JP2795500B2 - Polycarbonate resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polycarbonate resin and an unsaturated carboxylic acid-modified cyclic olefin-based random copolymer resin (hereinafter, referred to as “resin”).
It may be abbreviated as a modified cyclic olefin resin. More specifically, a polycarbonate resin composition having excellent heat resistance, scratch resistance, and chemical resistance, and having low water absorption, thickness dependency of impact strength, small notch sensitivity, and high mechanical strength. About things.

TECHNICAL BACKGROUND OF THE INVENTION Polycarbonate resins have been used in a wide variety of applications because of their excellent heat resistance, excellent impact resistance of thin-walled molded products, and low molding shrinkage. However, the conventional polycarbonate resin has the following problems.

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

ii) It has a high melt viscosity, easily sticks to a mold, and has poor moldability.

iii) Cracks (stress cracks) tend to occur under constant stress, especially under constant stress in a chemical atmosphere.

iv) Insufficient chemical resistance.

v) When molded in a state of being easily absorbed by moisture and insufficiently dried, it is hydrolyzed and deteriorates in physical properties.

Therefore, in order to solve the above problems i) and ii),
Although a styrene-based resin is blended with a polycarbonate resin, heat resistance is lowered and chemical resistance is also insufficient.
On the other hand, when a conventionally known crystalline polyolefin is blended, chemical resistance and hygroscopicity are improved, but there is a problem that heat resistance and molding shrinkage deteriorate.

By the way, it is known that a cyclic olefin having an ethylenic double bond in the ring has polymerizability, for example, it can be copolymerized with ethylene to obtain a cyclic olefin / ethylene copolymer. 60-168708, JP
63-243111, JP-A-63-305111, JP-A-63
-223013, JP-A-1-185307).

Such a cyclic olefin-based resin has transparency, water resistance and thermal properties required as an optical material, but as a result of further studies by the present inventors, such a cyclic olefin-based resin has By introducing a structural unit derived from an unsaturated carboxylic acid or a derivative thereof and blending the obtained unsaturated carboxylic acid-modified cyclic olefin-based resin (modified cycloolefin resin) with a polycarbonate resin,
It has been found that a polycarbonate resin composition having more excellent properties that can be used for various applications can be obtained.

Object of the invention The present invention is excellent in heat resistance, scratch resistance, chemical resistance, and water absorption, thickness dependency of impact strength and notch sensitivity are small, while maintaining excellent properties of polycarbonate resin,
It is intended to provide a polycarbonate resin composition having high mechanical strength.

The polycarbonate resin composition according to the present invention is a copolymer of a polycarbonate resin [A], ethylene and a cyclic olefin represented by a structural formula selected from the following formulas [I] to [IV]. A cyclic olefin random copolymer (hereinafter sometimes abbreviated as an unmodified cyclic olefin copolymer) is an unsaturated carboxylic acid-modified cycloolefin random copolymer modified with an unsaturated carboxylic acid or a carboxylic acid derivative thereof. The polycarbonate resin [A] and the unsaturated carboxylic acid-modified cyclic olefin-based random copolymer resin [B], which comprises a combined resin [B] (modified cycloolefin resin [B]).
Is 98/2 to 2/98 as [A] / [B] (weight ratio).
It is characterized by being.

(In the formula [I], 1 is 0 or a positive integer, and R ^{1 to} R
¹⁸ may be the same or different, and each is a hydrogen atom, an atom or a group selected from the group consisting of a halogen atom and a hydrocarbon group, and R ^{15 to} R ¹⁸ are bonded to each other to form a single ring or A polycyclic ring may be formed, and the monocyclic or polycyclic ring may have a double bond, and an alkylidene group may be formed by R ¹⁵ and R ¹⁶ or R ¹⁷ and R ^18. May be formed).

(In the formula [II], m is 0 or a positive integer, and R ^{1 to} R
¹⁰ may be the same or different, and each is an atom or group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ⁹ and R ¹⁰ form an alkylidene group; Good).

(In the formula [III], n is 0 or a positive integer, and R ^{1 to} R
¹² may be the same or different, each is an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ¹¹ and R ¹² form an alkylidene group; Good).

(In the formula [IV], p is 0 or an integer of 1 or more, q and r are 0, 1 or 2, and R ^{1 to} R ¹⁵ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon. Represents an atom or group from the group consisting of a group, an aromatic hydrocarbon group, and an alkoxy group, wherein R ⁵ (or R ⁶ ) and R ⁹ (or R ⁷ )
And may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be directly bonded without any group. The polycarbonate resin composition according to the present invention contains a polycarbonate resin [A] and a specific unsaturated carboxylic acid-modified cycloolefin-based random copolymer resin [B] (modified cycloolefin resin [B]). It has excellent properties such as excellent water resistance, scratch resistance and chemical resistance, small dependency on water absorption and impact strength, low notch sensitivity, and high mechanical strength.

Moreover, by blending such modified cyclic olefin resin [B], polycarbonate resin [A]
The excellent properties of are not impaired.

Next, the polycarbonate resin composition according to the present invention will be specifically described.

The polycarbonate resin composition according to the present invention is a cyclic olefin which is a copolymer of a polycarbonate resin [A], ethylene, and a cyclic olefin represented by a structural formula selected from the above formulas [I] to [IV]. Carboxylic acid-modified random olefin copolymer resin [B] (modified cycloolefin resin) in which a system random copolymer (unmodified cyclic olefin copolymer) is modified with an unsaturated carboxylic acid or a carboxylic acid derivative thereof. [B]).

The polycarbonate resin [A] constituting the polycarbonate resin composition of the present invention is a polycarbonate resin having a repeating unit having a structure represented by the following general formula.

[Wherein, s is a positive integer, and R ¹⁹ represents a divalent aliphatic group or an aromatic group. As such a polycarbonate resin, for example, R ¹⁹ of the general formula [i] is bisphenol A, bisphenol F, 1,1-bis (4-hydroxyphenyl) ethane,
4'-dihydroxyphenyl ether, 1,1-bis (4-
Hydroxyphenyl) cyclohexane, 1,1-bis (4
-Hydroxyphenyl) -1-phenylmethane, 4,4 '
-Dihydroxyphenyl sulfone, tetrabromobisphenol A, dihydroxynaphthalene, hydroquinone,
Polydioxydiphenyl-2,2-propane carbonate, polydioxydiphenylmethane carbonate, polydioxydiphenyl-1,1-ethane carbonate, polydioxydiphenyl ether carbonate, polydioxydiphenyl- which is a dihydric phenol residue such as resorcinol
1,1-cyclohexane carbonate, polydioxydiphenyl-1-phenylmethane carbonate, polyoxydiphenylsulfone carbonate, polydioxydiphenyl-2,2-tetrabromopropane carbonate, polydihydroxynaphthalene carbonate, polydihydroxyparaphenylcarbonate, polydihydroxymeta Aromatic polycarbonates such as phenyl carbonate; R ¹⁹ is ethylene glycol, propylene glycol,
Aliphatic polycarbonates such as polyethylene carbonate, polypropylene carbonate, polycyclohexane carbonate and polynorbornene carbonate which are dihydric alcohol residues such as dihydroxycyclohexane and dihydroxynorbornene; polycarbonates which are aromatic-aliphatic random or block copolymers; Among them, polyester polycarbonate containing the above-mentioned polycarbonate structure and polyester structure can be mentioned.

These polycarbonate resins can be used alone or in combination of two or more.

The melt flow rate of the above polycarbonate resin [A] at 290 ° C. and a load of 2.16 kg is 0.05 to 200 g / 10 min, preferably 0.1 to 100 g / 10 min.

The intrinsic viscosity [η] of the polycarbonate resin [A] measured in decalin at 20 ° C. is in the range of 0.05 to 5 dl / g, preferably 0.1 to 1 dl / g.

The glass transition temperature (Tg) of the polycarbonate resin [A] is desirably in the range of 50 to 250 ° C, preferably 100 to 200 ° C.

Next, the unsaturated carboxylic acid-modified cyclic olefin-based random copolymer resin [B] (modified cyclic olefin resin [B]) constituting the polycarbonate resin composition of the present invention will be described.

The unsaturated carboxylic acid-modified cyclic olefin-based random copolymer resin [B] (modified cyclic olefin resin [B]) constituting the polycarbonate resin composition of the present invention is a structural unit (a) derived from an ethylene component. And a structural unit (c) derived from an unsaturated carboxylic acid or its carboxylic acid derivative.

The cyclic olefin is at least one of the formulas [I] to [I
V] is a cyclic olefin represented by one of the structural formulas selected from the group consisting of

However, in the above formula [I], 1 is 0 or a positive integer, preferably 0 to 3. In the above formula [II], m is 0 or a positive integer, preferably 0 to 3
It is. In the above formula [III], n is 0 or a positive integer, preferably 0 to 3.

Then, R ^{1 to} R ¹⁸ (formula [I]), R ^{1 to} R ¹⁰ (formula [I
I]), R ^{1 to} R ¹² (formula [III] or R ^{1 to} R ¹⁵ (formula [IV])
May be the same or different, and are atoms or groups selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Further, as the hydrocarbon group, each independently has a normal carbon number of 1 to 10
Alkyl group, a cycloalkyl group having 5 to 15 carbon atoms, and specific examples of the alkyl group include
Methyl group, ethyl group, isopropyl group, isobutyl group,
n-amino group, neopentyl group, n-hexyl group, n-
Examples thereof include an octyl group, an n-decyl group, and a 2-ethylhexyl group. Specific examples of the cycloalkyl group include a cyclohexyl group, a methylcyclohexyl group, and an ethylcyclohexyl group.

In the above formula [I], R ¹⁵ and R ¹⁶ or
R ¹⁷ and R ¹⁸ may form an alkylidene group, and in the above formula [II], R ⁹ and R ¹⁰ may form an alkylidene group, and in the above formula [III], R ¹¹ And R ¹²
And may form an alkylidene group. Such an alkylidene group can usually include an alkylidene group having 3 to 10 carbon atoms, and specific examples thereof include:
Examples include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, and an isobutylidene group.

In the above formula [IV], R ⁵ (or R ⁶ ) and R 5
⁹ (or R ⁷ ) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be directly bonded without any group.

 Further, p in the formula [IV] is 0 or an integer of 1 or more, and is preferably an integer of 0 to 3.

Further, in the above formula [I], R ^{15 to} R ¹⁸ may be bonded to each other (together) to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may form a double bond. You may have.

The cyclic olefins represented by the formulas [I] to [IV] include:
The cyclopentadiene can be easily produced by condensing the corresponding olefin or cyclic olefin by a Diels-Alder reaction.

Specific examples of the cyclic olefins represented by the formulas [I] to [IV] include, for example, Tetracyclo such [4,4,0,1 ^2.5, 1 ^7.10] -3-dodecene derivatives; Pentacyclo such [4,7,0,1 ^2.5, 0 ^8.13, 1 ^9.12] -3
Pentadecene derivatives; Heptacyclo [7,8,0,1 ^3.6 , O ^2.7 , 1 ^10.17 , O ^11.16 ,
1 ^12.15 ] -4-Eicosene derivative; Nonacyclo [9,10,1,1 ^4.7 , 0 ^3.8 , 0 ^2.10 , 0 ^12.21 , 1
^13.20, 0 ^14.19, may be mentioned 1 ^15.18] -5-pentacosene derivatives.

And furthermore, Can be mentioned.

The weight ratio of the structural unit derived from the unsaturated carboxylic acid or its carboxylic acid derivative in the unsaturated carboxylic acid-modified cyclic olefin-based random copolymer resin [B] forming the resin composition according to the present invention is usually 0.001 to 5 weight%,
Preferably it is in the range of 0.01 to 3% by weight.

Modified cyclic olefin resin [B] used in the present invention
May be entirely modified with an unsaturated carboxylic acid or the like, or may be a modified cyclic olefin resin partially modified. Here, the partially modified resin includes a resin prepared by mixing a modified resin and an unmodified resin.

Examples of the structural unit (c) derived from the unsaturated carboxylic acid or a derivative thereof contained in the modified cyclic olefin resin [B] include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and citraconic acid. Acid, undecylenic acid, maleic anhydride, tetrahydrophthalic acid, isocrotonic acid, nadic acid (endosis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid), citraconic anhydride, nadic anhydride And the like. Structural units derived from unsaturated carboxylic acids such as the above or derivatives thereof such as acid anhydrides. The structural units (c) derived from these unsaturated carboxylic acids or derivatives thereof can be used alone or in combination.

In the unsaturated carboxylic acid-modified cyclic olefin-based random copolymer resin [B] constituting the resin composition according to the present invention, the composition of the constituent units excluding the unsaturated carboxylic acid is as follows:
It is desirable that the structural unit (a) derived from ethylene is contained in the range of 40 to 85 mol%, preferably 50 to 75 mol%. It is desirable that the structural unit (b) derived from a cyclic olefin is contained in a range of 15 to 60 mol%, preferably 25 to 50 mol%.

The intrinsic viscosity [η] of the modified cyclic olefin resin [B] constituting the resin composition according to the present invention measured in decalin at 135 ° C. is usually 0.05 to 10 dl / g, preferably 0.08 to 5 dl / g.
Range.

Further, as the modified cyclic olefin resin [B] constituting the resin composition according to the present invention, the softening temperature (TMA) measured with a thermomechanical analyzer is usually 70 ° C. or higher,
The temperature is preferably in the range of 90 to 250 ° C, more preferably 100 to 200 ° C.

The glass transition temperature (Tg) of the modified cyclic olefin resin [B] constituting the resin composition according to the present invention is usually 50 to 23.
It is desirably in the range of 0 ° C, preferably 70 to 210 ° C.

The crystallinity of the modified cyclic olefin resin [B] constituting the resin composition according to the present invention determined by X-ray diffraction analysis is usually 0 to 10%, preferably 0 to 7%, particularly preferably 0 to 0%. Desirably, it is within 5%.

The modified cyclic olefin resin [B] comprises a structural unit (a) derived from ethylene, a structural unit (b) derived from the cyclic olefin, and a structural unit (c) derived from an unsaturated carboxylic acid or a derivative thereof as essential structural units. However, in addition to these essential constitutional units, other copolymerizable constitutional units derived from unsaturated monomers may be contained as necessary within a range not to impair the object of the present invention. Specific examples of the unsaturated monomer which may be added and copolymerized as necessary include propylene, 1-butene, 4-
Methyl-1-pentene, 1-hexene, 1-octene,
Examples thereof include α-olefins having 3 to 20 carbon atoms, such as 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. The structural unit derived from these unsaturated monomers may be contained in an amount less than equimolar to the structural unit (a) derived from ethylene in the produced random copolymer.

Further, in the present invention, the above unsaturated carboxylic acid-modified cyclic olefin-based random copolymer [B]
May contain a cyclic olefin unit other than the cyclic olefins represented by the above formulas [I] to [IV] as long as the physical properties of the obtained polymer and the like are not impaired. Examples of such a cyclic olefin include cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclohexene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, 2,3,3a, 7a-tetrahydro-4 , 7-methano-1H-indene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene and the like; Bicyclo [2,2,1] hept-2-ene derivatives such as and the like; Tetracyclo such [4,4,0,1 ^2.5, 1 ^7.10] -3-dodecene derivatives; Hexacyclo such as [6,6,1,1 ^3.6, 1 ^10.13, 0 ^2.7 0 ^9.14]
-4-heptadecene derivatives; Octacyclo [8,8,0,1 ^2.9 , 1 ^4.7 , 1 ^11.18 , 1 ^13.16 ,
0 ^3.8 , 0 ^12.17 ] -5-docosene derivative; Pentacyclo such as [6,6,1,1 ^3.6, 0 ^2.7 0 ^9.14] -4
Hexadecene derivatives; A heptacyclo-5-icosene derivative or a heptacyclo-5-heneicosene derivative; Tricyclo [4,3,0,1 ^2.5] -3-decene derivatives such as; Tricyclo [4,4,0,1 ^2.5] -3-undecene derivatives such as; Pentacyclo such as [6,5,1,1 ^3.6, 0 ^2.7 0 ^9.13] -4
Pentacene derivatives and the like can be mentioned.

Such other cyclic olefins can be used alone or in combination.
Used in amounts.

As the modified cyclic olefin resin [B] constituting the polycarbonate resin composition according to the present invention, a graft copolymer obtained by graft-polymerizing the unsaturated carboxylic acid or a derivative thereof to an unmodified cyclic olefin copolymer by a known method is used. In addition to the polymer, for example, a random copolymer of ethylene with a cyclic olefin represented by one of the structural formulas selected from the formulas [I] to [IV] and an unsaturated carboxylic acid or a carboxylic acid derivative thereof Combination or the like can also be used.

If the modified cyclic olefin resin [B] is a graft copolymer obtained by subjecting the above unsaturated carboxylic acid or its derivative to gluft polymerization with an unmodified cyclic olefin copolymer, JP-A-62-27412 discloses It can be manufactured according to the method disclosed in the gazette. Specifically, for example, using an unsaturated carboxylic acid or a derivative thereof as a graft monomer, dissolving an unmodified cyclic olefin copolymer,
A method of dissolving an unmodified cyclic olefin copolymer in a solvent, a method of adding a graft monomer and performing graft copolymerization, a method of dissolving an unmodified cyclic olefin copolymer in a solvent, and a method of dissolving a graft in an unmodified cyclic olefin copolymer in a solvent It can be produced by a method in which a monomer is added, mixed well, and an unmodified cyclic olefin copolymer and a graft monomer are graft-copolymerized.

Such graft copolymerization is usually performed at a temperature of 60 to 350 ° C., preferably 80 to 300 ° C., and in order to efficiently graft copolymerize the graft monomer, the reaction is performed in the presence of a radical initiator. Is preferred. Examples of the radical initiator include organic peroxides, organic peresters, and other azo compounds. In particular, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) ) Hexin-3,
Preferred are dialkyl oxides such as 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropylbenzene).

In the polycarbonate resin composition of the present invention, the composition ratio between the polycarbonate resin component [A] and the unsaturated carboxylic acid-modified cyclic olefin-based random copolymer resin [B] (modified cycloolefin resin [B]) is [A]. component/
[B] component (weight ratio): 98/2 to 2/98, preferably 95/5
~ 5/95.

In addition to the components [A] and [B], the polycarbonate resin composition of the present invention may further contain a rubber component for improving impact strength, a heat stabilizer, a weather stabilizer,
Antistatic agents, slip agents, antiblocking agents, antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes and the like can be blended, and the blending ratio is an appropriate amount.
For example, as a stabilizer to be blended as an optional component, specifically, tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, β- (3,5-di- tert-butyl-4-hydroxyphenyl) propionic acid alkyl ester, a funol-based antioxidant such as 2,2'-oxamidobis [ethyl-3 (3,5-di-tert-butyl-4-hydroxyphenyl)] propionate, Fatty acid metal salts such as zinc stearate, calcium stearate, calcium 12-hydroxystearate, glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate Polyhydric alcohol fats etc. Acid esters and the like can be mentioned. These may be blended alone or in combination. For example, tetrakis [methylene-3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane and zinc stearate may be used. Examples thereof include a combination with glycerin monostearate.

In the present invention, it is particularly preferable to use a combination of a phenolic antioxidant and a fatty acid ester of a polyhydric alcohol.
It is preferable that the polyhydric alcohol is a polyhydric alcohol fatty acid ester in which a part of the alcoholic hydroxyl group of the polyhydric alcohol having a valency or higher is esterified.

As the fatty acid ester of such a polyhydric alcohol, specifically, glycerin monostearate, glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin distearate, glycerin fatty acid esters such as glycerin dilaurate, Pentaerythritol monostearate, pentaerythritol monolaurate, pentaerythritol dilaurate, pentaerythritol distearate,
Fatty acid esters of pentaerythritol such as pentaerythritol tristearate are used.

Such a phenolic antioxidant is used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 3 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the polycarbonate resin composition. The fatty acid ester of the polyhydric alcohol is used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the composition.

In the polycarbonate resin composition of the present invention, 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 flake, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide , Boron fiber, silicon carbide fiber,
Fillers such as polyethylene fibers, polypropylene fibers, polyester fibers, and polyamide fibers may be blended.

As a method for producing the polycarbonate resin composition according to the present invention, a known method can be applied, and a polycarbonate resin component [A] and an unsaturated carboxylic acid-modified cycloolefin-based random copolymer resin [B] (modified cycloolefin resin); And a method of mechanically blending other components to be added as required with an extruder, a kneader or the like, or each component is a suitable good solvent, for example, hexane, heptane,
A method of simultaneously dissolving in a hydrocarbon solvent such as decane, siloxane, benzene, toluene, xylene, or the like, separately dissolving and then mixing and removing the solvent, and a method of combining these two methods, and the like. Can be.

The polycarbonate resin composition obtained by the above method has a lower water absorption, a higher chemical resistance, and a substantially amorphous unsaturated carboxylic acid modification than the polycarbonate resin component [A]. Since the cyclic olefin resin [B] is blended, it has excellent heat resistance, scratch resistance, chemical resistance, moldability, thickness dependency of water absorption, impact strength and notch sensitivity while maintaining various properties of the polycarbonate resin. Is obtained.

Since the polycarbonate resin composition according to the present invention has the above-mentioned various properties, in addition to the use of the conventional polycarbonate resin, heat resistance, scratch resistance, chemical resistance, low water absorption, high impact strength and the like are required. Can be widely used in the field.

Examples of applications include power tools, OA equipment, cameras, pumps and other housings, chassis, precision equipment parts, instrument panels, radiator grills, cluster grills, console boxes, garnishes, wheel covers, column covers, Automotive interior and exterior materials such as fenders, bonnets and trunks, seats, cases such as connectors, coil bobbins and switches, covers, bottles, cast films, biaxially stretched films, films such as multilayer films, extruded foams, injection foaming Foams, such as a body, are mentioned.

Effect of the Invention As described above, according to the present invention, the [A] polycarbonate resin component is blended with the [B] modified cyclic olefin resin, so that the [A] component and the [B] component have good compatibility and are heat resistant. A polycarbonate resin composition having excellent water resistance, scratch resistance, chemical resistance, and moldability, and having small water absorption, thickness dependency of impact strength, and small notch sensitivity can be obtained.

[Examples] Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited to these Examples.

The methods for measuring and evaluating various physical properties in the present invention are described below.

(1) Melt flow index (MFR _T ) Measured at a predetermined temperature T ° C. and a load of 2.16 kg according to ASTM D1238.

(2) Preparation of Test Specimen Using an injection molding machine IS-50EPN manufactured by Toshiba Machine Co., Ltd. and a predetermined test specimen mold, molding was performed under the following molding conditions. The test pieces were left for 48 hours at room temperature after molding and then measured.

Molding conditions: cylinder temperature 220 ° C, mold temperature 60 ° C, injection pressure primary / secondary = 1000 / 800kg / cm ² injection speed (primary) 30mm / s
ec, screw rotation speed 150 rpm, (3) Bending test The bending test was performed according to ASTM D790.

Specimen shape: 5 x 1/2 x 1/8 ^t inches, distance between spans 51 mm Test speed: 20 mm / min Test temperature: 23 ° C (4) Tensile test The tensile test was performed according to ASTM D638.

(5) Heat distortion temperature (HDT) This was performed according to ASTM D628.

Specimen shape: 5 × 1/4 × 1/2 t inch Load: 264 psi (6) Softening temperature (TMA) Measured by thermal deformation behavior of a 1 mm thick sheet using a Thermo Mechanical Analyzer manufactured by DuPont. That is, put a quartz needle on the sheet, apply a load of 49 g, and apply 5 ° C /
The temperature rises at the speed of min, and the temperature at which the needle enters
TMA.

(7) Glass transition temperature (Tg) and melting point (Tm) (DSC
Method) Temperature rise rate using DSC-20 manufactured by SEIKO Electronics Co., Ltd.
Measured in ° C / min.

(8) Rockwell hardness Measured at 23 ° C. according to ASTM D785.

(9) Pencil hardness Measured at 23 ° C. according to JIS K 5400.

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

(11) Izod impact test was carried out according to ASTM D256.

Test piece mold shape: 5/2 × 1/8 × 1/2 ^t inch (with notch) Test temperature: 23 ° C. (12) Compatibility Judgment was made based on the appearance of the injection-molded bending test piece and the state of the fracture surface.

：: Both appearance and fracture surface were uniform.

Δ: The flow was slightly uneven in appearance, and the fracture surface was slightly non-uniform.

X: There was a skin layer, and the fracture surface was peeled off in a layered manner.

Example 1 A maleic anhydride-modified resin, which is an unsaturated carboxylic acid-modified cyclic olefin-based resin [B], was prepared by the following method.

Ethylene content measured by ¹³ C-NMR is 63 mol%, MFR
Ethylene with intrinsic viscosity [η] of 0.48 dl / g, TMA of 150 ° C and Tg of 140 ° C (Tm not observed) measured at _{260 ° C} in 32g / 10min, 135 ° C decalin, and 1,4,5, 8-Dimethano-1,2,3,4,4
a, 4b, 5,8,8a, 9a Maleic anhydride dissolved in 25 g of acetone in 5 kg of pellets of a random copolymer (ethylene / DMDF random copolymer) with decahydrofluorene (hereinafter abbreviated as DMDF) 5 g, 0.3 g of organic peroxide (Nippon Oil & Fats Co., Ltd., Perhexin 25B, trademark) are added and mixed well, and then melted at a cylinder temperature of 250 ° C. with a twin-screw extruder (PCM45, manufactured by Ikegi Tekko Co., Ltd.). The lower reaction was performed and pelletized with a pelletizer. The resulting maleic anhydride-modified resin has a maleic anhydride content of 0.07% by weight (as an acid anhydride group content).
0.05% by weight).

Next, 2.0 kg of pellets of a polycarbonate resin (trade name, Iupilon S-2000, manufactured by Mitsubishi Gas Chemical Co., Ltd.) are used as the component (A), and 2.0 kg of the maleic anhydride-modified resin pellets are sufficiently used as the component (B). After mixing, use a twin-screw extruder (PCM45, manufactured by Ikegu Iron Works Co., Ltd.) to adjust the cylinder temperature to 2
The mixture was melt-blended at 80 ° C. and pelletized with a pelletizer.

A test piece was prepared from the obtained pellets by the method described above, and the physical properties were evaluated. Table 1 shows the results.

Examples 2 and 3 The same operation was performed as in Example 1 except that the amounts of the components [A] and [B] were changed.

 Table 1 shows the results.

Comparative Example 1 Iupilone S-20 used as component [A] in Example 1
Molding was performed in the same manner as in Example 1 using only 00, and physical properties were evaluated.

 Table 1 shows the results.

Comparative Example 2 The same operation as in Example 1 was performed, except that the ethylene / DMDF random copolymer before modification with maleic anhydride was used as the component [B].

 Table 1 shows the results.

Example 4 Instead of the maleic anhydride-modified resin used in Example 1,
Ethylene / DMDF random copolymer (ethylene content: 63m
ol%, MFR _{260 ° C} : 32 g / 10 min, intrinsic viscosity [η] measured in decalin at 135 ° C: 0.48 dl / g, TMA: 150 ° C, Tg: 140 ° C (Tm
No ethylene oxide / propylene random copolymer (ethylene content: 80 mol%, MFR _{230 ° C} : 0.7%)
g / 10min, intrinsic viscosity [η] measured in decalin at 135 ° C:
A resin prepared by melt blending 20 parts by weight of 2.2 dl / g, Tg: -54 ° C.) with a twin-screw extruder (PCM45, manufactured by Ikegu Iron Works Co., Ltd.) and modified with maleic anhydride in the same manner as in Example 1 ( Maleic anhydride content is 0.08% by weight (as acid anhydride content
0.06% by weight)) was used in place of the component [B] in Example 1, and the same operation as in Example 1 was performed.

 Table 1 shows the results.

Example 5 Here, an example is shown in which a mixture of a modified cyclic olefin copolymer and an unmodified cyclic olefin copolymer is used, and three components are simultaneously melt-blended in the presence of a polycarbonate resin.

A maleic anhydride-modified resin, which is an unsaturated carboxylic acid-modified cyclic olefin-based random copolymer, was prepared by the following method.

Ethylene content measured by ¹³ C-NMR is 63 mol%, MFR
Random copolymerization of ethylene and DMDF with intrinsic viscosity [η] of 0.48 dl / g, TMA of 150 ° C, Tg of 140 ° C (Tm not observed) measured in decalin at 135 ° C and 32g / 10min at _{260 ° C} Maleic anhydride dissolved in 25 g of acetone in 5 kg of coalesced pellets
50 g, organic peroxide (manufactured by NOF CORPORATION, perhexin 2)
After adding 3 g of 5B (trademark) and mixing well, the mixture was melted at a cylinder temperature of 250 ° C. with a twin-screw extruder (PCM45, manufactured by Ikegai Iron Works Co., Ltd.) and pelletized with a pelletizer. The resulting maleic anhydride-modified resin had a maleic anhydride content of 0.8% by weight.

[A] Pellets of polycarbonate resin (Iupilon S-2000, trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a component
2.0 kg, as component [B], ethylene content measured by ¹³ C-NMR is 63 mol%, MFR _{260 ° C.} is 32 g / 10 min, intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.48 dl / g, TMA Is 150
℃, Tg 140 ℃ unmodified ethylene and DMON (1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene) random copolymer After thoroughly mixing 1.6 kg of the above-mentioned pellets and 0.4 kg of the above-mentioned maleic anhydride-modified random copolymer of ethylene and DMDF, the cylinder temperature was adjusted using a twin-screw extruder (PCM45, manufactured by Ikegai Iron Works Co., Ltd.). The mixture was melt-blended at 280 ° C. and pelletized with a pelletizer.

A test was prepared using the obtained pellets by the method described above, and the physical properties were evaluated.

 Table 1 shows the results.

Examples 6 to 8 A maleic anhydride-modified cyclic olefin copolymer was prepared in the same manner as in Example 1 except that the ethylene / DMDF copolymer used in Example 1 was replaced with a copolymer of ethylene and another cyclic olefin. A coalescence was prepared and used as the component [B]. Table 2 shows the physical properties of the obtained [B]. The same operation as in Example 1 was performed, except that the component [B] was used.

 Table 1 shows the results.

From the above results, the polycarbonate resin composition of the present invention in which the components [A] and [B] are blended has a higher heat denaturation temperature and a higher water absorption than the conventional polycarbonate resin which is the component [A]. It turns out that it is small. Further, it is found that the compatibility is better and the Izod impact strength is higher than that of a polycarbonate resin composition using a cyclic olefin copolymer containing no unsaturated carboxylic acid as the component [B].

Continuation of the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C08L 23/00-23/36 C08L 69/00 C08L 45/00 C08F 8/46 C08F 32/00-32/08 C08F 232 / 00-232/08

Claims (3)

(57) [Claims] 1. A polycarbonate resin [A] and a cyclic olefin random copolymer which is a copolymer of ethylene and a cyclic olefin represented by a structural formula selected from the following formulas [I] to [IV]: An unsaturated carboxylic acid-modified cyclic olefin-based random copolymer resin [B] modified with an unsaturated carboxylic acid or a carboxylic acid derivative thereof, wherein the polycarbonate resin [A] and the unsaturated carboxylic acid-modified cycloolefin-based A polycarbonate resin composition characterized by having a composition ratio of [A] / [B] (weight ratio) of 98/2 to 2/98 with the random copolymer resin [B]. (In the formula [I], 1 is 0 or a positive integer, and R ^{1 to} R
¹⁸ may be the same or different, and each is a hydrogen atom, an atom or a group selected from the group consisting of a halogen atom and a hydrocarbon group, and R ^{15 to} R ¹⁸ are bonded to each other to form a single ring or A polycyclic ring may be formed, and the monocyclic or polycyclic ring may have a double bond, and an alkylidene group may be formed by R ^{15 to} R ¹⁶ or R ¹⁷ and R ^18. May be formed). (In the formula [II], m is 0 or a positive integer, and R ^{1 to} R
¹⁰ may be the same or different, each is an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ⁹ and R ¹⁰ form an alkylidene group; Good). (In the formula [III], n is 0 or a positive integer, and R ^{1 to} R
¹² may be the same or different, each is an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ¹¹ and R ¹² form an alkylidene group; Good). (In the formula [IV], p is 0 or an integer of 1 or more, q and r are 0, 1 or 2, and R ^{1 to} R ¹⁵ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon. Represents an atom or group from the group consisting of a group, an aromatic hydrocarbon group, and an alkoxy group, wherein R ⁵ (or R ⁶ ) and R ⁹ (or R ⁷ )
And may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be directly bonded without any group. ) 2. The unsaturated carboxylic acid-modified cyclic olefin-based random copolymer resin [B], wherein a weight ratio of a structural unit derived from an unsaturated carboxylic acid or a derivative thereof is 0.001 to 5% by weight. Claim 1
Item 10. The polycarbonate resin composition according to item 1. 3. The intrinsic viscosity [η] of the unsaturated carboxylic acid-modified cyclic olefin-based random copolymer resin [B] measured in decalin at 135 ° C. is 0.005 to 10 dl / g. The polycarbonate resin composition according to claim 1.