JPH05320492A - Polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition improved in mechanical strengths by mixing a polyether imide resin comprising repeating units of a specified formula with an aromatic polycarbonate resin in a specified ratio. CONSTITUTION:An ether diamine of formula III is reacted with at least one tetracarboxylic acid dianhydride of formula IV, and the obtained polyamic acid is imidized to obtain a polyether imide having a main chain comprising repeating units of formula I (wherein R is a tetravalent group selected from among a 2C or higher aliphatic group, a cycloaliphatic group, a monocyclic aromatic group, a fused polycyclic aromatic group and a nonfused polycyclic aromatic group). 1-100 pts.wt. powdery aromatic polycarbonate comprising repeating units of formula II (wherein Y is a direct bond, a 1-10 C bivalent hydrocarbon group, a hexafluoroisopropylidene group, a carbonyl group, a sulfonyl group or a thio group; and R1 to R4 are each H, lower alkyl, lower alkoxyl, chloro or bromo) in a mixer or the like, and the obtained mixture is pelletized to obtain a polycarbonate resin composition.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a molding resin composition. More specifically, it relates to a polycarbonate resin composition having improved heat resistance, chemical resistance, mechanical strength and the like.

[0002]

2. Description of the Related Art Polycarbonate resin has excellent strength,
It has impact resistance, transparency, etc., and is widely used as an engineering resin in the manufacture of electrical parts, mechanical parts, building materials, etc., and will continue to be widely used in fields where these characteristics are required. Is expected.

However, even though it has excellent strength and impact resistance, the conventionally developed polycarbonate resin has the following advantages over heat resistant engineering plastics such as polyphenylene sulfide, polyether sulfone and polysulfone resin.
It is still inferior in mechanical strength and heat resistance. Also,
It is soluble in halogenated hydrocarbons and is not a satisfactory resin in terms of solvent resistance.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polycarbonate resin composition having improved heat resistance, chemical resistance, mechanical strength, etc. in addition to the excellent transparency and impact resistance inherent in polycarbonate resin. To get.

[0005]

Means for Solving the Problems As a result of intensive studies for achieving the above object, the present inventors have found that a resin composition comprising a polycarbonate resin and a specific polyetherimide resin is particularly effective for the above object. Therefore, the present invention has been completed. That is, the present invention is based on the formula (1)

[0006]

[Chemical 4]

[In the formula, R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group, either directly or by a crosslinking member. It represents a tetravalent group selected from the group consisting of linked non-fused polycyclic aromatic groups. ] An aromatic polycarbonate resin composition comprising 1 part by weight or more and less than 100 parts by weight of a polyetherimide resin having a repeating skeleton as a basic skeleton.

The polycarbonate resin used in the present invention has the general formula (2)

[0009]

[Chemical 5]

[Wherein Y is selected from the group consisting of a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a sulfonyl group, an ether group and a thio group. And R _{1 to} R ₄ represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine or bromine, and may be the same or different. ] A resin comprising a repeating unit of the above, wherein dioxydiarylalkanes and phosgene are reacted in the presence of an alkaline aqueous solution or an acid binder such as a tertiary amine and a solvent, and dioxydiarylalkanes and carbonic acid diesters. And transesterification of, for example, Lexan (trademark of Engineering Plastics Co., Ltd.), Panlite (Teijin Kasei Trademark), Iupilon (Mitsubishi Gas Chemical Trademark), Novalex (Mitsubishi Kasei Trademark)
And the like, and those having appropriate melt viscosity characteristics for the intended blend can be arbitrarily produced or can be selected on the market.

In the present invention, the heat resistance of the polycarbonate resin,
Polyetherimide used together for the purpose of improving mechanical strength and solvent resistance is represented by the following formula (1)

[0012]

[Chemical 6]

[In the formula, R represents an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group, either directly or by a crosslinking member. It represents a tetravalent group selected from the group consisting of linked non-fused polycyclic aromatic groups. ] A polyether imide resin comprising a repeating unit of the present invention, the present inventors have excellent mechanical properties, thermal properties, electrical properties, solvent resistance, transparency, etc., and a melt-moldable polyether It was found as an imide resin (Japanese Patent Laid-Open No. 63-243132, etc.), and as a diamine, it has the formula (4)

[0014]

[Chemical 7]

An ether diamine represented by the following formula: bis [4- {3- (4-aminophenoxy) benzoyl} phenyl] ether is used, and this is reacted with one or more tetracarboxylic dianhydrides. It is obtained by imidizing the obtained polyamic acid. The tetracarboxylic dianhydride used at this time is represented by the formula (5)

[0016]

[Chemical 8]

A tetracarboxylic dianhydride represented by the formula: wherein R is the same as above. That is, as the tetracarboxylic dianhydride used, ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ' , 4,4'-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3'-benzophenone tetracarboxylic dianhydride, 3,3'4,4'-biphenyltetracarboxylic dianhydride, 2 , 2 ', 3, 3'-
Biphenyl tetracarboxylic dianhydride, bis (3,4-
Dicarboxyphenyl) ether dianhydride, bis (3,3
4-dicarboxyphenyl) sulfone dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride,
1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxy) Phenyl) propane dianhydride, 4,4 '-(p-
Phenylenedioxy) diphthalic acid dianhydride, 4,4'-
(M-phenylenedioxy) diphthalic dianhydride, 2,
3,6,7-naphthalenetetracarboxylic dianhydride,
1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3, 4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, and the like. The tetracarboxylic dianhydride may be used alone or in combination of two or more.

The polyimide represented by the formula (1) used in the method of the present invention is obtained by reacting the diamine represented by the formula (2) with the tetracarboxylic dianhydride represented by the formula (3) as described above. can get. The reaction method is not particularly limited,
A conventionally known method can be used without restriction. Further, in addition to the above-mentioned two components of tetracarboxylic dianhydride and etherdiamine, it is effective to improve the moldability and heat resistance by reacting with dicarboxylic acid anhydride and / or monoamine. That's the method.

The molding resin composition of the present invention is used in the range of 1 part by weight or more and less than 100 parts by weight of the above polyether imide with respect to 100 parts by weight of the polycarbonate.
In order to improve the physical properties of polycarbonate, especially heat resistance, polyether imide is effective at 1 part by weight, preferably 5 parts by weight or more per 100 parts by weight of polycarbonate.

The polyetherimide used in the present invention is a thermoplastic resin that can be melt-molded, but its melt viscosity is at a higher level than that of the polycarbonate resin. Therefore, if 100 parts by weight or more is used, the moldability of the polycarbonate is lost, so it is preferable to use it in an amount less than 100 parts by weight.

When the composition according to the present invention is mixed and adjusted, it can be produced by a generally known method. For example, the following method is a preferable method. 1. The polyetherimide powder and the polycarbonate powder are pre-kneaded into a powder using a mortar, a Henschel mixer, a drum blender, a tumbler blender, a ball mill ribbon blender and the like. 2. The polyetherimide powder is dissolved or suspended in an organic solvent in advance, and polycarbonate is added to this solution or suspension to uniformly disperse it, and then the solvent is removed to obtain a powder. 3. Polycarbonate is suspended in an organic solvent solution of polyamic acid, which is a precursor of the polyetherimide of the present invention, and then heated at 100 to 400 ° C., or chemically imidized using a commonly used imidizing agent. After that, the solvent is removed to obtain a powder.

The powdery polycarbonate resin composition thus obtained is directly used for various molding applications, such as injection molding, compression molding, transfer molding, extrusion molding, etc., but it is further used after melt blending. This is the preferred method.

In particular, in mixing and preparing the composition, it is a simple and effective method to mix powders, mix pellets, or mix powders and pellets.

The melt blending can utilize equipment normally used for melt blending rubbers or plastics, such as hot rolls, Banbury mixers, Brabenders, extruders and the like. The melting temperature is set above the melting temperature of the compounding system and below the temperature at which the compounding system begins to thermally decompose, but the temperature is usually 280 to 420.
C., preferably 280 to 350.degree.

The molding method of the resin composition of the present invention includes:
Injection molding or extrusion molding, which is a molding method capable of forming a homogeneous melt blend and having high productivity, is suitable, but transfer molding, compression molding, sinter molding or the like may be applied.

One or more solid lubricants such as molybdenum disulfide, graphite, boron nitride, lead monoxide and lead powder can be added to the resin composition of the present invention. Further, one or more reinforcing agents such as glass fiber, carbon fiber, aromatic polyamide fiber, potassium titanate fiber and glass beads can be added.

With respect to the resin composition of the present invention, an antioxidant, a heat stabilizer,
UV absorber, flame retardant, flame retardant aid, antistatic agent, lubricant,
One or more conventional additives such as colorants can be added.

[0028]

EXAMPLES The present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples. Synthesis Example 1 Bis [4- {3- (4-aminophenoxy)] was placed in a container equipped with a stirrer, a reflux condenser, a water separator, and a nitrogen inlet tube.
Benzoyl} phenyl] ether 5.92 kg (10.
0 mol), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride 2.84 kg (9.65 mol), phthalic anhydride 0.1037 kg (0.7 mol), and cresylic acid 35.4 kg. Was charged, and the temperature was raised to 145 ° C. with stirring under a nitrogen atmosphere. 145 ° C
The reaction was carried out for 4 hours. After that, cool to room temperature, about 4
After charging 0 kg of methyl ethyl ketone, it was filtered off to obtain a yellow polyimide powder. This polyimide powder was washed with methyl ethyl ketone and then dried under reduced pressure at 180 ° C. for 24 hours to obtain 8.08 kg (yield 96%) of polyimide powder. The polyimide powder had an inherent viscosity of 0.51 dl / g, a glass transition temperature of 196 ° C., and Tc and Tm were not observed.

Examples 1 to 4 The polyimide powder obtained in Synthesis Example 1 and the polycarbonate powder (Panlite L-1225, a trademark of Teijin Kasei Co., Ltd.) were dry blended with various compositions as shown in Table 1, and then the compression ratio was 3 An extruder having a diameter of 40 mm equipped with a screw of 0.0 / 1 (processing temperature of 280 to 300 ° C.) was extruded while being melt-kneaded to obtain uniform blended pellets.

Next, the homogeneously blended pellets obtained above were subjected to injection molding in a usual injection molding machine at a molding temperature of 300 to 320 ° C. and a mold temperature of 100 ° C., and the physical and thermal properties of the molded product were measured. The results are shown in Table 1 as Examples 1 to 4.
In the table, tensile strength and breaking elongation are ASTM D-638,
The flexural strength and flexural modulus are according to ASTM D-790, and the heat distortion temperature is according to ASTM D-648.

Comparative Example 1 Using the composition outside the scope of the present invention, the physical and thermal properties of the moldings obtained by the same procedure as in Examples 1 to 4 were measured, and the results are shown in Table 1. This is shown as Comparative Example 1.

[0032]

[Table 1]

Synthesis Example 2 In place of 2.84 kg of 3,3 ', 4,4'-biphenyltetralbonic acid dianhydride in Synthesis Example 1, 3,3',
The logarithmic viscosity was 0.50 dl / in the same manner as in Synthesis Example 1 except that the reaction was carried out using 3.1 kg (9.65 mol) of 4,4′-benzophenonetetracarboxylic dianhydride.
A polyimide powder having a glass transition temperature of 197 ° C. was obtained.

Synthesis Example 3 In place of 2.84 kg of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride in Synthesis Example 1, 4,4'
-(P-Phenylenedioxy) diphthalic acid dianhydride 3.
A polyimide powder having a logarithmic viscosity of 0.58 dl / g and a glass transition temperature of 171 ° C. was obtained in the same manner as in Synthesis Example 1 except that the reaction was performed using 86 kg (9.6 mol).

Examples 5-10 and Comparative Example 2 Using the polyetherimide powders obtained in Synthesis Examples 2-3,
Uniformly blended pellets were obtained in the same manner as in Examples 1 to 4, and then injection-molded in the same manner, and the physical and thermal properties of the molded product were measured. Results of compositions within the scope of the present invention are shown in Examples 5-10.
Table 2 also shows the composition outside the range as Comparative Example 2.

[0036]

[Table 2]

Example 11, Comparative Example 3 A sheet of 5 cm square and 3 mm thick was made from the resin compositions of Example 4 and Comparative Example 1, and methylene chloride, chloroform, and
The samples were immersed in carbon tetrachloride at room temperature and their dissolution rates were compared.
The results are shown in Table 3.

[0038]

[Table 3]

[0039]

As is apparent from the examples, addition of the polyetherimide resin improves the mechanical strength, heat resistance and solvent resistance of the polycarbonate resin composition.

Claims (3)

[Claims] 1. A compound of the formula (1) (Chemical Formula 1) with respect to 100 parts by weight of the aromatic polycarbonate resin. [In the formula, R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group,
Represents a tetravalent group selected from the group consisting of a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a bridging member. .. ] An aromatic polycarbonate resin composition comprising 1 part by weight or more and less than 100 parts by weight of a polyetherimide resin having a repeating skeleton as a basic skeleton. 2. The aromatic polycarbonate resin has the formula (2) [In the formula, Y is a group selected from the group consisting of a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a sulfonyl group, an ether group and a thio group. In the formula, R _{1 to} R ₄ represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine or bromine, and may be the same as or different from each other. ] The polycarbonate resin composition of Claim 1 which consists of a repeating unit. 3. The aromatic polycarbonate resin has the formula (3) (Chemical Formula 3): The polycarbonate resin composition according to claim 1, which comprises a repeating unit of