JPH02142849A - Polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which can give a polycarbonate resin molding further improved in mechanical properties and moldability by mixing a composition comprising an aromatic polycarbonate resin and a thermoplastic liquid crystal resin with a small amount of an aromatic epoxy resin. CONSTITUTION:A polycarbonate resin composition is prepared by mixing 100 pts.wt. resin composition comprising 95-60wt.% aromatic polycarbonate (e.g., bisphenol A polycarbonate) and 5-40wt.% thermoplastic liquid crystal resin (desirably a polyester or a polyester-amide which can show liquid crystal property at 220-350 deg.C) with 0.05-5 pts.wt., desirably 0.1-3 pts.wt. aromatic epoxy resin (desirably bisphenol A diglycidyl ether or diglycidyl phthalate). This resin has high rigidity especially at a thin-wall part and excels also in weld strength, impact strength and flex resistance.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a polycarbonate resin composition, and more specifically, to a polycarbonate resin composition that further improves the excellent mechanical properties and improves the moldability. This invention relates to a polycarbonate resin composition that can be used in a wide range of applications.

[Conventional technology]

Aromatic polycarbonate resin has excellent mechanical and thermal properties, but to further improve its properties, it can be reinforced with inorganic reinforcing materials such as glass fiber and inorganic fillers, which are commonly used to reinforce punches. As a result, moldability deteriorates and the appearance becomes poor.

For this reason, it has been considered to mix an organic material as a reinforcing material, and it is known to mix a thermoplastic liquid crystal resin (JP-A-57-40551, JP-A-63-159467).
).

[Problem to be solved by the invention]

However, the compatibility between the polycarbonate resin and the liquid crystal resin is not sufficient, and the resulting molded product is likely to peel off, and its impact properties and weld strength are also unsatisfactory. Therefore, there has been a problem that a polycarbonate resin blended with an organic reinforcing material that has the reinforcing effect of an inorganic reinforcing material and also has improved moldability and appearance has not yet been obtained.

An object of the present invention is to provide a novel polycarbonate resin composition that can solve the conventional problems as described above.

[Failure to solve the problem]

As a result of intensive studies to achieve this objective, the present inventors have found that by blending an aromatic epoxy compound into a mixture of an aromatic polycarbonate resin and a thermoplastic liquid crystal resin, the compatibility between the two can be significantly improved. We have discovered for the first time that this is possible, and have arrived at the present invention. That is, the present invention provides a resin composition 1 comprising 95 to 60% by weight of an aromatic polycarbonate resin and 5 to 40% by weight of a thermoplastic liquid crystal resin.
The main feature of this composition is a polycarbonate resin composition comprising 0.00 parts by weight and 0.05 to 5 parts by weight of an aromatic epoxy resin, which has high rigidity, excellent appearance, good moldability, and impact properties. The object of the present invention is to provide a novel polycarbonate resin composition that has a high hardness and does not cause peeling.

The present invention will be specifically explained below.

The aromatic polycarbonate resin used as the main component in the present invention can be obtained by the phosgene method in which various dihydroxydiaryl compounds are reacted with phosgene, or the transesterification method in which the dihydroxydiaryl compound is reacted with a carbonate ester such as diphenyl carbonate. A typical copolymer is 2.2
- Polycarbonate resins made from bis(4-hydroquinophenyl)propane (bisphenol A). In addition to bisphenol A, the dihydroxydiaryl compounds 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-tert-butylphenyl)propane, 2,2-bis(4-hydroxy-3
-Fromophenyl)propane, 2,2-bis(4hydroxy-3,5→bromophenyl)furon;, 2,2-
Bis(hydroxyaryl)alkanes such as bis(4-hydroxy-3,5-dichlorophenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane bis(hydroxyaryl)cycloalkanes such as 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, dihydroxydiallyl ethers such as 1114,4'-dihydroxydiphenyl sulfide,
4. Dihydroxydiaryl sulfides such as 4'-dihydroxy-3,3'-dimethyldiphenyl tafite, 4.4'-dihydroxydiphenyl sulfoxide,
Dihydroxy diaryl sulfoxides such as 4.4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4.4'-dihydroxydiphenyl sulfone, and dihydroxy such as 4.4'-dihydroxy-3,3'-dimethyldiphenyl sulfone. Examples include diarylsulfones.

These may be used alone or in combination of two or more, but in addition to these, piperazine, dipiperidylhytroquinone, resorcinol, 4,4'-dihydroxydiphenyl, etc. may be used in combination.

In addition, the thermoplastic liquid crystal resin used as the essential second component in the present invention is not particularly limited in its structure as long as it exhibits thermotropic liquid crystallinity, but it is generally molded at 220°C, which is the molding temperature of polycarbonate resin. ~350
Preferably, the material exhibits liquid crystallinity between .degree. Examples of such liquid crystal resins include aromatic polyesters made of aromatic diols and aromatic dicarboxylic acids and/or aromatic hydroxycarboxylic acids, aromatic polyesteramides containing aromatic hydroxyamines and aromatic diamines, and polyazomethines. More specifically, polyester or polyester amide having the following structure as a main structural unit is preferable.

Polyester structure -〇-R-O CO-R-CO O-R-C0 Polyester amide structure -CO-R-C0-C)-R
-C0 -NH-R-C0 -Nu-R-NH R in the above structural formula can be arbitrarily selected from the group shown in Attached Table 1 below within the range that exhibits thermotropic liquid crystallinity.

Attached Table 1 = CH2- (CH2)2 (CH2)4 -(CH2)6 In addition, some of the aromatic rings, aliphatic groups, and alicyclic groups may be treated as follows within the range of maintaining liquid crystallinity. It may be substituted with a group.

Br, -C71, -COOH, -CONH2゜CH3,
-C(CH3), a) These thermoplastic liquid crystal resins are commercially available under trade names such as Econonol manufactured by Sumitomo Chemical (2), VECTRA manufactured by Hoechst (USA), and N0VACCURATE manufactured by Mitsubishi Chemical (2).

The mixing weight ratio of aromatic polycarbonate resin and thermoplastic liquid crystal resin is used within the range of 95:5 to 60:40.

The resin composition used in the present invention may further contain reinforcing agents within a range that maintains mechanical properties and does not cause sink marks or warpage. In particular, reinforcing agents such as glass fibers, glass flakes,
From glass reinforcing agents such as glass beads, and inorganic fillers such as mica, tar, calcium metasilicate, calcium carbonate, silica, alumina, silica-alumina clay minerals, silica-magnesium clay minerals, asbestos, etc. It is also desirable to use 0 to 40 parts by weight per 100 parts by weight of the resin composition.

In addition, various well-known additives, such as vinyl copolymers and their water-added products, acryloid compounds, impact modifiers such as modified olefins, lubricants such as lacquer-in wax and fatty acid esters, etc. ``Phenol,
Antioxidants such as phosphate esters and phosphites,
Weather resistance improvers such as triazine compounds, coloring agents such as pigments and dyes, fiber fillers such as glass fibers, carbon fibers, metal fibers, and various whiskers, mica, tar, calcium metasilicate, calcium carbonate, and silica. , alumina, silica-alumina clay minerals, silica-magnesium clay minerals, inorganic fillers such as asbestos, antistatic materials, flame retardants, and the like.

Further, the aromatic epoxy resin used as an essential third component in the present invention is an aromatic resin having two or more epoxy groups in the molecule, and is generally a bisphenol compound, phenoltuborac, aromatic It is obtained as a condensate of diols, aromatic dicarboxylic acids, and polymers containing these as basic structural units, and epihalohydrin. Among these, use of bisphenol A diglyzodyl ether and phthalic acid cyclidyl ester is particularly preferred.

The blending amount of aromatic epoxy resin is 100% of the resin composition consisting of aromatic polycarbonate resin and thermoplastic liquid crystal resin.
0.05 to 5 parts by weight, preferably 0.01 to 5 parts by weight
~ It is a triple metropolitan area.

If the amount is less than 0.05 parts by weight, no effect of improving compatibility will be observed, and if it exceeds 5 parts by weight, moldability and thermal stability will decrease.

The aromatic polycarbonate resin, thermoplastic liquid crystal resin, and aromatic epoxy resin may be blended by a known method, but melt mixing using an extruder Banbury mixer-Suher mixer, hot roll, kneader, etc. is particularly preferable.

The resin composition of the present invention also includes various known additives,
For example, impact modifiers such as vinyl copolymers and their water-added products, acryloid compounds, modified polyolefins,
Rough-in wax, lubricants such as fatty acid esters, hindered phenols, antioxidants such as phosphate esters and phosphite esters, weather resistance improvers such as triazine compounds, colorants such as pigments and dyes, glass fibers , carbon fibers, metal fibers, fibrous fillers such as various whiskers, mica, tar, calcium metasilicate, calcium carbonate, silica, alumina, silica-alumina clay minerals, silica-magnesium clay minerals, and inorganic materials such as asbestos. It may contain fillers, antistatic materials, flame retardants, etc.

The polycarbonate resin composition of the present invention can be processed by various known processing methods such as injection molding, extrusion molding, blow molding, and thermoforming, but since it exhibits the excellent rigidity that is a characteristic of the composition of the present invention, It is desirable for the thermoplastic liquid crystal resin to be blended into the molded product to be stretched and oriented in the molded product. High-speed injection molding with an injection speed of 50 cm/sec or higher is preferable, but if the wall thickness of the main part is 2.
Particularly desirable is a thin-walled molded product of 1 mm or less.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.

Examples 1 to 5 and Comparative Examples 1 to 4 As aromatic polycarbonate resin, viscosity average molecular weight 2
Using 2ooo bisphenol A polycarbonate resin (Tubalex 7022A manufactured by Mitsubishi Kasei ■), as a thermoplastic liquid crystal resin, N0VAccURAT manufactured by Mitsubishi Kasei (II) was used.
E Using E-322, a resin composition consisting of both of them and a commercially available aromatic epoxy resin were blended at each composition shown in Table 1 below, and each was heated to a resin temperature of 260 to 290.
The mixture was melt-mixed in a vent-type extruder with a screw diameter of 40 mm within a temperature range of 0.degree. C. to obtain each pellet. After drying each pellet thus obtained in a circulating hot air dryer at 120°C for 5 hours, using an injection molding machine with a mold clamping pressure of 75 tons, the resin temperature was 2.
Each test piece was created within the range of 80 to 300°C.

For each test piece obtained in this way, the following (1) to (6)
), bending strength, bending elastic modulus, weld part tensile strength, (2) ZOd impact strength, folding durability, fluidity, and appearance were evaluated. The evaluation results are shown in Table 2 below.

(1) Bending strength and bending modulus Length 5'' Width 1/2'' Thickness 1/16'' and 1/8°
0 (2) Tensile strength of weld part Conducted according to ASTM D-638 using a dumbbell-shaped test piece with gates on both ends and a weld formed in the center .

(3) Izod impact strength Tested according to ASTM D-256 using a test piece with a thickness of 1/2 Pa.

Folding Durability Tests were carried out in accordance with ASTM D-643 using test pieces with a length of 5 inches, a width of 1/2 degrees, and a thickness of 1/32 degrees.

Fluidity Length 5 Pa Width x/z" Thickness 1/16°' and l/8°
The mold containing the two types of test pieces was heated to a resin temperature of 2.
Injection molding was carried out at 90°C, and fluidity was measured by the resin pressure required at that time.

The presence or absence of jetting occurring at the gate portion of a test piece having an external length of 5 mm, width of 1/2° and thickness of 1/32°, and the presence or absence of a peeling phenomenon were visually observed.

〔Effect of the invention〕

As is clear from the above results, especially from the results shown in Table 2, the polycarbonate resin composition of the present invention can be improved particularly in thin-walled areas by blending a small amount of aromatic epoxy resin as an essential third component. It has high rigidity, high weld strength, high impact strength and bending resistance, and in addition, it does not suffer from jetting or peeling, which is the problem with conventional products.
This has a remarkable effect of industrial value.

Claims (1)

[Claims] (1) 0.05 to 100 parts by weight of an aromatic epoxy resin to 100 parts by weight of a resin composition consisting of 95 to 60% by weight of an aromatic polycarbonate resin and 5 to 40% by weight of a thermoplastic liquid crystal resin.
A polycarbonate resin composition containing 5 parts by weight.