JP3123071B2 - Thermoplastic resin composition - Google Patents

Description

The present invention relates to a thermoplastic resin composition containing a hydroxylated low molecular weight ethylene-α-olefin-nonconjugated diene copolymer, and more particularly, The present invention relates to a thermoplastic resin composition using a novel hydroxylated low molecular weight ethylene-α-olefin-non-conjugated diene copolymer and having excellent impact resistance, moldability and mold surface properties.

[Prior Art] Conventionally, a modified olefin polymer obtained by hydroxylating an ethylene-α-olefin-nonconjugated diene copolymer is known (JP-A-54-61229). However, there is a drawback that the dispersibility in the polymer is poor, and when used as an adhesive, a sealant, or a roofing agent, sufficient performance cannot be obtained due to poor fluidity. On the other hand, the unmodified low molecular weight ethylene-α-olefin copolymer is nonpolar, and therefore has a disadvantage that it has low compatibility with polar polymers and is inferior in performance as a modifier. Therefore, a thermoplastic resin composition excellent in impact resistance, molding processability and molded article surface properties could not be obtained even when the polymer was blended.

JP-A-63-305103 discloses a modified low-molecular-weight ethylene-α-olefin copolymer in which the terminal double bond is hydroxylated. Has only one hydroxyl group, it must have a very low molecular weight in order to obtain a highly polar hydroxylated ethylene-α-olefin copolymer, and since the hydroxyl group is present only at the terminal, Since no cross-linking reaction occurs between groups, the dispersing effect is poor. Therefore, even if the copolymer was blended, a thermoplastic resin composition excellent in impact resistance, molding processability and molded article surface properties could not be obtained.

Conventionally, thermoplastic resins such as polypropylene, AS resin, thermoplastic polyester, and polyamide have excellent mechanical strength, electrical properties, chemical resistance, moldability, and molded product surface properties. Widely used in electronic fields. Since these resins are inferior in impact resistance after being notched (cut), a method of blending a rubbery polymer, a plasticizer, or the like as a modifier has been adopted. However, a thermoplastic resin composition containing a rubber-like polymer has improved impact resistance, but has a drawback of poor moldability. There is a drawback that the surface property is reduced due to the emergence of the plasticizer.

[Problems to be Solved by the Invention] An object of the present invention is to eliminate the above-mentioned disadvantages of the prior art and to provide a specific hydroxylated low-molecular-weight ethylene-α-olefin-
An object of the present invention is to provide a thermoplastic resin composition excellent in impact resistance, molding processability and molded article surface properties using a non-conjugated diene copolymer.

[Means for Solving the Problems] The present invention relates to 100 parts by weight of a thermoplastic resin, (A) an ethylene component content of 30 to 75 mol% and an α-olefin component content of 25 to 70 mol%, and (B) a non- The conjugated diene component content is 3 to 100 in iodine value, and (C) ethylene having a weight average molecular weight in terms of polystyrene of 300 to 50,000 and carbon number 3
And a hydroxylated low molecular weight ethylene-α-olefin-non-hydroxylated non-conjugated diene component obtained by hydroxylating 10% or more of the double bonds of the non-conjugated diene component in a random low molecular weight copolymer composed of an α-olefin and a non-conjugated diene. The present invention relates to a thermoplastic resin composition containing 1 to 80 parts by weight of a conjugated diene copolymer (hereinafter, simply referred to as “hydroxylated low molecular weight copolymer”).

The low molecular weight copolymer used in the present invention comprises ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated diene, and has a (A) ethylene component [ethylene unit represented by CH ₂ CH ₂ ] content of 30. ~ 75 mol%, preferably 40-70 mol%, and the α-olefin component [ An α-olefin unit represented by the formula: wherein R is 1 carbon atom
(B) a non-conjugated diene component content of 3 to 100, preferably 10 to 80, and (C) a nonconjugated diene component in iodine value. The weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) is 300 to 50,000.
0, preferably 1,000 to 30,000, more preferably 10,000
3030,000. Molecular weight distribution (Mw / Mn
(Number average molecular weight in terms of polystyrene)] is preferably 4 or less, more preferably 1.2 to 3.5. If the Mw is less than 300, the mechanical strength of the composition is reduced, and if it exceeds 50,000, the fluidity is poor. Copolymers outside the above range are inferior in the effect of improving mechanical properties when used as a polymer modifier or the like.

Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene and 1-octene.
Decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like are used. The amount of the α-olefin 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 and the like are used. Of these, dicyclopentadiene is preferred from the viewpoint of improving the reactivity of hydroxylation.

The low molecular weight copolymer is a Ziegler-Natta type catalyst system comprising ethylene, α-olefin and non-conjugated diene as a general transition metal compound and an organometallic compound, such as vanadium and organoaluminum, and titanium and organoaluminum. It can be synthesized by a known method below.

The hydroxylated molecular weight copolymer used in the present invention is a copolymer obtained by hydroxylating 10% or more, preferably 20% or more, of the double bond of the non-conjugated diene component in the low molecular weight copolymer. is there. 1% hydroxylation
If it is less than 10, the effect of improving the mechanical properties when used as a polymer modifier or the like is inferior. The hydroxylation of the low molecular weight copolymer can be performed, for example, by (1) mixing the low molecular weight copolymer with formic acid,
An organic acid such as acetic acid, or reacted with a mixture of aqueous hydrogen peroxide, or m-chloroperbenzoic acid, a method of epoxidation with an organic peracid such as perbenzoic acid, followed by hydrolysis with an acid or alkali, (2) Diborane or 9-BBN (9-borabicyclo [3.3.
1) After hydroboration with nonane), it can be carried out by a method of oxidizing with hydrogen peroxide.

In the case of the method (1), the low-molecular-weight copolymer is kept in bulk or dissolved in an organic solvent such as an aromatic hydrocarbon such as toluene, xylene or benzene, or a saturated hydrocarbon such as hexane, heptane or octane. Used as a 5-50% solution. The amount of the organic acid is usually 0.2 to 2.0 times mol, preferably 0.4 to 1.7 times mol, of the double bond in the low molecular weight copolymer, and the amount of hydrogen peroxide used is usually 1.0 for double bond in low molecular weight copolymer
It is assumed to be 5.0 times mole. These mixed solutions are, for example, 10-60
An epoxidized low molecular weight ethylene-based random copolymer can be obtained by stirring and reacting at a temperature of 1 to 10 hours.

When reacting with an organic peracid such as m-chloroperbenzoic acid or perbenzoic acid, for example, the low molecular weight copolymer is made into a 5 to 50% solution of a halogenated hydrocarbon such as methylene chloride, and the organic peracid is reduced. 0.01 to the double bond of the molecular weight copolymer
An epoxidized low molecular weight copolymer can be obtained by adding 1.50 times, preferably 0.1 to 1.20 times mole, and reacting at room temperature for 1 to 10 hours. To this is added an excess of an acid, for example, hydrochloric acid, or an alkali, for example, an aqueous solution of sodium hydroxide, at 10 to 90 ° C., preferably at 30 to 70 ° C.,
By reacting for 1 to 10 hours, preferably 3 to 8 hours, a hydroxylated low molecular weight copolymer can be obtained.

In the case of the method (2), the low-molecular-weight copolymer is a 5 to 50% solution of an ether solvent such as tetrahydrofuran, which is added thereto in an amount of 0.1 to 1.50 moles, preferably 0.1 to 1.50 moles, per double bond in the low-molecular weight copolymer. Hydroboration is performed by adding 0.2 to 1.20 moles of diborane or 9-BBN. Hydrogen peroxide and sodium hydroxide are added in an amount of 3.0 to 5.0 times the molar amount of the diborane compound, and the mixture is hydrolyzed to obtain a hydroxylated low molecular weight copolymer.

The hydroxylated low molecular weight copolymer used in the present invention has a large number of hydroxyl groups in one molecule of the copolymer, has high polarity, and is excellent in dispersibility in a polymer. It has excellent performance as an agent, a lubricating oil additive, a dispersing aid for aqueous dispersants, etc., and as a paint and its modifiers, adhesives, sealants, roofing agents and the like. Further, a crosslinking reaction between hydroxyl groups is possible. Furthermore, the impact resistance, molding processability, and molded article surface properties can be improved by using as a component of a thermoplastic resin composition described later.

The thermoplastic resin composition of the present invention comprises 100 parts by weight of the thermoplastic resin and the hydroxylated low molecular weight copolymer 1 to 80.
Part by weight, preferably 2 to 60 parts by weight, is contained as an essential component. This composition further contains 0 to 80 parts by weight of a high molecular weight ethylene-α-olefin copolymer as a rubbery polymer,
Preferably, it can be contained in the range of 0 to 60 parts by weight. If the amount of the hydroxylated low molecular weight copolymer is out of the above range, the thermoplastic resin composition is inferior in the effect of improving the impact resistance, moldability, and surface properties of the molded article.

Examples of the thermoplastic resin used in the present invention include polystyrene, AS resin (meth) acrylic acid alkyl ester-styrene copolymer resin, impact-resistant polystyrene, ABS resin, and M
Styrene resin such as BS resin, olefin resin such as polyethylene and polypropylene, vinyl resin such as vinyl chloride resin and vinyl acetate resin, thermoplastic polyester, polyamide, polyaryl ether, polysulfone, polycarbonate, polyacetal, thermoplastic isocyanate resin , Polyphenylene ether, thermoplastic urea resin, polyarylene sulfide, polyimide, polyarylene ketone and the like. One or more of these thermoplastic resins are used.

Examples of the alkyl (meth) acrylate used in the alkyl (meth) acrylate-styrene copolymer resin include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, and 2-ethylhexyl. Acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, alkyl acrylate such as benzyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, Dodecyl methacrylate Octadecyl methacrylate, phenyl methacrylate, and methacrylic acid alkyl esters such as benzyl methacrylate and the like, which are used alone or two or more.

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

Examples of the rubbery polymer include polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, and hydrogenated styrene-butadiene random copolymer. Coal, hydrogenated acrylonitrile-butadiene copolymer, propylene, butene-1, pentene-1, hexene- as α-olefin
1, ethylene-α-olefin copolymers using 1, heptene-1, 4-methylpentene-1, 4-methylten, etc., ethylene-based ionomers, polyacrylate rubbers, ethylene-α-olefin-polyene copolymers, etc. Is mentioned. As the styrene-butadiene block copolymer and the hydrogenated styrene-butadiene block copolymer, AB type, ABA type, ABA taper type, radial teleblock type and the like can be used. One or more of these rubbery polymers are used.

Impact polystyrene is obtained by polymerizing an aromatic vinyl compound mainly composed of styrene in the presence of a rubbery polymer. As the aromatic vinyl compound, styrene, α-
Examples include methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, p-tert-butylstyrene, ethylstyrene, and the like, and these are used alone or in combination of two or more. .

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

The MBS resin is obtained by polymerizing the above-mentioned aromatic vinyl compound mainly composed of styrene and the alkyl (meth) acrylate mainly composed of methyl methacrylate in the presence of a rubbery polymer. As the alkyl (meth) acrylate, those described 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 therewith, preferably 30% by weight or less, more preferably 10% by weight or less. It can also be used in a range.

Examples of the other copolymerizable vinyl monomers include acrylic acid, methacrylic acid, unsaturated acids such as maleic acid, unsaturated acid anhydrides such as maleic anhydride, glycidyl methacrylate, epoxy group containing acrylic glycidyl ether and the like. 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 amide group-containing unsaturated compounds such as acrylamide Examples thereof include compounds, maleimide compounds such as N-phenylmaleimide and N-cyclohexylmaleimide, and vinyl acetate, N-vinylpyrrolidone, and the like. These are 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 the dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glitalic acid, adipic acid, speric acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, p-carboxyphenoxyacetic acid, p, p'-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'-dicarboxydiphenyloctane, 3-alkyl-4- (β
-Carboxyethoxy) benzoic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, derivatives thereof and the like are used. These are used alone or in combination of two or more, and terephthalic acid or a mixture of terephthalic acid and isophthalic acid is particularly preferred.

As the diol component, a fatty acid diol or an aromatic diol is used.

As the aliphatic diol, for example, ethylene glycol, 1,3-propylene glycol, 1,4-tetramethylene glycol, 1,6-hexylene glycol, 1,10-decamethylene glycol, 1,12-dodecamethylene glycol and the like A straight-chain alkylene glycol having 2 to 12 carbon atoms is exemplified. As aromatic diols, bisphenol A,
Examples include p-xylene glycol, pyrocatechol, resorcinol, hydroquinone, alkyl-substituted derivatives of these compounds, and derivatives thereof. These are used alone or in combination of two or more.

As the thermoplastic polyester, those obtained by copolymerizing a polyester obtained from p-hydroxybenzoic acid or a derivative thereof with the above-mentioned dicarboxylic acid and / or diol component, and a known polyester elastomer can also be used.

Preferred thermoplastic polyesters are polyethylene terephthalate, polybutylene terephthalate, terephthalic acid and / or isophthalic acid and bisphenol A
And a polyester having a p-hydroxybenzoic acid residue. Polyethylene terephthalate and polybutylene terephthalate are particularly preferred because they have a large effect of improving impact resistance.

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

Examples of the monoamino-monocarboxylic acid or a lactam thereof include ε-aminocarboxylic acid, butyrolactam,
Pivalolactam, caprolactam, caprylactam,
Enanthractam, undecanelactam, dodecanolactam, 3- and 4-aminobenzoic acid and the like.

Examples of the diamine include a general formula H ₂ N (CH ₂ ) nNH ₂ such as trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, octamethylene diamine, decamethylene diamine, dodecamethylene diamine, hexadecamethylene diamine, and the like. A diamine represented by the formula: n is an integer of 2 to 16;
Alkylated diamines such as dimethylpentamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine;
Aromatic diamines such as phenylenediamine, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylether, m-phenylenediamine and 4,4'-diaminodiphenylmethane; alicyclic diamines such as diaminodicyclohexylmethane Is mentioned. These are used alone or in combination of two or more.

As the dicarboxylic acid, aromatic dicarboxylic acid and / or
Alternatively, an aliphatic dicarboxylic acid is used.

Examples of the aromatic dicarboxylic acid include isophthalic acid, terephthalic acid, and the like.As the aliphatic dicarboxylic acid,
In addition to oxalic acid, general formulas such as sebacic acid, octadecandioic acid, glutaric acid, pimelic acid, and adipic acid, wherein HOOC • R • COOH [wherein R is a divalent aliphatic having at least two carbon atoms A dicarboxylic acid represented by the following formula: These various compounds are one or two
More than species can be used.

Known polyamide elastomers such as polyesteramide elastomer, polyetheresteramide elastomer, and polyetheramide elastomer can also be used as the polyamide. As a preferred polyamide,
Nylon 6, Nylon 66, Nylon 46, Nylon 12, Nylon MXD6 (polymethaxylene adipamide) and the like.

Examples of the polyaryl ether include a compound represented by the following general formula (I): O-OR-R ' And formula (III) R ′ is a residue of a dihydric phenol selected from
Formulas (II) and (IV) above A dibromon benzenoid compound residue or a jod benzenoid compound residue selected from
Is, -O -, - S -, - SO 2 - or a divalent hydrocarbon residue having 1 to 18 carbon atoms containing these groups (wherein, Q is -O
In the case of-, Q 'is other than -O-, and Q' is -O-
When-, Q is other than -O-, and when R is the formula (II), R 'is the formula (IV) and R' is the formula (II)
In the formula, R represents the formula (III)). ] The compound represented by these is used.

The polysulfone is contained in a repeating unit. [Wherein, Z represents an oxygen, sulfur or aromatic diol residue such as 4,4'-bisphenol. ]. Specific examples of this repeating unit include: Those having these repeating units at various ratios are exemplified. Preferred polysulfones include: Is mentioned.

As the polycarbonate, (In the formula, Ar is a phenylene group, or an alkyl group, an alkoxy group, a phenylene group substituted by 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, sulfur atom, enzyme atom or sulfoxide group, n represents an integer of at least 2. ] Is used. As a preferred polycarbonate, Ar in the general formula (VI) or (VII) is p-
A phenylene group, and those in which A has an isopropylidene group.

The polyacetal is a polymer obtained by polymerizing formaldehyde or trioxane.

Polyacetal produced from formaldehyde,
Has a structure represented by the formula CH ₂ -O _n, it is usually converted to increase thermal and chemical resistance, terminal groups to ester or ether. 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. And block copolymers with butadiene / acrylonitrile polymers or derivatives thereof.

The polyacetal obtained by polymerization of trioxane is usually copolymerized with another copolymerizable compound. Examples of the copolymerizable compound include aldehydes, cyclic ethers, vinyl compounds, ketone cyclic carbonates, epoxides, isocyanates, ethers and the like, and these compounds include ethylene oxide, 1,3-dioxolane,
1,3-dioxane, epichlorohydrin, propylene oxide, isobutylene oxide, styrene oxide and the like are included.

Examples of the thermoplastic isocyanate resin include toluene diisocyanate (TDI) and diphenylmethane-
4,4-diisocyanate (MDI), a wide range of polyols,
For example, polyurethane manufactured from polyoxyethylene glycol, polyoxypropylene glycol, hydroxy-terminated polyester, oxyethylene-oxypropylene glycol, or the like is used. As these thermoplastic polyurethanes, those having a crystalline melting point of usually 120 ° C. or higher, preferably 150 to 200 ° C. are used.

The polyphenylene ether, [In the formula, R ₁ , R ₂ , R ₃ and R ₄ represent the same or different residues of an alkyl group, an aryl group, a halogen atom, a hydrogen atom and the like, and n represents a degree of polymerization. ] It is a polymer which consists of a repeating structural unit represented by these.

Specific examples thereof include poly (2,6-dimethylphenylene-1,4-ether), poly (2,6-diethylphenylene-1,4-ether), and poly (2,6-dibromophenylene-).
1,4-ether), poly (2-methyl-6-ethylphenylene-1,4-ether), poly (2-chloro-6-methylphenylene-1,4-ether), poly (2-methyl-6 -Isopropylphenylene-1,4-ether), poly (2,6-di-n-propylenephenylene-1,4-ether), poly (2-chloro-6-bromophenylene-1,4)
-Ether), poly (2-chloro-6-ethylphenylene-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-phenylphenylene-1,4-) Ether), poly (2,4'-methylphenylphenylene-1,4-ether), poly (2,3,6-trimethylphenylene-1,4-ether), and copolymers thereof. Of these, a polymer obtained from 2,6-dimethylphenol and a copolymer obtained from 2,6-dimethylphenol and 2,3,6-trimethylphenol are particularly preferred.

The thermoplastic resin may be used alone or as a mixture of two or more kinds. Preferred combinations are polyphenylene ether and styrene resin, polyphenylene ether and polyethylene, and / or polypropylene, polyphenylene ether and polyamide, polyphenylene ether and thermoplastic polyester. And polyamide and polyethylene and / or polypropylene, thermoplastic polyester and polyethylene and / or polypropylene, 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 contains a high-molecular-weight ethylene-α-olefin copolymer as a rubbery polymer in a range of 0 to 80 parts by weight, preferably 0 to 60 parts by weight, if necessary. Can be.

As the rubbery polymer, in addition to the rubbery polymer described above, a copolymer of ethylene and a hydroxyl group-containing unsaturated compound, and a polymer obtained from a radically polymerizable vinyl monomer grafted onto the copolymer are grafted. A reaction product, a copolymer of ethylene and an unsaturated acid, or the like can be used. When the compatibility between the thermoplastic resin and the rubbery polymer is poor, it can be blended by a known compatibilizing method.

For example, for blending polyamide and rubber, (1) a method using a maleic anhydride-modified ethylene-α-olefin copolymer as a compatibilizer, (2) a method using a carboxyl group-containing ethylene polymer, (3) A method using an ethylene-glycidyl methacrylate- (vinyl acetate) copolymer is employed.

The above-mentioned (1) is used for blending thermoplastic polyester and rubber.
Or in addition to the method of (3), (4) an ethylene-glycidyl methacrylate copolymer is added to polymethyl methacrylate,
A method using a graft of polystyrene, acrylonitrile-styrene copolymer, or the like is employed.
(5) Carboxyl-modified AS resin or carboxyl-modified AB
A method using S resin is adopted. (6) Add an acid anhydride group, a carboxyl group, an amino group, a hydroxyl group, an epoxy group-containing unsaturated compound or a peroxide during kneading when mixing the polyphenylene ether, polyamide or thermoplastic polyester with the rubbery polymer. Method,
(7) a method using a rubbery polymer modified with an acid anhydride and a styrene-based resin modified with a specific functional group, (8)
A method using a polyphenylene ether modified with maleic anhydride is employed.

In the thermoplastic resin composition of the present invention, various cross-linking agents, fillers, heat stabilizers, anti-aging agents, cross-linking accelerators and the like can be blended and used as necessary. Since this thermoplastic resin composition contains the above-mentioned hydroxylated low molecular weight copolymer, it is excellent in impact resistance, molding processability and molded article surface properties.

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

 Various measurements in the examples were performed according to the following methods.

(1) Hydroxyl group content 1-2 g of a hydroxylated low molecular weight ethylene-α-olefin-non-conjugated diene copolymer was dissolved in 100 ml of tetrahydrofuran, and a calibration was obtained using 1,2-dihydroxycyclohexane as a standard substance. Measured by infrared absorption spectroscopy.

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

(3) Propylene content Measured by infrared absorption spectrum.

(4) Izod impact strength According to ASTM D-256, the thickness was measured at 23 ° C. and −30 ° C. with a notch and a 1/8 ″ thickness.

(5) Fluidity MFR (melt flow rate) was measured at 260 ° C. under a load of 10 kg according to JIS K-7210.

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

In the flask of Reference Example 13, a low molecular weight ethylene-propylene-nonconjugated diene copolymer having Mw of 10,000, a propylene content of 35 mol%, and an iodine value of 30 polymerized using a vanadium catalyst (hereinafter referred to as “low 2000 ml of a toluene solution in which 450 g of non-conjugated diene: dicyclopentadiene (molecular weight EPDM) was dissolved was introduced. To this solution was added 1 mol of formic acid and 2 mol of hydrogen peroxide as a 30% by weight aqueous hydrogen peroxide solution, and the mixture was heated with vigorous stirring. After stirring was continued for 7 hours while maintaining the temperature at 35 to 40 ° C., the stirring was stopped, and the separated aqueous layer was removed. After washing the polymer solution several times with water, it is poured into a large amount of methanol and epoxidized low molecular weight EP
Got MD. This epoxidized low molecular weight EPDM is dissolved in 2000 ml of toluene, and NaOH 100 g 500 m
The mixture was stirred with an aqueous solution at 90 ° C for 7 hours. After washing the polymer solution with water, it was poured into a large amount of alcohol to obtain a hydroxylated EPDM. After the hydroxylated EPDM was dried under reduced pressure, the hydroxyl group content was measured by infrared absorption spectroscopy. Hydroxyl content is 35mm
ol / 100 g, 15% of the double bonds in the starting low molecular weight EPDM
Was found to be hydroxylated. The infrared absorption spectrum of this hydroxylated low molecular weight ethylene-propylene-non-conjugated diene copolymer is shown in FIG.

Reference Example 2 The same operation as in Reference Example 1 was performed except that trichloroacetic acid was used instead of formic acid. The resulting hydroxylation
The hydroxyl group content of EPDM was 53 mmol / 100 g, indicating that 23% of the double bonds in the starting low molecular weight EPDM were hydroxylated.

Reference Example 3 In place of NaOH water, 200 ml of Hcl 15% aqueous solution was used.
l Except that the hydrolysis reaction with the aqueous solution was performed at 25 ° C,
The same operation as in Reference Example 1 was performed. The hydroxyl group content of the obtained hydroxylated EPDM is 85 mmol / 100 g,
It was found that 36% of the double bonds in the starting low molecular weight EPDM were hydroxylated.

Reference Example 4 Low molecular weight EPDM polymerized using a vanadium catalyst having Mw of 11,000, propylene content of 40 mol%, and iodine value of 19
Reference Example 2 except that (dicyclopentadiene) was used.
The same operation as described above was performed. The hydroxyl group content is 33 mmol
/ 100 g, indicating that 22% of the double bonds in the starting low molecular weight EPDM were hydroxylated.

Reference Example 5 20% HCl instead of 15% HCl, and hydrolysis reaction temperature
The same operation as in Reference Example 3 was performed, except that the operation was performed at 35 ° C. In the resulting hydroxylated EPDM, the starting low molecular weight EPDM
52% of the double bonds in were hydroxylated.

Reference Example 6 Using an aluminoxane and bis (cyclopentadienyl) zirconium chloride-based catalyst,
A low molecular weight ethylene-propylene copolymer having a propylene content of 55 mol% and an iodine value of 35 (hereinafter referred to as "low molecular weight EPM") polymerized according to the method described in Japanese Patent No. 305103 is disclosed.
T of 0.5M 9-BBN (9-borabicyclo [3.3.1] nonane)
The mixture was added dropwise to the HF solution and stirred. Further, a hydroxylated EPM was obtained by adding a NaOH aqueous solution and a hydrogen peroxide solution to oxidize, removing the solvent, and then drying. The hydroxyl group content was 13 mmol / 100 g.

Examples 1 to 7 and Comparative Examples 1 to 3 The following blends (a) to (j) were blended in the blending amounts shown in Table 1 and melt-kneaded to prepare a thermoplastic resin composition. At this time, the hydroxylated low molecular weight EPDM or the unmodified low molecular weight EPDM was added in the middle of the extruder using a pump. The obtained pellet-shaped composition was sufficiently dried with a dehumidifying dryer, and an evaluation test piece was molded with an injection molding machine. The physical properties of the test piece were evaluated, and the results are shown in Table 1.

(A) Polybutylene terephthalate (manufactured by Polyplastics, trade name; Schranex XD518) (b) Nylon 6 (manufactured by Toray Industries, trade name: Amilan CM101)
7) (c) Ethylene-glycidyl methacrylate copolymer grafted PMMA (trade name, manufactured by NOF CORPORATION; Modiper F42)
(D) Polycarbonate (trade name: A2200, manufactured by Idemitsu Co., Ltd.) (e) Ethylene-propylene copolymer (EP-01P, manufactured by Nippon Synthetic Rubber Co., Ltd.) (f) Hydroxylated low molecular weight EPDM obtained in Reference Example 1 (G) The hydroxylated low molecular weight EPDM obtained in Reference Example 2 (h) The hydroxylated low molecular weight EPDM obtained in Reference Example 5 (i) The low molecular weight EPDM used in Reference Example 1 (j) The hydroxyl obtained in Reference Example 6 Low molecular weight EPM From the results in Table 1, it is found that Examples 1 to 7 are superior in Izod impact strength as compared with Comparative Example, and Examples 1, 2 and 5
In the case of No. 7 to 7, it is shown that the fluidity is excellent.

Examples 8 and 9 and Comparative Example 4 Ethylene-propylene-non-conjugated diene copolymer (manufactured by Nippon Synthetic Rubber Co., EPDM) and hydrogenated styrene-butadiene-styrene triblock copolymer (manufactured by Shell) as rubbery polymers , SEBS, trade name; Clayton G1650)
An acrylonitrile-styrene copolymer [AS copolymer, (m)] was graft-polymerized to obtain graft copolymers (k) and (l). The components of the copolymer are
It is shown in the table.

Using this graft copolymer, a styrene-based thermoplastic resin composition was prepared according to the formulation shown in Table 3, and an evaluation test piece was molded and evaluated in the same manner as in Example 1. The results are shown in Table 3. It was shown to.

From the results in Table 3, it can be seen that Examples 8 and 9, which are compositions of a rubber-modified styrenic thermoplastic resin and a hydroxylated low molecular weight copolymer, are superior in both Izod impact strength and fluidity as compared with Comparative Examples. Is shown.

Example 10 and Comparative Example 5 Example 10 was added to 100 parts by weight of polybutylene terephthalate.
In Comparative Example 5, 66.6 parts by weight of the hydroxylated EPDM obtained in Reference Example 3 and Comparative Example 5 were added with 66.6 parts by weight of the low molecular weight EPDM used in Comparative Example 1, and 1.17 parts by weight of sulfur and 2.33 parts by weight of a crosslinking aid were added as a crosslinking agent. It was compounded, melt-kneaded in a kneader, and pressed. Thereafter, a JIS No. 3 dumbbell was punched out, and the tensile fracture characteristics were measured. The results are shown in Table 4.

From the results shown in Table 4, in this example, unmodified low molecular EP
It is shown that all of the breaking strength, breaking elongation and permanent elongation are improved as compared to the comparative example using DM.

[Effect of the Invention] The hydroxylated low molecular weight ethylene-α-olefin non-conjugated diene copolymer used in the present invention has excellent dispersibility, and is used as a polymer modifier, modifying aid, lubricating oil, additive, aqueous dispersion. Dispersing aids, paints and their modifiers, adhesives,
It can exhibit excellent performance as a sealant and its modifier, a roofing agent and its modifier, and the like.

Therefore, since the thermoplastic resin composition of the present invention contains the above-mentioned hydroxylated low molecular weight copolymer, it is excellent in impact resistance, molding processability and molded article surface properties.

[Brief description of the drawings]

FIG. 1 is a view showing an infrared absorption spectrum of the hydroxylated low molecular weight copolymer obtained in Reference Example 1.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-63-305103 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 101/00 C08L 23/26

Claims (1)

(57) [Claims] (1) 100 parts by weight of a thermoplastic resin, (A) an ethylene component content of 30 to 75 mol% and an α-olefin component content of 25 to 70 mol%, and (B) a non-conjugated diene component content of an iodine value. A non-conjugated diene in a random low-molecular-weight copolymer comprising 3 to 100 and (C) ethylene having a weight average molecular weight in terms of polystyrene of 300 to 50,000, an α-olefin having 3 to 20 carbon atoms and a non-conjugated diene; A thermoplastic resin composition comprising 1 to 80 parts by weight of a hydroxylated low molecular weight ethylene-α-olefin-nonconjugated diene copolymer obtained by hydroxylating 10% or more of the double bond of the component.