JPS63128060A - Molding polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain a molding resin composition, consisting of an aromatic polycarbonate resin, glass based filler, aromatic polycarbonate oligomer and polycaprolactone and having improved adhesive properties of coating materials, printing inks, etc., to the surfaces of molded articles. CONSTITUTION:A molding resin composition, obtained by blending (A) an aromatic polycarbonate resin having preferably 19,000-30,000 viscosity-average molecular weight with (B) a glass based filler, e.g. glass fibers having 5-15mum outside diameter and 0.02-10mm length, spherical glass beads having 10-100mum outside diameter, etc., (C) a polycarbonate oligomer having average 2-15 units expressed by the formula (R is 1-5C alkylidene, O, CO, etc.; R1-R4 are H, halogen or 1-3C alkyl) and (C) a polycaprolactone having preferably 5,000-100,000 number-average molecular weight, 60 deg.C melting point and about -60 deg.C glass transition point. The amounts of the components based on the total amount of the composition are as follows. 5-50wt% component (B), 2-30wt% component (C) and 0.3-5wt% component (D).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a glass-reinforced polycarbonate resin composition for molding that has improved adhesion of paints, printing inks, etc. to the surface of molded products.

Polycarbonate resin reinforced with glass fillers exhibits various excellent properties such as dimensional stability, mechanical strength, heat resistance, and electrical properties, and is therefore used in a wide range of industrial fields such as cameras, VTRs, and facsimiles.

[Conventional technology and its problems]

Conventionally, glass-reinforced polycarbonate resin has excellent mechanical and electrical properties, but its injection molded products do not have a beautiful appearance, and when used for parts that require good appearance performance such as housings and covers, molded products In order to give the product a good appearance, it is necessary to rely on secondary processing such as painting and printing.
As a result, the adhesion between the substrate and the coating film or printing ink has been a problem.

For molded products using glass-reinforced polycarbonate resin,
Unlike when using non-reinforced polycarbonate resin,
Even paints that exhibit good adhesion may not provide satisfactory adhesion to molded articles made of unreinforced polycarbonate resin.

As a result of investigating the cause of this problem, we found that when using a glass-reinforced polycarbonate resin molded product obtained by injection molding and applying cellophane tape to the surface and rapidly peeling it off, the surface layer peels off in an wafer shape. It was observed that This kind of phenomenon is more often found when the molded product is made as smooth as possible with the intention of painting it, and when painting is applied to the smoothed surface of the molded product, the paint film will cover the base, That is, it peels off together with the surface layer of the molded product. When the coating film was made thinner, the effect was more pronounced.

As a result of studying methods to eliminate this drawback, we found that a composition of aromatic polycarbonate resin and glass filler,
The present applicant discovered a method of blending aromatic polycarbonate oligomers and filed an application as Japanese Patent Application Laid-Open No. 58-111549.

However, the composition of JP-A-Sho also has some problems with the manufacturing conditions of the composition,
Drying conditions during injection molding may reduce performance and cause surface layer peeling, and similar surface layer peeling may occur when molded products with complex shapes are molded at higher temperatures. Ta.

[Means for solving problems]

As a result of intensive study on methods to solve the above-mentioned drawbacks, the present inventors have found that by further blending polycaprolactone, the composition can be easily influenced by conditions such as composition manufacturing, drying, injection molding temperature, and the shape of the molded product. The present inventors have discovered a composition with excellent adhesion, and have completed the present invention.

That is, the present invention provides (a) an aromatic polycarbonate resin, (b) a glass filler, and (c) an aromatic polycarbonate oligomer having an average of 2 to 15 structural units represented by the following general formula (1). and (d) a composition consisting of polycaprolactone, wherein the component (b) occupies 5 to 50% by weight of the total amount of the composition, and the component (c,) occupies 2 to 30% by weight of the total amount of the composition. The component (d) is a molding polycarbonate resin composition in which the component (d) accounts for 0.3 to 5% by weight of the entire composition.

(R in the formula is a substituted or unsubstituted alkylidene group having 1 to 5 carbon atoms, or -o-, -co-, -s-, -5O-
, -5O2-, and R9-R4 represents hydrogen, halogen, or an alkyl group having 1 to 3 carbon atoms. ) Hereinafter, the configuration of the present invention will be explained.

First, the polycarbonate resin of the present invention is produced by a method similar to the method for producing conventional polycarbonate resins, that is, by reacting an aromatic dihydric phenol compound with phosgene or carbonic diester. The aromatic homo- or copolycarbonate resin used in the present invention preferably has a viscosity average molecular weight in the range of 19.000 to 30.000.

Here, the aromatic dihydric phenol compounds include 2,
2-bis(4-hydroxyphenyl)propane, 2.2
-bis(4-hydroxy-3,5-dimethylphenyl)
Propane, bis(4-hydroxyphenyl)methane, 1
．． l-bis(4-hydroxyphenyl)ethane, 2,2
-bis(4-hydroxyphenyl)butane, 2゜2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2.2-bis(4-hydroxy-3,5-dipropylphenyl)propane, 1 .1-bis(4-hydroxyphenyl)cyclohexane, 1-phenyl-1,1-
Examples include bis(4-hydroxyphenyl)ethane, which may be used alone or as a mixture of two or more.

In addition, as a molecular weight regulator, ordinary phenol, p-t
-Long chain alkyl substituted phenols such as octylphenol, norylphenol, laurylphenol such as butylphenol, tribromophenol; Long chain alkyl esters of hydroxybenzoic acid such as octyl hydroxybenzoate, lauryl hydroxybenzoate, noryl hydroxybenzoate; octyl ether phenol (=octyloxyphenol), noryl ether phenol, lauryl ether phenol, and other long-chain alkyloxyphenols. It is in the range of 2.0 to 3.5 mol%.

Furthermore, it can also be used as a branched product, and examples of branching agents include phloroglycin, 2,6-dimethyl-2.4.6=)(4-hydroxyphenyl)hebutene-3,4, 6-cymethyl-2.4.6-)
(4-hydroxyphenyl)hebutene-2,1,3,
5-)su(2-hydroxyphenyl)penzole, 1,
1.1-tri(4-hydroxyphenyl)ethane, 2,
6-bis(2-hydroxy-5-methylbenzyl)-4
-Methylfuenol, α, α1. polyhydroxy compounds exemplified by α″-tri(4-hydroxyphenyl)-1,3,5-)lyisoprobylbenzene, and 3
．． Examples include 3-bis(4-hydroxyaryl)oxindole (=isatin bisphenol), 5-chloroisatin, 5,7-dichloroisatin, 5-bromiisatin, and the amount used is 0.02 of the dihydric phenol used.
It is in the range of 1.0 mol%.

The glass-based filler as component (b) of the present invention refers to a filler selected from the group consisting of glass fiber, glass beads, and glass flakes, and these may be used alone or in combination. 5~15-1 length 0.02~
10mm short fibers, for example, made by Asahi Fiberglass, product name: "Glasron Chopped Strand"
Or "Glaslon Milled Fiber", Nippon Sheet Glass ■
Glass beads are commercially available under the trade name ``Micro Glass Chopped Strand'' or ``Micro Glass Surf Strand,'' manufactured by the company, and have a spherical shape with an outer diameter of 10 to 100 m. Examples of glass flakes include those commercially available under the trade name rEGB 731J manufactured by Toshiba Baroty Nikasu. Thickness 1~20p1-side length 0.
05 to 1.0 plate-shaped, for example, Nippon Sheet Glass side part, product name ``Micro Glass Flake [: BF-48J
Examples include those commercially available as .

The amount of the glass filler added is 5 to 5 in the total amount of the composition of the present invention.
It is only necessary to select a range that accounts for 50% by weight, and 5% by weight.
If the value is lower than that, the material will be inferior in terms of dimensional stability (low shrinkage rate), strength, or rigidity, and will not function as a glass-reinforced resin material. On the other hand, if it exceeds 50% by weight, the fluidity becomes insufficient and molding becomes difficult, and the abrasion of the mold and cylinder increases, resulting in an economical disadvantage. The most preferred range is 8 to 40% by weight.

The aromatic polycarbonate oligomer as component (c) of the present invention is a low molecular weight polycarbonate having an average of 2 to 15 structural units of the above-mentioned general formula (1).

This aromatic polycarbonate oligomer is produced by a method similar to that of ordinary polycarbonate resins, and is usually produced in methylene chloride at 25°C with a temperature of ≦0.
．． It is a low molecular weight substance of No. 3.

The amount of the aromatic polycarbonate oligomer to be added may be selected within the range of 2 to 30% by weight based on the total amount of the composition of the present invention, and when it is less than 2% by weight, peeling of the cellophane tape from the surface layer of the molded article can be prevented. On the other hand, if it exceeds 30% by weight, the average molecular weight of the entire polycarbonate resin constituting the composition decreases, causing problems in physical properties such as stress scrubbing properties, which is disadvantageous. The most preferred range is 5 to 20% by weight.

The polycaprolactone of the component (d) of the present invention is a crystalline thermoplastic resin obtained by subjecting ε-caprolactone to a ring-opening polymerization reaction using an alcohol as a reaction initiator, and in the present invention, the polycaprolactone has a number average molecular weight of 5. 000-1
00.000, melting point 60℃, glass transition temperature about -60
Preferably, the temperature is about ℃.

Examples of such polycaprolactone include those commercially available as "Plaxel" manufactured by Daicel Chemical Industries, Ltd.

The amount of polycaprolactone added may be selected within the range of 0.3 to 5% by weight based on the total amount of the composition of the present invention, and
．． If it is less than 3% by weight, the effect of improving adhesion will be low, while if it exceeds 5% by weight, the polycaprolactone will decompose during high temperature molding, resulting in poor appearance and deterioration of physical properties. The most preferred range is 0.5 to 3% by weight.

The polycarbonate resin composition for molding of the present invention is prepared using the components explained above. The preparation method is not particularly limited, but for example, a method in which polycarbonate resin, polycarbonate oligomer, glass filler, and polycaprolactone are sufficiently mixed in a V-type blender, etc., and then pelletized in a vent-type uniaxial extruder; polycarbonate resin and polycarbonate oligomer are prepared in advance in a powerful mixer such as a super mixer, and then a glass filler is fed into a vented twin-screw extruder, mixed, and pelletized. Generally industrially used methods such as the following may be applied as appropriate.

In addition, these polycarbonate resins may optionally contain lubricants such as fatty acid esters, paraffin wax, and silicone oil; internal plasticizers such as polyethylene and ABS1 polyethylene terephthalate; geothermal stabilizers, antioxidants, light stabilizers, Additives such as colorants, inorganic fillers, glass fibers, carbon fibers, lubricants, antistatic agents and the like can of course be added.

〔Example〕

Examples-1 to 7 and Comparative Examples-1 to 8 Polycarbonate resin powder using bisphenol A (manufactured by Mitsubishi Gas Chemical Company, trade name: Kneepilon S-200)
0, viscosity average molecular weight 25.000), P-tertiary
Butylphenol-terminated bisphenol A oligomer powder (manufactured by Mitsubishi Gas Chemical ■, trade name: Niepiron AL, viscosity average molecular weight 5,000), glass fiber (manufactured by Asahi Fiberglass ■, trade name: Glassron Chop Strand [hereinafter (A) )], product name: Glasson Milled Fiber [hereinafter referred to as (B)]), glass beads (manufactured by Toshiba Ballotini, product name: BGB 731), or glass flakes (manufactured by Nippon Sheet Glass, product name: Micro Glass fillet CEP 48') and polycaprolactone (manufactured by Daicel Chemical Industries, trade name: Plaxel -
1) were mixed in a tumbler with the composition shown in Table 1, and each was extruded into pellets using a vented extruder with a negative shaft.

The obtained pellets are dried in a hot air circulation dryer at 120°C for 4 to 40 minutes.
After drying for 6 hours, Neomat 350/12 manufactured by Jujuki Kikai ■
Using a 0-type injection molding machine, the outer diameter is 58 mm, the thickness is 2 mm,
A cylindrical molded product with a height of 25fffffl was molded at a resin temperature of 32
0-340℃, mold temperature 90-100℃, holding pressure 1,
000 kg/cnf, an injection speed of 60 M/sec, and a molding cycle of 50 seconds (cooling 25 seconds, injection 1 second, holding pressure time 7 seconds).

The obtained molded product was subjected to a peel test using cellophane tape, and the results are shown in Table 4.

In addition, the cellophane tape peeling test and appearance in the table were described based on the following criteria.

- Cellophane tape peeling Condition in which nioblade-like peeling is clearly observed: x1 Condition in which peeling is difficult to recognize 20.

・Appearance 2: Condition in which glass filler such as glass fiber is floating on the surface: ×, condition in which floating is difficult to recognize.

Table 1 [Operations and Effects of the Invention] As described above, the polycarbonate resin composition for molding of the present invention improves surface properties, especially adhesiveness, without being affected by extrusion conditions, drying conditions during injection molding, injection temperature, etc. It can produce molded products with excellent properties and is effectively used in industrial fields such as cameras, VTRs, and facsimile machines.

Claims (1)

[Scope of Claims] 1 (a) aromatic polycarbonate resin, (b) glass filler, (c) aromatic polycarbonate having an average of 2 to 15 structural units represented by the following general formula (1) A composition consisting of an oligomer and (d) polycaprolactone, wherein the component (b) accounts for 5 to 50% by weight of the total amount of the composition, and the component (c) accounts for 2 to 30% by weight of the total amount of the composition. , the component (d) is present in an amount of 0.3 to 5 in the total amount of the composition.
% by weight of a polycarbonate resin composition for molding. General formula (1): ▲There are numerical formulas, chemical formulas, tables, etc.▼... (1) (R in the formula is a substituted or unsubstituted alkylidene group having 1 to 5 carbon atoms, or -O-, -CO -, -S-, -SO-
, -SO_2-, and R_1 to R_4 represent hydrogen, halogen, or an alkyl group having 1 to 3 carbon atoms. )2 applicable (b
) The glass-based filler is selected from the group consisting of glass fibers, glass flakes, and glass beads.
The resin composition described in .