following general formula (1) and / or general formula (2); 0.01 to 2% by weight relative to (A) + (B) + (C) + (D)

Wherein R ₁ , R ₂ and R ₃ are the same or different aliphatic alkyl groups having 1 to 30 carbon atoms

(F) polyfunctional compounds; 0.01 to 5% by weight relative to (A) + (B) + (C) + (D)

In the present invention, the butadiene-based core-shell copolymer resin is for improving the impact strength, the epoxy-containing olefin copolymer is heat resistance, the phosphorus compound is heat resistance, anti-oxidation and the like, the polyfunctional compound is compatible with polyester and polycarbonate This is to improve the efficiency of these, but if they are added less than the specified amount, of course, the effect can not be achieved, and if exceeded, it inhibits various mechanical properties, for example, when excessive addition of epoxy-containing olefin copolymer at tensile strength and low temperature There is a problem that the impact strength of the drop.

In the present invention, the thermoplastic polyester resin is a polymer obtained by a condensation reaction with a dicarboxylic acid or a derivative capable of forming an ester thereof and a derivative capable of forming a glycol or an ester thereof as a main component.

Such polyesters include polyethylene terephthalate, polybutylene terephthalate, and polybutylene sebacate. Polyethylene terephthalate and poly (1,4-butylene terephthalate) having excellent mechanical strength are preferred, and the crystallization rate is high. Particularly preferred is poly (1,4-butylene terephthalate), which is fast and requires no addition of nucleating agents.

The polyester used in the present invention had an intrinsic viscosity (measured at 25 ° C. in phenol / tetrachloroethane = 6/4) of 0.4 dl / g or more.

In the present invention, polycarbonates include homo polycarbonates, copolycarbonates or mixtures thereof, more suitable poly (bisphenol-A carbonate) polymerized by bisphenol-A and phosgene with an average molecular weight of 10,000 to 200,000, Preferably from 20,000 to 80,000 (measured relative viscosity at a concentration of 0.5% by weight in dichloromethane at 25 ℃).

In the present invention, the ratio of the two resins to each of the range of 10 to 90 is because it depends on what physical properties to take depending on the purpose of use, wherein if one exceeds 90% by weight (the other is 10% by weight) If it is less than%, the original resin mixing effect cannot be achieved.

Butadiene-based core-shell copolymers also have butadiene-based cores and methacrylate shells, and polymerize rubbery cores with at least 50 parts by weight of butadiene monomers alone or with vinyl monomers such as styrene, and then polymerize from methacrylates and crosslinkers. A thermoplastic resinous shell can be obtained, and a more specific method of preparation is described in US Pat. No. 4,044,494.

In the present invention, the epoxy-containing olefin copolymer is in a grafted form, the main chain of which is poly (ethylene-stat-glycidyl methacrylate) {Poly (ethylene-stat-glycidyl methacrylate)}, and polymethyl Methacrylates or polystyrenes or acrylonitrile / styrenes are grafted, with particular preference being given to grafted polymethylmethacrylates.

In the present invention, the phosphorus compound is a phosphate in the form of a monoester or a diester, and it is preferable to use at least one of the following compounds.

Methyl dihydrogen phosphate, ethyl dihydrogen phosphate, butyl dihydrogen phosphate, octyl dihydrogen phosphate, 2-ethyl hexyl dihydrogen phosphate, decyl dihydrogen phosphate, dodecyl dihydrogen phosphate, tridecyl dihydrogen phosphate Monoesters such as hydrogen phosphate, stearyl dihydrogen phosphate, oleyl dihydrogen phosphate, dimethyl hydrogen phosphate, diethyl hydrogen phosphate, dibutyl hydrogen phosphate, diisoamyl phosphate, dioctyl hydrogen phosphate And diesters such as diisooctyl hydrogen phosphate, bis (2-ethyl hexyl) phosphate, 2-ethyl hexyl-3-methyl butyl phosphate, didodecyl hydrogen phosphate and dioctadecyl hydrogen phosphate.

In the present invention, the polyfunctional compound may be an epoxy silane, a polyepoxy compound having two or more epoxy groups, a diimide compound having two or more imide groups, or a carboxylic anhydride.

The double epoxy silane compound is γ-glycidoxy propyl triepoxy silane, β- (3,4-epoxy cyclohexyl) trimethoxy silane, and the like, and the polyepoxy compound is roughly divided into aliphatic epoxy, aromatic epoxy and alicyclic epoxy compound. Examples of the aliphatic epoxy compound include arylglycidyl ether, epoxidized soybean oil, butadiene diepoxide, and epoxidized butadiene. Examples of the aromatic epoxy compound include bisphenol-diglycidyl ether and phthalic acid diglycidyl. Ethers and the like, and alicyclic epoxy compounds include 3,4-epoxy-6-methyl cyclohexane carbo xylate, 4- (3,4-epoxy-5-methyl cyclohexyl) butyl-3,4-epoxy cyclohexane Carbo xylates, compounds such as 3,4-epoxy-6-methyl cyclohexyl methyl-6-methylcyclohexyl methyl-6-methyl cyclohexane carbo xylate, and the like.

In addition, as the diimide compound, an isocyanate compound is prepared by heating and decarbonation, and specifically, diphenylcarimide, di (propylphenyl) carbodiimide, bis (dipropylphenyl) carbodiimide, and polyphenylenecarr Bodyimide, poly (propylphenylene) carbodiimide, poly (diphenylmethane) carbodiimide and the like, and examples of the carboxylic anhydride include naphthalene tetracarboxylic dianhydride and bis (3,4-dicarboxyphenyl) alkanes 2 anhydrides.

In the resin composition of the present invention, fillers may be added to improve mechanical properties, flame retardants such as phosphorus, halogen, nitrogen-based flame retardants, and antimony may be added to improve flame retardancy, and various heat stabilizers, antioxidants, and Hydrolysis stabilizers, weather stabilizers, antistatic agents, pigments, etc. may be added.

Examples of the filler include calcium carbonate, calcium silicate, clay, kaolin, talc, silica, mica, asbestos, barium sulfate, aluminum sulfate, glass fiber, glass beads, carbon fiber, and the like.

The resin composition of the present invention preferably melts and mixes using a single screw extruder or a multi-screw extruder, and can be molded using an injection molding machine.

The method for processing the resin composition of the present invention by the extruder described above is prepared by first preparing a sufficiently dried polyester, polycarbonate and butadiene core-shell copolymer, an epoxy-containing olefin copolymer, a phosphorus stabilizer, and a polyfunctional compound, respectively. Then, the mixture is mixed using a dry blend or a super mixer, put into a hopper of an extruder, and uniformly mixed in a mixing zone. The temperature at this time is somewhat different depending on the polyester to be used, but usually it may be maintained at 250 ℃ to 280 ℃. On the other hand, the inside of the extruder to maintain the vacuum in order to remove the reaction product in the extruder.

As mentioned in the introduction, the resin composition of the present invention having the above configuration exhibits high impact strength in a temperature range of various thicknesses, and exhibits excellent hydrothermal stability, and this effect is further described through the following examples. Will be obvious.

The present invention will be described in detail by way of examples. However, it is a matter of course that the present invention is not limited to the examples.

Example 1

Intrinsic viscosity (measured at 25 ° C in a solvent having phenol / tetrachloroethane = 6/4) 50 parts by weight of polybutylene terephthalate of 0.9 dl / g, 50 parts by weight of polycarbonate having an average molecular weight of 23,000 KM-653 10 parts by weight, 5 parts by weight of dimethyl anthyl methacrylate, Modipper A4200 (polyethylene methacrylate grafted with polyethylene glycidyl methacrylate as main chain, 7/3 weight ratio) 0.3 parts by weight of genphosphate, 1 part by weight of bisphenol-A diglycidyl ether and 1 part by weight of diphenylcarbodiimide were added and mixed in a supermixer, and then kneaded pellets were used at an extruder at 260 ° C. After the pellets were sufficiently dried at 105 ° C. for at least 4 hours, a specimen for measuring impact strength was prepared at 250 ° C. using an injection machine.

The specimen thus prepared was measured for impact strength according to ASTM D-256 and tensile strength according to ASTM D-638, and the water resistance evaluation was performed by filling about 2/3 of the reactor (50 L) with distilled water, and then placing the specimen in water. After the heat treatment for 70 hours under a pressure of 2kg / cm ² (internal temperature about 120 ℃) in the dipped state and evaluated by the tensile strength retention rate is shown in Table 1 together with the measurement results of other examples.

Example 2

The composition was carried out in the same manner as in Example 1 as follows.

50 parts by weight of polybutylene terephthalate

Polycarbonate 50 〃

Acryloid KM-653 10 〃

Modifier A4200 5 〃

Dodecyldihydrogenphosphate 0.3 〃

Dioctadecylhydrogen phosphate 0.3 〃

Bisphenol-A diglycidyl ether 1 〃

Diphenylcarbodiimide 1 〃

Example 3

The composition was carried out in the same manner as in Example 1 as follows.

50 parts by weight of polybutylene terephthalate

Polycarbonate 50 〃

Acryloid KM-653 10 〃

Modifier A4200 5 〃

Dioctadecylhydrogen phosphate 0.3 〃

γ-glycidoxypropyltriepoxysilane 1 〃

Bisphenol-A diglycidyl ether 1 〃

Diphenylcarbodiimide 1 〃

Comparative Example 1

The composition was carried out in the same manner as in Example 1 as follows.

50 parts by weight of polybutylene terephthalate

Polycarbonate 50 〃

Comparative Example 2

The composition was carried out in the same manner as in Example 1 as follows.

50 parts by weight of polybutylene terephthalate

Polycarbonate 50 〃

Acryloid KM-330 10 〃

(Rom & Haas Co., Ltd .; acrylate core-shell type)

Comparative Example 3

The composition was carried out in the same manner as in Example 1 as follows.

50 parts by weight of polybutylene terephthalate

Polycarbonate 50 〃

Acryloid KM-653 10 〃

[Comparative Example 4]

The composition was carried out in the same manner as in Example 1 as follows.

50 parts by weight of polybutylene terephthalate

Polycarbonate 50 〃

Acryloid KM-653 10 〃

0.3 parts by weight of di-n-octadecylphosphate

[Comparative Example 5]

The composition was carried out in the same manner as in Example 1 as follows.

50 parts by weight of polybutylene terephthalate

Polycarbonate 50 〃

Acryloid KM-653 10 〃

Modifier A4200 5 〃

Comparative Example 6

The composition was carried out in the same manner as in Example 1 as follows.

50 parts by weight of polybutylene terephthalate

Polycarbonate 50 〃

Acryloid KM-653 10 〃

Dioctadecylhydrogen phosphate 0.3 〃

Bisphenol-A diglycidyl ether 1 〃

Diphenylcarbodiimide 1 〃

Comparative Example 7

The composition was carried out in the same manner as in Example 1 as follows.

50 parts by weight of polybutylene terephthalate

Polycarbonate 50 〃

Acryloid KM-653 10 〃

Modifier A4200 25 〃

Dioctadecylhydrogen phosphate 0.3 〃

Bisphenol-A diglycidyl ether 1 〃

Diphenylcarbodiimide 1 〃

TABLE 1

Claims (6)

The thermoplastic resin composition, which is composed of (A) to (F) below. (A) thermoplastic polyester resin; 10 to 90 wt% (B) polycarbonate resin: 90 to 10% by weight (C) Butadiene type core-shell copolymer resin: 1-25 weight% with respect to (A) + (B) (D) Epoxy-containing olefin copolymer: 0.1 to 15% by weight based on (A) + (B) (E) phosphorus compounds of the following general formula (1) and / or general formula (2); 0.01 to 2% by weight relative to (A) + (B) + (C) + (D)

Wherein R ₁ , R ₂ and R ₃ are the same or different aliphatic alkyl groups having 1 to 30 carbon atoms (F) polyfunctional compound: 0.01 to 5% by weight relative to (A) + (B) + (C) + (D) The thermoplastic resin composition of claim 1, wherein the thermoplastic polyester is polybutylene terephthalate having an intrinsic viscosity of 0.4 dl / g, and the polycarbonate is poly (bisphenol-A carbonate) having an average molecular weight of 10,000 to 200,000. 2. The thermoplastic resin composition according to claim 1, wherein the butadiene-based core-shell copolymer resin has a structure of a butadiene-based core and a methacrylate-based shell. The thermoplastic resin composition according to claim 1, wherein the epoxy-containing olefin copolymer has a main chain of poly (ethylene-stat-glycidyl methacrylate) and polymethyl methacrylate is graftdon. The method of claim 1, wherein the phosphorus compound is in the form of a monoester or diester, methyl dihydrogen phosphate, methyl dihydrogen phosphate, butyl dihydrogen phosphate, octyl dihydrogen phosphate, 2-ethylhexyl dihydrogen phosphate , Decyl dihydrogen phosphate, dodecyl dihydrogen phosphate, tridecyl dihydrogen phosphate, stearyl dihydrogen phosphate, oleyl dihydrogen phosphate, dimethyl hydrogen phosphate, diethyl hydrogen phosphate, dibutyl hydrogen phosphate , Diisoamyl phosphate, dioctyl hydrogen phosphate, diisooctylhydrogen phosphate, bis (2-ethyl hexyl) phosphate, 2-ethyl-hexyl-3-methylbutyl phosphate, didodecyl hydrogen phosphate, dioctadecyl hydro Select at least one of genphosphate The thermoplastic resin composition, characterized in that the. The polyfunctional compound is selected from the group consisting of at least two of epoxy silanes, polyepoxy compounds having two or more epoxy groups, diimide compounds having two or more imide groups, or carboxylic anhydrides. Thermoplastic resin composition.