JPH06271718A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition which can give a molding improved in a balance between heat resistance and mechanical strength and appearance by mixing an alpha-olefin/hydroxy unsaturated monomer copolymer with a saturated polycarbonate. CONSTITUTION:This resin composition is prepared by mixing 10-90wt.% copolymer comprising 50-99.95mol% 3-12C alpha-olefin and 50-0.05mol% hydroxy-containing unsaturated monomer of the formula: CH2=CH-R-(OH)m (wherein R is a 1-20C hydrocarbon group; and (m) is 1-3) and having a number-average molecular weight of 3000 or above, a weight-average molecular weight of 10000 or above and a melting point of 40 deg.C or above with 90-10wt.% polycarbonate resin and optionally 1-70wt.% another thermoplasstic resin, 0.5-3wt.% antioxidant, weatherability improver, nucleator, flame retardant, and slip agent, 3-15wt.% plasticizer, flow modifier and mold release, 5-40wt.% organic or inorganic filler, etc., and the resulting mixture is kneaded at 100-400 deg.C.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a resin composition containing a hydroxyl group-modified polyolefin resin and a polycarbonate resin. This material is effective as a molding material for automobile parts, electric product parts, etc., and has impact resistance, rigidity, heat resistance,
Gives molded products with excellent water resistance and chemical resistance.

[0002]

2. Description of the Related Art Olefin resins are widely used in the production of molded products because they are excellent in molding processability, resistance to organic solvents, resistance to water absorption, etc., and have low specific gravity and are inexpensive, but their heat resistance is not so great. Not expensive, which is an obstacle to use for engineering plastics.

On the other hand, polycarbonate resin is heat resistant,
It is known as a resin with excellent weather resistance and dimensional stability, but injection molding and extrusion molding are difficult due to poor fluidity, and solvent resistance is also a problem. The thickness has a strong dependence on thickness, and there is a drawback that the impact resistance strength is significantly reduced in a thick region. As a trial when a single resin material cannot sufficiently satisfy various desired properties, a method of complementing insufficient properties by mixing other resin materials is often used. .

Thus, if a composition having good properties of both a polycarbonate resin and an olefin resin and complementing undesired points can be obtained, it is possible to provide an excellent resin material having a wide range of applications. However, since the polycarbonate resin and the olefin resin are incompatible and do not have an affinity, the adhesiveness at the interface of this two-phase structure is not good when both components are simply mixed. Therefore, the phase interface of the obtained molded product becomes a defective portion, and the mechanical strength is lowered. Further, the two phases are unlikely to be in a uniform and finely dispersed form, and when subjected to shear stress during molding such as injection molding, delamination is likely to occur.

As a method for solving the above-mentioned problems, Japanese Patent Laid-Open No. Hei 3
-39342 and JP-A-3-39344 disclose a composition comprising a hydroxyl group-containing (meth) acrylate-modified polypropylene resin or polyethylene resin and a polycarbonate resin, but the addition amount of the hydroxyl group-containing (meth) acrylate is practical. Not enough. Therefore, the effect of improving the compatibility is small, and the effect of improving the mechanical properties, particularly impact resistance is small, which is not practically satisfactory.

[0006]

DISCLOSURE OF THE INVENTION The present invention improves the compatibility of an olefin resin and a polycarbonate resin to have a stable dispersion structure which cannot be achieved by the prior art, and has excellent mechanical strength. An object is to provide a resin composition that gives a molded article.

[0007]

In order to overcome the above-mentioned problems, the present invention provides a composition containing a hydroxyl group-modified olefin resin and a polycarbonate resin having a hydroxyl group-containing unsaturated monomer introduced by a copolymerization method. The inventors have found that the object is achieved and completed the present invention. That is, the present invention provides a resin composition containing the following component (A) and component (B).

Component (A): 50 to 99.95 mol% of an α-olefin having 3 to 12 carbon atoms and 50 to 0.05 mol% of a hydroxyl group-containing unsaturated monomer represented by the general formula (I). Copolymer of 10 to 90% by weight

[0009]

Embedded image CH ₂ ═CH—R— (OH) _m (I) (wherein, R is a hydrocarbon group having 1 to 20 carbon atoms,
m represents an integer of 1 to 3. ) Component (B): Polycarbonate resin 90 to 10% by weight.

[0010]

When the compound is melt-mixed, the hydroxyl group (-OH) of the component (A) reacts with the carbonate bond (-COO-) or chlorine group of the polycarbonate of the component (B), or the component (A) and the component (B) are reacted. Since both components have a hydroxyl group, the compatibility between them is good.

[0011]

SUMMARY OF THE INVENTION (A) Copolymer The copolymer of component (A) contains 50 to 99.95 mol% of an α-olefin having 3 to 12 carbon atoms and a hydroxyl group represented by the above formula (I). It can be prepared by copolymerizing a mixture with 50 to 0.05 mol% of an unsaturated monomer with a Ziegler-Natta catalyst using the method and apparatus for producing an α-olefin polymer. Although the production method is not particularly limited, for example, JP-A-55-98209, U.S. Pat.
S. P3,492,277, 4,423,196
Issue, European Patent Publication No. 0363
As described in No. 990, it is preferable to complex an unsaturated monomer with a co-catalyst, a silicon compound or the like used at the time of polymerization, and then copolymerize with an α-olefin.

The hydroxyl group-containing unsaturated monomer represented by the formula (I) can be directly copolymerized with the α-olefin, but among them, those having R having 4 to 12 carbon atoms are preferable. For example, 4-penten-1-ol, 5-hexen-1-ol, 6-hepten-1-ol, 7-octen-1-
All, 8-nonen-1-ol, 9-decen-1-ol, 10-undecen-1-ol, 11-dodecen-1-ol and the like can be used.

These substituted α-olefins may be used alone or in combination of two or more kinds. The amount of the hydroxyl group-containing unsaturated monomer used is 0.05 to 50 mol%. If the amount of the monomer used is less than this, the compatibilizing effect is small, and improvement in mechanical properties of the alloy such as impact strength and tensile elongation cannot be expected. If it exceeds 50 mol%, the properties originally possessed by the polyolefin such as moisture absorption resistance, moldability, and organic solvent resistance will be impaired. The hydroxyl group-containing unsaturated monomer is preferably used in an amount of 1 to 30 mol%, particularly preferably 1.5 to 20 mol%.

Specific examples of the monomer α-olefin constituting the (α-olefin) copolymer include propylene and
1-butene, 1-hexene, 3-methyl-1-butene,
3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 4,4-dimethyl-1-pentene, 3-methyl-1-hexene, 4-methyl-1- Hexene, 4,4-dimethyl-1-hexene,
5-methyl-1-hexene, allylcyclopentane, allylcyclohexane, allylbenzene, 3-cyclohexyl-1-butene, vinylcyclopropane, vinylcyclohexane, 2-vinylbicyclo [2,2,1] -heptane, etc. You can Of these, preferred are propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene and the like. be able to. Especially propylene, 1-butene, 3-
Methyl-1-butene or 4-methyl-1-pentene is preferable from the viewpoint of improving physical properties by alloying with a polycarbonate resin, such as impact resistance.

These α-olefins may be one kind,
Also, two or more kinds may be used. When two or more α-olefins are used, each α-olefin may be randomly or block-distributed in the copolymer.
This α-olefin is 50 to 99.95 mol%, preferably 70 to 99 mol%, more preferably 80 to 98.
Used in a proportion of 5 mol%.

In the production of this copolymer, another copolymerizable monomer may be further contained up to about 15 mol% based on the total amount of both monomers. Examples of such monomers include methyl 4-pentenoate, ethyl 6-heptenoate, methyl 8-nonenate, methyl 10-undecenoate, ethyl 10-undecenoate, propyl 10-undecenoate, butyl 10-undecenoate, and -Cyclohexyl undecenoate, phenyl 10-undecenoate,
10-undecenoic acid-2,6-xylyl, 6-pentenoic acid, 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid, 1
0-undecenoic acid, 10-undecenylamine, divinylbenzene, 4-methyl-1,4-hexadiene, 5-
Methyl-1,4-hexadiene, 7-methyl-1,6-
Octadiene, 1,9-decadiene, 1,13-tetradecadiene and the like.

The number average molecular weight (Mn) of the copolymer having a hydroxyl group as the component (A) is 3,000 or more, preferably 6,000 to 200,000, and the weight average molecular weight (Mw).
Is 10,000 or more, preferably 50,000 to 70
The melting point (peak temperature of DSC curve) is 40 ° C or higher, preferably about 70 to about 300 ° C.

(B) Polycarbonate Resin The polycarbonate resin as the component (B) is prepared by a phosgene method in which various dihydroxydiaryl compounds are reacted with phosgene, or a transesterification method in which a dihydroxydiaryl compound is reacted with a carbonic acid ester such as diphenyl carbonate. The resulting polymer or copolymer,
A representative example is an aromatic polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and phosgene.

Examples of the dihydroxydiaryl compound as the above raw material include bis (4-
Hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) ) Phenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-t-butylphenyl) propane, 2,2-bis (4-hydroxy-) 3-bromophenyl) propane,
2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,
Bis (hydroxyaryl) alkanes such as 5-dichlorophenyl) propane, bis (hydroxyaryl) such as 1,1-bis (4-hydroxyphenyl) cyclopentane and 1,1-bis (4-hydroxyphenyl) cyclohexane Cycloalkanes, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-
Dihydroxy diaryl ethers such as 3,3'-dimethyldiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,
Dihydroxydiaryl sulfides such as 3'-dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-
Examples thereof include dihydroxydiaryl sulfoxides such as 3,3′-dimethyldiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfone, and dihydroxydiaryl sulfones such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone. To be

These may be used alone or in admixture of two or more, but in addition to these, piperazine, dipiperidyl hydroquinone, resorcin, and 4,4'-dihydroxydiphenyls may be mixed and used.

Thermoplastic resin composition Properties such as moldability, mechanical strength, solvent resistance, dimensional accuracy, and high temperature rigidity of the thermoplastic resin composition may be adjusted by the characteristics of each component and its compounding ratio. Although many, the conflicting properties of the expression mechanism, such as rigidity and impact strength, are often difficult to achieve at the same time. For practical purposes,
Usually, it is performed from the viewpoint of appropriately adjusting various properties such as moldability, mechanical strength, and high temperature rigidity. Therefore, in the case of a two-component system, the compounding ratio of each component of the composition in the present invention is
The component (A) copolymer is 10 to 90% by weight, preferably 20 to 80% by weight, more preferably 30 to 70% by weight,
The component (B) is 90 to 10% by weight, preferably 80 to 20
%, More preferably 70 to 30% by weight.

When the content of the component (A) is less than 10% by weight, the effect of improving the moldability, impact resistance and solvent resistance of the polycarbonate resin is not sufficient. Further, if it exceeds 90% by weight, the effect of improving heat resistance and rigidity is insufficient as compared with the olefin resin. In addition to these components (A) and (B), other thermoplastic resins such as polypropylene, polyethylene, propylene / ethylene copolymer, propylene / butene-1 copolymer, propylene / ethylene / butene-1 copolymer Coalescing,
Metal salts of ethylene / acrylic acid copolymer, ethylene / vinyl acetate copolymer, polystyrene, ethylene / methacrylic acid copolymer (Li ⁺ , Na ⁺ , K ⁺ , Zn ⁺⁺ , Al
⁺⁺⁺ ), maleic anhydride grafted polypropylene, polyphenylene ether, hydroxyalkylated polyphenylene ether, nylon 6, nylon 6,6, nylon 6,10, nylon 6,12, polyethylene terephthalate, polybutylene terephthalate, etc. in the resin composition 1 to 70% by weight may be contained.

Other additional components may be added to the thermoplastic resin composition of the present invention. For example, 0.5 to 3% by weight of antioxidant, weather resistance improver, nucleating agent, flame retardant and slip agent, 3 to 15% by weight of plasticizer, fluidity improver and release agent, and tetrakis ( 2-ethylhexoxy)
A catalyst such as titanium or dibutyltin oxide can be used as an additional component. Further, organic / inorganic fillers and reinforcing agents, particularly glass fiber, mica, talc, wollastonite, potassium titanate, calcium carbonate, silica, etc. added to the resin composition in an amount of 5 to 40% by weight, rigidity, heat resistance, It is effective for improving dimensional accuracy and dimensional stability. For practical use, various colorants and their dispersants can be used in a proportion of 1 to 10% by weight. Furthermore, addition of a rubber component, particularly styrene-butadiene copolymer rubber, or styrene-isoprene copolymer rubber, and hydrogenated products thereof, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, Further, modified products of α, β-unsaturated carboxylic acid anhydrides and modified products of unsaturated glycidyl esters or unsaturated glycidyl ethers, and copolymers of unsaturated epoxy compounds and ethylene or unsaturated epoxy compounds, ethylene and ethylene. A copolymer or the like composed of a system unsaturated compound is effective for improving the impact strength of the composition. The amount of rubber compounded varies depending on the target physical property value. For example, in the case of improving the balance between rigidity and impact strength of the composition,
It is 5 to 30% by weight in the composition.

<Preparation Method and Molding Method of Composition> The method for obtaining the thermoplastic resin composition of the present invention is not particularly limited, such as a melting method, a solution method and a suspension method. Is preferred. As the melt-kneading method, a kneading method which is generally and practically used for thermoplastic resins can be applied. For example, if necessary, the powdery or granular components, together with the additives described in the additional components section, are uniformly mixed by a Henschel mixer, a ribbon blender, a V-type blender, etc., and then uniaxial or multiaxial. It can be kneaded with a kneading extruder, roll, Banbury mixer, or the like.

The melting and kneading temperature of each component is 100
In the range of ℃ to 400 ℃, preferably 120 to 300
It is in the range of ° C. Further, the kneading order and method of the respective components are not particularly limited, and for example, a method of kneading the hydroxyl group-modified olefin resin (A) and the polycarbonate resin (B) and the additional components at once, a part or the whole amount After kneading the hydroxyl group-modified olefin resin and the polycarbonate resin, the remaining components may be kneaded, those having higher viscosities may be sequentially mixed, and the methods may be carried out under reduced pressure.

Further, during melt kneading, chlorobenzene,
It is also possible to add an organic solvent such as trichlorobenzene or xylene. Further, a catalyst for promoting the reaction between the hydroxyl group of the component (A) and the polycarbonate resin of the component (B) may be added during the melt-kneading. The molding method of the thermoplastic resin composition of the present invention is not particularly limited, molding methods generally used for thermoplastic resins, namely injection molding, blow molding, extrusion molding, thermoforming,
Various molding methods such as press molding can be applied.

[0027]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In the following, parts and percentages are based on weight.

(Production Example-1) Production of Copolymer Resin (I)
In a glass flask of concrete 300ml, heptane 100m
10-undecen-1-ol 10.2 after adding 1
After adding g and 50.4 ml of a heptane solution of diethylaluminum chloride (20% by weight), the temperature was raised to 70 ° C. and the mixture was stirred for 1 hour. The total volume of this solution is 25
Heptane was added to 0 ml.

Heptane solution 1 of diethylaluminum chloride prepared above was placed in a stainless steel autoclave having an internal volume of 1 liter equipped with a stirring and temperature control device.
4.4 ml, 0.7 g of TiCl ₃ catalyst manufactured by Marubeni Solvay
Was introduced, 110 ml of hydrogen was added, and then propylene pressure was supplied to 0.5 kg / cm ² G, and polymerization was carried out at 65 ° C. for 2 hours.

After the completion of the polymerization, 50 m of butanol was added to the polymerization solution.
1 and 800 ml of methanol were added, and the mixture was stirred and filtered to collect the resin. 500 ml of this recovered resin
The mixture was placed in a glass flask equipped with a stirrer, 280 ml of isopropanol and 20 ml of hydrochloric acid (36%) were added, and the mixture was stirred at 55 ° C for 2 hours. The obtained reaction product was filtered, washed with isopropanol, and dried under reduced pressure to obtain 88.4 g of copolymer resin (I). Infrared spectroscopic analysis showed absorption at 3340 cm ^-1 due to the hydroxyl group. The MFR of this resin was 1.1 g / 10 min, and the hydroxyl group content was 0.75 mol% from ¹ H-NMR.
The number average molecular weight was 78,000.

(Production Example-2) Production of copolymer resin (II)
A copolymer (II) was obtained by carrying out under the same conditions as in Production Example 1 except that 6.8 g of 10-undecen-1-ol as a solution prepared in advance and 34 ml of a heptane solution of diethylaluminum chloride were used. .

Yield: 95.13 g MFR: 1.7 g / 10 minutes Hydroxyl group content: 0.33 mol% Number average molecular weight: 69,000

(Production Example-3) 2-hydroxypropyl
Methacrylate modified polypropylene resin (HPMA-P
Production of P) (for comparison) Homopolymer powder of propylene (MFR at 230 ° C .; 1
g / 10 minutes, melting point about 164 ° C.) 250 g and 85 g of 2-hydroxypropyl methacrylate were charged in a glass flask equipped with a stirrer and having an internal volume of 10 liters, which had been sufficiently purged with nitrogen, and 5 liters of chlorobenzene were charged. In addition, it was heated and stirred at 110 ° C. to be dissolved.

To this solution, 20 g of benzoyl peroxide dissolved in 500 ml of chlorobenzene was added dropwise over 2 hours, and after the addition was completed, the reaction was further carried out at 110 ° C. for 3 hours. The reaction product thus obtained was poured into 15 liters of acetone, and the product was precipitated and filtered and washed three times. Then, the product was dried under reduced pressure to give a 2-hydroxypropyl methacrylate graft-modified propylene resin (III). Got The content of 2-hydroxypropyl methacrylate of this graft-modified propylene resin was 0.21 mol% by infrared spectroscopic analysis. MFR is 15g / 10
It was a minute.

Examples 1-5 and Comparative Examples 1-2 Hydroxyl group-modified polypropylene resins obtained in Production Examples 1-3 [copolymer resin (I), copolymer resin (II), HPMA
-PP] and unmodified polypropylene (Mitsubishi Petrochemical Co., Ltd .: Mitsubishi Polypro MA3 (trade name), MFR: 10 g / 10)
Min., Abbreviated as “PPMA3”) and aromatic polycarbonate resin (Mitsubishi Gas Chemical Co., Inc .: Iupilon S-2000)
(Trade name) "PC S-2000 and abbreviation")
According to the composition ratio shown in Table 1, each component was used at 250 ° C. and 180 ° C. using a Labo Plastomill kneader (manufactured by Toyo Seiki Seisakusho)
After kneading for 5 minutes by rotation, it was pulverized to obtain a granular resin composition.

The characteristics of the obtained resin composition are measured by the injection molding machine [Custom Scientific (Custom S
The test piece injection-molded at a temperature of 280 ° C. using CS183MMX minimax manufactured by Scientific Company) was measured and evaluated by the following method. The measurement results are shown in Table 1. During the kneading and molding, the polycarbonate and the resin composition were dried at 120 ° C. for 5 hours immediately before that.

(1) Elastic modulus: length 47 mm, width 5 mm,
A test piece having a thickness of 2 mm was injection-molded and the temperature dependence of the storage rigidity (E ') was measured under the condition of a frequency of 1 Hertz using a solid viscoelasticity measuring device RSAII manufactured by Rheometrics Far East Co., Ltd. The values of storage rigidity (E ′) at 30 ° C. and 80 ° C. were obtained. (2) Impact resistance strength: length 31.5 mm, width 6.2 mm,
A 3.2 mm-thick test piece was injection-molded, and using a Mini Scientific Izod impact tester model CS-138TI manufactured by Custom Scientific Co., there was no notch at 23 ° C. and the notch tip R had a depth of 0.25 mm and a depth. Is 1.2m
The Izod impact strength with a notch of m was measured.

(3) Tensile strength: Tensile test pieces having a parallel part length of 7 mm and a parallel part diameter of 1.5 mm were injection-molded, and a tensile tester CS-183 manufactured by Custom Scientific Co., Ltd.
A TE type was used to perform a tensile test at a tensile rate of 1 cm / min to measure tensile stress at break and elongation at break. (4) Appearance of molded product: The test piece molded in (1) above was evaluated for delamination and delamination. Those that have no practical problems are indicated by O, those that require improvement are indicated by Δ, and extremely defective ones are indicated by X.

(5) Dispersion form: A part of the test piece molded in the above (1) is cut out and subjected to ion etching,
The dispersed particle size was observed with a scanning electron microscope (Hitachi, S-2400). (6) MFR: Measured according to JIS K-7210 under the conditions of a temperature of 280 ° C. and a load of 2.16 kg.

[0040]

[Table 1]

[0041]

The thermoplastic resin composition of the present invention has good compatibility between the alcohol-modified olefin resin (A) and the polycarbonate resin (B), excellent heat resistance and mechanical strength balance, and good appearance. Give engineering plastics moldings.

Claims (1)

[Claims] 1. Component (A): 50 to 99.95 mol% of an α-olefin having 3 to 12 carbon atoms and 50 to 0.05 mol of a hydroxyl group-containing unsaturated monomer represented by the general formula (I). % Copolymer 10 to 90% by weight CH ₂ ═CH—R— (OH) _m (I) (wherein R is a hydrocarbon group having 1 to 20 carbon atoms,
m represents an integer of 1 to 3. ) Component (B): Saturated polycarbonate resin 90 to 10
% By Weight A thermoplastic resin composition containing the component (A) and the component (B).