JPH10139985A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition excellent in workability, impact resistance and heat resistance. SOLUTION: This composition comprises 100 pts.wt. resin component comprising 95-5 pts.wt. polyester resin (A) having an intrinsic viscosity of 0.5-2.0dl/g, 5-95 pts.wt. olefin resin (B), and 0.03-30 pts.wt. copolymer (C) comprising 5-80wt.% polyester resin part (a) reactive with resin (A) in a melt kneading step and 95-20wt.% olefin resin part (b) being compatible with resin (B) and chemically combined with component (a).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester / polyolefin resin composition having a relatively balanced impact resistance, chemical resistance, moldability, heat resistance and the like.

[0002]

2. Description of the Related Art Polyester resins have excellent mechanical properties, electrical properties and heat resistance, and have been used as high-performance resins. However, applications are narrow and limited due to poor dimensional stability and impact resistance.

As a method for improving the moldability of the polyester resin, a method of mixing a polyester resin and a polyolefin resin has been disclosed. However, the compatibility between the polyester resin and the polyolefin resin is low, and a simple physical blend cannot be used. A macro phase-separated structure was formed, and the obtained resin composition had poor mechanical properties and low impact resistance.

As a method for overcoming these disadvantages, JP-A-55-21,430 discloses a method of introducing an acid anhydride into a polyolefin resin, and JP-A-63-178,119 discloses a polyester resin and a polyolefin. A method of copolymerizing with a base resin is disclosed. However, even when modified with an acid anhydride or modified with an olefin resin with glycyl methacrylate, the compatibility between the polyester resin and the polyolefin resin may be insufficient, and the desired mechanical strength and impact resistance may be reduced. It was difficult to get. Further, even when a polyester resin and a polyolefin-based resin are copolymerized, the mechanical properties of the resin alone are insufficient, so that it is difficult to apply to a structural material.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a novel resin composition having excellent workability, impact resistance and heat resistance.

[0006]

That is, the present invention relates to a polyester resin (A) having an intrinsic viscosity of 0.5 to 2.0 dl / g (95 to 5 parts by weight) and a polyolefin resin (B) 5
5 to 80% by weight of a polyester resin part (a) capable of reacting with the polyester resin (A) in the melt-kneading process with 100 parts by weight of the resin consisting of .about.95 parts by weight; Copolymer (C) 0.005 to 20% by weight of resin part (b) chemically bonded
A resin composition obtained by blending 3 to 30 parts by weight, and a resin composition obtained by melt-kneading the resin composition.

Hereinafter, the present invention will be described in detail. The polyester resin (A) used in the present invention includes a hydroxycarboxylic acid compound residue, a dicarboxylic acid residue and a diol residue, or a hydroxycarboxylic acid compound residue, a dicarboxylic acid residue and a diol compound residue as constituent units. Is a thermoplastic polyester resin. Further, a mixture thereof may be used.

Examples of the hydroxycarboxylic acid compound forming the hydroxycarboxylic acid compound residue include p-hydroxybenzoic acid, p-hydroxyethylbenzoic acid, and 2-hydroxybenzoic acid.
(4-hydroxyphenyl) -2- (4′carboxyphenyl) propane and the like, and these may be used alone or in combination of two or more.

Examples of the dicarboxylic acid compound forming a dicarboxylic acid residue include terephthalic acid, isophthalic acid, orthophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid. Acid, 2,7-naphthalenedicarboxylic acid,
Aromatic dicarboxylic acids such as diphenic acid, adipic acid, bimeric acid, sebacic acid, malonic acid, succinic acid, malic acid, and aliphatic dicarboxylic acids such as citric acid, and the like,
These may be used alone or in combination of two or more.

Next, diol compounds forming a diol residue are exemplified by 2,2'-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as "bisphenol A"), bis (4-hydroxyphenyl) Methane, bis (2-hydroxyphenyl) methane, o-hydroxyphenyl-p-hydroxyphenylmethane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4
-Hydroxyphenyl) diphenylmethane, bis (4-
(Hydroxyphenyl) -p-diisopropylbenzene,
Bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3-methyl-4-hydroxyphenyl) methane, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (3,5-dimethyl -4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-)
Hydroxyphenyl) sulfide, 1,1-bis (4-
Hydroxyphenyl) ethane, 1,1-bis (3,5-
Dimethyl-4-hydroxyphenyl) ethane, 1,1-
Bis (4-hydroxyphenyl) cyclohexane, 1,
1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4
-Hydroxyphenyl) -1-phenylmethane, 2,2
-Bis (4-hydroxyphenyl) propane, 2,2-
Bis (4-hydroxyphenyl) butane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2 -Bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane,
2,2-bis (3-chloro-4-hydroxyphenyl)
Propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (4-hydroxyphenyl) propane, 4,4 '-Biphenol, 3,3', 5,5 '
-Tetramethyl-4,4'-dihydroxybiphenyl,
Aromatic diols such as 4,4'-dihydroxybenzophenone, ethylene glycol, propylene glycol,
1,4-butanediol, pentamethylene glycol,
Examples thereof include aliphatic diols such as hydrogenated bisphenol A, and these may be used alone or in combination of two or more. Further, the polyester resins obtained therefrom may be used alone or in combination of two or more.

The polyester resin (A) used in the present invention
May be composed of a combination of these residues, and among them, is preferably an aromatic polyester resin composed of an aromatic dicarboxylic acid residue and a diol residue.

Examples of the preferred polyester resin (A) used in the present invention include polyethylene terephthalate,
Examples thereof include polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexylene dimethylene terephthalate, and polyethylene-2,6-naphthalate. Of these, polyethylene terephthalate and polybutylene terephthalate having appropriate mechanical properties are most preferable.

The polyester resin (A) used in the present invention
Has an intrinsic viscosity of 0.5 to 2.0 dl / g, preferably 0.65 to 1.7 dl / g, more preferably 0.8 to 2.0 dl / g.
1.5 dl / g. When the intrinsic viscosity is lower than 0.5 dl / g, the mechanical strength is low because the resin does not mix uniformly with the polyolefin resin (B), and when the intrinsic viscosity is higher than 2.0 dl / g, the moldability becomes poor, and both are not preferred.

The intrinsic viscosity is measured at a concentration of 0.5% in orthochlorophenol at 25 ° C.
It was obtained by: In the formula, C represents the concentration represented by the number of grams of resin per 100 ml of the solution, t ₀ represents the flow time of the solvent, and t represents the flow time of the solution.

(Equation 1)

Next, the polyolefin resin (B) used in the present invention is a homopolymer or a copolymer of an aliphatic olefin such as ethylene, an aromatic olefin such as styrene, or a vinyl compound which is a substituted product thereof. Besides being able to
It may be a homopolymer of a diene-based compound, a hydrogenated product thereof, or a resin obtained by copolymerizing another diene-based monomer or a hydrogenated diene-based monomer with the olefin or the like as a main component. Also, one of these resins may be used,
A mixture of these resins may be used.

Examples of polyolefin resins obtained by polymerization of aliphatic olefins include those having the following repeating units.

Embedded image

(Wherein, R ₁ , R ₂ and R ₃ each independently represent hydrogen or an alkyl group having 1 to 12 carbon atoms)

Examples of the repeating unit include α-olefins such as propylene, 1-butene, 1-pentene, 4-methyl-1pentene, 1-hexene, 1-octene, 1-decene, and 1-dodecene. Examples include a repeating unit that appears when polymerized, and a repeating unit that appears when isobutene is addition-polymerized.

Examples of aromatic olefins include, in addition to styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene,
-Methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, alkylated styrenes such as t-butylstyrene, halogenated styrenes such as monochlorostyrene, styrene monomers such as α-methylstyrene, and the like. Can be

Examples of vinyl compounds include acrylic acid,
Acrylic esters such as methyl acrylate and ethyl acrylate, acrylic derivatives such as methacrylic acid, methacrylic esters such as methyl methacrylate and ethyl methacrylate, acrylonitrile, maleic anhydride, imide derivatives of maleic anhydride, vinyl chloride, etc. Is mentioned.

Examples of the polyolefin resin (B) used in the present invention include homopolymers of styrene monomers such as α-olefin homopolymers such as polyethylene, polypropylene, polybutene, polypentene, polyhexene and polyoctenylene. Polystyrene, poly α
Homopolymers of -methylstyrene and polar vinyl monomers include polymethyl methacrylate and the like. Also,
As α-olefin copolymers, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-propylene-1,6-hexadiene copolymer, ethylene-propylene-5-ethylidene-2-norbornene copolymer, Styrene-acrylonitrile copolymer (SA) is used as a copolymer of a styrene monomer and a polar vinyl monomer.
N), a styrene-methyl methacrylate copolymer, a styrene-maleic acid copolymer, and the like. Further, polybutadiene which is a homopolymer of a diene monomer, butadiene-styrene copolymer, a hydrogenated product of a butadiene-styrene copolymer, and a styrene-ethylene-butadiene-styrene copolymer in the case of a diene monomer and a styrene copolymer (SEBS), acrylonitrile-styrene-butadiene copolymer (ABS), acrylonitrile-butadiene copolymer, and the like.

Further, when a rubbery polymer is used as the polyolefin resin (B), the polyolefin resin (B) is used to improve the compatibility between the polyolefin resin (B) and the polyester resin (A). An unsaturated compound having a specific functional group or a polar bond and a known radical initiator or chain transfer agent can also be added. Specific examples of such a functional group include a carboxyl group, a hydroxyl group, and an amide group. Examples of such a polar group include an amide bond, an ester bond, and a carbonate bond. The amount of the radical initiator or chain transfer agent to be added is 0.01 to 50 parts by weight, preferably 0.1 to 50 parts by weight, based on the rubbery polymer or the thermoplastic elastomer.
The amount is 1 to 10 parts by weight, more preferably 0.1 to 15 parts by weight. When the amount of the radical initiator or the chain transfer agent exceeds 50 parts by weight, the depolymerization reaction is excited, and the function as an impact-resistant reinforcing agent is reduced. If the amount is less than 0.01 part by weight, the radical generating function is weak, and the compound cannot be introduced into a rubbery polymer or a plastic elastomer.

The number average molecular weight (Mn) of the polyolefin resin (B) used in the present invention is from 2,000 to 1,0.
00,000, preferably 5,000 to 500,
000, more preferably 10,000 to 200,00
0, more preferably 10,000-100,000. If the molecular weight is too high, the melt viscosity will be high, the compatibility will be reduced and sufficient mechanical strength cannot be exhibited. If the molecular weight is too low, it is thermally unstable.

The copolymer (C) used in the present invention comprises a polyester resin part (a) capable of reacting with the polyester resin (A) during the kneading process, and an olefin resin part compatible with the polyolefin resin (B). (B) is a chemically bonded copolymer. The polyester resin part (a) is 5 to 80% by weight, and the olefin resin part (b)
Is 95 to 20 parts by weight.

Polyester resin (A) and copolymer (C)
The reaction with the polyester resin part (a) is a transesterification reaction, an exchange reaction between bonding hands, esterification of terminal groups,
The formation of polar bonds such as hydrogen bonds and ionic bonds. It is preferably a transesterification reaction. Whether the reaction between the polyester resin (A) and the polyester resin part (a) is possible,
After melt-mixing an appropriate amount of the polyester resin (A) and the copolymer (C) at an appropriate temperature, the mixture is extracted with a solvent that dissolves either the copolymer (C) or the polyester resin (A), and the solvent is removed. The determination can be made by analyzing the change in weight or the component of the dissolved component by a known analysis method such as nuclear magnetic resonance or infrared spectroscopy. Specifically, the weight part of the soluble part / the weight part by weight is 9
It can be considered that the reaction is possible when the content is 9% or less, or when the soluble component contains 1% or more of the insoluble component.

The polyester resin part (a) comprises the above-mentioned hydroxycarboxylic acid compound residue, dicarboxylic acid residue and diol residue, or hydroxycarboxylic acid compound residue, dicarboxylic acid residue and diol compound residue as constituent units. Thermoplastic polyester resin, a thermoplastic polycarbonate having a diol residue as a constituent unit, or a polyester polycarbonate which is a copolymer of these polyester resins and polycarbonate, among which bisphenol A residues, terephthalic acid and isophthalic acid residues A polyester resin as a constituent unit is most preferable. The copolymer having the ester resin portion can easily excite transesterification with the polyester resin (A), and functions as a highly reactive reactive compatibilizer. Further, the polyester resin part (a) of the copolymer (C) of the present invention may be a copolymer with polyamide or polyimide as long as the polyester resin is the main component. The main component means that the constituent unit is 50 parts by weight or more.

The distinction between compatibility and incompatibility between the olefin resin part (b) and the polyolefin resin (B) of the copolymer (C) is based on the olefin resin alone constituting the olefin resin part (b). And the polyolefin resin (B) can be determined by measuring the χ parameter by a known method and measuring the χ parameter, or measuring the glass transition temperature of the mixed sample by a known method. Specifically, if the measured χ parameter is less than 0.5, the glass transition temperature is compatible when only one measured glass transition temperature is observed.
χFor the method of measuring parameters, see, for example, H.yang Macrom
Olecules vol.245218 (1991) may use a method of measuring with DSC or the like.

The polyolefin resin constituting the olefin resin portion (b) of the copolymer (C) is a homopolymer of the above-mentioned α-olefin, styrene monomer or polar vinyl monomer, and two or more α-olefins. -Olefin, styrene-based monomer, copolymer of polar vinyl monomer, homopolymer of diene-based monomer and hydrogenated product thereof, and α-olefin, styrene-based monomer, polar vinyl monomer-based other diene-based A resin obtained by copolymerizing a monomer or a hydrogenated diene monomer.

The weight ratio of the polyester resin part (a) of the copolymer (C) to the olefin resin part (b) ((a)
/ (B)) needs to be 5/95 to 80/20. If the polyester resin part (a) is less than 5%, it is difficult to use the polyester resin (A) as a reaction part. On the other hand, if the content of the polyolefin resin part (b) is less than 20%, the copolymer formed by the reaction is difficult to be fixed on the phase separation interface, and cannot be used as a suitable compatibilizer. More preferably, the weight ratio of the polyester resin part (a) to the olefin resin part (b) is 5/95 to 50/50, more preferably 5/95 to 30/70. When the weight ratio of the polyester resin part (a) increases, Takashi Inoue Polymer Vol.45
As shown in No. 7450 1996, the copolymer (C) independently forms a microphase-separated structure and hardly functions as a compatibilizer. When this is in the range of 5/95 to 30/70, it is difficult to form a phase-separated structure, and the copolymer (C) can easily function as a reactive compatibilizer using the polyester resin part (a) as a reaction part.

In the copolymer (C) used in the present invention, it is important that the polyester resin part (a) and the olefin resin part (b) are chemically bonded, and that they are bonded at the terminal. Or may be bonded to a side chain. Preferably, a polyester resin part (a) is provided at the end of the styrene resin part (b).
Is a block copolymer bonded. E. Helfand J. Che
As disclosed in m.Phys. vol. 57 1812 (1970), the terminal of the molecular chain is more likely to exist at the polymer-polymer interface, and the polyester resin portion (a) and the polyester resin (A) The reaction efficiency with liable to increase easily.

Further, the molecular weight of the polyester resin part (a) and the olefin resin part (b) of the copolymer (C) is as follows:
There is no particular restriction. However, regarding the polyester resin part (a), the number average molecular weight is preferably 10,000 or less. If it exceeds 10,000, the polyester resin part (a) often forms a domain in the resin (B) phase, and it is difficult to excite the reaction at the phase separation interface. Further, regarding the olefin-based resin part (b),
It is desirable that the number average molecular weight is 1,000 or more. 1
When the copolymer (C) is lower than 000, the copolymer (C) is hardly fixed to the phase separation interface, and cannot be used as a suitable compatibilizer.

The method for producing the copolymer (C) includes the following:
Known methods can be adopted, and there is no particular limitation.
For example, the olefin-based monomer is polymerized using a functional group-containing polymerization initiator such as valeric acid to prepare a styrene-based resin having a functional group introduced into a terminal, and then the styrene-based resin is mixed with the appropriate amount of oxycarboxylic acid. There is a known polycondensation reaction method using an appropriate polycondensation catalyst together with an acid, dicarboxylic acid and diol. Alternatively, an appropriate amount of oxycarboxylic acid, dicarboxylic acid, diol and a monohydroxy compound having a vinyl bond such as paraisopropeniphenol are polycondensed under a suitable polycondensation catalyst to form a vinyl group terminal. There is a known method of producing a polyester resin and subjecting it to a known addition polymerization together with an appropriate amount of the olefin-based monomer described above. In any case, the copolymer (C) of the present invention
It is sufficient that the polyester resin part (a) 5 to 80% by weight and the olefin resin part (b) 95 to 20% by weight are chemically bonded, and the production method is not limited to the above method.

The resin composition of the present invention contains 0.003 to 30 parts by weight of the copolymer (C) based on 100 parts by weight of the polyester resin (A) and the polyolefin resin (B). It costs. If the amount is less than 0.003 parts by weight, the compatibility between the resin (A) and the resin (B) cannot be sufficiently improved. On the other hand, when the amount exceeds 30 parts by weight, the reaction between the resin (A) and the polyester resin part (a) of the copolymer (C) proceeds too much, and the physical properties of the resin composition are easily impaired.

The resin composition of the present invention is melt-kneaded at a predetermined temperature, for example, 200 to 300 ° C., using a known various extruder or various mixers such as a Brabender, kneader, and Banbury mixer. Can be manufactured. In order to improve the reactivity between the polyester part (a) of the copolymer (C) and the polyester resin (A) during melt kneading, it is possible to add an appropriate catalyst. The addition amount of the catalyst is desirably 3 parts by weight or less based on 100 parts by weight of the whole resin composition. When the amount of the catalyst exceeds 3 parts by weight, the decomposition reaction of the copolymer (C) may be promoted.

For the purpose of improving rigidity and linear expansion characteristics, the resin composition of the present invention contains various fillers, for example, fiber reinforcing agents such as glass fiber, metal fiber, potassium whisker, carbon fiber, and the like. A filler-type reinforcing agent such as talc, calcium carbonate, mica, glass flake, milled fiber, metal flake, and metal powder may be mixed.
Of these fillers, glass fibers and carbon fibers desirably have a fiber diameter of 6 to 60 μm and a fiber length of 30 μm or more. The amount of these additives is preferably 5 to 15 parts by weight based on the total weight of the resin composition.

Further, according to the purpose, the present resin composition may contain
It is also possible to add appropriate amounts of heat stabilizers, antioxidants, light stabilizers, mold release agents, lubricants, pigments, flame retardants, plasticizers, antistatic agents, antibacterial and antifungal agents.

When the resin composition of the present invention is melt-kneaded, a reaction occurs between the polyester resin (A) and the polyester resin part (a) of the copolymer (C), and the polyolefin resin (B) The copolymer (C) is compatible with the olefin resin portion (b). Therefore, after melt-kneading, another resin composition in which the polyester resin (A), the polyolefin-based resin (B), and the copolymer (C) of the resin composition of the present invention are integrated is formed. Thereby, it is considered that moldability, heat resistance, impact resistance, chemical resistance, mechanical strength, and the like are improved as compared with a conventionally known resin composition of a polyester resin and a polyolefin resin.

[0038]

The present invention will be described below in more detail with reference to examples and comparative examples. In the following, the molecular weight refers to a number average molecular weight (Mn) and a weight average molecular weight (Mw) measured using a gel permeation chromatograph (GPC) (corrected with a monodispersed PS). The composition of the aromatic polyester resin-polystyrene polymer was calculated from the ratio of NMR proton spectra. Polybutylene terephthalate (PBT) used in Examples and Comparative Examples was manufactured by Toray Industries, Inc.
401-X04, acrylonitrile-styrene-butadiene copolymer (ABS) has an acrylonitrile / styrene weight ratio of 27/73, a rubber content of 40%, Mn = 150,
The molecular weight (Mn) of 000, polymethyl methacrylate (pMMA) is 180,000. The Izod impact value was measured according to ASTM-D-256.

Reference Examples 1-3 [Production of styrene-acrylonitrile carboxylate copolymer (SAN-COOH)] 4,4'-Azobiscyanovaleric acid was used as a polymerization initiator, and a styrene monomer and acrylonitrile were used as monomers. Radical polymerization, SAN-COOH
(Mn = 60,000, 21,000, 5,
000). The obtained PS-COOH was subjected to neutralization titration, and CO
The equivalent of the OH group was measured (in each case, COOH equivalent = 2.
00 / molecule, acrylonitrile / styrene weight ratio = 2
7/73).

Reference Examples 4 to 8 [Production of Aromatic Polyester Resin-SAN Block Copolymer (SAN-b-PAr)] The SAN-COOH of Reference Examples 1 to 3 was added to a 5-fold equivalent of triphenyl based on the terminal carboxyl group. By reacting with 5-fold equivalent of bisphenol A in the presence of phosphine, hexachloroethane, and triethylamine, a phenolic terminal styrene resin (SAN-OH) was produced, and this SAN-OH was mixed with bisphenol A and iso / terephthalic acid dichloride. Was added in accordance with the ratio of SAN to PAr, and solution condensation polymerization was carried out in the presence of triethylamine and calcium hydroxide.After the polymerization was completed, a large amount of acetic acid aqueous solution was added to the reaction solution to remove unreacted substances. After removing the aqueous layer from the acidified reaction solution, a large amount of methanol was added to recover the polymer. To obtain a SAN-b-PAr shown in Table 1.

[0041]

[Table 1]

Reference Example 9 [Aromatic polyester resin-S
Production of AN Graft Copolymer (SAN-g-PAr)] According to Example 1 of JP-A-3-11,413, radical polymerization of a vinyl group-terminated aromatic polyester resin (vinyl PAr) and a styrene monomer is initiated. Radical polymerization was performed at 60 ° C. in the presence of an agent (azobisisobutyronitrile) to obtain an aromatic polyester resin-SAN graft copolymer (SAN-g-PAr). Vinyl PAr part (Mn = 5,000, Mw = 18,000)
0) SAN-g-PAr (Mn = 6,600, Mw = 20,
000, SAN / PAr = 85/15)

Reference Example 10 [One-terminal amino group-containing SAN
Production of (SAN-NH ₂ ) In accordance with the examples in JP-A-5-9354, a styrene monomer and an acrylonitrile monomer were combined with a radical polymerization initiator (azobisisobutyronitrile) and a chain transfer agent (2-aminoethanethiol). ) Was subjected to radical polymerization to obtain SAN (SAN-NH ₂ ) containing an amino group at one terminal. The amino equivalent was calculated by neutralization titration with an aqueous hydrochloric acid solution (Mn = 25,000, amine equivalent = 1.0).
1).

REFERENCE EXAMPLE 11 [Production of SAN-b-PAr] (SAN-NH ₂ ) of Reference Example 10, bisphenol A and iso / terephthalic acid dichloride were mixed with SAN and PA.
The solution was polymerized in the presence of triethylamine and calcium hydroxide. After the completion of the polymerization, a large amount of an aqueous acetic acid solution was added to the reaction solution to remove the unreacted substances to make the reaction solution acidic. After removing the aqueous layer from the acidified reaction solution, a large amount of methanol was added to recover the polymer.
An aromatic polyester resin-polystyrene block copolymer (PS-b-PAr) shown in Table 1 was obtained. SAN-b-PAr (Mn = 35,000, Mw = 8
0000, SAN / PAr = 85/15)

Reference Example 12 [Production of SAN-GMA copolymer] Styrene monomer, acrylonitrile, and glycyl methacrylate were mixed in a predetermined mixture, and radically polymerized using azobisisobutyronitrile as a polymerization initiator. . The molecular weight and composition of the obtained polymer were Mn = 70,
000, S / AN = 75/25 (S + AN) / GMA =
95/5.

Examples 1 to 7 85 parts by weight of PBT and PS of Reference Examples 4 to 9 and Reference Example 11
Each of 15 parts by weight of the -PAr copolymer was added, and the mixture was kneaded with two batch-type closed rolls at 260 ° C and 80 rotations for 7 minutes. After kneading, the kneaded product was collected, pulverized with a coffee mill, extracted with tetrahydrofuran (soluble only in the copolymer of Reference Example) for 48 hours, and the extract was dried. Example 1, 1.5 parts by weight, Example 2, 1.8 parts by weight, Example 3, 1.5 parts by weight, Example 4, 1.7 parts by weight, Example 5, 3 parts by weight, Example 6 was 4 parts by weight and Example 7 was 0.3 parts by weight, and all the polymers were able to react with PBT.

Example 8 In place of PBT of Example 7, PET (intrinsic viscosity 0.72)
dl / g) and extracted with a solvent. 0.5 parts by weight of the extract was able to react with PET.

Examples 9 to 13 8.4 g of ABS and SAN-b-PAr of Reference Examples 4 to 8
1.4 g and 260 ° C., 80
Kneaded by rotation for 3 minutes. After kneading, 19.6 g of PBT was added and kneaded under the same kneading conditions for 7 minutes. The kneaded material was collected, cooled to liquid nitrogen temperature and cut, and the section was ultrasonically washed with tetrahydrofuran for 30 minutes to dissolve the PPE dispersed phase. After washing, gold was vapor-deposited, and the average diameter of the ABS dispersed phase was measured with a scanning electron microscope (SEM). Table 2 shows the measurement results.

[0049]

[Table 2]

Example 14 8.4 g of ABS and 1.4 g of SAN-g-PAr of Reference Example 9
g was kneaded with two batch-type closed rolls at 260 ° C. and 80 rotations for 3 minutes. After kneading, 19.6 g of PBT was added,
Kneading was performed for 7 minutes under the same kneading conditions. When the PPE dispersed particle size of the kneaded product was measured in the same manner as in Examples 9 to 13, the average particle size was 450 nm.

Example 15 8.4 g of ABS and SAN-b-PAr of Reference Example 11
4 g was kneaded with two batch-type closed rolls at 260 ° C. and 80 rpm for 3 minutes. After kneading, 19.6 g of PBT was added and kneaded under the same kneading conditions for 7 minutes. PPE of kneaded material
When the dispersed particle size was measured in the same manner as in Examples 9 to 13, the average particle size was 200 nm.

COMPARATIVE EXAMPLE 1 8.4 g of ABS and 19.6 g of PBT were kneaded with two batch-type closed rolls at 260 ° C. and 80 rpm for 7 minutes, and the PPE dispersed phase was dissolved in the same manner as in Examples 1 to 4, followed by SEM. When the dispersed particle size was measured, the average particle size was 5 μm.

Comparative Example 2 In place of the SAN-b-PAr of Examples 9 to 14, SANGMA and ABS of Reference Example 12 were kneaded for 3 minutes under the same conditions.
After kneading, the same amount of PBT and tetra-n-butyl titanate was added in an amount of 0.005 part by weight based on the total weight, kneaded under the same conditions for 7 minutes, and the ABS dispersed particle size of the kneaded product was measured. It was 1 μm. The dispersed particle diameters of the ABSs of the resin compositions of Examples 9 to 15 are all 1 μm or less, and are known PBT / ABS (Comparative Example 1) and PBT / ABS / SA.
It is smaller than the dispersed particle size of NGMA (Comparative Example 2) and has excellent compatibility.

Examples 16 to 19 50 parts by weight of ABS, 50 parts by weight of PBT, ABS and PB
5 parts by weight of the SAN-PAr copolymer relative to the total weight with T was added and dry blended. 30 of this blend
260 ° C, 15 mm mm with a twin screw extruder (L / D = 28)
The mixture was kneaded at 0 rpm and cooled with water to obtain resin pellets. Izod impact test specimens were formed at 260 ° C. using the pellets (with a ８ inch notch), and the impact resistance values were measured. Table 3 shows the results. According to this, Examples 15 to 1
8 is a known PBT / ABS (Comparative Example 3)
As compared with, the Izod impact value is large and the impact resistance is excellent.

[0055]

[Table 3]

Comparative Example 3 50 parts by weight of ABS and 50 parts by weight of PBT were used in Examples 16-1.
The mixture was kneaded under the same conditions as in Example 9, and the Izod impact value was measured in the same manner. As a result, it was 5 kg-cm / cm ² .

Example 20 50 parts by weight of PMMA, 50 parts by weight of PBT and Reference Example 11
Of SAN-b-PAr was added in an amount of 5 parts by weight based on the total weight of ABS and PBT, followed by dry blending. The blend was extruded with a 30 mm φ twin screw extruder (L / D = 28) to 26
The mixture was kneaded at 0 ° C. and 150 rpm and cooled with water to obtain resin pellets. An Izod impact test piece was formed at 260 ° C. using the pellet (with a イ ン チ inch notch), and the Izod impact resistance value was measured to be 10 kg-cm / cm ² . This resin composition was PMMA / PBT (Comparative Example 4)
The impact resistance is better than that of

Comparative Example 4 50 parts by weight of PMMA and 50 parts by weight of PBT were used in Examples 16 to
The mixture was kneaded under the same conditions as in Example 19, and the Izod impact value was measured in the same manner. The result was 0.5 kg-cm / cm ² .

Example 21 In place of PBT in Example 18, PET (intrinsic viscosity 0.7
2dl / g), and the Izod impact value was measured in the same manner. As a result, it was 20 kg-cm / cm ² (with 1/8 inch notch). This is superior in impact resistance as compared with PET / ABS (Comparative Example 5).

Comparative Example 5 The kneading was carried out using the PET of Example 21 in place of the PBT of Comparative Example 3, and the Izod impact value was measured in the same manner. As a result, it was 5 kg-cm / cm ² .

[0061]

The resin composition of the present invention comprises a polyester resin (A) and a polyolefin resin (B), an ester resin portion (a) capable of reacting with the polyester resin (A) by melt-kneading, and a polyolefin resin (A). It comprises a resin composition in which an appropriate amount of a copolymer (C) in which B) and a compatible olefin-based resin part (b) are chemically bonded. Therefore, the reaction between the ester resin part (a) of the copolymer (C) and the polyester resin (A) and the compatibility between the olefin resin part (b) and the polyolefin resin (B) are used to make the polyester. It has become possible to compatibilize the resin (A) and the polyolefin-based resin (B). As a result,
The resin composition of the present invention has higher compatibility than conventionally known resin compositions comprising a polyester resin and a polyolefin resin, and is excellent in moldability, heat resistance, impact resistance, chemical resistance, mechanical strength, etc. , Industrial parts, electronic equipment, housings, general equipment, miscellaneous goods and the like.

Claims (5)

[Claims] 1. A polyester resin having 100 to 100 parts by weight of a resin comprising 95 to 5 parts by weight of a polyester resin (A) having an intrinsic viscosity of 0.5 to 2.0 dl / g and 5 to 95 parts by weight of a polyolefin resin (B). (A) 5-80% by weight of a polyester resin part (a) capable of reacting in the melt-kneading process, and 95-20% by weight of an olefin-based resin part (b) compatible with the polyolefin resin (B). A resin composition comprising 0.003 to 30 parts by weight of a copolymer (C) bonded to a resin. 2. The resin composition according to claim 1, wherein the polyester resin portion (a) of the copolymer (C) comprises an aromatic diol residue and an aromatic dicarboxylic acid residue. 3. The weight ratio of the polyester resin part (a) to the polyolefin resin part (b) of the copolymer (C) is as follows:
The resin composition according to claim 1, wherein the ratio is from 5/95 to 30/70. 4. The resin composition according to claim 1, wherein the polyolefin resin of the olefin resin part (b) of the copolymer (C) is a styrene resin. 5. A resin composition obtained by melt-kneading the resin composition according to claim 1.