JPH044204A - Epoxidized low-molecular weight ethylene-alpha-olefin copolymer and thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject resin composition excellent in impact resistance, molding processability and surface properties of molded products by specifying the contents of an ethylene component, an alpha-olefin component and a non- conjugated diene component within specific ranges and epoxidizing part of double bonds in the non-conjugated diene component. CONSTITUTION:The objective copolymer is obtained by copolymerizing ethylene with a 3-20C alpha-olefin (e.g. propylene) and a non-conjugated diene (e.g. dicyclopentadiene) using a radical polymerization catalyst, then adding hydrogen peroxide thereto, vigorously stirring and reacting the mixture. The aforementioned copolymer has 30-70mol% content of the ethylene component, 25-70mol% content of the alpha-olefin component, 3-100 content of the non- conjugated diene component expressed in terms of iodine value and 300-50000 weight-average molecular weight expressed in terms of polystyrene. More than 1% of double bonds in the non-conjugated diene component of the random low-molecular weight copolymer composed of ethylene, the 3-20C alpha-olefin and the non-conjugated diene are epoxidized.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to epoxidized low molecular weight ethylene-α-olefin copolymers and thermoplastic resin compositions, and more particularly to the modification of various rubbery or resinous polymers. A novel epoxidized low molecular weight ethylene-α-olefin copolymer suitable as a modifying agent or a modification aid, an adhesive, a sealant, a roofing agent, etc., and impact resistance, moldability and The present invention relates to a thermoplastic resin composition with excellent surface properties of molded products.

[Conventional technology]

Hitherto, a modified olefin polymer obtained by epoxidizing an ethylene-α-olefin-nonconjugated diene copolymer has been known (Japanese Patent Laid-Open No. 168750/1983). However, because the modified copolymer has a high molecular weight, it has poor dispersibility in rubbers and resins, and when used as adhesives, sealants, and roofing agents, it has poor fluidity, so it is difficult to obtain sufficient performance. The disadvantage is that it cannot be used. On the other hand, since unmodified low molecular weight ethylene-α-olefin copolymers are non-polar, they have a drawback of low compatibility with polar rubbers and polar resins, and poor performance as modifiers.

Furthermore, JP-A-63-305104 discloses a modified low molecular weight ethylene-α-olefin copolymer in which the terminal double bond is epoxidized. Since there are only 3 epoxy groups, the molecular weight must be extremely low in order to obtain a highly polar epoxidized ethylene-α-olefin copolymer.Also, since epoxy groups exist only at the ends, the epoxy groups Since the crosslinking reaction does not occur, the dispersion effect is poor.

Furthermore, conventionally, thermoplastic resins such as polypropylene, AS resin, thermoplastic polyester, and polyamide have excellent mechanical strength, electrical properties, chemical resistance, molding processability, and molded product surface properties, so they are used in the automotive field. Widely used in electrical and electronic fields. Since these resins have poor impact resistance after notching, a method of blending rubbery polymers, plasticizers, etc. as modifiers has been adopted.

However, when a rubbery polymer is used, the impact resistance is improved, but it has the disadvantage of poor moldability, and when a plasticizer is used, the plasticizer remains on the surface of the molded product. It has the disadvantage that the surface quality deteriorates because it stands out.

Recently, there has been a demand for improved performance of modifiers, modifiers, adhesives, sealants, roofing agents, etc. for various resins or rubber-like polymers.

[Problems to be Solved by the Invention] The first object of the present invention is to eliminate the drawbacks of the prior art,
Epoxidized low molecular weight ethylene-α-olefins with excellent dispersibility when used as modifiers and modifiers for various resins or rubbery polymers, and excellent performance as adhesives, sealants, and roofing agents. The purpose is to provide a polymer.

A second object of the present invention is to provide a thermoplastic resin composition that uses the above-mentioned epoxidized low molecular weight ethylene-α-olefin copolymer and has excellent impact resistance, moldability, and surface properties of molded products. be.

[Means to solve the problem]

The first aspect of the present invention is that (A) the ethylene component content is 30 to 75
Mol% and α-olefin component content are 70 to 25 mol%, (B) non-conjugated diene component content is 3 to 10 in terms of iodine value.
0 and (C) polystyrene equivalent weight average molecular weight is 3
00-50,000, ethylene and carbon number 3-20
Epoxy obtained by epoxidizing 1% or more of the double bonds of the non-conjugated diene component in a random low-molecular-weight copolymer (hereinafter simply referred to as "low-molecular-weight copolymer") consisting of an α-olefin and a non-conjugated diene. epoxidized low molecular weight ethylene-α-olefin copolymer (hereinafter simply referred to as "epoxidized low molecular weight copolymer").

The second aspect of the present invention is a thermoplastic resin containing 100 parts by weight of a thermoplastic resin, 1 to 80 parts by weight of the above-mentioned epoxidized low molecular weight copolymer, and 0 to 80 parts by weight of a high molecular weight ethylene-α-olefin copolymer. The present invention relates to a resin composition.

The low molecular weight copolymer used in the first invention consists of ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated diene, and includes (A) an ethylene component [ethylene units represented by -CH2CH2+] content; is 30 to 75 mol%, preferably 40 to 70 mol% and α-olefin component C+C
α-olefin unit represented by H28H+, where R represents an alkyl group having 1 to 18 carbon atoms] content is 70 to 25 mol%, preferably 60 to 30 mol%, (B) non-conjugated diene component content is iodine Value of 3 to 100, preferably 10 to 100
80 and (C) polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 300 to 50 000, preferably 1.0
00 to 30,000. Molecular weight distribution [Mw/Mn (polystyrene equivalent number average molecular weight)] is 4
The following are preferable, and 1.2 to 3.5 are more preferable. Mw
If it is less than 300, the mechanical strength of the compound will be reduced;
,000, the fluidity is poor. Further, copolymers outside the above range are inferior in the effect of improving mechanical properties when used as a modifier for various resins or rubber-like polymers.

Examples of α-olefins having 3 to 20 carbon atoms include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, -octadecene, 1-eicosene, etc. are used. The amount of the α-olefin used is preferably 25 to 70 mol%, more preferably 30 to 70 mol%, based on the low molecular weight copolymer.
It is in the range of 60 mol%.

Non-conjugated dienes include 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene,
2,5-norbornadiene, 2-methyl-2,7-octadiene, etc. are used. Among these, dicyclopentadiene is preferred from the viewpoint of improving the reactivity of epoxidation.

The low molecular weight copolymer is a Ziegler-Natsuta type catalyst system consisting of ethylene, an α-olefin and a non-conjugated diene, and a transition metal compound and an organometallic compound, such as vanadium and organoaluminium, titanium and organoaluminum, etc. It can be synthesized by a known method in the presence of.

The epoxidized low molecular weight copolymer of the first invention is characterized in that one of the double bonds of the non-conjugated diene component in the low molecular weight copolymer is
% or more, preferably 10% or more, more preferably 20%
This is a copolymer obtained by epoxidizing the above. If the epoxidation content is less than 1%, the effect of improving mechanical properties when used as a modifier for various resins or rubber-like polymers is poor.

Epoxidation of a low molecular weight copolymer can be carried out by, for example, (1) a method of reacting a mixture of a low molecular weight copolymer, an organic acid such as formic acid or acetic acid, and aqueous hydrogen peroxide; (2) a method of reacting a low molecular weight copolymer with an organic acid such as formic acid or acetic acid; This can be carried out by a method of reacting with an organic peroxide such as m-chloroperbenzoic acid or perbenzoic acid.

In the case of the former method, the low-molecular-weight copolymer is either left in bulk or dissolved in an organic solvent such as an aromatic hydrocarbon such as toluene, xylene, benzene, or a saturated hydrocarbon such as hexane, heptane, or octane. Used as a 50% solution. The amount of organic acid used is usually 0.2 to 2.0 times the mole, preferably 0.4 to 1.7 times the mole of double bonds in the low molecular weight copolymer. The amount of water used is usually 1% per double bond in the low molecular weight copolymer.
．． 0 to 5.0 times the mole. An epoxidized low molecular weight ethylene random copolymer can be obtained by stirring and reacting these mixed liquids at a temperature of, for example, 10 to 60°C for 1 to 10 hours.

In the case of the latter method, for example, the low molecular weight copolymer is prepared as a 5 to 50% solution of a halogenated hydrocarbon such as methylene chloride, and an organic peracid is added to the solution to reduce the double bonds in the low molecular weight copolymer. .01 to 1.50 times mole, preferably 0.1 to 1
．． An epoxidized low molecular weight copolymer can be obtained by adding 20 times the mole amount and reacting at room temperature for 1 to 10 hours.

The epoxidized low molecular weight copolymer of the first invention has many epoxy groups in one molecule of the copolymer and has high polarity, so it has excellent dispersibility in rubbers, resins, etc., and is suitable for modification of these. It has excellent performance as a lubricating oil additive, a dispersion aid for aqueous dispersants, a paint and its modifier, an adhesive, a sealant, a roofing agent, etc. Furthermore, crosslinking reactions between epoxy groups are possible.

Furthermore, by using it as a component of a thermoplastic resin composition described later, impact resistance, molding processability, and surface properties of molded products can be improved.

The thermoplastic resin composition of the second invention comprises 100 parts by weight of a thermoplastic resin and 1 part by weight of the epoxidized low molecular weight copolymer.
~80 parts by weight, preferably 2 to 60 parts by weight, as an essential component. The composition may further contain a high molecular weight ethylene-α-olefin copolymer as a rubbery polymer in an amount of 0 to 80 parts by weight, preferably 0 to 60 parts by weight. If the amount of the epoxidized low molecular weight copolymer used is outside the above range, the effects of improving the impact resistance, moldability and surface properties of molded products of the thermoplastic resin composition will be poor.

The thermoplastic resin used in the second invention includes polystyrene, AS resin, (meth)acrylic acid alkyl ester-styrene copolymer resin, high-impact polystyrene, AB
Styrene resins such as S resin and MBS resin, olefin resins such as polyethylene and polypropylene, vinyl resins such as vinyl chloride resin and vinyl acetate resin, thermoplastic polyester, polyamide, polyarylether, polysulfone, polycarbonate, polyacetal, heat Plastic iso-cyanate resin, polyphenylene ether, thermoplastic urea resin, polyarylene sulfide, polyimide,
Examples include polyarylene ketones. These thermoplastic resins may be used alone or in combination of two or more.

The (meth)acrylic acid alkyl ester used in the (meth)acrylic acid alkyl ester-styrene copolymer resin includes methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, and 2-ethyl acrylate. Acrylic acid alkyl esters such as hexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl Examples include methacrylic acid alkyl esters such as methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, and benzyl methacrylate;
Used in one species or in combination of two or more.

The impact-resistant polystyrene, ABS resin, or MBS resin is usually polymerized in the presence of a rubbery polymer. The proportion of the rubbery polymer in these rubber-modified resins is usually 1 to 70% by weight, preferably 5 to 60% by weight.

As the rubbery polymer, polybutadiene, styrene-
Butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-butadiene random copolymer, hydrogenated acrylonitrile-butadiene copolymer Coalescence, propylene as α-olefin, butene-11 pentene-11 hexene-11
Ethylene-α-olefin copolymers using hebutene-1,4-methylpentene-1,4-methyltene, etc., ethylene ionomers, polyacrylic acid ester rubbers, ethylene-α-olefin-polyene copolymers, etc. Can be mentioned. Further, in the styrene-butadiene block copolymer and hydrogenated styrene-butadiene block copolymer, AB type, ABA type, ABA tapered type, radial teleblock type, etc. can be used. These rubbery polymers may be used alone or in combination of two or more.

Impact-resistant polystyrene is obtained by polymerizing an aromatic vinyl compound mainly composed of styrene in the presence of a rubbery polymer. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromustyrene, dibromostyrene, P-tert-butylstyrene, ethylstyrene, etc. These may be used alone or in combination of two or more.

ABS resin is obtained by polymerizing the above-mentioned aromatic vinyl compound mainly composed of styrene and a vinyl cyanide compound mainly composed of acrylonitrile in the presence of a rubbery polymer. As the vinyl cyanide compound, acrylonitrile,
Examples include methacrylate trile.

The MBS resin is obtained by polymerizing the above-mentioned aromatic vinyl compound mainly composed of styrene and a (meth)acrylic acid alkyl ester mainly composed of methyl methacrylate in the presence of a rubbery polymer. As the (meth)acrylic acid alkyl ester, those mentioned above can be used.

The impact-resistant polystyrene, ABS resin or MBS resin contains, in addition to the aromatic vinyl compound, other vinyl monomers copolymerizable with these, preferably at most 30% by weight.
More preferably, it can be used in a range of 10% by weight or less. Examples of the other copolymerizable vinyl monomers include unsaturated acids such as acrylic acid, methacrylic acid, and maleic acid, unsaturated acid anhydrides such as maleic anhydride and maleic anhydride, glycidyl methacrylate, and allyl glycidyl ether. epoxy group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds such as 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate, amino group-containing unsaturated compounds such as p-aminostyrene and aminoethyl acrylate, and amides such as acrylamide. group-containing unsaturated compounds,
Maleimide compounds such as N-phenylmaleimide and N-cyclohexylmaleimide, vinyl acetate, N-vinylpyrrolidone, and the like may be mentioned, and these may be used alone or in combination of two or more.

The thermoplastic polyester is obtained, for example, by condensation polymerization of a dicarboxylic acid and a diol component.

Examples of dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glitaric acid, adipic acid, superric acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, p-carboxyphenoxyacetic acid, and P.

p9-dicarboxydiphenyl, p, p”-dicarboxydiphenyl sulfone, p-carboxyphenoxyacetic acid, p-carboxyphenoxypropionic acid, P-carboxyphenoxybutyric acid, P-carboxyphenoxyvaleric acid, p-carboxyphenoxyhexanoic acid, p , p'-dicarboxydiphenylmethane, p,p'-dicarboxydiphenylpropane, p,p'-dicarboxydiphenyl octane, 3-alkyl-4-(β-carboxyethoxy)benzoic acid, 2,6-naphthalene dicarboxylic acid ,2
．． 7-naphthalene dicarboxylic acid, derivatives thereof, etc. are used. These may be used singly or in combination, and terephthalic acid and a mixture of terephthalic acid and isophthalic acid are particularly preferred.

As the diol component, aliphatic diols or aromatic diols are used. Examples of aliphatic diols include ethylene glycol, 1,3-propylene glycol,
1.4-tetramethylene glycol, 1,6-hexylene glycol, 1゜10-decamethylene glycol, 1
, 12-dodecamethylene glycol, etc. having 2 to 1 carbon atoms
2 linear alkylene glycols are mentioned. Examples of aromatic diols include bisphenol A, p-xylene glycol, pyrocatechol, resorcinol, hydroquinone, alkyl-substituted derivatives of these compounds, and derivatives thereof. These may be used alone or in combination of two or more.

In addition, as thermoplastic polyesters, polyesters obtained from P-hydroxybenzoic acid and its derivatives,
Those obtained by copolymerizing the above dicarboxylic acid and/or diol components, and further known polyester elastomers can also be used.

Preferred thermoplastic polyesters include polyethylene terephthalate, polybutylene terephthalate, polyesters made of terephthalic acid and/or isophthalic acid and bisphenol A, and polyesters having p-hydroxybenzoic acid residues. It is particularly preferred since it has a large effect of improving impact resistance.

The polyamide is a condensation product containing as a constituent a repeating unit having aromatic and/or aliphatic amide groups, for example, a monoamino compound having at least 2 carbon atoms between an amino group and a carboxylic acid group. - A method of polymerizing a monocarboxylic acid or a lactam thereof, a method of condensation polymerization of a diamine having at least two carbon atoms between one amino group and a dicarboxylic acid or a derivative thereof in substantially equimolar amounts, the monoamino - Obtained by condensation polymerization of monocarboxylic acid or its lactam together with substantially equimolar amounts of diamine and dicarboxylic acid.

Examples of monoamino-monocarboxylic acids or lactams thereof include ε-aminocarboxylic acid, butyrolactam, bivalolactam, caprolactam, capryllactam, enantholactam, undecanolactam, dodecanolactam, 3- and 4-aminobenzoic acid, and the like. It will be done.

Examples of diamines include those with the general formula H2N (CHz), NH2, such as trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, dodecamethylenediamine, and hexadecamethylenediamine.
(in the formula, n is an integer of 2 to 16); for example, 2.2=dimethylpentamethylenediamine, 2,2
．． 4-trimethylhexamethylenediamine, 2.44-
Alkylated diamines such as trimethylhexamethylene diamine; aromatic diamines such as P-phenylene diamine, 4,4'-diaminodiphenyl sulfone, 4,41-diaminodiphenyl ether, m-phenylene diamine, 4,4'-diaminodiphenylmethane, etc. ; Examples include alicyclic diamines such as diaminodicyclohexylmethane. These may be used alone or in combination of two or more.

As the dicarboxylic acid, aromatic dicarboxylic acids and/or aliphatic dicarboxylic acids are used.

Examples of aromatic dicarboxylic acids include isophthalic acid and terephthalic acid, and examples of aliphatic dicarboxylic acids include oxalic acid and general formulas such as sebacic acid, octadecanedioic acid, glutaric acid, pimelic acid, and adipic acid. H
Examples include dicarboxylic acids represented by 00C-R-C00H (wherein R is a divalent aliphatic group having at least 2 carbon atoms). These various compounds can be used alone or in combination of two or more.

Furthermore, known polyamide elastomers such as polyesteramide elastomer, polyetheresteramide elastomer, and polyetheramide elastomer can also be used as the polyamide. Preferred polyamides include nylon 6, nylon 66, nylon 46, and nylon 12.
, nylon MXD6 (polymethaxylylene adipamide), and the like.

The polyarylether is a residue of a dihydric phenol selected from the general formula (1) -(-0-R-0-R'→-, and R' is the residue of the above formula (If) and ( In the formula, Z represents oxygen, sulfur, or an aromatic diol residue such as 4.4-bisphenol.Specific examples of this repeating unit include dipromohenze selected from is a noid compound residue or a short benzenoid compound residue, and Q and Ql are -〇-1-S--SO□- or a divalent hydrocarbon residue having 1 to 18 carbon atoms containing these groups ( However, when Q is 10-, Qo is other than 10-, and when Q" is -0-, Q is other than 0-, and R is of the formula (I
t), R'' is the formula (IV), and R'' is the formula (II
), R is the formula (IN)] is used.

Examples of the polysulfone include those having H3 repeating units in various proportions in the repeating unit. A preferred polysulfone is CH3.

The polycarbonate has general formula (VI) general formula (■)-〇(-A r-0-C-0→T (wherein, Ar is a phenylene group, or an alkyl group, an alkoxy group, a halogen atom, or a nitro group). A is a carbon-carbon bond, an alkylidene group, a cycloalkylidene group, an alkylene group, a cycloalkylene group, an azoimino group, a sulfur atom, an oxygen atom or a sulfoxide group, and n is an integer of at least 2. Preferred polycarbonates include those in which Ar in formula (■) or (■) has a P-phenylene group and A has an isopropylidene group.

The polyacetal is a polymer obtained by polymerizing formaldehyde or trioxane. Polyacetals made from formaldehyde have the formula −+C
It has the structure H2-0h-, and the end groups are usually converted to esters or ethers to increase thermal and chemical resistance. Also included are polyacetal copolymers, which include monomers or prepolymers of other substances capable of providing active hydrogen to formaldehyde, such as alkylene glycols, polythiols, vinyl acetate-acrylic acid copolymers, etc. block copolymers with butadiene/acrylonitrile polymers or derivatives thereof. The polyacetal obtained by polymerizing trioxane is usually copolymerized with other copolymerizable compounds. Examples of the copolymerizable compound include aldehydes, cyclic ethers, vinyl compounds, ketone cyclic carbonates, epoxides, isocyanates, and ethers, and these compounds include ethylene oxide, 1,3-dioxolane, 13-dioxane, epichlorohydrin, Includes propylene oxide, isobutylene oxide, styrene oxide, etc.

The thermoplastic isocyanate resins include, for example, toluene diisocyanate (TDI), diphenylmethane-4,4-diisocyanate (MDI), a wide range of polyols such as polyoxyethylene glycol, polyoxypropylene glycol, hydroxy-terminated polyesters, oxyethylene-oxy Polyurethane made from propylene glycol or the like is used. These thermoplastic polyurethanes usually have a temperature of 120°C or higher, preferably 15°C or higher.
Those having a crystalline melting point of 0 to 200°C are used.

The polyphenylene ether is represented by (wherein R+, Rz, R:+ and R1 are the same or different alkyl groups, aryl groups, halogen atoms, hydrogen atoms, etc., and n indicates the degree of polymerization). It is a polymer consisting of repeating structural units.

Specific examples include poly(2,6-dimethylphenylene-1,4-ether), poly(2,6-diethylphenylene-1,4-ether), and poly(2,6-diprophenylene). -1,4-ether), poly(2-methyl-6
-Nitylphenylene 1,4-ether), Poly(2-chloro-6methylphenylene-1,4-ether), Poly(2-methyl-6-itsuprobylphenylene-1゜4-
ether), poly(2,6-di-n-propylphenylene-1,4-ether), poly(2-chloro-6-propylphenylene-1,4-ether), poly(2-chloro-6-nitylphenylene 1. 4-ether), poly(2
-methylphenylene-1,4-ether), poly(2-
chlorophenylene-1,4-ether), poly(2-phenylphenylene-1,4-ether), poly(2-methyl-6-phenylphenylene-1,4-ether), poly(2-bromo-6-phenyl) phenylene-1,4-ether), poly(2,4'methylphenylphenylene-
1,4-ether), poly(2,3,6-)methylphenylene-14-ether), and copolymers thereof. Among these, particularly preferred are polymers obtained from 2,6-dimethylphenol and copolymers obtained from 2,6-dimethylphenol and 2,3,6-trimethylphenol.

Thermoplastic resins can be used singly or in a mixture of two or more, but preferred combinations include polyphenylene ether, styrene resin, phenylene ether, polyethylene and/or polypropylene,
polyphenylene ether and polyamide, polyphenylene ether and thermoplastic polyester, polyamide and polyethylene and/or polypropylene, thermoplastic polyester and polyethylene and/or polypropylene,
Examples include polyphenylene sulfide and ABs resin, polysulfone and ABS resin, polyacetal and thermoplastic isocyanate resin, polycarbonate and ABS resin, and the like.

The thermoplastic resin composition of the present invention may contain a high molecular weight ethylene-α-olefin copolymer as a rubbery polymer in an amount of 0 to 80 parts by weight, preferably 0 to 60 parts by weight, if necessary. I can do it. In addition to the above-mentioned rubbery polymer, the rubbery polymer includes a copolymer of ethylene and an unsaturated compound containing an epoxy group, and a polymer obtained from a radically polymerizable vinyl monomer grafted onto the copolymer. A reacted product, a copolymer of ethylene and an unsaturated acid, etc. can be used. If the thermoplastic resin and the rubbery polymer have poor compatibility, they can be blended by a known compatibilization method.

For example, when blending polyamide and rubber, (1) a method using an ethylene-α olefin copolymer modified with maleic anhydride as a compatibilizer, (2) a method using a carboxyl group-containing ethylene polymer, (3) a method using ethylene A method using a -glycidyl methacrylate-(vinyl acetate) copolymer is adopted. In addition to the method (1) or (3) above, the thermoplastic polyester and rubber can be blended by (4) ethylene-glycidyl methacrylate copolymer grafted with polymethyl methacrylate, polystyrene, acrylonitrile-styrene copolymer, etc. Methods such as using a For blending polyamide and ABS resin, (5)
A method using an AS resin modified with a carboxyl group or an ABS resin modified with a carboxyl group is adopted. When blending polyphenylene ether, polyamide, or thermoplastic polyester with a rubbery polymer, (6) adding an unsaturated compound or peroxide containing an acid anhydride group, carboxyl group, amino group, hydroxyl group, or epoxy group during kneading. (7) A method using a rubbery polymer modified with an acid anhydride and a styrene resin modified with a specific functional group, (8) A method using a polyphenylene ether modified with maleic anhydride, etc. will be adopted.

The thermoplastic resin composition of the present invention may contain various crosslinking agents, fillers, heat stabilizers, anti-aging agents, crosslinking accelerators, and the like, if necessary.

Since this thermoplastic resin composition contains the above-mentioned epoxidized low molecular weight copolymer, it has excellent impact resistance, moldability, and surface properties of molded products.

[Examples] Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples.

Various measurements in the examples were carried out according to the following methods.

(1) 100 mj of epoxidized low molecular weight ethylene-α olefin copolymer with an epoxy group content of 1 to 2 g! of chloroform and using tetramethylammonium bromide as a catalyst. I
It was determined by titration of N with HCfO4.

(2) Molecular weight of low molecular weight ethylene-α-olefin copolymer Measured by GPC using trichlorobenzene as a solvent.

(3) Propylene content Measured by infrared absorption spectrum.

(4) Izot impact strength Measured according to ASTM D 256 with a 1/8" thick notch at 23°C and -30°C.

(5) Fluidity 260°C 1 load 1 according to JIS K 7210
MFR (melt flow rate) was measured at 0 kg.

(6) Tensile breaking strength, elongation and permanent elongation JIS K
Measured according to 6301.

Example 1 3! A low molecular weight ethylene-propylene-nonconjugated diene copolymer (hereinafter referred to as “low molecular weight E
2000 mf of a toluene solution in which 450 g of PDM (non-conjugated diene: dicyclopentadiene) was dissolved was introduced. To this solution, 1 mole of formic acid and 2 moles of hydrogen peroxide were added as a 30% by weight hydrogen peroxide solution, and the mixture was heated with vigorous stirring. After stirring was continued for 7 hours while maintaining the temperature at 35-40°C, stirring was stopped and the separated aqueous layer was removed. The polymer solution was washed several times with water and then poured into a large amount of methanol to obtain epoxidized low molecular weight EPDM. After drying this epoxidized low molecular weight EPDM under reduced pressure, the content of epoxy groups was measured. The epoxy group content was found to be 53 mmol/100 g, indicating that 45% of the double bonds in the low molecular weight EPDM were epoxidized.

The infrared absorption spectrum of this epoxidized low molecular weight EPDM is shown in FIG.

Example 2 An epoxidized low molecular weight EPDM was obtained in the same manner as in Example 1, except that low molecular weight EPDM with Mwll, 000, propylene content of 40 mol %, and iodine value of 19 was used.

The epoxy group content of the EPDM is 31 mmol/100g
It was found that 41% of the double bonds in the low molecular weight EPDM were epoxidized.

Example 3 An epoxidized low molecular weight EPDM was obtained by carrying out the same operation as in Example 1 except that benzoic acid was used instead of formic acid. The epoxy group content of the EPDM was 16 mmol/100 g, indicating that 14% of the double bonds in the low molecular weight EPDM were epoxidized.

Example 4 The same operation as in Example 1 was performed except that methylene chloride was used instead of toluene as the solvent.
Epoxidized low molecular weight EPDM was obtained. The epoxy group content of the EPDM was found to be 40 mmol/100 g, and 34% of the double bonds in the low molecular weight EPDM were epoxidized.

Examples 5 to 6 and Comparative Example 1.2 The following blends (a) to (g) were blended in the amounts shown in Table 1 and melt-kneaded to prepare thermoplastic resin compositions. At this time, the epoxidized low molecular weight EPDM or unmodified low molecular weight EPDM was added midway through the extruder using a pump. The obtained pellet-like composition was sufficiently dried in a dehumidifying dryer, and an evaluation sample was molded in an injection molding machine. The physical properties of the test piece were evaluated and the results are shown in Table 1.

(a) Polybutylene terephthalate (Product name: Shuranex XD518, manufactured by Polyplastics Co., Ltd.) (b) Nylon 6 (Product name: Amilan CM, manufactured by Toshi Co., Ltd. (C) Ethylene-glycidyl methacrylate copolymer graph) PMMA (Product name, manufactured by NOF Corporation) (Modiper F A4200) (d) Polycarbonate (Ikosha product name A22 (e)
Ethylene-propylene copolymer (manufactured by Japan Synthetic Rubber Co., Ltd. E
P-01P) (f) Epoxidized low molecular weight EPDM obtained in Example 1 (g
) Below the low molecular weight EPDM used in Example 1 From the results in Table 1, Examples 5 to 9 are superior in Izot impact strength, and Examples 5.6 and 9 are superior in fluidity, compared to Comparative Examples. It is shown that

Examples 1O to 11 and Comparative Example 3 As rubbery polymers, ethylene-propylene-nonconjugated diene copolymer (EPDM, manufactured by Japan Synthetic Rubber Co., Ltd.) and hydrogenated styrene-butadiene-styrene triblock copolymer (SEBS, shell (Product name: Clayton G1650)
and acrylonitrile-styrene copolymer (A
Graft copolymerization was performed on S copolymer (j)) to obtain graft copolymers (h) and (i). The components of the copolymer are shown in Table 2.

Table 2 Using this graft copolymer, a styrenic thermoplastic resin composition was prepared according to the formulation shown in Table 3, and evaluation test pieces were molded and evaluated in the same manner as in Example 1. Third
Shown in the table.

Table 3 shows that both the impact strength and fluidity are excellent.

Example 12 and Comparative Example 4 66.6 parts by weight of epoxidized low molecular weight EPDM was added to 100 parts by weight of polybutylene terephthalate, and 1.17 parts by weight of sulfur as a crosslinking agent and 2.33 parts by weight of a crosslinking aid were added. The mixture was melt-kneaded in a kneader and press-molded. Thereafter, JIS No. 3 dumbbells were punched out and their tensile fracture properties were measured, and the results are shown in Table 4.

From the results in Table 3 in the margin below, it can be seen that Example 10.11, which is a composition of rubber-modified styrenic thermoplastic resin and epoxidized low molecular weight copolymer, does not stretch as compared to the comparative example in Table A *1. From the results in Table 4, in this example, unmodified low-molecular EP
It is shown that the breaking strength, elongation at break, and permanent elongation are all improved compared to the comparative example using DM.

(Effects of the Invention) The epoxidized low molecular weight ethylene-α-olefin copolymer of the present invention has excellent dispersibility, and can be used as a modifier for various rubber-like or resinous polymers, a modification aid, a lubricating oil additive, It can exhibit excellent performance as a dispersion aid for aqueous dispersants, paints and their modifiers, adhesives, sealants and their modifiers, roofing agents and their modifiers, etc.

Furthermore, since the thermoplastic resin composition of the present invention contains the above-mentioned epoxidized low molecular weight copolymer, it has excellent impact resistance, molding processability, and surface properties of molded products.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing an infrared absorption spectrum of the epoxidized low molecular weight copolymer obtained in Example 1.

Claims (2)

[Claims] (1) (A) ethylene component content of 30 to 75 mol% and α-olefin component content of 25 to 70 mol%, (B) non-conjugated diene component content of 3 to 100 in terms of iodine value, and (C) polystyrene equivalent weight Average molecular weight is 300-50
,000, epoxidized by epoxidizing 1% or more of the double bonds of the non-conjugated diene component in a random low molecular weight copolymer consisting of ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated diene. Low molecular weight ethylene-α-olefin copolymer. (2) 100 parts by weight of thermoplastic resin, 1 to 80 parts by weight of the epoxidized low molecular weight ethylene-α-olefin copolymer according to claim (1), and 0 to 80 parts by weight of the high molecular weight ethylene-α-olefin copolymer. A thermoplastic resin composition containing.