JPH02232246A - Polyester resin composition - Google Patents

Abstract

PURPOSE:To obtain a polyester resin composition having excellent heat resistance and chemical resistance and low water absorptivity and molding shrinkage without detriment to the properties of a polyester resin by mixing a polyester resin with a specified modified cycloolefin addition (or ring-opening) polymer. CONSTITUTION:A polyester resin (A) (desirably polyethylene terephthalate or polybutylene terephthalate) is mixed with a modified cycloolefin addition (or ring-opening) polymer (B) prepared by introducing an unsaturated carboxylic acid or its derivative component into an addition polymer or ring-opening polymer of ethylene with a cycloolefin components of formulas I and/or II (wherein R<1>-R<10> are each H, a halogen atom or a hydrocarbon group; n and m are each 0 or a positive integer, and l is an integer >=3) or a hydrogenation product thereof (and having an intrinsic viscosity [eta] of 0.05-10 dl/g at 135 deg.C in decalin) in an A/B weight ratio of 98/2-2/98 to obtain a polyester resin composition.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a polyester resin composition that has excellent heat resistance and chemical resistance, low water absorption and molding shrinkage, and high mechanical strength. [Prior art] Polyester resins, such as polyethylene terephthalate and polybutylene terephthalate, have a relatively high melting point when crystallized, so products containing fillers have a high heat distortion temperature and excellent heat resistance. There is. However, when fillers are added, moldability deteriorates and the physical properties of the molded product become anisotropic. On the other hand, those without filler have a high molding shrinkage rate, lack dimensional accuracy, and have poor heat resistance. In addition, polyester resin has poor acid resistance and alkali resistance, and has a high water absorption rate, so
If drying is insufficient, there is a problem in that the material is hydrolyzed during molding and physical properties deteriorate. [Problems to be Solved by the Invention] In order to solve the above-mentioned problems, the purpose of the present invention is to create a polyester resin that maintains the properties of polyester resin, has excellent heat resistance and chemical resistance, and has low water absorption and mold shrinkage. At the same time, the objective is to obtain a polyester resin composition with high mechanical strength. [Means for Solving the Problems] The present invention provides the following polyester resin composition. (1) (A) Polyester resin, (133 Intrinsic viscosity measured in decalin at 135°C (
q) is 0.05 to lOdl2/ku (a) Addition polymer consisting of an ethylene component and a cyclic olefin component represented by the following general formula [I] and/or [■], an unsaturated carboxylic acid or its derivative An unsaturated carboxylic acid is added to the modified cyclic olefin addition polymer into which the component has been introduced, or (b) the ring-opening polymer of the cyclic olefin component represented by the following general formula [Natsu] and/or (n), or its hydrogenated product. or a modified cyclic olefin ring-opening polymer into which a derivative component thereof is introduced, and the weight ratio of component (A)/component (8) is 987.
A polyester resin composition characterized in that it has a polyester resin composition of 2 to 2/98. This is a general formula. [In the formula, n and m are both O or a positive integer, ρ is an integer of 3 or more, and R1 to HiO each represent a hydrogen atom, a halogen atom, or a hydrocarbon group. ] Polyester resin (Al is a polyester resin having a shoulder repeating unit represented by the following general formula (III)
Z R12 each represents aliphatic, alicyclic or aromatic recycled hydrogen or a derivative thereof, and p represents a positive integer. ] Such polyester resins (A) include, for example, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid.
4,4'-diphenoxyethanedicarboxylic acid, adibic acid, sebacic acid. Examples include polyesters of dicarboxylic acids such as cyclohexanedicarboxylic acid and diols such as ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, bisphenol A, hydroquinone, and resorcinol, with polyethylene terephthalate and polybutylene terephthalate being particularly preferred. ．． These polyester resins can be used alone or in combination of two or more. 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). Below, [B]
Among the components, first is the modified cyclic olefin addition polymer (a).
Next, the modified cyclic olefin ring-opening polymer (b) will be explained. The general formula (1) or (I
The cyclic olefin represented by I) has the following general formula (rV
) or (V). General formula [where n. m. Q and Ri to R111 are the same as above.] The cyclic olefin constituting the modified cyclic olefin addition polymer (a) component in the present invention has the above general formula [! ] and ([at least one cyclic olefin selected from the group consisting of unsaturated monomers represented by The cyclic olefin represented by the general formula [■] can be easily produced by condensing the cyclopentadiene and the corresponding cyclic olefin by the Diels-Alder reaction. It can be easily produced by condensation through reaction.Specifically, the cyclic olefin represented by the general formula (1) includes the compounds listed in Table 1, or I, 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
-Octahide naphthalene, 2-ethyl-1.4,5.
8-dimethano-1.2,3,4,4a,5,8,8a-
Octahyde naphthalene, 2-probyl-1.4,5.
13-dimethano-1.2,3,4,4a,5,8,8a
-Octahide 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-Octahide naphthalene, 2-methyl-3-ethyl-1.4,5.8-dimethano-1. 2, 3, 4.4
a,5,8.8a-octahyde naphthalene, 2-chloro-1. , 4, 5. 8-dimethano-1.2
,3,4,4a,5,8,8a-octahyde-naphthalene,2-bromo-1,4.5,8-dimethano-1.2,
3,4,4a,5,8,8a-octahyde-naphthalene,2-fluoro1,4,5,8-dimethano-1,2,
3,'+L4a,5,8,8a-octahyde-naphthalene, 2,3-dichloro-1,4,5,8-dimethano-1
．． 2,3,4.4a,5,8.8a-octahyde-naphthalene, 2-cyclohexyl-1.4,5.8-dimethano-1. , LL4,4a,5,8,8a-octahyde naphthalene, 2-n-butyl! ,4,5,+3-dimethano-1,2,3,4,4a,5,8.8a-octahyde-naphthalene,2-inbutyl-1,4,5.8-
octahydo-naphthalenes such as dimethanol-1.2,3,4,4a,5,8,8a-octahydronaphthalene,
Examples include the compounds listed in Table 2. Further, specific examples of the cyclic olefin represented by the general formula ([3) include, for example, the compounds shown in Table 3 and Table 4. Examples of the unsaturated carboxylic acid or its derivative component which is a constituent component of the cyclic olefin addition polymer (a) include acrylic acid, methacrylic acid, crotonic acid, fumaric acid, itaconic acid, cyclolaconic acid, undecylenic acid, and anhydride. Maleic acid, tetrahydrophthalic acid, incrotonic acid, nadic acid (endocys-bicycloC2, 2.
1] Hebut-5-ene-2,3-dicarboxylic acid), unsaturated carboxylic acids such as citraconic anhydride, nadic anhydride, and derivatives of these acid anhydrides. The modified cyclic olefin addition polymer (a) constituting the resin 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 above components, other unsaturated monomer components may be contained as necessary within a range that does not impair the purpose of the present invention. Specifically, the unsaturated monomer which may be optionally copolymerized includes, for example, propylene, 1=butene, etc. in an amount less than equimolar to the ethylene component unit in the resulting copolymer. 4-methyl-1-pentene, 1-hexene, 1-octene, edecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. having 3 to 20 carbon atoms
α-olefin; cyclobutene, cyclobentene, cyclohexene, 3,4-dimethylcyclobentene, 3-methylcyclohexene, 2-(2-methylbutyl)-1-
Cyclohexene, styrene, α-methylstyrene, dicyclopentadiene, ethylidene norbornene, 2,
3. 3a, ? a-tetrahydride-4,7-methanol-indene, 3a, 5, 6. 7a
Examples include -tetrahydride-4,7-methanol-IH-indene. Those having a double bond in the molecule can also be hydrogenated and used 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%. The unsaturated carboxylic acid or its derivative component is suitably in the range of 0.001 to 5% by weight, preferably 0.05 to 2% by weight as a carboxyl group or its derivative group. The intrinsic viscosity [η] of the modified cyclic olefin addition polymer (a) constituting the resin composition of the present invention measured in decalin at 135°C is 0.05 to 10 a/g, preferably 0.
．． It is in the range of 08 to 5 dQ/g. The modified cyclic olefin addition polymer (a) 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 100°C or higher, as measured by a thermomechanical analyzer. ~20
0℃ range, glass transition temperature (Tg) is usually 50-23
0°C, preferably in the range of 70 to 210°C, crystallinity measured by X-ray diffraction method is 0 to 10%, preferably 0 to 210°C.
7%, particularly preferably in the range of 0 to 5%. The modified cyclic olefin addition polymer (a) constituting the resin composition of the present invention is first prepared by adding ethylene and a cyclic olefin to 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 component. It can also be introduced through copolymerization. The method for producing the above-mentioned ethylene/cyclic olefin addition polymer is already known, and is disclosed in Japanese Patent Application Laid-open No. 168708/1983. ，
JP-A-61-12081.6, JP-A-61-11
Publication No. 5912. JP-A-61-115916, JP-A-61-2/1308, JP-A-61-2/22
No. 16, JP-A-62-252406. By selecting appropriate conditions according to the method described in Japanese Patent Application Laid-Open No. 62-252407, m-manufacturing can be performed. In order to graft-copolymerize the unsaturated carboxylic acid or its derivative component to the above-mentioned ethylene/cyclic olefin addition polymer, for example, the ethylene/cyclic olefin addition polymer is melted using the 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. It can be produced by adding dissolved graft monomers, mixing thoroughly, and graft copolymerizing. When such graft copolymerization is carried out, the reaction is usually carried out at a temperature of 60 to 350°C, and is preferably carried out in the presence of a radical initiator in order to efficiently graft copolymerize the graft monomer. Examples of radical initiators include organic peroxides, organic bersesters, and other azo compounds. As the component [B] of the present invention, instead of the modified cyclic olefin addition polymer (a), the general formula [I] and/or
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 [11] 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 contains 0 as a carboxyl group or its derivative group.
．． A suitable range is from 0.001 to 5% by weight, preferably from 0.05 to 2% by weight. The modified cyclic olefin ring-opening polymer (b) constituting the resin composition of the present invention has an intrinsic viscosity (η) of 0.05 to 1OdQ/g, preferably 0.0 as measured in decalin at 135°C.
It is in the range of 8 to 5 dQ/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. Preferably 100-2
00℃ range, glass transition temperature (Tg) is usually 50~2
30°C, preferably in the range of 70-210'C(7), and the crystallinity measured by X-ray diffraction is O-10%, preferably in the range of 0 to 7%, particularly preferably in the range of 0 to 5%. preferable. In the ring-opening polymer before hydrogenation of the hydrogenated product of the ring-opening polymer of the cyclic olefin component, the general formula [!
] or (■) The cyclic olefin component represented by the following general formula (VI) or [■] mainly forms a green return unit having a structure represented by the following general formula (VI) or [■]. or HAD are the same as above.] The method for producing the modified cyclic olefin ring-opening polymer (b) involves carrying out ring-opening polymerization of monomers selected from the above general formulas [I] and (Il) in advance, and using the resulting open polymer. A common method is to graft-copolymerize a ring polymer as it is or after hydrogenation with an unsaturated carboxylic acid or its derivative component.The ring-opened polymer before hydrogenation has the general formula [I] and ( It can be produced by a conventional ring-opening polymerization method for cyclic olefins, using as raw materials a heptanomer component selected from II) and other monomer components to be polymerized if necessary.
Other monomer components include, for example, cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclobentene, 3-methylcyclohexene. 2-(2-
methylbutyl)-1-cyclohexene, dicyclopentadiene, ethylidene norbornene, 2,3,3a,7
a-tetrahydride-4,7-methanol IH-indene.
Examples include cyclic olefins such as 3a,5,6,7a-tetrahydride-4,7-methanol-IH-indene. Examples of polymerization catalysts include systems consisting of halides such as ruthenium, rhodium, palladium, osmium, iridium, platinum, molybdenum, and tungsten, nitrates or acetylacetone compounds, and reducing agents such as alcohols and tin compounds, or titanium, vanadium, zirconium, A system consisting of a halogen compound such as tungsten or molybdenum, an acetylacetone compound, etc., and an organic aluminum compound, etc. 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, nickel, etc. /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 octenoate/n
-Butyllithium, Nikkenoleacetylacetonate/
Triethylaluminum, etc.' Nj. consisting of a Co compound and an organometallic compound of metals from Groups ■ to ■ of the periodic table;
Alternatively, examples include 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 can be adjusted by hydrogen pressure, reaction temperature, reaction time, catalyst concentration, etc., but the weather resistance of the resin composition of the present invention,
In order to improve heat aging resistance, it is preferable that 50% or more, preferably 80% or more, and more preferably 90% or more of the main chain double bonds in the polymer be hydrogenated. In the case of the modified cyclic olefin addition polymer (a), 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, It can be done in the same way. In the polyester resin composition of the present invention, the blending ratio of component (A) and component [8] is the weight ratio of component (A)/[
B] Component is 9872 to 2/98, preferably 9575 to 2/98
It is 5/95. The resin composition of the present invention includes the above-mentioned (A) component and (B)
In addition to the ingredients, resins containing unsaturated carboxylic acids or derivatives thereof, such as ethylene-brobylene random copolymers graft-copolymerized with maleic anhydride, 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, and rubber components to improve impact strength may be blended. The mixing ratio is appropriate. for example,
Specifically, stabilizers that can be added as optional ingredients include:
Tetrakis [methylene-3 (3,5-di-t-butyl-4-hydro-a-xyphenylene) propionate] methane,
β-(3,5-di-t-butyl-4-hydroxyphenyl)probionic acid alkyl ester, 2.2/-oxamidobis[ethyl-3(3.5-di-t-butyl-4
Phenolic antioxidant pressure agents such as -hydroxyphenyl)propionate, fatty acid metal salts such as zinc stearate, calcium stearate, and calcium 12-hydroxystearate, glycerin. Examples include polyhydric alcohol fatty acid esters such as monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol 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 may contain silica, diatomaceous earth, and alumina within a range that does not impair the object of the present invention. 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 5 asbestos, glass fiber, glass flakes. Glass beads, keiso calcium, montmori kuchinite. Fillers and reinforcing materials such as bentonite, graphite, anoleminium powder, molybdenum sulfide, boron fibers, silicon carbide fibers, polyethylene fibers, polypropylene fibers, polyester fibers, and polyamide fibers may be added. The method for producing the polyester resin composition according to the present invention includes:
Known methods can be applied, such as mechanically blending the [A] component and (Bl component) and other components added as necessary using an extruder, kneader, etc., or dissolving each component in a suitable good solvent, Alternatively, a method of dissolving each separately and then mixing them to remove the solvent, or a method of combining these two methods, etc. The polyester resin composition obtained by the above method is a polyester resin (A ) is blended with component (B), which has a higher glass transition temperature than polyester resin, excellent chemical resistance, low water absorption, and has substantially no quality and low molding shrinkage. A polyester resin composition with excellent heat resistance and chemical resistance and low water absorption and molding shrinkage can be obtained while maintaining its properties.When the polyester resin (A) and the cyclic olefin polymer are blended here. has low mechanical strength such as impact strength due to poor compatibility between the two, but by blending a modified cyclic olefin addition polymer or a modified cyclic olefin ring-opening polymer [B] instead of the cyclic olefin polymer. , the compatibility with the polyester resin (A) can be improved, thereby increasing the mechanical strength.The polyester resin composition of the present invention has the above-mentioned properties.
In addition to applications where polyester resin is used, it can be used in a wide range of fields that require heat resistance, chemical resistance, low water absorption, and low mold shrinkage. [Effects of the Invention] As described above, according to the present invention, component [A] and (83
Because the ingredients are blended, it has excellent heat resistance and chemical resistance, and has low water absorption and molding shrinkage.
B] A polyester resin composition with good compatibility of components and high mechanical strength such as impact strength can be obtained. (Examples) The present invention will be specifically explained below with reference to Examples, but 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 (MFR...+JASTM
Measured at a temperature of 260°C and a load of 2.16kg according to 01238. (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°C, mold temperature 60'C,
Injection pressure primary/secondary = 1000/800kg/cd,
Injection speed (primary) 30+wm/see, screw rotation speed 15Orpm, cycle ((injection + holding pressure)/cooling)
= 1 0/30 sec (3) Bending test Conducted according to ASTM D790. Test piece shape: 5 x 1/2 x l. /8t inch, span distance [51mm Test speed: 20mm/win Test temperature: 23°C (4) Tensile test Conducted according to ASTM 063g. Two types of test piece shapes ■ Test speed: 50m+w/++in Test temperature = 23℃ (5) Heat distortion temperature (l{DT) ASTM 06
4g. Test piece shape: 5 x 1/4 x l/2t inch Load: 264psi (6) Softening temperature (TMA) DuPont f! ! IThermo Mechanica
The thermal deformation behavior of a sheet with a thickness of lam was measured using an Analyzer. That is, a quartz needle is placed on a sheet, a load of 49 g is applied, the temperature is raised at a rate of 5°C/win, and the temperature at which the needle penetrates 0.635 m + m is TM.
(7) Glass transition temperature (Tg) (D sc
Method: Measured using DSC-20 manufactured by SEIKO Electronics Co., Ltd. at a temperature increase rate of 0°C/win. (8) Pencil hardness Measured at 23°C according to JIS K 5400. (9) Water absorption rate The value was measured after 24 hours according to JIS K 7209 A method. (io) Izod 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 (11) Compatibility Judgment was made based on the appearance of the injection molded bending test piece and the state of the fractured surface. 0: Both appearance and fracture surface were uniform. Δ: The appearance was slightly uneven in flow, and the fracture surface was slightly uneven. ×: There was a skin layer, and the fracture surface 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 13C-NMR is 62 mol
%, MFRz so c is 35g/10+++in,
Intrinsic viscosity [η] measured in decalin at 135°C is 0.4
7dQ/g. Ethylene with TMA of 148°C and Tg of 137°C and 1.4,5.8-dimethano-1.2,3,4,
4a,5,8,8a-octahyde-natalene (structural formula [
5 kg of pellets of random copolymer (ethylene/DMON random copolymer) with DMON), 5 g of maleic anhydride dissolved in 25 g of acetone, and organic peroxide (manufactured by NOF Corporation, Perhexine 25B,
After adding 0.3 g of the mixture (Trademark) and mixing thoroughly, a reaction was carried out under melting conditions using a twin screw extruder (manufactured by Ikegai Tekko Co., Ltd., PCM 45) at a cylinder temperature of 250°C, and the mixture was pelletized 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). Next, as the [A] component, polyester (Mitsui PET Resin ■
Pellets 2 of polyester resin J125 (product name)
．． 0kg. After thoroughly mixing 2.0 kg of the maleic anhydride-modified resin described above as component [B], melt blending was performed using a twin-screw extruder (manufactured by Ikegai Tekko ■, PCM 45) at a cylinder temperature of 280°C, and then using a pelletizer. It was pelletized. Using the obtained beresotho, test pieces were prepared by the method described above, and the 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 In Example 1- (using only the polyester resin J125 used as the Al component), molding was performed in the same manner as in Example 1, and the physical properties were evaluated. The results are shown in Table 5. Comparative Example 2 In Example 1 , (The same operation as in Example 1 was performed except that the ethylene/DMON random copolymer before modification with maleic anhydride was used as the Bl component. The results are shown in Table 5. Example 4 The anhydride used in Example 1 Instead of maleic acid modified resin, ethylene/DMON random copolymer (ethylene content:
62mol%, MFRzt,o<: 35g/10
aLn, intrinsic viscosity measured in decalin at 135°C [η)
: 0.47dQ/g. TMA: 148℃, T
g: 137°C) and 80 parts by weight of ethylene/propylene random copolymer (ethylene content: 80 mol%,
Tg: -54℃- MFRiioy: Q, 7g/L
ogin, intrinsic viscosity measured in decalin at 135°C [η
) : 2.2dΩ/g) 20 parts by weight were added to a twin screw extruder (
A resin melt-blended with PCM45, manufactured by Ikegai Tekko Co., Ltd., was modified with maleic anhydride in the same manner as in Example 1 (maleic anhydride content: 0.08% by weight (acid anhydride group content: o.ofS). The same operation as in Example 1 was performed except that % by weight)) was used in place of component [B] in Example 1. The results are shown in Table 5. From the above results, the polyester resin composition of the present invention containing component (A) and component [8] has a higher heat distortion temperature and lower water absorption than the conventional polyester resin which is component [A]. I understand. It can also be seen that the composition has better compatibility and higher Izod impact strength than a polyester resin composition using a cyclic olefin copolymer containing no unsaturated carboxylic acid as component (B).

Claims (1)

[Claims] (1) [A] Polyester 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 polyester resin composition characterized in that it has a molecular weight 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 positive integers. Yes, l is an integer greater than or equal to 3, and R^1 to R^1^0
each represents a hydrogen atom, a halogen atom, or a hydrocarbon group. ]