JPH0431459A - Polycarbonate resin composition for molding - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in mechanical strengths and being useful as, e.g. a molding material in the field of precision industries by mixing an aromatic polycarbonate resin with aluminum borate whiskers and an organic compound having a specified number of oxazoline rings. CONSTITUTION:An aromatic biphenol compound is reacted with phosgene or a carbonic diester in the presence of optionally a molecular weight modifier, a branching agent, etc., to obtain an aromatic polycarbonate resin of a viscosity- average mol.wt. of 19000-30000. A starting material which can generate Al2O3 and B2O3 at 1000 deg.C or above is mixed with a chloride, sulfate or carbonate of an alkali metal as a flux not taking part in the reaction, and the mixture is heated to 1000-1200 deg.C to obtain aluminum borate whiskers of 9Al2O3.2B2O3. The polycarbonate resin is mixed with 5-50wt.% whiskers B and 0.01-5wt.% organic compound having two or more oxazoline rings in the molecule.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is an aromatic polycarbonate resin composition for molding, which is formed by blending aluminum borate whiskers and an organic compound having two or more oxazoline rings in the molecule. , cameras that require good surface appearance and high elastic modulus,
It can be suitably used in VTR, facsimile, and other wide industrial fields.

[Conventional technology and its problems]

Aluminum borate whiskers have high strength, high elasticity,
Furthermore, since it is almost neutral, it is a suitable reinforcing material for aromatic polycarbonate resins.

However, when used as a reinforcing material for aromatic polycarbonate resin, the composition was still insufficient to fully utilize the high strength of this whisker.

[Means to solve the problem]

The inventors of the present invention have arrived at the present invention as a result of intensive studies on methods for solving the above-mentioned drawbacks.

That is, the present invention provides an aromatic polycarbonate resin (a
), aluminum borate whiskers (c), and an organic compound (c) having at least two or more oxazoline rings in the molecule as essential components, provided that component 5 to 50% by weight, and the (c) component is 0.01 to 5% by weight of the entire composition, and the aluminum borate whisker (b) is present in the molecule. A polycarbonate resin composition for molding, characterized in that it is used as an aluminum borate whisker (5)' which is surface-treated using a surface treatment solution containing an organic compound (c) having at least two or more oxazoline rings. It is.

The configuration of the present invention will be explained below.

First, the aromatic polycarbonate resin (a) of the present invention is
It is produced by the same method as the conventional method for producing polycarbonate resins, that is, by reacting an aromatic dihydric phenol compound with phosgene or carbonic acid diester. The aromatic homo- or copolycarbonate resin used in the present invention preferably has a viscosity average molecular weight of 19.000 to 30.00.
The range is 000.

Here, as aromatic dihydric phenol compounds, 2.
2-bis(4-hydroxyphenyl)propane (=bisphenol A), tetramethylbisphenol A1 tetrabromobisphenol A1 tetraethylbisphenol A1 bis(4-hydroxyphenyl)methane, ■, 1
-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(
4-hydroxyphenyl)cyclohexane, 1-phenyl-1,1-bis(4-hydroxyphenyl)ethane,
Examples include bis(4-hydroxyphenyl)-P-diisopropylbenzene, 4,4-dihydroxydiphenyl, hydroquinone, resorcinol, and 4,4'-dihydroxydiphenyl, which may be used individually or as a mixture of two or more. In particular, bisphenol A is preferred in the present invention.

In addition, as a molecular weight regulator, ordinary phenol, p-t
Long-chain alkyl-substituted phenols such as octylphenol, norylphenol, and laurylphenol, such as ert-butylphenol and tribromophenol: Long-chain alkyl esters of hydroxybenzoic acid, such as octyl hydroxybenzoate, lauryl hydroxybenzoate, and noryl hydroxybenzoate; octyl ether Examples include monovalent phenolic compounds such as long-chain alkyloxyphenols such as phenol (=octyloxyphenol), noryl ether phenol, and lauryl ether phenol, and the amount used is 1 to 10 mol% of the dihydric phenol used, preferably 2 It is in the range of .0 to 3.5 mol%. It can also be used as a branched product, and examples of branching agents include phloroglucin, 2.6-cymethyl-2.4.6
- ) li (4-hydroxyphenyl)hebutene-3,
4,6-dimethyl-2.4,6-tri(4-hydroxyphenyl)hebutene-2,4,6-dimethyl-2.4
．． 6-)su(4-hydroxyphenyl)hebutane, 1
．． 3.5-) IJ (4-hydroxyphenyl)benzene, 1,1.1-)! Polyhydroxy compounds exemplified by J (4-hydroxyphenyl)ethane, and 3゜3-bis(4-hydroxyaryl)oxindole (= isatin bisphenol), 5-chloroisatin, 5.7-dichloroisatin, 5- Examples include bromysatin, and the amount used is in the range of 0.02 to 1.0 mol% of the dihydric phenol used.

Component (b) of the present invention is aluminum borate whiskers, 9A1zOa.2B20. and 2A1203・B2
There is O3, but 9A1□03・2B20. - Boat fishing. Synthesis methods include a melting method, a gas phase method, an internal flux method, and an external flux method, but the external flux method is preferred in the present invention. This external flux method uses 100
For raw materials that generate Al2O3 and B2O3 at temperatures above 0°C,
Add alkali metal chloride, sulfate or carbonate as a flux that does not participate in the reaction, and heat at 1000-1200℃.
Heat to 9A1□03・2B20. This is to grow whiskers, and at this time the heating temperature is 800 to 100.
At 0℃, 2A1□0.・B20. You will get whiskers. This aluminum borate whisker has higher strength and higher elasticity than potassium titanate whisker.
It is expected that engineering plastics with unprecedented high strength and high elasticity will be obtained.

The amount of aluminum borate whiskers as component (b) added is 5 to 50% by weight, preferably 8 to 40% by weight of the composition.
It is selected from a range of 5% by weight, and if it is less than 5% by weight, it will be inferior in terms of strength, rigidity, and dimensional stability, and if it exceeds 50% by weight, fluidity will be insufficient and molding efficiency will be affected.

Furthermore, in the (b) I& component of the present invention, for the purpose of improving the anisotropy of the molded article, etc., other fillers and reinforcing agents can also be used in combination. Such fillers include silica, alumina, titanium oxide, calcium sulfate powder, gypsum, gypsum whiskers, barium sulfate, talc, mica, asbestos, glass peas, glass flakes, calcium silicate, carbon black, graphite, iron powder. , copper powder, molybdenum disulfide, carbon fiber, silicon carbide, silicon carbide fiber, silicon nitride, silicon nitride fiber, brass fiber, stainless steel fiber, potassium titanate fiber or whisker, aromatic polyamide fiber, etc. Examples include fibrous, plate-like, flake-like, or powder-like fillers.

The organic compound (c) having at least two oxazoline rings in the molecule of component (c) of the present invention is a general term for compounds in which the oxazoline ring is bonded to an aliphatic or aromatic group, and is represented by the following general formula (J). shown.

(R in the formula represents an aliphatic group, an aromatic group, or a hydrocarbon group consisting of an aliphatic group and an aromatic group, xl, X2, X's X4 represents hydrogen or a lower alkyl group, and n represents an integer of 2 or more. ) A typical example of this compound is a condensate of a polyhydric carboxylic acid or a derivative such as its chloride and a 2-amino alcohol.

Specific examples of condensates of dicarboxylic acids or their chlorides and 2-amino alcohols include 1,3-bis(2-oxazolin-2-yl)benzene and 1,3-bis(2-oxazolin-2-yl)benzene derived from isophthalic acid. (4,4-dimethyl-2-oxazolin-2-yl)benzene, analogues derived by replacing isophthalic acid with terephthalic acid, phthalic acid; naphthalene dicarboxylic acids, such as naphthalene-1,4-
1,4-bis(2-xacillin-2-yl)naphthalene, 1,4-bis(4,4) derived from dicarboxylic acid
-dimethyl-2-oxazolin-2yl)naphthalene;
1,3-bis(2-oxazolin-2-yl)ethane, 1,3-bis(4,4-dimethyl-2-oxazolin-2-yl)ethane derived from succinic acid; 1 derived from glutaric acid , 3-bis(2-oxazolin-2-yl)propane, 1,3-bis(4,4dimethyl-2-oxazolin-2-yl)propane; 1,4-bis(2-yl) derived from adipic acid Examples include oxazolin-2-yl)butane and 1,4-bis(4,4-dimethyl-2-oxazolin-2-yl)butane. As a derivative of tricarboxylic acid, 1 derived from trimellitic acid
, 2.4-tris(2-oxazolin-2-yl)
Examples include benzene. Among these, isophthalic acid,
Those derived from terephthalic acid are preferred.

Component (c) of the present invention is o, oi ~ 5% by weight in the composition.
If it is less than 0.01% by weight, the effect of improving strength is low, and if it exceeds 5% by weight, decomposition of (c) ff1 occurs during high temperature molding, resulting in a decrease in strength, which is not preferable.

Furthermore, in the present invention, it is effective to coat the component (b) with the component (c). In this case, the aluminum borate whiskers are treated in advance with a solution of (c)ti, and the component (c) is coated with the component (c). It can be suitably used as an aluminum borate whisker (b)'. When using this aluminum borate whisker (b)', (c
) Ingredients have the advantage of being effective in relatively small amounts.

The composition of the present invention may be prepared by any conventional method, and is not particularly limited. For example, components (a), (c), (c), or (c)' may be mixed with other additives in a V-blender. A method in which components (a) and (c) or other appropriate additives are mixed thoroughly using a mixing means such as a supermixer, and then made into pellets using a vented shaft extruder; Prepare a pre-mixed mixture using
Appropriately apply methods generally used industrially, such as feeding this to a vent-type twin-screw extruder, feeding the ingredients (or ingredients) from the middle, mixing them, and forming them into pellets. be done.

In addition, these polycarbonate resins may contain lubricants such as fatty acid esters, paraffin wax, silicone oil, etc., internal plasticizers such as polyethylene, ABS, polyethylene terephthalate, etc., geothermal stabilizers, antioxidants, and light stabilizers. Naturally, additives such as colorants, lubricants, antistatic agents, etc. can be added.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. In addition, the blending amounts in Examples and the like are based on weight unless otherwise specified.

Examples 1 to 4 and Comparative Example 1.2 Polycarbonate resin powder using bisphenol 8 (manufactured by Mitsubishi Gas Chemical, trade name: Nipiron S-200)
0, viscosity average molecular weight 25.000) and aluminum borate whiskers (manufactured by Shikoku Kasei ■, trade name: Arborex S-1, aminosilane treated product), Example 1.3
Next, 1.3 to phenylenebis-2-oxazoline was further blended in the amounts listed in Table 1, mixed in a tumbler, and heated to a cylinder temperature of 270°C using a single-screw vented extruder.
It was extruded into a beret. In addition, in Example 2.4, in the surface treatment process of aluminum borate whiskers, 1
The procedure was the same except that oxazoline surface-treated aluminum borate whiskers (hereinafter referred to as "S-1°") obtained by using a surface treatment liquid containing , 3-phenylenebis-2-oxazoline were used.

The obtained pellets were dried in a hot air circulation dryer at 120℃ for 5 minutes.
After drying for several hours, a test piece was molded using an injection molding machine at a resin temperature of 280°C. Table 1 shows the results of measuring the strength of the molded products obtained.

Note) Book: Unit: kg/cnf.

Table 1-2 Note) Book: Unit: kg/cat.

[Operation and effects of the invention]

From the above detailed description of the invention, Examples, and Comparative Examples, the composition of the present invention has extremely excellent mechanical strength.

Therefore, it is understood that this is a molding material that can be effectively used in precision industrial fields such as cameras and vTR1 facsimiles.

Patent applicant: Mitsubishi Gas Chemical Co., Ltd.

Claims (1)

[Scope of Claims] 1. A resin composition containing as essential components an aromatic polycarbonate resin (a), an aluminum borate whisker (b), and an organic compound (c) having at least two or more oxazoline rings in the molecule. The component (b) is 5 to 50% by weight of the total composition, and the component (c) is 0% by weight of the total composition.
．． 01 to 5% by weight of a polycarbonate resin composition for molding. 2 Aluminum borate whiskers (b)' obtained by surface treating the aluminum borate whiskers (b) using a surface treatment solution containing an organic compound (c) having at least two or more oxazoline rings in the molecule. The polycarbonate resin composition for molding according to claim 1.