JP2775836B2 - Thermoplastic resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having excellent surface gloss, appearance, moldability, and impact resistance. More specifically, the present invention relates to a thermoplastic resin composition comprising a polypropylene, a maleimide-based copolymer resin, and an inorganic filler.

[Prior art] Polypropylene has various excellent physical properties, chemical properties, mechanical properties, moldability, and is widely used in many industrial fields due to its low cost. I have. However, since polypropylene is non-polar, it has the disadvantage that it is difficult to combine various types of equipment, such as various metals, inorganic materials such as glass, and polar materials such as polar polymer materials, because of its poor adhesion. is there.

As an effective method for remedying this drawback, a polar group is introduced by graft-modifying a polypropylene with an unsaturated carboxylic acid such as acrylic acid or maleic acid or an unsaturated carboxylic anhydride to impart adhesiveness. Methods are known.

Also, various modified polyolefin-based compositions have been proposed for the purpose of further improving the adhesion to metals, polymer materials, and the like. For example, a composition obtained by adding an unsaturated carboxylic anhydride such as maleic anhydride and a metal oxide such as magnesium oxide to a polyolefin and graft-modifying the resulting mixture under melting (for example, JP-B-51-48195, Four
No. 9-98484, JP-A-50-10837), a composition comprising a polyolefin modified with acrylic acid or maleic anhydride and a metal oxide such as magnesium oxide added thereto (for example, JP-A-51-23544). And Japanese Patent Application Laid-Open No. 52-121059).

[Problems to be Solved by the Invention] However, even if glass fiber is mixed with the modified polypropylene modified with an acid anhydride under the melting of polypropylene as described above, the adhesiveness is still insufficient, and the adhesion to the surface of the molded article during injection molding is still insufficient. This raises a problem when glass fibers are raised and the surface gloss and appearance are poor and secondary processing such as painting is performed.

[Means for Solving the Problems] The present inventors have made intensive efforts to solve the above problems, and have completed the present invention.

That is, the present invention is a polypropylene resin 20 to 96.5% by weight,
A thermoplastic resin composition comprising 2 to 25% by weight of an acid-modified polypropylene resin, 0.5 to 50% by weight of a maleimide copolymer resin and 1 to 50% by weight of an inorganic filler.

Examples of the polypropylene resin used in the present invention include a melt flow rate (measured at 230 ° C. under a load of 2.16 kg according to JIS K-6758) of 0.5 to 50 g / 10 min, such as a polypropylene homopolymer or a polypropylene-ethylene copolymer. There is no particular limitation.

The acid-modified polypropylene resin used in the present invention is not particularly limited as long as it is modified with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride.
~ 10 wt% is preferred. Examples of a method for obtaining such an acid-modified polypropylene resin include a method in which an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride is mixed under melting of polypropylene, and a method in which a copolymer is formed.

Unsaturated carboxylic acids include acrylic acid, methacrylic acid, and unsaturated carboxylic anhydrides include maleic anhydride, itaconic anhydride, citraconic anhydride, hymic anhydride, and bicyclo (2,2,2) oct-5- Ene 2,3-dicarboxylic anhydride, 4-methylcyclohex-4-ene-1,
2-dicarboxylic anhydride, 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic anhydride, bicyclo (2,2,1) oct-7-ene- 2,3,5,6-tetracarboxylic acid-2,3,5,6-dianhydride, 7-octabicyclo (2,2,1)
Hept-5-ene-2,3-dicarboxylic anhydride and the like. Of these, maleic anhydride is particularly preferably used.

Glass fiber as the inorganic filler used in the present invention,
Reinforcing filler such as carbon fiber, ceramic fiber such as alumina fiber, aramid fiber, wholly aromatic polyester fiber, metal fiber, potassium titanate whisker, calcium carbonate, mica, talc, silica, barium sulfate, calcium sulfate, kaolin, Clay, pyroferrite, pentonite, sericite, zeolite, nepheline sinite, attapulgite, warite knight, ferrite, calcium silicate, magnesium carbonate, dolomite, antimony trioxide, zinc oxide, titanium oxide, magnesium oxide, iron oxide, Molybdenum disulfide, graphite, gypsum, glass beads, glass powder, glass balloon,
Examples thereof include inorganic fillers such as quartz and quartz glass, and inorganic pigments. As glass fiber, for example, fiber length 1.5
1212 mm, chopped strands having a fiber diameter of 6-13 μm, milled fibers having a fiber diameter of 3-8 μm, glass flakes and glass powder having a size of 325 mesh or less.

The maleimide-based copolymer resin used in the present invention is obtained by copolymerizing a maleimide or a maleimide derivative and a monomer copolymerizable therewith, and preferably contains 20% by weight or more of the maleimide or the maleimide derivative. More preferably, (a) 1 to 98% by weight of a maleimide derivative (b) 1 to 98% by weight of an aromatic vinyl compound (c) at least one vinyl monomer 1 copolymerizable with (a) and (b) It is a maleimide copolymer resin obtained by polymerizing a monomer represented by 5050% by weight.

The maleimide derivative (a) may be any as long as it satisfies the formula (1).

(Wherein, R ₁ and R ₂ are each hydrogen, halogen, carbon number 1-20
Represents a substituted or unsubstituted hydrocarbon residue, R ₃ is hydrogen,
Represents a substituted or unsubstituted hydrocarbon residue having 1 to 20 carbon atoms. As specific examples, maleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, Nt-butylmaleimide, N-phenylmaleimide, α-methyl-N-phenylmaleimide, No-methylphenyl Maleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, N-cyclohexylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, N
-P-hydroxyphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenylmaleimide, No
-Chlorophenylmaleimide, Nm-chlorophenylmaleimide, Np-chlorophenylmaleimide, N-
Examples thereof include o-carboxyphenylmaleimide, Nm-carboxyphenylmaleimide, Np-carboxyphenylmaleimide, N-dichlorophenylmaleimide, and N-naphthylmaleimide. These can be used alone or in combination of two or more.

Examples of the aromatic vinyl compound (b) include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene, α-methylstyrene, and α-ethylstyrene. And nuclear alkyl-substituted α-methylstyrene, nuclear halogen-substituted α-methylstyrene, vinylnaphthalene, and the like.

(B) Vinyl monomers copolymerizable with (b) (c)
Examples thereof include unsaturated nitrile compounds, alkyl esters of α, β-unsaturated carboxylic acids, and unsaturated acids such as maleic anhydride, itaconic anhydride, citraconic anhydride, acrylic acid and methacrylic acid.

Examples of the unsaturated nitrile compound include acrylonitrile and methacrylonitrile.

Examples of the α, β-unsaturated carboxylic acid alkyl ester compounds include acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate, methyl methacrylate, ethyl methacrylate, and lauryl methacrylate. And methacrylic esters such as stearyl methacrylate.

In the present invention, as a method for producing the maleimide copolymer resin, a method such as solution polymerization, suspension polymerization or emulsion polymerization in the presence of water, an initiator, a suspending agent, or an emulsifier can be used. For example, in a solution polymerization method, 1 to 98% by weight of an aromatic vinyl compound (b), a vinyl monomer (c) 1
0-50% by weight in an organic solvent in the presence of a radical initiator
The formula (1) takes several tens minutes to several hours while stirring at ~ 150 ° C. (Wherein R _{1 to} R ₃ are the same as above), and 1 to 98% by weight of a maleimide derivative represented by
Further, it can be produced by reacting for several minutes to several hours.

The total concentration of the raw materials is generally selected in the range of 50 to 500 g / l solvent. The initiator concentration is generally selected in the range of 0.001 to 0.1 g / g total raw material.

Various solvents can be used as the organic solvent, and examples thereof include dimethylformamide, dimethylsulfoxide, tetrahydrofuron, toluene, 1.4-dioxane, and p-ethylphenol.

The radical initiator is not particularly limited as long as it is used as a usual radical polymerization initiator, and examples thereof include azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, t-butyl hydroperoxide and the like. Can be mentioned.

The content of the maleimide-based copolymer resin in the composition of the present invention is desirably 0.5 to 50% by weight. If it is less than 0.5% by weight, the effects of surface gloss, appearance, and heat resistance are low, and if it exceeds 50% by weight, the effect is not changed but the practicality such as cost is lacking.

The content of the inorganic filler in the composition of the present invention is desirably 1 to 50% by weight. If it is less than 1% by weight, the resulting molded article has insufficient rigidity, heat deformation temperature and dimensional stability. If it exceeds 50% by weight, molding, especially injection molding, becomes difficult. There is no particular limitation on the inorganic filler of the composition of the present invention, whether it is surface-treated or not.

The method of blending each component of the thermoplastic resin composition of the present invention is as follows: 1) A method of mixing each component with a mixer or the like, followed by melt-kneading using an extruder and then pelletizing 2) Obtaining by the method of 1). There is a method of obtaining a molded product by using an injection molding machine after the obtained pellets are used alone or after adding and mixing each component.

It is also possible to use a known mixing device such as a Banbury or a kneader for each of the above methods.

The thermoplastic resin composition of the present invention can be used after being processed into various molded articles by injection molding, sheet molding, vacuum molding, irregular-shaped molding, foam molding, or the like.

In addition, known antioxidants, ultraviolet absorbers, lubricants, flame retardants, antistatic agents, foaming agents, heat stabilizers, plasticizers, fluorescent agents, and the like, which are commonly used, can be added.

[Function] The thermoplastic resin composition of the present invention has good adhesiveness to inorganic materials such as glass, and also has excellent surface gloss, appearance, and heat resistance. Can be used.

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

Reference Example (Production Method of Maleimide-Based Copolymer Resin) Maleimide-based copolymer resins (a) to (d) having the compositions shown in Table 1 were produced by the following method.

(A) Equipped with a stirrer, thermometer, nitrogen inlet tube, and cooler
In a 5000 ml four-necked flask, 100 g (0.96 mol) of styrene, 70 g (0.7 mol) of methyl methacrylate and 1,4-dioxane 10
Add 00 ml, stir to dissolve, raise the temperature to 70 ° C, add azobisisobutyronitrile 4.8 g (30 mmol), and add 1,4
A solution of 135 g (0.62 mol) of N- (p-carboxyphenyl) maleimide dissolved in 1500 ml of dioxane was added dropwise over 4 hours. After stirring for 20 hours after the dropwise addition, the mixture was cooled to room temperature, poured into a large amount of methanol to precipitate a polymer, and the polymer was filtered. Next, the polymer was purified by dissolving in 1,4-dioxane and reprecipitating in methanol, followed by vacuum drying at 120 ° C. for 24 hours to obtain 230 g (75%) of a white powder of N- (carboxyphenyl) maleimide copolymer. Obtained.

In a similar manner, N-phenylmaleimide copolymers (b) to (d) were prepared.

Examples 1 to 4, Comparative Example 1 Maleimide copolymer resin (a) synthesized in Reference Example
(D), a polypropylene resin (Tosoh Polypro J5100A MFI11 manufactured by Tosoh Corporation), an acid-modified polypropylene resin (maleic anhydride 2% modified polypropylene manufactured by Tosoh Corporation) and glass fiber (fiber 13μ chopped strand) They were mixed at the mixing ratios shown in the table and pelletized using a pressure kneader. Next, after drying the pellets, a cylinder temperature was set to 300 ° C. and a mold temperature was set to 30 ° C. to obtain a molded product.

The tensile strength (JIS K7113) flexural modulus (JI
S K7203) Izod impact strength (JIS K7110) gloss (JI
S K7105) and measure the appearance with glass fiber (G
F) was evaluated based on the amount of embossing. Further, the surface roughness meter was used to measure and evaluate the Rp value (difference from the average height to the maximum height) shown in FIG. The Rp value is preferably 2 μm or less. Table 3 shows the results of these measurements.

[Effects of the Invention] As described in detail above, the resin composition of the present invention has good adhesion to inorganic materials such as glass, and furthermore has excellent surface gloss and appearance, so that surface modification such as painting, plating and vapor deposition is performed. It has an excellent effect on secondary processing and its industrial value is high.

[Brief description of the drawings]

FIG. 1 explains the Rp value indicating the surface roughness of a molded product. The waveform pattern shown in the figure shows the surface condition of the molded product.

Claims (1)

(57) [Claims] 1. A thermal method comprising 20 to 96.5% by weight of a polypropylene resin, 2 to 25% by weight of an acid-modified polypropylene resin, 0.5 to 50% by weight of a maleimide copolymer resin and 1 to 50% by weight of an inorganic filler. Plastic resin composition.