JPH0247143A - Polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To improve moldability, chemical resistance and heat resistance and to decrease water absorption, thickness dependence of impact strength and notch sensitivity while retaining the characteristics of a polycarbonate resin by compounding a polycarbonate resin with a specified cyclic olefin random copolymer. CONSTITUTION:2-98wt.% polycarbonate resin (A) is compounded with 2-98wt.% cyclic olefin random copolymer (B) consisting of an ethylene component and a cyclic olefin component of formula I or II (wherein n and m are each 0 or a positive integer; l is an integer of 3 or larger; R<1>-R<10> are each a hydrogen atom, a halogen atom or a hydrocarbon group), having an intrinsic viscosity [eta]measured in decalin at 135 deg.C of 0.05-10dl/g and a softening temp. (measured by TMA) of 70 deg.C or higher. In the component B, it is pref. that the ethylene component is 50-75mol% and the cyclic olefin component is 25-50mol%.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a polycarbonate resin composition that has excellent moldability and chemical resistance, and has low water absorption, low thickness dependence of impact strength, and low notch sensitivity. .

[Conventional technology]

Polycarbonate resin has excellent heat resistance and impact resistance for thin-walled molded products, and has a low mold shrinkage rate, so it is used for commercial purposes. However, there are the following problems.

i) Thickness dependence of impact strength and notch sensitivity are large.

i) It has a high melt viscosity and tends to stick to the mold, resulting in poor moldability.

i) Cracks (stress cracks) are likely to occur under constant stress, particularly under constant stress in a chemical atmosphere.

■) Chemical resistance is insufficient.

It easily absorbs moisture, and if molded without sufficient drying, it will hydrolyze and cause a decline in physical properties.

Therefore, in order to solve the problems 1) and ii) above,
Although styrene resin is blended, the heat resistance is reduced and the chemical resistance is insufficient. On the other hand, when conventionally known crystalline polyolefins are blended, chemical resistance and moisture absorption are improved, but there is a problem that heat resistance and molding shrinkage rate are deteriorated.

[Problem to be solved by the invention]

The purpose of the present invention is to solve the above problems while maintaining the properties of polycarbonate resin, improving moldability, chemical resistance,
The object of the present invention is to obtain a polycarbonate resin composition which has excellent heat resistance, and has low thickness dependence of water absorption and impact strength, and low notch sensitivity.

[Means to solve the problem]

[A] Polycarbonate resin 2 to 98% by weight
and CB) ethylene component and the following - format [1) or (I
Consisting of a cyclic olefin component represented by I), 135
Intrinsic viscosity [η] measured in decalin at ℃ is 0.05~
10d12/g and 2 to 98% by weight of a cyclic olefin random copolymer having a softening temperature (TMA) of 70°C or higher.

General formula [where n and m are both 0 or a positive integer, Q is an integer of 3 or more, and R1 to RIQ each represent a hydrogen atom, a halogen atom, or a hydrocarbon group.

] The polycarbonate resin (A) constituting the polycarbonate resin composition of the present invention is a polycarbonate resin having a repeating unit represented by the following format [111].

H○-R11-○Ch (m)
II p [In the formula, p is a positive integer, and Hll represents a divalent aliphatic group or an aromatic group. ] Such polycarbonate resins include, for example, -format (Ill) in which R11 is bisphenol A, bisphenol F, 1,1-bis(4-hydroxyphenyl)ethane, 4,4'-dihydroxyphenyl ether,
1.1-bis(4-hydroxyphenyl)cyclohexane, 1゜l-bis(4-hydroxyphenyl)-1-phenylmethane, 4,4'-dihydroxyphenylsulfone, tetrabromobisphenol A, dihydroxynaphthalene, hydroquinone, resorcinol Dihydric phenol residues such as polydioxydiphenyl-2,2-propane carbonate, polydioxydiphenylmethane carbonate, polydioxydiphenyl-I, 1-ethane carbonate, polydioxydiphenyl ether carbonate, polydioxydiphenyl-1゜1-cyclohexane Fragrances such as carbonate, polydioxydiphenyl-1-phenylmethane carbonate, polyoxydiphenylsulfone carbonate, polydioxydiphenyl-2,2-tetrabromopropane carbonate, polydihydroxynaphthalene carbonate, polydihydroxyvaraphenyl carbonate, polydihydroxymethaphenyl carbonate, etc. Group polycarbonate; R11 is ethylene glycol, propylene glycol,
Aliphatic polycarbonates such as polyethylene carbonate, polypropylene carbonate, polycyclohexene carbonate, and polynorbornene carbonate which are dihydric alcohol residues such as dihydroxycyclohexane and dihydroxynorbornene; Polycarbonates which are aromatic-aliphatic random or block copolymers; Molecules Examples include polyester polycarbonate containing the above-mentioned polycarbonate structure and polyester structure.

These polycarbonate resins are used alone.

Alternatively, two or more types can be used in combination.

The cyclic olefin random copolymer (B) is a cyclic olefin random copolymer composed of an ethylene component and a specific cyclic olefin component. The above-mentioned cyclic olefin component is a cyclic olefin represented by the above-mentioned -formation [■] or general formula (If), and in the cyclic olefin-based random 5 copolymer CB) of the present invention, the following -
It forms a repeating unit of the structure represented by formation [IV) or - formation [■].

[In the formula, n, m-Ω and R1 to HfF4 are the same as above. ] The cyclic olefin as a component of the cyclic olefin random copolymer (B) constituting the resin composition of the present invention is selected from the group consisting of unsaturated monomers represented by -formation (1) and CII). and at least one cyclic olefin.

The cyclic olefin represented by the general formula [I] is prepared by combining cyclopentadiene and the corresponding olefin with the Diels method.
It can be easily produced by condensation by Alder reaction. Furthermore, the cyclic olefin represented by -formation [11] can also be easily produced by condensing cyclopentadiene and the corresponding cyclic olefin by the Diels-Alder reaction.

- Specifically, the cyclic olefin represented by formation (1) is a compound listed in Table 1, or 1 is 1°4.5.
8-dimethano-1,2,3,4,4a,5,8,8a-
In addition to octahydronaphthalene, 2-methyl-1,4,
5,8-dimethano-1,2,3,4,4a,5,8,8
a-octahydronaphthalene, 2-ethyl-1,4,5
,8-dimethano-lt 2 v 3 * 4 + 4
a * 5 t 8 v 8 a -Octahydronaphthalene, 2-propyl-1,4,5,8-dimethano-1
,2,3,4,4a,5,8,8a-octahydronaphthalene,2-hexyl-1,4,5,8-dimethanol-1
,2,3,4゜4a,5,8,8a-octahydronaphthalene,2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a -octahydronaphthalene, 2-methyl-3-ethyl-1,4,5,8
-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-chloro-1,4,5,8-
Dimethano-1g2t3,4Aa*5.8,8a-octahydronaphthalene, 2-bromo-1,4゜5.8-dimethano-1,2,3,4t4a,5,8,8a-octahydronaphthalene, 2- Fluoro-1,4,5,8-dimethano-1,2゜3.4,4a,5,8,8a-octahydronaphthalene, 2.3-dichloro-1,4,5,8-
Dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-cyclohexyl-1,4,5
゜8-dimethano-1,2,3,4,4a,5,8,8a
-octahydronaphthalene, 2-n-butyl-1,4,
5,8-dimethano-1,2,3゜4.4a, 5,8,8
a-octahydronaphthalene, 2-inbutyl-1,4
,5,8-dimethano-1,2,3,4,4a,5,8,
Examples include octahydronaphthalenes such as 8a-octahydronaphthalene, and the compounds listed in Table 2.

Furthermore, specific examples of the cyclic olefin represented by -formation (ff) include the compounds shown in Tables 3 and 4.

The cyclic olefin random copolymer CB] constituting the resin composition of the present invention has an ethylene component and the above-mentioned cyclic olefin component as essential components, but in addition to these two essential components, the object of the present invention If necessary, other copolymerizable unsaturated monomer components may be contained within a range that does not impair the properties.

Specifically, the optionally copolymerized unsaturated monomers include, for example, propylene, 1-butene, and 4-methyl-1 in an amount less than equimolar to the ethylene component unit in the random copolymer to be produced. - Examples include α-olefins having 3 to 20 carbon atoms such as pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. be able to.

In the cyclic olefin random copolymer (B) constituting the resin composition of the present invention, the repeating unit (a) derived from the ethylene component is 40 to 85 mol%, preferably 50
The repeating unit (b) derived from the cyclic olefin component is in the range of 15 to 60 mol%.

Preferably, a range of 25 to 50 mol% is appropriate, and the repeating unit (a) derived from the engineered ethylene component and the repeating unit (b) derived from the cyclic olefin component are randomly arranged substantially linear cyclic olefin random units. Forms a copolymer. That the cyclic olefin random copolymer (B) is substantially linear and does not have a gel-like crosslinked structure can be confirmed by completely dissolving the copolymer in decalin at 135°C.

The intrinsic viscosity [η] of the cyclic olefin random copolymer CB) constituting the resin composition of the present invention measured in decalin at 135°C is 0.05 to 1 (1/g, preferably 0.
It is in the range of 08 to 5 dll/g.

The cyclic olefin random copolymer [8] constituting the resin composition of the present invention has a softening temperature (TMA) of 70°C or higher, preferably 90 to 250°C, more preferably 90 to 250°C, as measured by a thermomechanical analyzer. 100
-200°C, the glass transition temperature (Tg) of the cyclic olefin random copolymer CB) is usually 50-230°C
, preferably in the range of 70 to 210°C.

Further, the crystallinity of the cyclic olefin random copolymer (83) measured by X-ray diffraction is preferably in the range of 0 to 10%, preferably 0 to 7%, particularly preferably 0 to 5%.

As the cyclic olefin copolymer (Bl) constituting the resin composition of the present invention, a copolymer consisting only of those having physical properties within the above range may be used, but a copolymer having physical properties outside the above range may be used. may be partially included, and in this case, it is sufficient that the overall physical property value is within the above range.

The cyclic olefin random copolymer CB) constituting the resin composition of the present invention is disclosed in JP-A-60-168708, JP-A-61-120816, and JP-A-61-11.
5912, JP 61-115916, JP 61-271308, JP 61-2722
It can be produced by appropriately selecting conditions according to the method proposed by the present applicant in JP-A No. 16, JP-A No. 62-252406, JP-A No. 62-252407, etc.

In the polycarbonate resin composition of the present invention, (A)
The composition ratio of the component polycarbonate resin and the [B] acid component cyclic olefin random copolymer is [A] component/[
B] Acid component weight ratio) is 9872 to 2/98, preferably 9515 to 5/95.

In addition to the above components (A) and (B), the resin composition of the present invention also includes a heat stabilizer, a weather stabilizer, an antistatic agent, a slip agent, an antiblocking agent, an antifogging agent, a lubricant, a nucleating agent, and a dye. , pigments, natural oils, synthetic oils, waxes, and rubber components for improving impact strength can be blended in appropriate amounts. For example, specific stabilizers that may be added as optional ingredients include tetrakis[methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate comethane, β-(3,5-di-t-butyl-4-hydroxyphenyl), −
t-Butyl-4-hydroxyphenyl)propionic acid alkyl ester, 2,2'-oxamidobis[ethyl-
Phenolic antioxidants such as 3(3,5-di-t-butyl-4-hydroxyphenyl)propionate, fatty acid metal salts such as zinc stearate, calcium stearate, and calcium 12-hydroxystearate, glycerin monostearate, glycerin monolaurate,
glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate,
Examples include polyhydric alcohol fatty acid esters such as pentaerythritol tristearate. These may be blended alone or in combination,
For example, te, trakis C methylene-3 (3,5-di-t
A combination of -butyl-4-hydroxyphenyl)propionate comethane, zinc stearate and glycerin monostearate, etc. can be exemplified.

Furthermore, the resin composition of the present invention includes silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic Magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate.

Calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, poron fiber, silicon carbide fiber.

Fillers and reinforcing materials such as polyethylene fibers, polypropylene fibers, polyester fibers, and polyamide fibers may also be blended.

As a method for producing the polycarbonate resin composition according to the present invention, known methods can be applied, and polycarbonate resin [A
] and the cyclic olefin random copolymer [B], as well as other components added as necessary, are mechanically blended using an extruder, kneader, etc., or each component is dissolved in a suitable good solvent, or Examples include a method in which each is dissolved separately and then mixed to remove the solvent, and a method in which these two methods are combined.

The polycarbonate resin composition obtained as described above contains a polycarbonate resin (A) and a substantially non-grade cyclic olefin-based random copolymer [B] which has a lower water absorption than the polycarbonate resin and has excellent chemical resistance. Because of the blending process, while maintaining the various properties of polycarbonate resin,
Formability and chemical resistance.

A polycarbonate resin composition having excellent heat resistance and low thickness dependence of water absorption and impact strength and low notch sensitivity can be obtained.

Due to the above characteristics, the polycarbonate resin composition of the present invention can be used not only in applications where polycarbonate resins are used, but also in a wide range of fields where moldability, chemical resistance, low water absorption, high impact strength, etc. are required. Can be done.

〔Effect of the invention〕

As described above, according to the present invention, since the acid component [B] is blended with the component (A), it has excellent moldability, chemical resistance, and heat resistance, and has low water absorption, low thickness dependence of impact strength, and low notch sensitivity. A polycarbonate resin composition is obtained.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples. In addition,
The methods for measuring and evaluating various physical property values in the present invention are shown below.

(1) Melt flow index (MFR, go-e) ASTM
Measurement was conducted at a temperature of 260° C. and a load of 2.16 kg according to 01238.

(2) Preparation of test piece The test piece was molded under the following molding conditions using an injection molding machine 15-35 manufactured by Toshiba Machine Corporation and a specified mold for the test piece.

After molding, the test piece was left at room temperature for 48 hours and then subjected to measurement.

Molding conditions Nijilinda temperature 280°C, mold temperature 60°C,
Injection pressure car secondary/secondary = 1000/800kg/d,
Injection speed (-next) 30 mm/see, screw rotation speed 15 Orpm, cycle ((injection + holding pressure) / cooling) =
10/30 sec (3) Bending test It was conducted according to ASTM 0790.

Test piece shape: 5 x 1/2 x 1/8 inches, distance between spans 51 - Test speed: 20 am/a+in Test temperature: 23°C (4) Tensile test Conducted according to ASTM 063g.

Mold type for test piece■ Test speed: 50mm/win Test temperature: 23℃ (5) Heat distortion temperature (HDT) It was carried out according to ASTM 064g.

Test piece shape: 5X1/4X1/2 inch Load: 264
psi (6) Softening temperature (TMA) Thermo Mechanical A manufactured by DuPont
The thermal deformation behavior of a 1 mm thick sheet was measured using a nalyzer. That is, a quartz needle was placed on the sheet, a load of 49 g was applied, the temperature was raised at a rate of 5° C./min, and the temperature at which the needle penetrated 0.635 mm was defined as TMA.

(7) Rockwell hardness Measured at 23°C according to ASTM 0785.

(8) Pencil hardness It was measured at 23°C according to JIS K 5400.

(9) Water absorption The value after 24 hours was measured according to the JIS K 7209A method.

Example 1 A pellet 2 of polycarbonate resin (manufactured by Mitsubishi Gas Chemical Co., Ltd., Kneepilon S-2000, trade name) as the component (A)
．． 0kg, [B] Ethylene content measured by C-NMR as acid component fli2mol1%, MFR,...c 35
g/10IIIin, intrinsic viscosity [η) measured in decalin at 135°C 0.474/g, TMA 148°C ethylene and 1.4,5.8-dimethano-xt2t3+4t
After thoroughly mixing 2.0 kg of random copolymer pellets of 4at5.8,8a-octahydronaphthalene (structural formula (hereinafter referred to as DMON)), they were mixed using a twin-screw extruder (manufactured by Ikegai Tekko@, pcM 45). The mixture was melt-blended at a cylinder temperature of 280°C and pelletized using a pelletizer.

A test piece was prepared using the obtained pellet according to the method described above, and its physical properties were evaluated. The results are shown in Table 5.

Example 2.3 The same operation as in Example 1 was performed except that the amounts of component (A) and component [8] were changed. The results are shown in Table 5.

Nipiron S-20 used as the [A] acid component in Comparative Example Example 1
It was molded in the same manner as in Example 1 using only 00, and the physical properties were evaluated. The results are shown in Table 5.

From the above results, the polycarbonate resin composition of the present invention containing component (A) and component (Bl) has a lower water absorption rate than the polycarbonate resin that is component (A), and also contains component (B). It can be seen that the decrease in heat deformation temperature due to this is also small.

Claims (1)

[Claims] (1) [A] 2 to 98% by weight of polycarbonate resin;
[B] Ethylene component and the following general formula [I] or [
II], consisting of a cyclic olefin component represented by 135
Intrinsic viscosity [η] measured in decalin at ℃ is 0.05~
10 dl/g and 2 to 98% by weight of a cyclic olefin random copolymer having a softening temperature (TMA) of 70° C. or higher. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] [In the formula, n and m are both 0 or a positive integer, and l is 3 or more is an integer between R^1 and R^1^0
each represents a hydrogen atom, a halogen atom, or a hydrocarbon group. ]