JP2766843B2 - Polycarbonate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molding resin composition. More specifically, the present invention 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 components, mechanical components, building materials, etc., and will continue to be widely used in fields where these properties are required. Expected.

[0003] Despite being excellent in strength and impact resistance, the conventionally developed polycarbonate resin is, as compared with 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 to the polycarbonate resin. To get.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, a resin composition comprising a polycarbonate resin and a specific polyetherimide resin is particularly effective for the above object. And completed the present invention. That is, the present invention relates to formula (1)
With respect to 100 parts by weight of an aromatic polycarbonate resin composed of a repeating unit represented by

Embedded image Formula (2)

Embedded image [ Wherein X is a direct _bond , a divalent chain hydrocarbon group represented by —C _n H _2n — (n = 1 to 10) , a hexafluorinated isopropylidene group, a carbonyl group, a sulfonyl group and a sulfide. Represents a group selected from the group consisting of groups, and the bonding position of the nitrogen atom of the imide ring is meta or para to the ether bond. An aromatic polycarbonate resin composition comprising a polyetherimide resin 1 part by weight or more than 100 parts by weight of the repeating unit represented by].

[0006] The polycarbonate resin used in the present invention is an aromatic polycarbonate resin comprising a repeating unit represented by the formula (1) (Formula 5) .

Embedded image

The polycarbonate resin used in the present invention is prepared by reacting a dioxydiaryl alkane with phosgene in the presence of an alkaline aqueous solution or an acid binder such as a tertiary amine and a solvent, a dioxydiaryl alkane and a carbonate diester. And transesterification, for example, Lexan (trademark of Engineering Plastics), Panlite (trademark of Teijin Chemicals),
It is commercially available as Iupilon (Mitsubishi Gas Chemical Trademark), NOVAREX (Mitsubishi Chemical Trademark), etc., and optionally manufactures a product having an appropriate melt viscosity characteristic for a target blend.
Or you can choose in the market.

In the present invention, the heat resistance of the polycarbonate resin,
The polyetherimide used in combination for the purpose of improving mechanical strength and solvent resistance is represented by the following formula (2)

[0009]

Embedded image

[Wherein X is a direct _bond and is represented by -C _n H _2n-
A divalent chain hydrocarbon group (n = 1 to 10) , a group selected from the group consisting of a hexafluorinated isopropylidene group, a carbonyl group, a sulfonyl group and a sulfide group. Is at the meta or para position with respect to the ether bond. ] In a polyetherimide resin repeating a unit represented, mechanical properties to the present inventors, have previously thermal properties, excellent and electrical properties, solvent resistance and transparency, and can be melt-molded (Japanese Patent Laid-Open No. 63-1280)
25) that is, as a tetracarboxylic dianhydride,
Formula (3)

[0011]

Embedded image

4,4 '-(p-phenylenedioxy) diphthalic dianhydride represented by the formula (4)
(Formula 8)

[0013]

Embedded image

Wherein X is a direct _bond and is represented by —C _n H _2n —
A divalent chain hydrocarbon group (n = 1 to 10) , a group selected from the group consisting of a hexafluorinated isopropylidene group, a carbonyl group, a sulfonyl group and a sulfide group. Is at the meta or para position with respect to the ether bond. A polyetherimide resin obtained by dehydrating and cyclizing a polyamic acid obtained by reacting with one or more ether diamines represented by the following formula:

The ether diamine used in this method includes bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4
-(3-aminophenoxy) phenyl] ethane, 1,2
-Bis [4- (4-aminophenoxy) phenyl] ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane , 2,2-bis [4- (3
-Aminophenoxy) phenyl] butane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane,
2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl]- 1,1,1,3,3,3-hexafluoropropane, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (3 -Aminophenoxy) phenyl]
Ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3 -Aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, etc., and these may be used alone or as a mixture of two or more.

The reaction method is not particularly limited, and a conventionally known method can be used without any restriction. Further, performing the reaction in the presence of a dicarboxylic anhydride and / or a monoamine in addition to the two components of the above-described tetracarboxylic dianhydride and ether diamine is effective for improving the moldability and heat resistance. It is a way.

The molding resin composition of the present invention is used in an amount of 1 part by weight or more and less than 100 parts by weight of the polyetherimide per 100 parts by weight of the polycarbonate.
In order to improve the physical properties of the polycarbonate, especially the heat resistance, the polyetherimide is effective in an amount of usually 1 part by weight, preferably 5 parts by weight or more based on 100 parts by weight of the polycarbonate.

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

In mixing and adjusting the composition according to the present invention, 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 using a mortar, Henschel mixer, drum blender, tumbler blender, ball mill ribbon blender, etc. to make a powder.

2. The polyetherimide powder is dissolved or suspended in an organic solvent in advance, and polycarbonate is added to the solution or suspension and uniformly dispersed. Then, the solvent is removed to obtain a powder.

3. The polycarbonate is suspended in an organic solvent solution of polyamic acid, which is a precursor of the polyetherimide of the present invention, and then heat-treated at 100 to 400 ° C or chemically imidized using a commonly used imidizing agent. After that, the solvent is removed to form a powder.

The powdery polycarbonate resin composition thus obtained is used for various molding applications as it is, such as injection molding, compression molding, transfer molding, and extrusion molding. This is the preferred method.

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

For the melt blending, a device used for melt-blending ordinary rubber or plastics, for example, a hot roll, a Banbury mixer, a Brabender, an extruder or the like can be used. The melting temperature is set to a temperature higher than the melting temperature of the compounding system and lower than the temperature at which the compounding system starts to thermally decompose.
° C, preferably 280-350 ° C.

The method for molding the resin composition of the present invention includes:
Injection molding or extrusion molding, which is a molding method that forms a homogeneous melt blend and has high productivity, is suitable, but other transfer molding, compression molding, sintering, and the like may be applied.

It is to be noted that 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. In addition, one or more reinforcing agents such as glass fiber, carbon fiber, aromatic polyamide fiber, potassium titanate fiber, and glass beads can be added.

The resin composition of the present invention may contain an antioxidant, a heat stabilizer and a heat stabilizer within a range not to impair the object of the present invention.
UV absorbers, flame retardants, flame retardant aids, antistatic agents, lubricants,
One or more conventional additives such as a coloring agent can be added.

[0029]

The present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples. Synthesis Example 1 4,4′-bis (3-aminophenoxy) was placed in a container equipped with a stirrer, a reflux condenser, a water separator, and a nitrogen inlet tube.
2.211 kg (6.0 mol) of biphenyl, 4,4'-
(P-phenylenedioxy) diphthalic dianhydride
111 kg (5.7 mol), 0.0888 phthalic anhydride
kg (0.6 mol), and 13.4 kg of cresylic acid
145 ° C. while stirring under a nitrogen atmosphere.
The temperature was increased until heating. During this time, distillation of about 200 cc of water was confirmed. The reaction was further performed at 145 ° C. for 4 hours. Thereafter, the mixture was cooled to room temperature, charged with about 7 kg of methyl ethyl ketone, and filtered to obtain a yellow polyimide powder. After washing this polyimide powder with methyl ethyl ketone,
And dried under reduced pressure for 24 hours to obtain 4.12 kg (97% yield) of polyimide powder. The logarithmic viscosity of this polyimide powder is 0.50 dl / g, the glass transition temperature is 201 ° C.,
Tc and Tm were not observed.

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

Next, the uniformly mixed pellets obtained above were injection-molded at a molding temperature of 300 to 320 ° C. and a mold temperature of 100 ° C. using a usual injection molding machine, and the physical and thermal properties of the molded product were measured.

The results are shown in Table 1 as Examples 1 to 3.
The tensile strength and elongation at break in the table are ASTM D-638,
The flexural strength and flexural modulus are based on ASTM D-790, and the thermal deformation temperature is based on ASTM D-648.

Comparative Example 1 The results of measuring the physical and thermal properties of the molded products obtained by the same operation as in Examples 1 to 3 using the composition outside the scope of the present invention are shown in Table 1. This is shown as Comparative Example 1.

[0034]

[Table 1]

SYNTHESIS EXAMPLES 2-5 Various polyimides were prepared in the same manner as in Synthesis Example 1 except that various diamines were used instead of 4,4'-bis (3-aminophenoxy) biphenyl in Synthesis Example 1. A powder was obtained. Table 2 shows the conditions for synthesizing the polyimide resin.

[0036]

[Table 2]

Examples 4 to 13 and Comparative Example 2 Using the polyetherimide powders obtained in Synthesis Examples 2 to 5,
Uniformly blended pellets were obtained in the same manner as in Examples 1 to 3, and then injection molded in the same manner, and the physical and thermal properties of the molded product were measured.

The results for compositions within the scope of the present invention are shown in Example 4.
Tables 3 to 13 also show compositions outside the range as Comparative Example 2.

It can be seen that as the polyimide content increases, the mechanical strength and the heat distortion temperature increase.

[0040]

[Table 3]

[0041]

[Table 4]

Example 14, Comparative Example 3 A 5 cm square, 3 mm thick sheet was prepared from the resin compositions of Example 3 and Comparative Example 1, and methylene chloride, chloroform,
They were immersed in carbon tetrachloride at room temperature and their dissolution rates were compared.
Table 4 shows the results.

[0043]

[Table 5]

[0044]

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

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Osamu Yasui 30 Asamuta-cho, Omuta-shi, Fukuoka Prefecture Inside Mitsui Toatsu Chemicals Co., Ltd. Examiner in the Company Tatsuya Ando (56) References JP-A-1-110530 (JP, A) JP-A-3-47837 (JP, A) JP-A-59-168030 (JP, A) Special Table Sho-60 501413 (JP, A)

Claims (1)

(57) [Claims] (1) a repeating unit represented by the formula (1) :
Per 100 parts by weight of the aromatic polycarbonate resin consisting of Formula (2) [ Wherein X is a direct _bond , a divalent chain hydrocarbon group represented by —C _n H _2n — (n = 1 to 10) , a hexafluorinated isopropylidene group, a carbonyl group, a sulfonyl group and a sulfide. Represents a group selected from the group consisting of groups, and the bonding position of the nitrogen atom of the imide ring is meta or para to the ether bond. ] Consisting polyetherimide resin 1 part by weight or more than 100 parts by weight of the repeating unit represented by the aromatic polycarbonate resin composition.