JPH02233742A - Polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, containing a polycarbonate resin and modified cyclic olefin ring opening polymer in a specific proportion, excellent in moldability, chemical and heat resistance having small dependence of water absorptivity and impact strength on thickness with low notch sensitivity and a high mechanical strength. CONSTITUTION:The objective composition containing (A) a polycarbonate resin and (B) a modified cyclic olefin addition polymer, prepared by introducing (ii) and unsaturated carboxylic acid or derivative component thereof and having 0.05-10dl/g intrinsic viscosity [eta] in decalin at 135 deg.C into (i) an addition polymer consisting of a cyclic olefin component expressed by formulas I and/or II (n and m are 0 or integers; 1 is >=3; R<1> to R<10> are H, halogen or hydrocarbon) or ring opening polymer of the cyclic olefin component or a derivative thereof at (98/1)-(2/98) weight ratio.

Description

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

[Conventional technology]

Polycarbonate resin has excellent heat resistance, excellent impact resistance for thin-walled molded products, and low mold shrinkage, so it is used in a wide range of applications. However, there are the following problems.

1) 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 above problems i) and i), styrene resin is blended, but the heat resistance is reduced and the chemical resistance is also 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-mentioned 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 that has excellent heat resistance, low water absorption, low thickness dependence of impact strength, and low notch sensitivity, and high mechanical strength.

(Means for solving problems) The present invention is the following polycarbonate resin composition.

(1) (A) polycarbonate resin and [B] 135
Intrinsic viscosity [η] measured in decalin at ℃ is 0.05~
(a) A modified cyclic polymer in which an unsaturated carboxylic acid or a derivative component thereof is introduced into an addition polymer consisting of an ethylene component and a cyclic olefin component represented by the following general formula [I] and/or (II). Olefin addition polymer, or (b) the following general formula [! ] and a modified cyclic olefin ring-opening polymer in which an unsaturated carboxylic acid or a derivative component thereof is introduced into the ring-opening polymer of the cyclic olefin component represented by /r or (II) or its hydrogenated product. , the weight ratio of component (A)/component [B] is 987.
2 to 2798. [In the formula, n and m are both O or a positive integer, Q is an integer of 3 or more, and R1 to Hall each represent a hydrogen atom, a halogen atom, or a hydrocarbon group. ] The polycarbonate resin (Al is a polycarbonate resin having a repeating unit represented by the following general formula (ml) that constitutes the polycarbonate resin composition of the present invention. represents an aliphatic group or an aromatic group.] Examples of such polycarbonate resins include, for example, when 1<11 in general formula (III) 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-
Polydioxydiphenyl-2,2-propane carbonate, polydioxydiphenylmethane carbonate, which is a dihydric phenol residue such as phenylmethane, 4,4'-dihydroxyphenyl sulfone, tetrabromopisphenol A, dihydroxynaphthalene, hydroquinone, and resorcinol; Polydioxydiphenyl-1.1-ethane carbonate, polydioxydiphenyl ether carbonate, polydioxydiphenyl-1.1-cyclohexane carbonate, polydioxydiphenyl-l-phenylmethane carbonate, polyoxydiphenylene snorrefone carbonate , polydioxydiphenyl-2,2
- Aromatic polycarbonates such as tetrabromopropane carbonate, polydihydroxynaphthalene carbonate, polydihydroxyparaphenyl carbonate, and polydihydroxymethaphenyl carbonate; Aliphatic polycarbonates such as polyethylene carbonate, polypropylene carbonate, polystyrene hexene carbonate, and polynorbornene carbonate; polycarbonates that are aromatic-mono-aliphatic random or block copolymers; polycarbonates containing the above polycarbonate structure and polyester in the molecule Examples include polyester polycarbonate containing a structure. These polycarbonate resins can be used singly or in combination.
A mixture of two or more species can be used.

Component [B] used in the present invention may be either the modified cyclic olefin addition polymer (a) or the modified cyclic olefin ring-opening polymer (b).

Hereinafter, among component [B], the modified cyclic olefin addition polymer (a) will be explained first, and then the modified cyclic olefin ring-opening polymer (b) will be explained.

The cyclic olefin represented by the general formula [■] or (11) has a structure represented by the following general formula (IV) or (V) in the addition polymer constituting the modified cyclic olefin addition polymer (a). It mainly forms repeating units. General formula [where n. m. Q and RL to Pl1 are the same as above. ] The cyclic olefin constituting the modified cyclic olefin addition polymer (a) component in the present invention has the general formula [! ] and at least one cyclic olefin selected from the group consisting of unsaturated monomers represented by (n).

The cyclic olefin represented by the general formula (I) can be easily produced by condensing cyclopentadiene and a corresponding olefin by a Diels-Alder reaction. Similarly, the cyclic olefin represented by the general formula (n) can be easily produced by condensing cyclopentadiene and the corresponding cyclic olefin by Diels-Alder reaction.

Specifically, the cyclic olefin represented by the general formula (1) includes the compounds listed in Table 1, or l, 4, 5.8
-dimethano-1.2,3,4,4a,5,8.8a-octahyde-naphthalene as well as 2-methyl-1.4,5
．． 8-dimethano-1.2,3,4.4a,5,8,8a
-Octahyde naphthalene, 2-ethyl-1.4,5.
8-dimethano-1.2,3,4,4a,5,8,8a-
Octahyde naphthalene, 2-probyl-1.4,5.
8-dimethano-1,2,3,4,4a,5,8,8a-
Octahydride naphthalene, 2-hexyl-1.4,5.
8-dimethano-1.2,3,4,4a,5,8
, 8a-octahyde-naphthalene, 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-chloro1.4,5.8-dimethano-1.2,3.
4,4a,5,8,8a-octahyde naphthalene, 2
-bromo1.4,5,8-dimethano-1.2,3,4
．． 4a,5,8,8a-octahyde naphthalene, 2-
Fluoro-1,4,5,8-dimethano-1,2.3,4
,4a,5,8,8a-octahyde naphthalene,2,
3-dichloro1.4,5.8-dimethano-1.2,3
,4.4a,5,8,8a-octahyde naphthalene,
2-cyclohexyl-1.4,5.8-dimethano-1.
2,3,4,4a,5,8,8a-octahyde naphthalene, 2-n-butyl-1,4,5.8-dimethano-1
,2,3,4,4a,5,8,8a-octahyde-naphthalene,2-isobutyl-1,4,5.8-dimethano-
1.Octahide naphthalenes such as 2,3,4,4a,5,8,8a-octahydronaphthalene, and Table 2
Examples include the compounds described in . Further, specific examples of the cyclic olefin represented by the general formula (Il) include the compounds shown in Tables 3 and 4. The unsaturated carboxylic acid or its derivative component which is a constituent component of the modified cyclic olefin addition polymer (a) constituting the resin composition of the present invention is as follows. For example, acrylic acid, methacrylic acid, crotonic acid, fumaric acid, itaconic acid, citraconic acid, undecylenic acid,
Maleic anhydride, tetrahydrophthalic acid, isocrotonic acid, nadic acid (endocystic acid (2,2.1)
Examples include unsaturated carboxylic acids such as hept-5-ene-2,3-dicarboxylic acid), citraconic anhydride, nadic anhydride, and derivatives of these acid anhydrides.

The modified cyclic olefin addition polymer (a) constituting the citron fat composition of the present invention has an ethylene component, the cyclic olefin component, and the unsaturated carboxylic acid or its derivative component as essential components. In addition to the essential components, other unsaturated monomer components may be contained as necessary within a range that does not impair the object of the present invention. Specific examples of unsaturated monomers that may be optionally copolymerized include propylene, 1-butene, 4-methyl-1-
Pentene, l-hexene, l-octene, l-thecene,
1-Dodecene! -tetradecene, 1-hexadecene,
3-2 carbon atoms such as l-octadecene and 1-eicosene
0 α-olefin; cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene,
3-methylcyclohexene, 2-(2-methylbutyl)
-1-cyclohexene, styrene, α-methylstyrene, dicyclopentadiene, ethylidene norbornene,
Examples include 2,3,3a,7a-tetrahydride-4,7-methanol-18-indene and 3a,5,6,7a-tetrahydride-4,7-methanol-IN-indene. Those having a double bond in the molecule can also be used after being hydrogenated for the purpose of improving weather resistance and heat aging resistance.

In the modified cyclic olefin addition polymer (a) constituting the resin composition of the present invention, the ethylene component is 40 to 90 mol%, preferably 50 to 80 mol%, and the cyclic olefin component is 10 to 60 mol%, preferably 20 mol%. ~50 mol%, the unsaturated carboxylic acid or its derivative component is o. A suitable range is from ooi to 5% by weight, preferably from 0.05 to 2% by weight.

The intrinsic viscosity [η] of the modified cyclic olefin addition polymer (a) constituting the resin composition of the present invention is 0.05 to IOJI/g, preferably 0.05 to IOJI/g, as measured in decalin at 135°C.
It is in the range of 08 to 5d1/H.

Book. The modified cyclic olefin addition polymer (a) constituting the resin composition of the invention has a softening temperature (TMA) of 70°C or higher, preferably 90 to 250°C, more preferably 100 to 250°C, as measured by a thermomechanical analyzer. 2
00℃ range, glass transition temperature (Tg) is usually 50~2
Preferably, the temperature is 30 DEG C., preferably 70 DEG to 210 DEG C., and the crystallinity measured by XI@diffraction method is O-10%, preferably 0 to 7%, particularly preferably 0 to 5%.

The modified cyclic olefin addition polymer (a) constituting the resin composition of the present invention is prepared by first preparing ethylene and a cyclic olefin in a hydrocarbon medium in the presence of a catalyst formed from a hydrocarbon-soluble vanadium compound and a halogen-containing organoaluminum compound. It is common to produce an ethylene/cyclic olefin addition polymer by polymerizing the above, and then graft copolymerizing an unsaturated carboxylic acid or its derivative. It can also be introduced by polymerization.

The method for producing the above-mentioned ethylene/cyclic olefin addition polymer is already known, and is disclosed in JP-A-60-168708, JP-A-61-120816, and JP-A-61-11.
5912, JP 61-115916, JP 61-271308, JP 61-27
It can be produced by appropriately selecting conditions according to methods such as those disclosed in JP-A No. 2216, JP-A-62-252406, and JP-A-62-252407.

Further, in order to graft copolymerize an unsaturated carboxylic acid or its derivative component to an ethylene/cyclic olefin addition polymer, for example, melt the ethylene/cyclic olefin addition polymer using an unsaturated carboxylic acid or its derivative component as a graft monomer, A method of graft copolymerization by adding a graft monomer, or a method of dissolving an ethylene/cyclic olefin addition polymer in a solvent, and adding a graft monomer to perform graft copolymerization, or a method of adding a solvent to the ethylene/cyclic olefin addition polymer. It can be produced by adding a graft monomer dissolved in a polymer, mixing thoroughly, and graft copolymerizing. When carrying out such graft copolymerization, the reaction is usually carried out at a temperature of 60 to 350°C, and in order to efficiently graft copolymerize the graft monomer, it is preferable to carry out the reaction in the presence of a radical initiator. Examples of radical initiators include organic peroxides, organic bersesters, and other azo compounds. As the component [8] of the present invention, instead of the modified cyclic olefin addition polymer (a), the general formula [1] and /
Alternatively, a modified cyclic olefin ring-opening polymer (b) in which an unsaturated carboxylic acid or a derivative component thereof is introduced into the ring-opening polymer of the cyclic olefin component represented by (n) or its hydrogenated product may be used. Ring-opening polymers of cyclic olefin components are disclosed, for example, in JP-A-60-26024, and hydrogenated products of ring-opening polymers can be easily prepared by applying known hydrogenation methods. ．． As the unsaturated carboxylic acid or its derivative component which is a component of the modified cyclic olefin ring-opening polymer (b), the same ones as in the case of the modified cyclic olefin addition polymer (a) can be used.

In the modified cyclic olefin ring-opening polymer (b) constituting the resin composition of the present invention, the unsaturated carboxylic acid or its derivative component has a carboxyl group or its derivative group of 0.
A range of 0.001 to 5% by weight, preferably 0.05 to 2% by weight is suitable.

The intrinsic viscosity Cη] of the modified cyclic olefin ring-opening polymer (b) constituting the resin composition of the present invention measured in decalin at 135°C is 0.05 to 10 dl! /g. Preferably 0.
It is in the range of 08 to 5 dll/g. The modified cyclic olefin ring-opening polymer (b) 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. 100-20
0℃ range, glass transition temperature (Tg) is usually 50-23
0°C, preferably in the range of 70 to 210'C(7), and the crystallinity measured by X-ray diffraction is in the range of 0 to 10%, preferably in the range of 0 to 7%, particularly preferably in the range of 0 to 5%. Preferably, in the ring-opening polymer before hydrogenation of the hydrogenated product of the ring-opening polymer of the cyclic olefin component, the general formula (1
) or (II). The lefin component mainly forms repeating units having a structure represented by the following general formula (VI) or [■].

General formula [in the formula. n, m, ρ and R1 to JIIO are the same as above. ] The method for producing the modified cyclic olefin ring-opening polymer (b) includes ring-opening polymerization of monomers selected from the general formulas [I] and [■] above, and the resulting ring-opening polymer as it is.
Alternatively, after hydrogenation, a common method is to graft copolymerize an unsaturated carboxylic acid or its derivative component. The ring-opening polymer before hydrogenation is prepared by a conventional ring-opening polymerization method for cyclic olefins using a heptanomer component selected from the general formulas [I] and (113) and other monomer components to be polymerized as necessary. It can be manufactured.
Examples of other heptanomer components include cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene, dicyclopentadiene, ethylidene norbornene, 2,3 ,3a,7a-tetrahydride-4.7-methanol-1-indene,3a,
Examples include cyclic olefins such as 5,6,7a-tetrahydride-4,7-methanol-IH-indene. Examples of polymerization catalysts include ruthenium, rhodium, palladium, osmium, iridium, platinum,
Systems consisting of halides such as molybdenum and tungsten, nitrates or acetylacetone compounds and reducing agents such as alcohols and tin compounds, or titanium, vanadium,
A system consisting of a halogen compound such as zirconium, tungsten, or molybdenum, an acetylacetone compound, and an organic aluminum compound can be used.

The hydrogenated product of the ring-opened polymer of the cyclic olefin component is obtained by hydrogenating the ring-opened polymer obtained as described above. Hydrogenation of the ring-opened polymer is carried out by conventional hydrogenation methods.

As the hydrogenation catalyst, those used in the hydrogenation of olefin compounds can generally be used. Specifically, heterogeneous catalysts include nickel, palladium, platinum, etc., or solid catalysts in which these metals are supported on supports such as carbon, silica, diatomaceous earth, alumina, titanium oxide, etc., such as nickel/silica, Examples include nickel/diatomaceous earth, palladium/carbon, palladium/silica, palladium/diatomaceous earth, palladium/alumina, etc. Homogeneous catalysts include those based on metals from group Ⅰ of the periodic table, such as nickel naphthenate/triethylaluminum, cobalt octate/lobethyllithium, and nickel acetylacetonate/triethylaluminum. ．． Examples include those consisting of a Co compound and an organometallic compound of metals from groups ① to ② of the periodic table, or Rh compounds.

The hydrogenation reaction of the ring-opening polymer of the cyclic olefin component is 1
It is carried out at a temperature range of 0 to 180°C, preferably 20 to 100°C, under a hydrogen pressure of ~150 atmospheres. The hydrogenation rate is
Depends on water tooth pressure, reaction temperature, reaction time, catalyst concentration, etc.! I
However, in order to improve the weather resistance and heat aging resistance of the resin composition of the present invention, at least 50%, preferably at least 80%, and more preferably at least 90% of the main chain double bonds in the polymer. % or more is preferably hydrogenated. In order to graft copolymerize the unsaturated carboxylic acid or its derivative component to the ring-opened polymer of the cyclic olefin component obtained as described above or its hydrogenated product, in the case of the modified cyclic olefin addition polymer (a), It can be done in the same way.

In the polycarbonate resin composition of the present invention, (A)
The weight ratio of component and [B] component is 9872 to 2798 component (A) component/[8] component, preferably 95/component [8] component.
It is 5 to 5/95.

In addition to the components [A] and CB), the resin composition of the present invention may also contain unsaturated materials such as an ethylene-propylene random copolymer obtained by graft copolymerizing maleic anhydride to the extent that the object of the present invention is not impaired. Resins containing carboxylic acids or derivatives thereof, heat-resistant stabilizers, weather-resistant stabilizers, antistatic agents, slip agents, anti-blocking agents, antifogging agents, lubricants,
Nucleating agents, dyes, pigments, natural oils, synthetic oils, waxes, rubber components for improving impact strength, and the like can be blended in appropriate amounts. For example, specific examples of the stabilizer that may be added as an optional ingredient include tetrakis[methylene-3 (3.5-di-t-butyl-4
-Hydroxyphenyl)propionate]methane, β
-(3.5-di-t-butyl-4-hydroxyphenyl)propionic acid alkyl ester, 2,2'-oxamidobis[ethyl-3(3.5-di-t-butyl-4-hydroxyphenyl]propionate) and other phenolics Antioxidants, fatty acid metal salts such as zinc stearate, calcium stearate, calcium 12-hydroxystearate, glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol Examples include polyhydric alcohol fatty acid esters such as erythritol tristearate.These may be blended alone or in combination; for example, tetrakis[methylene-
3 (3.5-di-t-butyl-4-hydroxyphenyl)propionate] A combination of methane, 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, asbestos, glass fiber, glass flakes, glass beads, calcium silicate, montmori stomatite, bentonite, graphite, aluminum Fillers and reinforcing materials such as powder, molybdenum sulfide, boron fibers, silicon carbide fibers, 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. Components [A] and [B] and other components added as necessary are mechanically mixed using an extruder, seconder, etc. Examples include a method of blending, a method of dissolving each component in a suitable good solvent, a method of dissolving each component separately and then mixing and removing the solvent, and a method of combining these two methods. can.

The polycarbonate resin composition obtained as described above contains the polycarbonate resin [A] and the substantially non-grade component [8], which has a lower water absorption than the polycarbonate resin and has excellent chemical resistance. It is possible to obtain a polycarbonate resin composition that has excellent moldability, chemical resistance, and heat resistance, and has low thickness dependence of water absorption and impact strength, and low notch sensitivity while maintaining various properties.
Here, when the polycarbonate resin (A) component and the cyclic olefin polymer are blended, mechanical strength such as impact strength is low due to poor compatibility between the two, but instead of the cyclic olefin polymer, By blending a modified cyclic olefin addition polymer or a modified cyclic olefin ring-opening polymer [B], compatibility with the polycarbonate resin [A] can be improved, thereby increasing mechanical strength. ．． Due to the above-mentioned properties, the polycarbonate resin composition of the present invention can be widely used in fields where moldability, chemical resistance, low water absorption, high impact strength, etc. are required, in addition to applications where polycarbonate resins are used. Can be done. [Effects of the Invention] As described above, according to the present invention, component (A) and [8]
Because of the combination of ingredients, 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 with good compatibility between component A) and component (8) and high mechanical strength such as impact strength can be obtained. [Example] The present invention will be specifically explained below with reference to Examples. However, the present invention is not limited to these examples.
The methods for measuring and evaluating various physical property values in the present invention are shown below. (1) Melt flow index (MFR2G.,)^STM 01
238, t1 was determined at a temperature of 260°C and a load of 2.16kg. (2) Preparation of test piece Test pieces were molded under the following molding conditions using an injection molding machine IS-35 manufactured by Toshiba Machine ■ and a specified mold for test pieces. After molding, the test piece was left at room temperature for 48 hours and then subjected to measurement.

・Molding conditions: cylinder temperature 280℃, mold temperature 60℃,
Injection pressure primary/secondary = 1000/800kg/C!
J, injection speed (primary) 30 mm/sac, screw rotation speed 15 Orpm. Cycle ((injection + holding pressure)/cooling) = 10/30 seconds (3) Bending test Conducted according to ASTM 0790. Test piece shape: 5 x 1/2 x 1/8t inch,
Distance between spans: 51s+i* Test speed: 20 liters/in Test temperature: 23°C (4) Tensile test Conducted according to ASTM 0638. Test piece shape: Type ■ Test speed: 50m+i/I1in Test temperature: 23°C (5) Heat distortion temperature (HDT) Conducted according to ASTM D648.

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 sheet with a thickness of 1 serving was measured using a nalyzer. That is, a quartz needle was placed on the sheet, a load of 49 g was applied, and the temperature was raised at a rate of 5° C./n+in, and the temperature at which the needle penetrated 0.635101 was defined as TMA.

(7) Glass transition temperature (Tg) (DSC method) SIEI
Measurement was performed using KO Electronics Industry II DSC-20 at a temperature increase rate of 10'C/mjn.

(8) Logwell hardness Measured at 23°C according to ASTM 0785.

(9) Pencil hardness Measurement was performed at 23°C according to JTS K 5400.

(1O) Water absorption The value after 24 hours was measured according to JIS κ7209 A method. (1l) Izosotho impact test was conducted according to ASTM 0256.

Test piece shape. 5/2 x 1/8 x 1/2 inch (notched) Test temperature = 23°C (12) Compatibility Judgment was made based on the appearance of injection molded bending test pieces and the condition of the fractured surface.

0: Both appearance and fracture surface were uniform.

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

×: A skin layer was present, and the fractured surface was peeled off in layers.

Example 1 A maleic anhydride-modified resin, which is a modified cyclic olefin addition polymer (a), was prepared by the following method.

"Ethylene content measured by C-NMR is 62 mo
1%, MFR2sa-=35g/10min. 1
Intrinsic viscosity [η] measured in decalin at 35°C is 0.47
dΩ/g. TMA is 1. 4 8℃, Tg is 137℃
of ethylene and 1,4,5,8-dimethano-1,2,3,
4. Add acetone to 5 kg of pellets of random copolymer (ethylene/DMON copolymer) with 4a,5,8,8a-octahyde-natalene (structural formula [abbreviated as DMON]). anhydrous malein r dissolved in 25 g
! a5g. After adding 0.3 g of organic peroxide (manufactured by Nippon Oil & Fats Co., Ltd., Perhexine 25B, trademark) and thoroughly mixing, the reaction was carried out under melting at a cylinder temperature of 250°C using a twin screw extruder (manufactured by Ikegai Tekko Co., Ltd., PCM45). It was made into pellets using a pelletizer. The maleic anhydride content of the obtained maleic anhydride-modified resin was 0.07% by weight (0.05% by weight as acid anhydride group content).

2.0 kg of polycarbonate resin (manufactured by Mitsubishi Gas Chemical Co., Ltd., Iupilon S-2000, trade name) as component (A) and 2.0 kg of the above maleic anhydride modified resin as component [B] were thoroughly mixed. Thereafter, the mixture was melt-blended using a twin-screw extruder (manufactured by Ikegai Iron Works, PCM 45) at a cylinder temperature of 280° C., and pelletized using a pelletizer.

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

Examples 2 and 3 The same operations as in Example 1 were performed except that the blending amounts of component (A) and component [B] were changed. The results are shown in Table 5.

Comparative Example 1 Iupilon S-20 used as component (A) in 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.

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

The results are shown in Table 5.

Example 4 Instead of the maleic anhydride modified resin used in Example 1, ethylene/DMON random copolymer (ethylene content:
62+io1%, MFR2io. c: 35g/1
Intrinsic viscosity [η
): 0.47dΩ/g. TMA: 148℃, T
g: 137°C) and 80 parts by weight of ethylene/propylene random copolymer (ethylene content: 80 mol%)
, Tg: -54°C. MFR. ). , : 0.
A resin obtained by melt-blending 20 parts by weight of intrinsic viscosity (η): 2.2 dM/g) measured in decalin at 7 g/10 min, 135°C in a twin-screw extruder (manufactured by Ikegai Tekko Co., Ltd., PCM45) was mixed with maleic anhydride. Example 1 except that a modified product (maleic anhydride content: 0.08% by weight (acid anhydride group content: 0.06% by weight)) was used in place of the [B] component in Example 1. A similar operation was performed. The results are shown in Table 5.

Claims (1)

[Claims] (1) [A] Polycarbonate resin and [B] Intrinsic viscosity measured in decalin at 135°C [η]
is 0.05 to 10 dl/g (a) An addition polymer consisting of an ethylene component and a cyclic olefin component represented by the following general formula [I] and/or [II] is added with an unsaturated carboxylic acid or its derivative component. An unsaturated carboxylic acid or its and a modified cyclic olefin ring-opening polymer into which a derivative component has been introduced, and the weight ratio of [A] component/[B] component is 98/
A polycarbonate resin composition characterized in that it has a hardness of 2 to 2/98. 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. ]