JPS63254117A - Improving agent for improving impact resistance and knit line strength of thermoplastic resin and resin composition containing the same - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to epoxy-functionalized elastomeric materials for use as modifiers for thermoplastic resins, and more particularly for use as modifiers for thermoplastic resins. The present invention also relates to glycidyl methacrylate or glycidyl acrylate grafted EPDM impact modifiers for thermoplastic molding compositions with improved impact resistance, particularly for thermoplastic polyester, copolyester and polyblend molding compositions.

Common thermoplastic resins, such as yp IJ carbonate, polyester, polyphenylene ether, polyamide, etc., have properties and properties suitable for the production of molded articles. Such resins typically exhibit, inter alia, good elongation, good tensile strength and good impact resistance. However, it is widely recognized that such resins are notch brittle and are susceptible to brittle failure when subjected to impact due to low grain growth resistance and weakness in the knit lines. These deficiencies in superior physical properties severely limit the usefulness of articles molded from these resins.

Improving the notch brittleness and knit line strength of thermoplastics and preventing brittle failure on impact has been the subject of historical research and development. Generally, these problems are attempted to be solved by adding or mixing into the thermoplastic resin additives that improve notch brittleness without substantially adversely affecting other properties of the thermoplastic resin. There is.

The most common types of such additives are rubber-like or nidistomeric materials that form individual particles dispersed throughout the thermoplastic, such as ethylene/propylene copolymer (EPM), ethylene /propylene/polyene terpolymer (EPDM). However, since the compatibility between such rubber-like or elastomeric materials and many thermoplastics is relatively low, the addition of such rubber-like or elastomeric materials
The desired level of improvement has not been achieved.

The above problems can be overcome by modifying the rubber-like or elastomeric material to provide sites that bond to the thermoplastic and thus increase compatibility with the rubber-like or elastomeric material. Attempts have been made to increase the compatibility between thermoplastic resins and thermoplastic resins.

U.S. Pat. No. 3,435(35)3 (Cope) discloses that polyethylene terephthalate;
A copolymer of alpha olefins of CH=C'H2 (R is hydrogen (in this case ethylene) or an alkyl group of 1 to 3 carbon atoms (in this case propylene or ethene)); Blends of ionic hydrocarbon copolymers modified with alpha-beta ethylenically unsaturated carboxylic acids containing 3 to 5 carbon atoms are disclosed. The test components of the additives used in the implementation are not described or suggested ().

U.S. Patent No. 4,172,859 (Epstein; Epst.
ein, published October 30, 1979), the above-mentioned intermittent fusion is directly expressed. The Epstein patent is somewhat vague in that it attempts to discuss the use of a myriad of substances and combinations thereof as additives to improve the toughness and impact strength of polyesters and polycarbonates.

In the Epstein patent, emphasis is placed on the particle size and tensile modulus of copolymer additives. Epstein describes the use of ethylene-propylene copolymers and ethylene-propylene-polyene terpolymers, among a number of other various materials, and alpha as a modifier to provide bonding sites to the matrix resin.・Although it is intended to use ethylenically unsaturated carboxylic acids, dicarboxylic acids and their anhydrides,
The concept of the invention was not recognized by Epstein.

U.S. Pat. Might make a good impact modifier for polyester (
The invention is based on the idea that if the two are compatible (the present invention is an improvement of that invention), but the two are relatively incompatible (if their rubber-like properties are Polymers are hydrocarbons, whereas polyesters are much more polar substances.) Therefore, it is an object of the present invention to improve the compatibility of ethylene/monoolefin/polyene copolymer rubbers with polyesters. The goal is to significantly modify the copolymer rubber to provide an impact modifier for thermoplastic polyester resins.

Related prior art includes, for example, U.S. Pat. No. 3,886,227.
No. 4,026,967. Also, somewhat related prior art is U.S. Patent No. 3.8134.
, No. 882, No. 3.2'74, 289, No. 3,484
．． 4' (No. 13, No. 3.8 s 2:194, No. 4
, No. 017,557, No. 4,147,740, No. 4,
No. 346,194, No. 3,376,182 and Special Publication No. 45-3 (35). It is described in the specification of No. 43.

The concept of the present invention is embodied in a modifier for improving the impact strength and knit line strength of thermoplastic resins, which modifier is blended and dispersed in the matrix resin. .

The modifier according to the invention consists of an EPM or EPDM backbone rubber subjected to a craft polymerization reaction with an alpha-ethylenically unsaturated hydrocarbon having an epoxy functional surface, the graft polymerization reaction being The process is carried out in bulk at elevated temperatures in the presence of a catalyst. This graft polymerization reaction product is.

Gel content of 5-100%, preferably 7-65%, 10
It is characterized by an epoxy functionality of 2.5 to about 13 per 00 carbon atoms and a degree of grafting of 25 to 8%.

If the graft polymerization is carried out in bulk at elevated temperatures in the presence of a peroxide catalyst, the modifier with the above-mentioned properties is combined with ethylene and one or more C3-C16 monoolefins, preferably propylene. (EPM) or preferably by copolymerization of ethylene, one or more (13-C16 monoolefins (preferably propylene) and one or more polyenes). It is manufactured using the obtained EPDM im.

In the practice of this invention, all or part of the EPDM component can be replaced with EPM rubber.

The EPM rubber is composed of ethylene and one or more monoolefins (preferably propylene, but including 1-butene, 1- is nonane or other (13-C□2 monoolefins) in the presence of a Ziegler-type catalyst. ethylene/monoolefin copolymer, preferably ethylene/monoolefin copolymer made by copolymerization in a solvent solution of
You can use propylene copolymer. The ratio of ethylene:propylene (or (13-C12 monoolefin) is 1
0 to 95 moles of ethylene: 90 to 5 moles of propylene (
or other monoolefins).

The preferred ratio range of ethylene:propylene or other monoolefin is 45 to 75 moles of ethylene = 55
~25 moles of propylene (or other monoolefin).

In the production of EPDM terpolymer rubber, polyene monomers containing multiple carbon-carbon double bonds are
Open-chain polyunsaturated hydrocarbons containing from 4 to 20 carbon atoms (e.g. 1,4-hexadiene), monocyclic polyenes, and polycyclic polyenes.

Polyunsaturated bridged ring hydrocarbons or halogenated bridged ring hydrocarbons are preferred. Examples of such bridged ring hydrocarbons include polyunsaturated derivatives of bicyclo(2,2,1)hebutane in which at least one double bond is present in one of the bridged rings [e.g. Dicyclo is ntadiene, bicyclo(2,2,1)-1'ter-2,5-diene]; alkylidenenorbornenes, especially alkylidene groups of 1 to 20
5-alkylidene-2-norbornenes containing carbon atoms, preferably 1 to 8 carbon atoms; alkenylnorbornenes;
% has about 3 to 20 fulkenyl groups, preferably 3 to 10
5-alkenyl-2-norbornenes containing 5 carbon atoms. Other suitable bridged ring hydrocarbons include polyunsaturated derivatives of bicyclo(2,2,2)octane, typified by bicyclo(3,2,1)octane, and bicyclo(3,3,1)nonane. and polyunsaturated derivatives of bicyclo(3,2,2)nonane.

Specific examples of preferred crosslinked ring compounds include 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-n-propylidene-2-norbornene, 5-isobutylidene-2-norbornene, and 5-n-butylidene-2-norbornene. 2-Norbornene.

5-isobutyritene-2-norbornene, dicyclo is phthalene; 5-(2-methyl-2-butenyl)-2-norbornene or 5-(3-methyl-2-butenyl)-
methylbutenylnorbornenes, such as norbornene;
and 5-(3,5-dimethyl-4-hexenyl)-,2
-Norbornenes. Nidistomer made from 5-ethylidene-2-norbornene has excellent properties,
Highly preferred as it has many very impressive results.

The EPDM main chain rubber has a chemical bond molar ratio of ethylene:propylene or other (13-C16 monoolefin) of 95:10 to 5:10, preferably 70:
It is preferred to present an ethylene:propylene (or other C3-C3-C16 monoolefin) ratio of 30 to 55:45. yp +Jene or substituted polyene is D
PI)M is preferably chemically bonded in the main chain rubber in an amount of 0.1 to 10 mol, preferably 0.3 to 1 mol. The level of unsaturation in the backbone rubber may range from about 0 to 20 double bonds per 01000 carbon atoms in the polymer chain.

What is the final polymerization reaction for producing EPM and EPDM?

It is carried out in a solvent in the presence of a catalyst. The polymerization solvent is
Any suitable inert organic solvent that is liquid under the reaction conditions may be used. Examples of satisfactory hydrocarbon solvents include straight-chain paraffins having 5 to 8 carbon atoms (best results are often obtained with the use of hexane); aromatic hydrocarbons, preferably; Such as sulfur, toluene, etc.
Aromatic hydrocarbons having five or more ring nuclei; Saturated cyclic hydrocarbons having a boiling point in approximately the same range as the linear paraffinic hydrocarbons and aromatic hydrocarbons mentioned above, preferably five or more rings in the ring nucleus; There are saturated cyclic hydrocarbons having 6 carbon atoms. The solvent used may be an aliphatic/naphthenic hydrocarbon mixture having approximately the same boiling range as n-hexane. that the solvent is dry;
It is also desirable that the material does not contain any substance that interacts with the Ziegler type catalyst used in the polymerization reaction.

The copolymerization reaction is carried out in the presence of Ziegler catalysts of well known type. Ziegler-type catalysts are described in U.S. Pat.
No. 33,480, No. 3, (35) No. 3,620, No. 3,
(35) No. 3,621, No. 3,211,7(35), and No. 3,113,115. Examples of Ziegler catalysts include elements 11/a, ■a, ■b, and ■ of the Mendefre Periodic Table of Elements.
Compounds of heavy metals of Group A (e.g. halides of titanium, vanadium and chromium) are organic metal compounds of metals of Groups 1, 1 or 2 of the Mendelev Periodic Table of the Elements, with at least one carbon-metal bond. (e.g., trialkylaluminum halides, allylaluminum halides, in which the alkyl group contains 1 to 20 carbon atoms, preferably 1 to 4 carbon atoms). .

Preferred Ziegler catalysts are made from vanadium compounds and alkyl aluminum halides. Examples of suitable vanadium compounds include vanadium trichloride, vanadium tetrachloride, vanadium oxy[hydride], vanadium acetylacetonate, and the like. Particularly preferred activators include alkylaluminum chlorides of the general formula RIA 42 and R2A!lCυ, as described in U.S. Pat. No. 3,113,115;
Afi. Cρ3 sesquichloride (R is methyl, ethyl,
propyl, butyl or isonotyl). The aluminum:vanadium molar ratio of the aluminum compound and vanadium compound in the catalytic system is 5:1 to 2.
00:1, preferably in the range of 15:1 to 60:1, with 40 parts aluminum: 1 part vanadium.
0 molar ratio appears to give the best results. These molar ratios also apply to the corresponding compounds of other heavy metals used in place of the vanadium compounds and to the corresponding organometallic compounds of Groups 1, 1 and 2 metals used in place of the aluminum compounds. The catalyst made from alkylaluminum sesquichloride S (e.g. methyl or ethylaluminum sesquichloride S) and vanadium oxychloride 8 is preferably in a ratio of 81 moles vanadium oxychloride per 5 to 300 moles aluminum and 15 to 60 moles aluminum. A ratio of 91 moles of vanadium oxychloride per mole is more preferred, with best results being obtained with 40 moles of aluminum per mole of vanadium.

The polymerization is carried out in a reaction vessel closed to the atmosphere and equipped with a stirrer, a cooling device, a device for continuously supplying components such as monomers, catalysts, promoters, and a conduit device for continuously removing the solution containing the nidistomer. It is preferable to carry out the process in a continuous manner. The catalyst is deactivated by the addition of a catalyst deactivator.

The production of EPM and EPDM polymers is well known, eg, US Pat. No. 2,933,480.

No. 3, (35) No. 3,621, No. 3,211,7 (35
) No. 3,646,168, No. 3,790,519
No. 3,884,993, No. 3,894,999, and No. 4,059,654.

Epoxy functionality can also be expressed in the form of monovalent compounds of general formula I below.

(Here, R3 is hydrogen or methyl, R2 is hydrogen,
or alkyl having 1 to about 6 carbon atoms;
R1 is alkylene having 1 to 10 carbon atoms). Preferably R1 is methylene, R2 is hydrogen and R3 is hydrogen (ie the compound of formula I is glycidyl). The epoxy functionality of formula I above is:
attached to the alpha-ethylenically unsaturated moiety of the monomer through any number of organic groups containing carbon-carbon bonds, through amide groups, through ether bonds, or through ester bonds. sell. Appropriately.

Epoxy-functional grafting monomers include glycidyl ethers of unsaturated alcohols, i.e. allyl glycidyl ether, methallyl glycidyl ether; glycidyl esters of unsaturated carboxylic acids, i.e. glycidyl-2-
These include ethyl acrylate, glycidyl-2-propyl acrylate, glycidyl acrylate; glycidyl ethers of alkylphenols, that is, isoproR nylphenyl cricidyl ether; vinyl esters and allyl esters of epoxycarboxylic acids; vinyl esters of epoxidized oleic acid, and the like. Glycidyl methacrylate (GMA) is preferred as the graft monomer in the present invention.

Of course, the main chain formed in the copolymerization reaction need not be a homopolymer or consist entirely of graft monomers that are epoxy functional. for example,
Combinations of the epoxy-functional grafting monomers described above, as well as combinations of such monomers with other alpha-beta ethylenically unsaturated hydrocarbons, can be used. Suitable alpha-ethylenically unsaturated hydrocarbons for use as comonomers include alkenes (including allyl compounds), acrylates and alkyl acrylates, methacrylates and alkyl methacrylates, acrylonitrile, methacrylateryl, styrene. compounds, and vinyl halides. Particularly useful such comonomers are glycidyl methacrylate and methyl methacrylate.

It is important to the present invention that the gel content of the elastomeric material be controlled to be greater than about 5% by weight, preferably greater than about 10% by weight during the polymerization reaction or in the processing described below. The gel content may range up to approximately 100% by weight.

Gel content according to ASTM D-36'16 is measured as a percentage of the weight of diostomeric material remaining after extraction in hexane or toluene. Gel content is a measure of the degree of crosslinking in the elastomeric material. Those skilled in the art are familiar with various methods of controlling the degree of crosslinking and therefore gel content. The crosslinking reaction is a direct bonding of a rubber backbone to a rubber backbone, a bonding of an epoxy functionality to an epoxy functionality or a rubber backbone, or a bonding of a grafted chain to another grafted chain or rubber backbone. sell. Furthermore, cross-linking can also be effected by the addition of cross-linking agents which effectively achieve any of the above-mentioned bonds. Accordingly, any of several means to control gel content may be implemented. Gel content can be increased by thermal aging. Gel content can be increased by increasing the amount of epoxy functional monomer. Gel content can be increased by increasing the amount of polyene monomer in the rubber backbone. Gel content can be increased by adding crosslinking agents. Gel content can be increased by the use of monomers with a greater propensity to crosslink; for example, homopolymer grafts of glycidyl acrylate
It will crosslink more easily than homopolymers of glycidyl methacrylate or copolymers of glycidyl acrylate and methyl methacrylate.

As mentioned above, the gel content of the nidistomer material is approximately 1
00% by weight. However, those skilled in the art will appreciate that cross-linking may also be carried out above a gel content of 100 wt. However, such high levels of crosslinking would cause the elastomeric material to lose its rubbery properties, resulting in a brittle network polymer.

High levels of localized crosslinking will also create areas of weakness within the elastomeric material, thus reducing the rubbery properties of the elastomeric material. It is clear that crosslinking should be kept to the minimum required to achieve a given gel content. Furthermore, such crosslinks should be uniformly distributed throughout the nidistomer material.

This reaction is carried out according to a preferred embodiment of the invention.

It is carried out in a single step bulk reaction method, in which
The individual components forming the modifier are transferred to the injection machine 1. 176.6-2878°C (350-550°F') in the melt processing section of equipment such as Z-burry and similar heat treatment equipment
Preferably 204.4-232.2°C (400-450°C
(°F) for reaction. This results in various reactions between the components, resulting in a more desirable homogeneous system, which (m) functions more effectively in the final formulation with the IJ Sox resin, resulting in improved properties. molded articles can be manufactured from the resin.

The reaction is carried out in the presence of peroxide catalysts such as di-alkyl peroxide 9, dicumyl peroxide 9, t-butylhydronoξ-oxide, benzoyl peroxide, t-butyl ξ-octanoate, di-t -butylno ξ-oxide, t-butylhuman 90 peroxide 8, cumene human 90 peroxide, t-butyl perbenzoate, 2,5-dimethyl-2,5-cy(t-
7'tylnoξ-oxy)hexane, or other sources of hydrogen-absorbing free radicals, such as alkyl peroxy esters, alkyl peroxides, alkyl hydroxides, diacyl peroxides, and the like.

The catalyst is added to the reactor in bulk along with the EPM, reactants and polyamide 8. Such catalyst components are used in amounts ranging from 0.1 to 3 parts by weight per 100 parts by weight of the reactant components comprising the modifier.

The modifier produced according to the present invention exhibits excellent compatibility with the matrix resin with which it is blended, resulting in a more homogeneous product.

In use, the modifiers of the present invention are physically dispersed in the thermoplastic polymer melt and present in the continuous phase of the thermoplastic matrix resin or blend in the form of individual discrete modifier particles. Generally, this requires that the modifier constitute at least 2 parts by weight per 100 parts by weight of the total thermoplastic component including modifier. The matrix resin may contain the elastomeric material up to a phase inversion (ie, up to the point where the elastomeric material becomes the continuous phase).

However, if a rigid article is to be molded from a molding composition containing a modifier, the molding composition should contain no more than about 40 parts by weight of modifier per 100 parts by weight of total thermoplastic components. Should. Dispersion is standard method 1
It is easily carried out, for example, by a simple meltlund method, a dry mixing method, or a melt extrusion method at an appropriate elevated temperature for a given thermoplastic matrix. The resulting mixture is then formed into thermoplastic pieces of specific dimensions.

Alternatively, it may be further extruded into a film or sheet product.

When using the modifier of the invention, it has been found to be advantageous to pre-blend the modifier with a portion (but not all) of the IJ sock fat to form a masterbatch.

Such masterbatches or concentrates can be easily made by coextrusion of the modifier and the concentrate resin.

The molding composition can be made by blending the masterbatch with the remaining resin during an extruder reaction as described above.

Thermoplastic resins suitable for use as masterbatches or matrix resins include epoxy resins, polyolefins, polyimides, polyarylethers, polyphenylene sulfides, polysulfonates, polycarbonates, polyesters, polyphenylene ethers, polyamide 1, etc., and blends thereof. be. In the present invention, the epoxy functionality of the nystomeric material and the hydroxy, carboxyne or amine functionality of the matrix or concentrate resin (reactive derivatives thereof, e.g. esters, salts, It is also contemplated that there may be adhesion reaction products made of (containing ether groups, etc.); The matrix resin, especially the masterbatch, has terminal or in-chain hydroxy, carboxyne, or amine functionality (
(including reactive human 90x or carboxy derivatives)
It may be preferable to have an adhesion reaction. Accordingly, preferred matrix resins, particularly preferred concentrate resin lines, polyamides, polyesters, polycarbonates, polyphenylene ethers, and polymers containing terminal phthalic acid or phthalic anhydride groups.
This is J imido. When concentrate resins having hydroxyl or carboxy functionality are more compatible with the matrix resin compared to the nidistomeric material, such concentrate resins can be used to improve the compatibility of the elastomeric material with the matrix resin. The scales are immediately obvious.

Polyesters suitable for use in the present invention are:

It may be any known linear or branched polyester. Generally, polyesters are Ol=C1o alkyl glycols such as ethylene glycol, furopylene dalicol, 1.4-7' tandiol, etc.

(2) consisting of linear saturated polyesters derived from cycloaliphatic glycols such as 4-cyclohexane dimetatool, and mixtures of these glycols; and one or more aromatic dicarboxylic acids; . Preferably, the polyester is poly(CI) made by known methods.
-□6 alkylene terephthalate). Such known preparations include transesterifying an ester of terephthalic acid alone or a mixture of esters of terephthalic acid and isophthalic acid with a glycol or a mixture of glycols and then polymerizing them; heating the glycol with the free acid or its... and similar methods. These methods are described in U.S. Pat. No. 2,465,319;
It is described in the specification of the same No. 3,047,539. Furthermore, blends of these polyesters or copolyesters can also be used. Appropriate poly (1
, 4-notylene terephthalate) resins are commercially available from General Electric Company under the trademark VALOX 315 J, and ethylene terephthalate resins are also well known and available in abundance.

Polycarbonates suitable for the present invention can be prepared by reacting dihydric phenolic compounds with carbonate precursors such as phosgene, noroformates or ester carbonates. Typically, such polycarbonates will have repeating structural units of the formula % where A is the divalent aromatic radical of the dihydric phenol used in the polymer forming reaction. Preferably, the aromatic carbonate polymer has a temperature of 0.30 to 0.30 when measured in methylene chloride at 25°C
1. It has an intrinsic viscosity of Odfi/9. "Dihydric phenol compound" refers to a mononuclear or polynuclear aromatic compound having two hydroxyl radicals, each of which is bonded to a carbon atom of the aromatic nucleus. means. Typical dihydric phenolic compounds are bisphenols linked by alkylene radicals, ether linkages, or sulfur linkages. Examples of preferred bisphenols include 2,2-his-(4-human90xyphenyl)furopane; 2,2-bis-(3,5
-dimethyl-4-human-80xyphenyl)propane; 4
,4'-Shicht90xy diphenyl ether; His(
2-human quinphenyl)methane; mixtures thereof;
etc. A preferred aromatic carbonate polymer for use in the present invention is 2,2-bis(4-human90xyphenyl)furopane, a homopolymer derived from Sunawati bisphenol A. Suitable polycarbonates, polymerization methods, and starting monomer components are described in U.S. Pat. Nos. 2,999,835 and 3,028,365.

No. 3,334,154, No. 4,131,575, No. 4,018,750 and No. 4,123,436.

Poly(ester carbonate) can also be used as the polycarbonate resin in the present invention. In addition to the dihydric phenols and carbonate precursors mentioned above, poly(ester carbonates) are polymerized from aromatic dicarboxylic acids such as isophthalic acid or terephthalic acid. The production of poly(ester carbonates) is described in U.S. Pat.
(No. 130,331, No. 3,169,121, No. 3,
No. 207,814, No. 4,194, (No. 138 and No. 4
．． 1.56,069.

Polyphenylene ether compounds are also suitable for use in the present invention. Such compounds are generally prepared by oxidative coupling of phenolic compounds with oxygen or oxygen-containing gas in the presence of a catalyst to form homopolymers or copolymers such as those exemplified below. Examples of such polymers include poly(2,6-diphenyl-1°4-phenyl)ether; poly(2,6-cyclo-1,4-phenylene)ether; and the like. Particularly preferred polyphenylene ethers include homopolymers or copolymers having C□-C4 alkyl substituents in the two positions ortho to the oxygen ether atom. As an example of this kind - c is, y (2,
6-dimethyl-1,4-phenylene)ether; poly(
2,6-diethyl-1,4-phenylene) ether; poly(2,6-diprobyl-1,4-phenylene) ether; poly(2-ethyl-6-furopylene-1,4-phenylene) ether; and the like. The most preferred polyphenylene ether is poly(2,6-dimethyl-1,4-phenylene) ether.

Polyphenylene ethers are well known in the art and can be prepared from the corresponding phenols or their reactive derivatives by a number of catalytic or non-catalytic reaction methods. Polyphenylene ethers and their production methods are described in U.S. Pat.
, No. 257,357, No. 3,257,358, No. 3,
No. 337,501 and No. 3,787,361.

Imides suitable for use in the present invention are reaction products of dianhydrides and diamines.

Preferred dianhydrides are bis(aromatic anhydrides), especially bis(aromatic ether anhydrides). Preferred diamines are aromatic diamines and bis(aromatic amines). Preferred polyamides and The method of manufacturing them is described in U.S. Patent No. 4,024,1.
It is described in the specification of No. 01.

Significant improvements in impact strength and knit line strength are experienced with blends of the impact strength modifiers of the present invention and polyamide resins. In this specification, the term "polyamide resin" includes all polymers having repeating carbon amide groups in the main chain and having a molecular weight of 2,000 or more. 1 molecular weight here” means
The number average molecular weights for polyamide 9 are similar (see Flory, Principals of Polymer Chemistry, p. 273; Cornell University Press, 1953).

Typically, polyamide 8 resins are prepared by condensation of 1 equimolar amount of a C2-C2° dicarboxylic acid or derivative thereof with a 02-C15 diamine; or by lactam polymerization by well-known methods. Preferred polyamides of class 1 are those based on lactams and on aliphatic diamines condensed with aliphatic or aromatic dicarboxylic acids. Examples of products in this building include Teha, polyhexamethyleneadipamide'' (nylon 6.6), polycaprolactam (nylon 6), poly(undecaneamide'') (nylon 11).
), polyhexamethylene sebamide (nylon 6.10
), polyhexamethylene isophthalamide, polyhexamethylene tele- and isophthalamide, and mixtures or copolymers thereof.

Similar polyamides are available from Allied under the trademark Capr.
on 8202 Cl and indications “LSM” and “BA
J, and also from Firestone Rubber Company under the trademark R, 228-001. J (low viscosity) and the designation H8 (which means heat stabilized).

Lund products such as those mentioned above can be used alone in the form of let for molding or mixed with other polymers, and can be used as fillers such as glass fibers and mica, as well as pigments, dyes, etc.
It may also contain stabilizers, plasticizers, etc.

The chain component forming the modifier of the present invention is prepared by first reacting two olefinic components in the presence of a Ziegler type catalyst to form a backbone rubber, and then adding a component containing epoxy functionality to the backbone rubber in a solvent solution. Put them together so that they form a graft. An important feature of the present invention lies in the discovery that significant improvements in the properties of the modifier are achieved when the components making up modifier 1 are brought together in a bulk reaction in one step. This not only provides a cheap and easy method for the preparation of modifiers (but also unexpectedly provides a desired degree of epoxy functionality as well as a desired gel content (which is outside the range achievable with solution polymerization methods). The result is a matrix resin blend that exhibits improved knit line strength, an important property for molded products.

The present invention is superior to the prior art in the use of peroxide catalysts in bulk reaction processes, particularly in the presence of unsaturated groups in the reaction components, to achieve the desired high level of crosslinking. Such high levels of crosslinking are a significant factor in achieving improved knit line strength in molded articles made from Blend 8. In the prior art, such crosslinking modifiers were considered undesirable and there was a desire to reduce crosslinking as much as possible.

The present invention will be explained below with reference to Examples. These examples are for the purpose of illustrating the invention and are not intended to limit the invention thereto. The products of the examples were tested in one or more of the following tests.

The degree of grafting (DOG) was measured by IR using a correction curve of the value obtained by IR: the value obtained by filtration. This correction curve was created based on the take for solution polymers.

Gel measurements: Micronized polymer 19 was shaken with 100 Ul of toluene for 4 hours at room temperature. The undissolved polymer was filtered out with glass wool. The percentage of solids in the filtrate was measured and the gel (% insoluble) was determined by difference (ASTM
D3616).

Notched Izo impact strength was measured according to ASTM D256.

Knitline Izo impact strength was measured on unnotched Danorgate molded samples.

Except for this modification, the procedure was similar to ASTM D256.

Tensile strength was measured by ASTM D256.

R8V (reduced solution viscosity) was measured with a 0.1% solution gradient at 135°C.

Mooney viscosity was measured according to ASTM D1646. ML+4 (125°C).

Notchless double gate isot impact strength measurement is AS
A modified method of TM D256, the specimen was double gate injection molded from opposite sides under conditions such that the adhesive line between the ends of the specimen was centered.

Procedure: 20% by weight modifier and 80% by weight “■a10x31
5” [Trademark: Poly(1) manufactured by General Electric Co.
, 4-butylene terephthalate)] to 1 inch (2,54 CrrL) with an L/D ratio of 2071.
It was made by three consecutive extrusions through a single souffler extruder (K11lion J). The temperatures used for this extrusion were 232.2°C (4506F) in zone 1;
232.2°C (4506F) at and 218.3°C at die
(425°F). The extruded strand 8 was air cooled and cut into islets.

The pellets were molded using a plunger injection molding machine at 276.
Test specimens were molded for tensile and notched Izot impact testing at a cavity temperature of 7-282.2°C (530-540°F) and a mold temperature of 93.3°C (200°F). Knitline impact strength samples were molded using a double gate mold attached to a Sfreera injection molding machine. The molded specimens were stored in moisture-resistant polyethylene bags for at least 16 hours prior to testing.

Example 1 2,2 RS V, molar ratio 66/34 Ethylene knob o Helene 8% by weight ethylidenenorbornene EPDM polymer (trademark "EP8yn55"; Copolymer Rubber Antachne Chemical Co.; 9 carbons per 1000 carbon atoms・Carbon double bond C=C) was fed into a twin screw extruder (Warner Ant 9 Fry Puller [Z8 to 30J12 barrel) at a rate of 4.6 lb e/hr. (manufactured by K-tron). The set temperature in the extruder is 70°C in zone 1.
°C, and 200 °C in all other bands. Glycidyl methacrylate/2,5-dimethyl-2,5-di(
A 10/L (w/w) mixture of t-butylperoxy)hexane was fed to the third barrel of the extruder at a rate of 0.385 lb/hr. The extrudate was cooled in a water bath and pelletized. The R-let was dried at 70°C for 4 hours. The dried pellet had a degree of grafting of 586 and a gel content of 17% (toluene method).

Example 2 The same operation as in Example 1 was performed, but the rubber supply amount was 6.
3 lb/hr and the monomer/initiator feed rate was -(13 lb/hr. The dry R let was 4.(1 lb/hr).
The degree of grafting was 3 and the gel content was 14% (toluene method).

Example 3 The same procedure as in Example 1 was carried out, but the rubber feed rate was 6 lb/hr and the monomer/initiator feed rate was 0.214
It was Pound S/hour. Upon drying, the lettuce had a degree of kraft of 2.5 and a gel content of 12% (toluene method).

Example 4 The same operation as in Example 1 was performed, but with the following changes.

(a) The rubber was 2.5R8V 66/34 (mole ratio) ethylene propylene, 4.5% by weight ethylidene norbornene EPDM (Copolymer Rubber Ann 1゛° Chemi-Ryoku' Co., Ltd. "EP Japan: Trademark"). Ta.

(b) Comb feed rate was 5.7 pounds S/hour.

(e) Monomer/initiator feed rate was 0.5 lb/hr.

The dried pellet had a degree of grafting of 48 and a gel content of 65% (toluene method).

Example 5 The same operation as in Example 1 was performed, but with the following changes.

fa) Rubber is 2.2R8V 83/17 (-E-
(ratio) ethylene/propylene, 4.5 wt-i% ethylidene norbornene EPDM (EP: Copolymer/syn manufactured by Rubber & Chemical Co., Ltd.) was torn.

(b) One weight of rubber was 6 pounds/hour.

(C) Monomer/initiator supply amount is 0.45 Bond''
’/ It was the hour.

The dried pellets had a degree of kraft of 4.2 and a gel content of 11% (toluene method).

Example 6 The following ingredients were prepared using cam plate 8 of 4QRPM.
Mixed in a Norabender plasticorder for 5 minutes at 00°C.

2.2R3V, 66/34 (mole ratio) ethylene/propylene, 8 weight ratio ethylidene norbornene EPDM (1
'-EP8yn55 J, manufactured by Copolymer Rubber Antoine Chemical Co.)...60g; Glycidyl methacrylate...4.2g; 2.5-dimethyl-2,5-di(1-butylperoxy)hexane ・...0.429 The obtained product was crushed in pre-goo. Craft level is 4.
It was 5.

Example 7 The same operation as in Example 6 was repeated, but the rubber used was 1,9R8v, 60/40 (mole ratio) ethylene/propylene, o, 5% by weight vinyl norbornene (EP syn
4106: Copolymer Rubber and Chemical Co.). The craft degree was 4.5.

Example 8 The same operation as in Example 6 was carried out, but the rubber used was 2.7
5R8V, 60/40 (mole ratio) ethylene/propylene EPM (EPsyn; manufactured by Copolymer Rubber and Chemical Company). Grafting degree is 0.62
Met.

Example 9 A similar procedure was carried out as in Example 8, but using 4.89 glycidyl acrylate instead of 42 min glycidyl methacrylate, and 0.429 2°5-dimethyl-
0.489 was used in place of 2,5-di(t-butylperoxy)hexane.

Example 10 The same procedure as in Example 8 was carried out, but using 3.69 talindyl acrylate instead of 4.29 glycidyl methacrylate, and 0.42 g of 2,5-dimethyl-2.5-:) 0.369 was used instead of (t-butylperoxy)hexane.

Example 011 The procedure of Example 7 was repeated using allyl glycidyl ether in place of glycidyl acrylate.

Example 12 2,2R8V instead of the rubber used in Example 11.

66/34 (mole ratio) ethylene/propylene, 8% by weight
Ethylidene norbornene EPDM (EP8yn55; Copolymer Rubber Antoine Chemical Company) was used.

Example 13 The operation of Example 9 was repeated, but the result was 429 instead of 4.89.
glycidyl acrylate and 0.4]J instead of 0
．． 21 g of 2,5-dimethyl-2,5-di(t-butylperoxy)hexane was used.

The products of Examples 1 to 13 (in an amount of 20%) were added to polynotylene terephcrate [manufactured by General Electric Co. [V
alox 315 J) (80% amount) and the Lunds were injection molded into specimens for tensile and impact strength as described above.

Control I: This is non-denatured Valox 315
It was J itself.

Control n: This was an 80720 blend of "■a10x315" and the starting rubber of Example 1.

Control ■: This was the same as Example 5 except that the modifier was grafted with a bath solution.

Table 1 summarizes the data for Examples 14-26 and Controls I-■.

The above embodiments describe EPM (ethylene monoolefin, e.g. ethylene propylene) or EPDM (ethylene monoolefin polyene) for dispersion grafting into a thermoplastic matrix resin such as a polyester or polyamide resin. The present invention is believed to demonstrate the superior utility of the bulk polymerization process for producing impact modifiers based on the present invention.

It is clear that the bulk polymerization process of the present invention provides degree of grafting (DOG) and gel content values that are not achievable with conventional solution polymerization processes.

Polymerization method DOG (1) Gel content (1) Solution Less than 2.8 Less than 5 lumpy
Up to 8 5-100 (preferably 7
~65) Glycidyl methacrylate-grafted EPDM and talindyl acrylate-grafted EPM provide comparable properties in polyester Lund products if they are made with the bulk polymerization process of the present invention. If such modifiers are made by solution polymerization methods, glycidyl acrylate grafted polymers yield much poorer properties.

Polyester matrix resins blended with modifiers with a low degree of grafting, such as 2.5% or less, have poor notched eye-jet impact strength.

A gel content of 2.5 inches appears to be the lower limit for the degree of grafting in modifiers (Example 16).

The weight of the initiator used in the preparation of the glycidyl-grafted EPM polymer has a significant effect on the impact strength of the polyester diluent (see Examples 22 and 26).

Unlike blends containing modifiers made by solution polymerization, blends containing modifiers made by bulk polymerization have better knit line impact strength values (1 compared to 4).
(value of 4 or higher).

Example 27 “EP 55 J™ was injected into a twin extruder (Werner & Friederer) at a rate θyn of 4.6 lb S/hr.
Wener, Pfleiderer's "ZsK-3"
0 to 12 barrels). Glycidyl methacrylate/2,5-dimethyl-2,5-di(t-butylnoξ-
1071 mixture of oxy)hexane to the third part of the extruder.
The barrel was fed at a rate of 0.385 lb''/hour. The extrudate was cooled in a water bath and pelletized. The properties of the pellet were: D, O, G, = 5.86° Grafting Efficiency - 82%, gel content = 17%.
Polybutylene terephthalate (1"'V)
alox 315 J, 80% amount), extruded and injection molded into specimens for testing physical properties. Physical properties are tensile strength = 4,390
psi, elongation 43%, bending modulus -210.13
0 psi, Rockwell hardness -R96, 25°C and -2
Notched Izot impact strength at 0℃ 15 each
．． 4 and 4.6 ft-lb"/in, and the unnotched knit line impact strength is 13.0 ft-lb"
'/inch.

Example 28 The same operation as in Example 1 was repeated, but the rubber feed rate was 6.0 yt''/hour and the monomer/initiator feed rate was 0.214 yt''/hour. . The properties of the halet are D, O, G = 2.5, grafting efficiency -79%
, gel content=12%. "'Valox315"
The physical properties of the blend with tensile strength 4 (130 p
si, elongation 50%, bending modulus 194.600p
si, notched isot impact strength was 3.8 ft·lb 97 inches (25°C).

From the above, it can be seen that (a) the grafting efficiency is almost unchanged regardless of the amount of glycidyl methacrylate fed, and (b) there is a significant drop in impact strength at low O, G, and gel contents (15,11 It is clear that there is a drop from ' to 3.8).

(4 other people)

Claims (72)

[Claims] (1) A modifier dispersed in a thermoplastic resin to improve the impact strength and knit line strength of the resin, the modifier comprising: (i) (a) 1 containing ethylene and 3 to 16 carbon atoms;
(b) EPDM rubber obtained by copolymerization of ethylene, one or more C_3 to C_1_6 monoolefins and a polyene; The selected elastomeric backbone polymer and (ii) a graft monomer in the form of an alpha-beta ethylenically unsaturated hydrocarbon having epoxy functionality are graft-polymerized in bulk at elevated temperatures in the presence of a peroxide catalyst. 5% of the bulk polymerization reaction product.
Greater gel content, from 2.5 per 1000 carbon atoms
Epoxy functionality within the range of 13.0 and at least 2
．． The above-mentioned improving agent is characterized in that it has a degree of grafting of 5%. (2) The improving agent according to claim 1, wherein the bulk polymerization reaction product has a gel content in the range of 7 to 65%. (3) The main chain polymer is 2 to 20 carbon atoms per 1000 carbon atoms.
The improving agent according to claim 1, which contains carbon-carbon double bonds. (4) The epoxy functional graft monomer has the general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (where R^3 is hydrogen or methyl, and R^2 is hydrogen or alkyl having 1 to 6 carbon atoms. , and R
^1 is alkylene having 1 to 10 carbon atoms. ) The improver according to claim 1, which is an alpha-beta ethylenically unsaturated hydrocarbon having the following properties. (5) The improving agent according to claim 1, wherein the graft monomer is selected from the group consisting of glycidyl acrylate and glycidyl methacrylate. (6) EPDM rubber contains ethylene, propylene and 5-
The improving agent according to claim 1, which is a copolymer of ethylidene-2-norbornene. (7) The improver according to claim 1, wherein the EPM rubber is a copolymer of ethylene and propylene. (8) The improver according to claim 7, wherein ethylene and propylene are present in a combined state in a ratio of 10 to 95 moles of ethylene:90 to 5 moles of propylene. (9) The modifier of claim 1, wherein the grafting monomer is present in an amount providing an epoxy functionality of 2.5 to 13 per 1000 carbon atoms in the bulk polymerization reaction product. (10) The improver according to claim 1, wherein the peroxide catalyst is used in an amount within the range of 0.1 to 3.0 parts by weight per 100 parts by weight of the main chain polymer. (11) (I) (a) EPM rubber obtained by copolymerization of ethylene with one or more monoolefins containing from 3 to 16 carbon atoms; and (b) ethylene, one or more monoolefins containing 3 to 16 carbon atoms. Grafting in the form of an elastomeric backbone polymer selected from the group consisting of EPDM rubbers obtained by copolymerization of C_3 to C_1_6 monoolefins and polyenes and (II) an alpha-beta ethylenically unsaturated hydrocarbon with epoxy functionality. It consists of a step of bulk reacting monomers at elevated temperatures in the presence of a peroxide catalyst,
and a thermoplastic resin, characterized in that the bulk reaction product has a gel content of greater than 5%, an epoxy number of greater than 2.5 per 1000 carbon atoms and a degree of grafting of at least 2.5%. A method for making a modifier that improves the impact strength and knit line strength of the resin when mixed. (12) The method according to claim 11, wherein the various components are reacted in bulk in a single step in a melt processing device. (13) The method according to claim 11, wherein the bulk reaction is carried out at a temperature within the range of 176.6 to 287.8°C. (14) Main chain polymer is 2 to 2 per 1000 carbon atoms
Claim 11 containing 0 carbon-carbon double bonds
The method described in section. (15) The method according to claim 11, wherein the gel content of the reaction product is within the range of 7 to 65%. (16) Reaction product is 2.5 to 1000 carbon atoms
12. The method of claim 11 having an epoxy functionality within the range of 13.0. (17) The method according to claim 11, wherein the graft monomer is an alpha-beta ethylenically unsaturated hydrocarbon. (18) The method according to claim 17, wherein the graft monomer is selected from the group consisting of glycidyl acrylate and glycidyl methacrylate. (19) The graft monomer is added to the main chain polymer from 0.1 to
12. The method of claim 11, wherein the method is present in an amount within the range of 3.0% by weight. (20) The improving agent according to claim 1, wherein the degree of grafting is within the range of 2.5 to 8. (21) The method according to claim 11, wherein the degree of grafting is within the range of 2.5 to 8. (22) (a) high molecular weight thermoplastic polyester, and (
b) Grafting at least 2% by weight based on the EPDM terpolymer with glycidyl methacrylate or glycidyl acrylate or mixtures thereof alone or in combination with C_1-C_1_8 alkyl methacrylates or acrylates or mixtures thereof. an effective amount of an impact modifier comprising an EPDM terpolymer, and component (b) is about 10 to
A thermoplastic resin composition with improved impact resistance characterized by having a gel content in the range of about 80% by weight. 23. The composition of claim 22, wherein at least about 60% by weight of the impact modifier has a particle size greater than about 1 micron in diameter. (24) The grafted EPDM terpolymer is approximately 45
23. The composition of claim 22, which is derived from ~70 mole percent ethylene, about 30-55 mole percent propylene, and a small amount of 5-ethylidene-2-norbornene. 25. The composition of claim 22, wherein the glycidyl ester grafted EPDM terpolymer is present in an amount of about 1.5 to 80% by weight based on the total composition. (26) The grafted EPDM is approximately 10
23. The composition of claim 22, wherein the composition is present in an amount of -55% by weight. (27) High molecular weight thermoplastic polyester resin is poly(
23. The composition of claim 22, wherein the composition is selected from the group consisting of ethylene terephthalate), poly(1,4-butylene terephthalate), copolyesters, or any combination thereof. (28) The composition according to claim 27, wherein the thermoplastic polyester resin is poly(1,4-butylene terephthalate). (29) The composition according to claim 27, wherein the thermoplastic polyester resin is poly(ethylene terephthalate). (30) Thermoplastic polyester resins are derived from one or more aliphatic and/or aromatic dicarboxylic acids and one or more linear or branched aliphatic and/or cycloaliphatic glycols. 28. The composition of claim 27, which is a polyester copolyester. (31) The composition according to claim 30, wherein the copolyester is a random copolyester. (32) The composition according to claim 30, wherein the copolyester is a block copolyester. (33) The composition according to claim 27, wherein the thermoplastic polyester resin is a polyblend of poly(ethylene terephthalate) and poly(1,4-butylene terephthalate). (34) Grafting 2% by weight or more based on the EPDM terpolymer of glycidyl methacrylate or glycidyl acrylate, or a mixture thereof alone, or a combination of the above and a C_1 to C_1_8 alkyl methacrylate or acrylate, or a mixture thereof. blending an impact modifier comprising an EPDM terpolymer with a high molecular weight thermoplastic polyester resin in an amount effective to improve impact strength; Approximately 80
characterized by having a gel content in the range of % by weight,
A method of producing an impact-enhancing thermoplastic molding composition. 35. The method of claim 34, wherein about 60% by weight or more of the impact modifier has a particle size of about 1 micron or more in diameter. (36) High molecular weight thermoplastic polyester resin is poly(
Claim 24 selected from the group consisting of ethylene terephthalate), poly(1,4-butylene terephthalate), copolyester or any combination thereof.
The method described in section. (37) High molecular weight thermoplastic polyester is poly(1,4
- butylene terephthalate)
The method described in Section 6. (38) An article comprising a container blow-molded from the impact-improved thermoplastic composition according to claim 22. (39) In preparing thermoplastic polyester or polyamide-based compositions with improved toughness and impact strength: (a) first in the presence of a free radical initiator in an amount less than the total amount of the polyester or polyamide matrix resin; (I) ethylene, one or more C_
a backbone rubber selected from EPDM rubber obtained by copolymerization of 3 to C_1_6 monoolefins and polyenes, EPM rubbers obtained by copolymerization of ethylene and one or more C_3 to C_1_6 monoolefins, or mixtures thereof; (II) forming a masterbatch by reaction with an acrylic or methacrylic ester having epoxy functionality; (b) then blending the masterbatch with the remainder of the matrix resin. . (40) The method according to claim 39, wherein the ethylene/monoolefin/polyene copolymer rubber is an ethylene/propylene/5-ethylidene-2-norbornene copolymer rubber. (41) The method according to claim 39, wherein the ethylene/monoolefin copolymer rubber is ethylene/propylene rubber. (42) A method according to claim 41, wherein the ethylene and propylene are present in combination in a ratio of 10 to 95 moles of ethylene:90 to 5 moles of propylene. 43. The method of claim 40, wherein the ethylene and propylene are present in the copolymer in a ratio of 10 to 95 moles of ethylene:90 to 5 moles of propylene. 44. The method of claim 40, wherein the polyene is present in an amount to provide 0 to 20 C═C groups per 1000 carbon atoms in the copolymer. (45) The method according to claim 44, wherein the ester of methacrylic acid is glycidyl methacrylate. (46) The method according to claim 44, wherein the ester of acrylic acid is glycidyl acrylate. (47) Ester with epoxy functionality is main chain rubber 1
40. A method according to claim 39, wherein the amount is within the range of 2 to 15 parts by weight per 00 parts by weight. (48) The method according to claim 39, wherein the reaction is carried out at elevated temperature in the presence of a peroxide catalyst in an amount ranging from 0.1 to 3.0 parts by weight per 100 parts by weight of main chain rubber. . (49) The method of claim 39, wherein the masterbatch is formulated to contain 20-80% of the matrix resin present in the final blend. (50) The method of claim 39, wherein the masterbatch is formulated to contain 20-60% of the matrix resin present in the final blend. (51) The method according to claim 39, wherein the ratio of main chain rubber to matrix resin in the masterbatch is within the range of 50 to 80 parts by weight of main chain rubber: 50 to 20 parts by weight of matrix resin. . (52) The method according to claim 39, wherein the ratio of main chain rubber to matrix resin in the masterbatch is within the range of 60 to 80 parts by weight of main chain rubber: 40 to 20 parts by weight of matrix resin. . (53) The method according to claim 39, wherein the components for making the masterbatch are reacted in a single step in a melt processing apparatus. (54) 176.6 reaction to make masterbatch
40. The method of claim 39, carried out at a temperature in the range of -287.8<0>C. (55) A polyester-based thermoplastic molding composition produced by the method according to claim 39. (56) A polyester-based thermoplastic molding composition made by the method according to claim 45. (57) The method according to claim 39, wherein the main chain rubber and the ester of acrylic acid or methacrylic acid are reacted in advance with a matrix resin in an amount smaller than the total amount of matrix resin constituting the masterbatch. (58) A product produced by the method according to claim 57. (59) In producing a masterbatch for blending with a polyester or polyamide matrix resin to make a thermoplastic molding composition: Matrix resin less than the total amount of matrix resin in the final product; EP
a backbone rubber selected from DM copolymer rubber, EPM copolymer rubber, mixtures thereof; and an acrylic or methacrylic ester having epoxy functionality; from reacting in the presence of a free radical initiator. A method for producing the above-mentioned molding composition. (60) EPDM is a copolymer of ethylene/one or more C_3 to C_1_6 monoolefins/polyene, and the ethylene:monoolefin ratio bonded in the copolymer is 90 to 5. 10-9
59. The method of claim 59, wherein the amount of propylene is within the range of No. 5 propylene. (61) The polyene is 5-ethylidene-2 present in an amount giving up to 20 C═C groups per 1000 carbon atoms.
- norbornene. The method of claim 60. (62) EPM consists of ethylene and one or more C_
59. The method according to claim 59, wherein the copolymer is a copolymer with 3 to C_1_6 monoolefin. (63) EPM is a copolymer in which ethylene and propylene are combined in the rubber in a ratio of 10 to 95 moles of ethylene:90 to 5 moles of propylene.
The method described in Section 1. (64) Ester of methacrylic acid has 100% of main chain rubber.
60. The method of claim 59, wherein the glycidyl methacrylate is present in an amount within the range of 2 to 15 parts by weight per part by weight. (65) The reaction was carried out in the presence of a peroxide catalyst from 176.6 to
60. The method of claim 59, carried out at elevated temperatures within the range of 287.8<0>C. 66. The method of claim 65, wherein the catalyst is present in an amount ranging from 0.1 to 3.0 parts by weight per 100 parts by weight of rubber. (67) The method according to claim 59, wherein the masterbatch contains a ratio of 50 to 80 parts by weight of main chain rubber to 50 to 20 parts by weight of polyester. (68) The method of claim 59, wherein the masterbatch is made in a single step in a melt processing apparatus. (69) The masterbatch is prepared by reacting the main chain rubber and the epoxy component in the presence of a peroxide catalyst and dispersing the reaction product in less than the total amount of the polyester matrix resin. The method according to item 59. (70) A masterbatch produced by the method according to claim 59. (71) A masterbatch produced by the method according to claim 69. (72) A masterbatch produced by the method according to claim 68.