JPH06184368A - Thermoplastic resin composition and its production - Google Patents

Abstract

PURPOSE:To combine a number of engineering plastics with each other so as to form subject composition which can exhibit their characteristics as fully as possible without detriment to the processability. CONSTITUTION:This resin composition is prepared by melt-kneading at least one thermoplastic resin selected from among polyamide, polyester, polyoxymethylene, polycarbonate and polyphenylene ether resins, a polyolefinic resin, at least one compound selected from among a dihydroxyaromatic compound and its polymer, an ether compound, a tetrahydroaromatic compound and cyclopentane compound, and at least one compound having a functional group selected from among carbonyl, cyclic iminio ether, epoxy, hydroxy, amino and cyano groups.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a modified thermoplastic resin composition and a method for producing the same. Specifically, at least one compound selected from dihydroaromatic compounds or polymers thereof, ether compounds, tetrahydroaromatic compounds, cyclopentane compounds and carbonyl group, cyclic iminoether group, epoxy group, hydroxy group, A compound having a functional group such as an amino group and a nitrile group (hereinafter referred to as a compound having a functional group), and optionally, in the presence of a radical generator, a polyamide resin, a polyester resin, a polyoxymethylene resin, a polycarbonate resin. The present invention relates to a modified thermoplastic resin composition characterized by modifying at least one kind of thermoplastic resin and polyolefin resin selected from polyphenylene ether resins at a temperature equal to or higher than its melting point or softening point, and a method for producing the same.

[0002]

2. Description of the Related Art Polyamide resins represented by nylon 6, nylon 66 and the like are resins having excellent rigidity and heat resistance, but their impact strength is somewhat insufficient and their use is limited. Further, it has a polar group due to an amide bond in the molecule and easily absorbs water. The water-absorbed polyamide-based resin has a slightly improved impact strength, but its rigidity is remarkably reduced, which is not preferable.

The polyester resin is a resin having excellent rigidity and heat resistance like nylon, but its impact strength is slightly insufficient. In particular, polyethylene terephthalate resin and the like have a very low crystallization rate and poor moldability. Further, when it is exposed to hot water, the ester bond is hydrolyzed, so that its use is limited.

Polyoxymethylene resin has excellent solvent resistance and hot water resistance in addition to rigidity, heat resistance and abrasion resistance, but has a high specific gravity, is weak against acid, and cannot impart flame retardancy.
It has drawbacks such as large molding shrinkage, and especially lacks impact strength.

Polycarbonate resins also have excellent rigidity, heat resistance, and impact resistance, but since they are amorphous, they have poor chemical resistance and poor moldability.

The polyphenylene ether resin has excellent mechanical strength, heat resistance and thermal properties, but lacks oil resistance and solvent resistance and is somewhat difficult to mold.

On the other hand, the polyolefin resin is
It has extremely good moldability, and also has excellent solvent resistance and impact resistance. It has low water absorption, and even if it absorbs water, there is almost no deterioration in its physical properties, but it is inferior in terms of rigidity and heat resistance.

Therefore, an attempt has been made to improve the moldability and other properties while maintaining the rigidity and heat resistance of the thermoplastic resin by blending the thermoplastic resin and the polyolefin resin. There is.

However, in general, resins of different types are often incompatible with each other as they are, and it is usual to add a third component as a compatibilizing agent.

Conventionally, a method of grafting a compound having a functional group has been known for the purpose of modifying a thermoplastic resin.

In particular, carboxylic acids such as carboxylic acids, carboxylic acid esters, carboxylic acid amides, acid anhydrides and acid halides or derivatives thereof, monomers containing carbonyl groups such as ketones, aldehydes, lactones, lactams or derivatives thereof, epoxies. A composition obtained by graft-modifying a containing monomer, a hydroxy group-containing monomer, an amino group-containing monomer, a nitrile group-containing monomer, a cyclic iminoether group-containing monomer or a derivative thereof is highly reactive, and therefore an adhesive, an impact modifier, a phase It is used as a solubilizer.

Further, these modified thermoplastic resins have excellent coatability and can be coated without pretreatment such as a primer, and are usefully utilized for automobile parts such as bumpers, home appliances, and electronics.

As a method of graft-modifying using a compound having such a functional group, an organic peroxide has been generally used conventionally (see, for example, US Pat. Nos. 4,147,740 and the same). 4,639,495 and 4,7
88, 264, etc.), organic peroxides are radical generators having a very strong activity, and therefore various side reactions occur in addition to the desired graft reaction.

When a peroxide-disintegrating resin such as polypropylene is used, thermal decomposition of the organic peroxide rapidly occurs, and as a result, a molecular cleavage reaction is unavoidable and a composition having high fluidity is obtained. Although it is convenient for a composition for injection molding, on the other hand, mechanical properties such as flexural modulus and tensile yield strength and adhesiveness are deteriorated.

On the other hand, when a peroxide cross-linking resin such as polyethylene is used, an extreme cross-linking reaction proceeds and the fluidity is remarkably reduced, and in some cases gelation occurs and processing becomes impossible. There is a problem that it will end up.

The residual peroxide deteriorates the thermal stability and weather resistance. Further, when these compositions are extrusion-molded, problems such as deterioration of drawdown resistance due to a molecular cleavage reaction, surface roughness of a molded product due to an extreme crosslinking reaction, and insufficient elongation are problems. In addition, there are problems associated with stability and safety during storage and modification of the free radical generator, and thermal decomposition loss due to adhesion to the heated inner wall of the processing machine.

Therefore, the method of modifying using only a peroxide is not sufficiently satisfactory in practical use in terms of mechanical strength and the like, and it has been desired to develop a more improved modified product and modification method.

In view of the above points, the present invention is to improve the drawbacks of the peroxide modification method involving an excessive crosslinking reaction, a local crosslinking reaction or a molecular cleavage reaction, and a modification showing a mild modification reaction. A dihydroaromatic compound or a polymer thereof, an ether compound, a tetrahydroaromatic compound, a cyclopentane compound, and a small amount of a radical generator that does not impair mechanical properties and processability as necessary, and a polyamide system And / or graft modification of a resin and a polyolefin resin in the presence of a compound having a functional group
Alternatively, a crosslinked modified product and a thermoplastic resin composition containing the modified product, which is a thermoplastic resin composition capable of accelerating the impact resistance of a polyamide resin and a compatibilization with a polyolefin resin and exhibiting mutual characteristics. It is to provide things.

[0019]

The inventors of the present invention have achieved the present invention as a result of diligent studies in view of the above problems. That is, 1 of the present invention is a thermoplastic resin composition characterized by comprising a melt-kneaded product of the following components (A) to (D):

(A) Polyamide resin (A1), polyester resin (A2), polyoxymethylene resin (A
At least one thermoplastic resin selected from 3), a polycarbonate resin (A4), and a polyphenylene ether resin (A5).

(B) Polyolefin resin

(C) At least one compound selected from the following (C1) to (C4) C1: Dihydroaromatic compound or polymer thereof C2: Ether compound C3: Tetrahydroaromatic compound C4: Cyclo Pentane compound

(D) At least one compound containing the following functional groups (D1) to (D6) D1: Carbonyl group D2: Cyclic iminoether group D3: Epoxy group D4: Hydroxy group D5: Amino group D6: Nitrile group

According to the second aspect of the present invention, the following (A) to
A method for producing a thermoplastic resin composition, which comprises melt-kneading the component (D).

(A) Polyamide resin (A1), polyester resin (A2), polyoxymethylene resin (A
At least one thermoplastic resin selected from 3), a polycarbonate resin (A4), and a polyphenylene ether resin (A5).

(B) Polyolefin resin

(C) At least one compound selected from the following (C1) to (C4) C1: Dihydroaromatic compound or polymer thereof C2: Ether compound C3: Tetrahydroaromatic compound C4: Cyclo Pentane compound

(D) At least one compound containing the following functional groups (D1) to (D6) D1: Carbonyl group D2: Cyclic iminoether group D3: Epoxy group D4: Hydroxy group D5: Amino group D6: It is a nitrile group.

The present invention will be described in detail below.

The (A1) polyamide resin used in the present invention is obtained by polycondensation of diamine and dicarboxylic acid, self-condensation of ω-amino acid, and ring-opening polymerization of lactams. Such polyamides include nylon 6, nylon 66, nylon 46, nylon 69, nylon 610, nylon 11, nylon 12, nylon 1
Aliphatic nylon such as 212, and nylon MXD6
And the like, which are nylons partially or wholly composed of aromatic rings, and these may be used alone or as a mixture.

The (A2) polyester resin used in the present invention is a high molecular weight thermoplastic resin having an ester bond in the main chain of the molecule, and specifically, it is obtained from dicarboxylic acid or its derivative and dihydric alcohol. A polycondensation product obtained;
Examples thereof include polycondensates obtained from dicarboxylic acids or derivatives thereof and cyclic ether compounds; polycondensates obtained from metal salts of dicarboxylic acids and dihalogen compounds; ring-opening polymerization products of cyclic ester compounds. Here, the derivative of dicarboxylic acid refers to an acid anhydride, an ester compound or an acid chloride. The dicarboxylic acid may be aliphatic or aromatic, and examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxylphenylacetic acid and p-phenic acid. Dilenacetic acid, m-phenylenediglycolic acid, p-
Phenylenediglycolic acid, diphenyldiacetic acid, diphenyl-p, p'-dicarboxylic acid, diphenyl-m, m '
-Dicarboxylic acid, diphenyl-4,4'-diacetic acid, diphenylmethane-p, p'-dicarboxylic acid, diphenylethane-m, m'-dicarboxylic acid, stilbene dicarboxylic acid, diphenylbutane-p, p'-dicarboxylic acid, Benzophenone-4,4'-dicarboxylic acid, naphthalene-
1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, p-carboxyphenoxyacetic acid, p-carboxyphenoxybutyric acid, 1,2-diphenoxypropane-p, p ' -Dicarboxylic acid, 1,3-diphenoxypropane-p, p'-dicarboxylic acid, 1,4-diphenoxypropane-p, p '
-Dicarboxylic acid, 1,5-diphenoxypentane-p,
p'-dicarboxylic acid, 1,6-diphenoxyhexane-
p, p'-dicarboxylic acid, p- (p-carboxyphenoxy) benzoic acid, 1,2-bis (2-methoxyphenoxy) -ethane-p, p'-dicarboxylic acid, 1,3-bis (2-methoxy) Phenoxy) -propane-p, p'-dicarboxylic acid, 1,4-bis (2-methoxyphenoxy)
-Butane-p, p'-dicarboxylic acid, 1,5-bis (2
-Methoxyphenoxy) -3-oxapentane-p,
p′-dicarboxylic acid and the like, and examples of the aliphatic dicarboxylic acid include oxalic acid, succinic acid,
Examples thereof include adipic acid, corkic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, undecanedicarboxylic acid, maleic acid and fumaric acid. Examples of preferred dicarboxylic acids are aromatic dicarboxylic acids, and more preferred are terephthalic acid, isophthalic acid and phthalic acid.

Examples of the dihydric alcohol include ethylene glycol, propylene glycol, trimethylene glycol, butane-1,3-diol, butane-1,4-.
Diol, 2,2-dimethylpropane-1,3-diol, cis-2-butene-1,4-diol, tran
Examples include s-2-butene-1,4-diol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, heptamethylene glycol, octamethylene glycol and decamethylene glycol. Examples of preferred dihydric alcohols are ethylene glycol, propylene glycol, trimethylene glycol,
Butane-1,3-diol or butane-1,4-
Among the diols, ethylene glycol and butane-1,4-diol are more preferable. Examples of the dihydric phenol compound include hydroquinone, resorcinol, bisphenol A and the like.

Examples of the cyclic ether compound include ethylene oxide and propylene oxide, and examples of the cyclic ester compound include δ-valerolactone and ε-caprolactone. The dihalogen compound to be reacted with the dicarboxylic acid metal salt means a compound obtained by substituting the two hydroxyl groups of the above dihydric alcohol or dihydric phenol compound with halogen atoms such as chlorine or bromine.

The polyester resin used in the resin composition of the present invention may be produced by a known method using the above-mentioned raw materials, and these may be used alone or as a mixture.

The (A3) polyoxymethylene resin used in the present invention is a substantially oxy resin produced from a cyclic oligomer such as formaldehyde monomer or its trimer (trioxane) or tetramer (tetraoxane). Oxymethylene units and C ₂ produced from oxymethylene homopolymers containing only methylene units and the above-mentioned raw materials and cyclic ethers such as ethylene oxide, propylene oxide, epichlorohydrin, 1,3-dioxolane, glycol formal, and diglycol formal. It includes oxymethylene copolymers comprising the above oxyalkylene units, which may be used alone or as a mixture.

The (A4) polycarbonate resin used in the present invention is a solvent method, that is, in the presence of a known acid acceptor and a molecular weight modifier in a solvent such as methylene chloride, a dihydric phenol and a carbonate precursor such as phosgene. Or a transesterification reaction between a dihydric phenol and a carbonate precursor such as diphenyl carbonate.

Here, bisphenols are preferably used as the dihydric phenol, and 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is particularly preferable. Further, a part or all of bisphenol A may be replaced with another dihydric phenol. As dihydric phenols other than bisphenol A,
For example, hydroquinone, 4,4-dihydroxydiphenyl, bis (4-hydroxyphenyl) alkane, bis (4-hydroxyphenyl) cycloalkane, bis (4
Compounds such as -hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ether or bis (3,5-dibromo-
Mention may be made of halogenated bisphenols such as 4-hydroxyphenyl) propane, bis (3,5-dichloro-4-hydroxyphenyl) propane. These dihydric phenols may be homopolymers of dihydric phenols or copolymers or blends of two or more thereof.

The polycarbonate resin used in the present invention is
From the viewpoint of mechanical strength and moldability, the viscosity average molecular weight is preferably 10,000 to 100,000, and more preferably 20,000 to 70,000.

The (A5) to polyphenylene ether resins used in the present invention have the general formula

[0040]

[Chemical 1]

[In the formula, R _{1 to} R ₅ are selected from hydrogen, a halogen atom, a monovalent hydrogen group, or a substituted hydrocarbon group, and one of them is always a hydrogen atom]

It is a polymer obtained by oxidatively polymerizing the phenol compound represented by the formula (1) with oxygen or an oxygen-containing gas using a coupling catalyst.

Specific examples of R _{1 to} R ₅ in the above general formula are hydrogen, chlorine, fluorine, iodine, methyl, ethyl, propyl, butyl, cocoroethyl, hydroxyethyl, phenylethyl, benzyl, hydroxymethyl, carboxyethyl, Methoxycarbonylethyl, cyanoethyl, phenyl, chlorophenyl, methylphenyl, dimethylphenyl, ethylphenyl and the like can be mentioned.

Specific examples of the above general formula include phenol, o, m or p-cresol, 2,6-, 2,5.
-, 2,4-, or 3,5-dimethylphenol, 2
-Methyl-6-phenylphenol, 2,6-diphenylphenol, 2-methyl-6-ethylphenol,
Examples include 2,3,5-, 2,3,6- and 2,4,6-trimethylphenol. Two or more kinds of these phenol compounds can be used.

Further, it may be a copolymer of a phenol compound other than the above general formula, for example, a dihydric phenol such as bisphenol A, tetrabromobisphenol A, resorcin, hydroquinone and the like and a phenol compound of the above general formula.

The thermoplastic resins (A1) to (A5) may be used alone or as a mixture of two or more kinds.

The (B) polyolefin resin used in the present invention is an α-olefin (co) polymer having 2 to 12 carbon atoms, such as high-medium density polyethylene, high-pressure low-density polyethylene, linear low-density polyethylene, and super-high density polyethylene. Low density polyethylene, polypropylene, poly-1-butene, poly-4-
Methyl-1-pentene or interpolymers of α-olefins such as ethylene, polypropylene, butene-1, hexene-1, 4-methyl-1-pentene, ethylene.
Examples thereof include copolymers of ethylene and a polar group monomer such as unsaturated carboxylic acid ester copolymers and ethylene / carboxylic acid unsaturated ester copolymers, and these may be used alone or as a mixture.

Among these, ethylene (co) polymers and / or polypropylene resins are most preferable because they have a good balance of mechanical strength.

In the present invention, the (C1) dihydroaromatic compound or polymer thereof added as the component (C) is a compound containing one or more aromatic rings, and at least one aromatic ring is dihydrogenated. Say something. The term “aromatic ring” as used herein means the definition of aromaticity (for example, “Basics of Organic Chemistry” translated by Toshio Goto, pages 105 to 106, Ltd.
Tokyo Kagaku Dojin (1976) [Richard S. M
on-son & John C. Shelton; F
undamments of OrganicChe
mistry, MacGraw-Hill, INC (1
974)] is a ring structure in which the number of π-electrons is 4n + 2 (n is an integer) and includes, for example, pyridine and quinoline.

Accordingly, the dihydroaromatic compounds used in the present invention also include dihydro derivatives of quinoline.

Further, the dihydroaromatic compound used in the present invention may have a substituent, and a substitution product by an alkyl group and various elements and a substitution derivative by a functional group are used. Such a dihydroaromatic compound can be arbitrarily synthesized by applying a known chemical reaction, but if the currently available compounds are exemplified, 1,2-dihydrobenzene, c
In addition to is-1,2-dihydrocatechol, 1,2-dihydronaphthalene, 9,10-dihydrophenanthrene and the like, 6-decyl-2,2,4-trimethyl-1,2-dihydroquinoline, 6-ethoxy-2 , 2,4-trimethyl-1,2-dihydroquinoline and 2,2,4-trimethyl-1,2-dihydroquinoline-based compounds.
It may also be a polymer of these compounds.

Among the dihydroaromatic compounds of the present invention are:
Conventionally, there are known antiaging agents, but this is the present invention, that is, the recognition that the dihydroaromatic compound and its polymer induce radicals, or the compound containing the dihydroaromatic compound and a functional group. The effect of promoting a mild denaturation reaction by using these together has not yet been recognized.

The (C2) ether compound used in the present invention may be linear or cyclic, and may have a substituent. Specific examples include cyclic ethers such as 1,3-dioxolane and 1,4-dioxane, linear ethers such as ethyl ether and isopropyl ether, and 3,4-dihydro-2-pyran and 4H-chromene. Non-aromatic cyclic vinyl ether, furfuryl alcohol, furfuryl aldehyde, benzofuran, furan derivative represented by furfuryl acetate, n-octadecyl vinyl ether, linear vinyl ether compound represented by ethyl vinyl ether, ketene acetal, isoacetate These are enol ethers and enol esters of carbonyl compounds such as ketones, esters, lactones, aldehydes, amides and lactams, which are represented by propenyl, vinyl acetate and 1-amino-1-methoxyethylene. These may have a substituent,
Substitutes with an alkyl group, various elements, and derivatives substituted with a functional group are used. Moreover, these may be individual or a mixture. Preferred is vinyl or alkenyl ether.

The (C3) tetrahydroaromatic compound used in the present invention is a compound in which at least one aromatic ring is tetrahydrogenated. The aromatic ring here is the same as the definition of aromaticity described above, and includes, for example, furan, benzene, naphthalene, and the like. Also, Piran etc. are excluded. Therefore, the tetrahydroaromatic compound used in the present invention also includes a tetrahydro derivative of naphthalene. Further, the tetrahydroaromatic compound used in the present invention may have a substituent, and a substitution product by an alkyl group, various elements and a substitution derivative by a functional group are used.
Such a tetrahydroaromatic compound can be arbitrarily synthesized by applying a known chemical reaction, but if the currently available ones are exemplified, 1,2,3,4-tetrahydronaphthalene, tetrahydrobenzene and tetrahydrofuran are Can be mentioned. It may also be a polymer of these compounds.

The (c4) cyclopentane compound used in the present invention is a compound containing at least one cyclopentane, cyclopentane or cyclopentadiene skeleton, that is, a 5-membered ring having only carbon atoms. It is a ring compound. Specifically, cyclopentane,
This includes cyctopentene, cyclopentadiene, dicyclopentadiene, indene, indane, fluorene and the like. Of course, these may have substituents,
Substitutes with an alkyl group, various elements, and derivatives substituted with a functional group are used. These may be used alone or as a mixture.

The compound having a functional group (D) used in the present invention is essentially any compound other than the functional group as long as it is a compound having a functional group of (D1) to (D6), For example, it may be an aliphatic group, an alicyclic group, an aromatic group or a combination thereof, but a compound having an olefinic double bond (hereinafter sometimes referred to as a monomer) is particularly preferable. Usually, a group consisting of an aliphatic group having at least one olefinic double bond, an alicyclic group, an aromatic group or a combination thereof is used. The carbon number of these is not particularly limited, but is usually about 2 to 12. Further, these monomers can be added to other polymers in advance, such as modifying an olefin polymer with maleic anhydride, and then used in the present invention. When a compound having no olefinic double bond is used, it is preferable to use a polyfunctional monomer described later in combination.

Examples of the (D1) carbonyl group-containing monomer include carboxylic acids such as carboxylic acids, carboxylic acid esters, carboxylic acid amides, acid halides and acid anhydrides or derivatives thereof, carbonyl groups such as ketones, aldehydes, lactones and lactams, or There are monomers containing their derivatives.

Specifically, α such as methyl vinyl ketone,
β-unsaturated ketones, α, β-unsaturated aldehydes such as acrolein, δ or γ-valerolactam, ketones represented by α, β-unsaturated lactam derivatives such as γ-butenolactam, aldehydes, lactones, lactams, etc. A carbonyl group or a derivative thereof means an α, β-unsubstituted compound such as maleic acid, fumaric acid, citraconic acid, itaconic acid, 5-norbornene-2,3-dicarboxylic acid, 1,2,3,6-tetrahydrophthalic acid. Saturated dicarboxylic acid,
Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, butenoic acid and pentenoic acid, their esters and amides, and in the case of dicarboxylic acids, anhydrides, half esters and metal salts.

Examples of the (D2) cyclic imino ether group-containing monomer include an alkenyl cyclic imino ether represented by the following structural formula or a derivative thereof.

[0060]

[Chemical 2]

Here, n is 1, 2 and 3, preferably 2 and 3, and more preferably 2. Also R ¹ ,
R ² , R ³ and R each represent a C _{1 to} C ₁₂ inactive alkyl group and / or hydrogen, and the alkyl group may have an inactive substituent. The term "inert" as used herein means that the graft reaction and the function of the product are not adversely affected. Also, all R need not be the same. Preferably R ¹ = R ² = H, R ³ = H or M
e, R = H, that is, 2-vinyl or 2-isopropenyl-2-oxazoline, 2-vinyl or 2-isopropenyl-2-oxazoline, 2-vinyl or 2-isopropenyl-5,6-dihydro-4H-. It is 1,3-oxazine. These may be used alone or as a mixture. Among these, especially 2-vinyl and 2-isopropenyl-2-
Oxazoline is preferred.

(D3) Epoxy-containing monomer includes
Examples include glycidyl (meth) acrylate, butadiene oxide, and isoprene oxide.

Examples of the (D4) hydroxy group-containing monomer include 1-hydroxypropyl (meth) acrylate and 2
-Hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate and the like.

(D5) The amino group-containing monomer includes
Examples include aminoethyl (meth) acrylate.

Examples of the (D6) nitrile group-containing monomer include acrylonitrile.

The above-mentioned compound containing various functional groups may be linear or cyclic, may have a substituent which does not inhibit the modification reaction, and may be a mixture of compounds which do not inhibit the modification reaction. Moreover, these derivatives may be used.

Other unsaturated monomers may coexist when modifying with a compound containing the above functional group. Examples of the other unsaturated monomers include propylene, 1-butene, 1- Examples include olefins such as hexene, 1-decene, 1-octene and styrene; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; vinyl chloride; vinyl methyl ether; vinyl ethers such as vinyl ethyl ether.

The compound having a functional group (D) is used in combination with at least one compound selected from (C1) to (C4) to improve adhesion and reactivity by grafting and / or crosslinking. It is possible to add the modified product, and the modified product or the composition containing the modified product is suitably used as an adhesive, an impact modifier, a compatibilizer, and the like.

Among these, unsaturated (di) carboxylic acids typified by maleic anhydride are particularly preferable because they are highly reactive when used in combination with the (C) modifier.

Alkenyl cyclic imino ethers or derivatives thereof are also preferable because they are highly reactive with various functional groups, have high adhesiveness and reactivity, and are highly effective as adhesives and compatibilizers.

In the present invention, a small amount of (E) radical generator may be used in combination when obtaining the modified product.

The (E) radical generator may be an ordinary radical generator, and examples thereof include organic peroxides, azonitriles, oxygen and ozone.

Examples of organic peroxides include alkyl peroxides, aryl peroxides, acyl peroxides, ketone peroxides, peroxycarbonates, peroxycarboxylates and the like. Alkyl peroxides include diisopropyl peroxide, ditertiary butyl hydroperoxide, tertiary butyl hydroperoxide, α, α′-bis- (tertiary butylperoxyisopropyl) -benzene, and aryl peroxides such as dicumyl peroxide, cumyl hydroperoxide and acyl. Examples of the peroxide include lauroyl peroxide, examples of the aroyl peroxide include dibenzoyl peroxide, and examples of the ketone peroxide include methyl ethyl ketone peroxide and cyclohexanone peroxide. Examples of azonitriles include azobisisobutyronitrile and azobisisopropionitrile. These may be used alone or as a mixture. By combining an appropriate amount of this (E) radical generator, the function as an adhesive or a compatibilizer is remarkably improved.

Further, in the present invention, the periodic table I
during the above modification of a carbonate or oxide of a group a or IIa metal such as sodium carbonate, potassium carbonate, lithium carbonate, magnesium carbonate, calcium carbonate, calcium oxide, sodium oxide, potassium oxide, magnesium oxide, lithium oxide and Alternatively, it may be modified after being modified by blending.

If necessary, a polyfunctional monomer, for example, methacrylic acid ester represented by trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, vinyl represented by divinylbenzene, triallyl isocyanurate, diallyl phthalate. Monomers, N, N'-m-phenylene bismaleimide, and bisimide represented by N, N'-m-ethylene bismaleimide are blended and crosslinked simultaneously with modification to enhance mechanical properties and improve heat resistance. It is possible. These may be used alone or as a mixture, but among them, bismaleimides are preferable since they not only enhance the cross-linking reactivity but also contribute to the adhesion.

The above modification may be carried out in a temperature range not lower than the melting point or softening point of the resin but not higher than the decomposition point, such as dynamic kneading, melt kneading, or reaction in a solvent, and is not particularly limited.

In melt kneading, it is preferable that radicals are easily generated in the mixture by using a mixer which gives a high shear rate.

The modified product of the present invention is (A) polyamide resin (A1), polyester resin (A2), polyoxymethylene resin (A3), polycarbonate resin (A4).
At least one kind of thermoplastic resin selected from among
By appropriately selecting the compounding ratio of the (B) polyolefin-based resin, for example, 99 to 1/1 to 99, preferably 95
˜5 / 5 to 95, more preferably 90 to 10/10
When it is used together in the range of 90, a wide range of required physical properties can be satisfied.

The compounding amount of the compound having a functional group (C) of the present invention is 0.00 based on 100 parts by weight of the thermoplastic resin.
It is 1 to 8 parts by weight, and preferably 0.01 to 5 parts by weight.

When the amount added is less than 0.001 part by weight, the modification reaction does not proceed sufficiently, and when it exceeds 8 parts by weight, coloring of the resin or increase in cost is unfavorable.

The compounding amount of the compound (D) having a functional group is 0.01 to 3 with respect to 100 parts by weight of the thermoplastic resin.
It is selected in the range of 0 parts by weight.

When the amount added is less than 0.01, the adhesiveness, reactivity and other costs are low, and when the amount added exceeds 30 parts by weight, the adhesiveness is not further improved and the reactivity is extremely improved. However, it may cause curing or discoloration of the resin, which is not preferable.

The content of the radical generator (E) is 5 parts by weight or less based on 100 parts by weight of the thermoplastic resin. If the addition amount exceeds 5 parts by weight, not only the modification reaction but also the molecular cleavage reaction of the resin and the excessive crosslinking reaction proceed, so that the fluidity and the mechanical properties are deteriorated, which is not preferable.

In the present invention, a softening agent may be added during and / or after the heat treatment.

As the softening agent, oils such as paraffinic, naphthenic and aromatic oils, and not only these petroleum fractions but also synthetic oils such as liquid polyisobutene can be used.

The blending amount of the softening agent varies depending on the purpose, application, etc., but is usually 10 parts by weight per 100 parts by weight of the resin.
It is mixed up to 0 parts by weight.

In the present invention, an unmodified polyamide-based resin, polyester-based resin, polyoxymethylene resin, polycarbonate resin, polyolefin-based resin or the like can be appropriately added to the above resin composition.

When the above-mentioned modified thermoplastic resin composition is used as an adhesive, the concentration of the compound (D) having a functional group in the composition is 0.001 to 0.001 relative to the thermoplastic resin component. It is desirable to prepare it so as to be in the range of 20% by weight.

If the concentration is less than 0.001% by weight, the adhesive strength is not sufficient, and if the concentration exceeds 20% by weight,
It is not preferable because the adhesiveness is not further improved and the resin may be discolored.

Since the modified product or modified thermoplastic resin composition of the present invention has a highly reactive functional group, it is effective as an impact modifier or compatibilizer for various resins.

The modified thermoplastic resin composition of the present invention, or the composition using the same may optionally contain a stabilizer, an antioxidant, an ultraviolet absorber, a lubricant, a foaming agent, an antistatic agent,
A flame retardant, a filler, a plasticizer, a dye, a content and the like can be appropriately mixed.

These additive components may be organic compounds or inorganic compounds, and their shapes may be powdery, scaly, acicular, spherical, hollow and fibrous.

More specifically, stabilizers represented by hindered phenol compounds, benzotriazole compounds, hindered amine compounds and amide compounds; inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide;
Calcium carbonate, magnesium carbonate, calcium sulfate,
Calcium silicate, clay, diatomaceous earth, talc, alumina,
Glass powder, iron oxide, metal powder, graphite, silicon carbide,
Silica, boronitride, aluminum nitride, carbon black, mica, glass plate, sericite, pyrophyllite, aluminum flakes, graphite, shirasu balloon, metal balloon, pumice, glass fiber, carbon fiber, graphite fiber, whiskers, metal fiber, Silicon carbide fiber,
Inorganic fillers represented by asbestos, wollastonite and the like; dyes such as azo dyes and indigo dyes; pigments such as red iron oxide can be used.

Particularly, when the above-mentioned inorganic compound is filled, the one surface-treated with a silane coupling agent, an organic titanate coupling agent, a metal salt or the like may be used.

The modified product or modified thermoplastic resin composition modified with an unsaturated carboxylic acid or derivative according to the method of the present invention has a polar group in particular, so that it is highly suitable for compounding agents such as inorganic fillers. Can be filled.

These filler components can be blended at any time, but it is desirable to knead them simultaneously at the time of melt kneading.

Further, the modified thermoplastic resin composition of the present invention is excellent in coatability, but in order to further improve its effect, it may be irradiated with high energy rays such as ultraviolet rays and plasma.

[0098]

Use of the present invention Since the modified product of the present invention and the modified thermoplastic resin composition containing the modified product have excellent adhesiveness, they can be used as a resin material in applications requiring coating, printing and adhesion. Further, the modified product, a thermoplastic resin using a modified thermoplastic resin composition containing the modified product has excellent properties, for example, fibers, electricity, electronics, automobiles, ships,
It is used as a panel, packaging material, furniture, household article, etc. in various fields such as aircraft, construction and civil engineering, and can be molded by any molding method of plastic such as injection molding method, extrusion molding method and compression molding method. More specifically, (1) rear finisher, sill, rear coater panel, engine hood, trunk lid, fender, door panel, protector, bumper fascia, energy absorber, air spoiler, side molding, weather strip, shock absorber dust. boots,
Vacuum onector, rack and pinion boots,
Automotive parts such as instrument panels, armrests, door liners, seat backs, duct covers, mudguards, etc. (2) Home appliances parts such as coolers and interiors and exteriors of refrigerators (3) House materials such as roof panels and heat insulation walls (4) Dining table, desk surface, furniture panel, kitchen cabinet, daily necessities such as ice boxes, furniture, etc. (5) Others

In addition, extruded products such as sheets and films,
It is used as a resin composition or a masterbatch for molding applications such as injection molded products.

Further, the modified product or modified thermoplastic resin composition is adhered to another material (eg, metal, inorganic material, plastic, etc.) in a molten state as an adhesive resin to form a strongly adhered laminated structure. It becomes possible to do.

[0101]

EXAMPLES AND COMPARATIVE EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention.

Examples 1 to 12 and Comparative Examples 1 to 12 (A1) Polyamide resin at the ratios shown in Tables 1 and 2,
(B) Polyolefin resin, (C) component compound, (D) functional group-containing compound, and (E) radical generator were melt-kneaded, if necessary. Unless otherwise specified, test pieces obtained by injection molding were used after annealing treatment.

The method for producing the composition, the conditions for producing a test piece by injection molding, and the test method are as follows.

Method for producing the composition 1) (A) polyamide resin, (B) polyolefin resin, (C) component compound and (D) functional group-containing compound, and (E) radical generation if necessary The agents were mixed in the mixing ratio and mixed with a Henschel mixer.

2) A biaxial continuous kneading extruder (30 mmφ, Plastic Engineering Laboratory Co., Ltd.) was used for the mixture obtained above.
Manufactured by the company), the resin temperature is 240 to 300 ° C., the rotation speed is 20.
The mixture was melt-kneaded at 0 rpm and pelletized. During kneading, the unreacted monomer was completely removed by a vent (-700 mmHg). If you need to inject a softener,
It was added from a reciprocating metering pump connected to the ventro.

Injection molding conditions Molding machine IS-90B (manufactured by Toshiba Machine Co., Ltd.) Injection pressure 1,000 kg / cm ² Molding temperature 230-290 ° C Mold temperature 70-90 ° C

Test / Measurement Method 1. Flexural Modulus Measured according to ASTM D-790. 2. Izod impact strength Measured according to JIS K-6758. 3. Deflection Temperature Under Load (HDT) Measured according to JIS K-7207. 4. Water Absorption Measured according to ASTM D-570. 5. Flow mark For a mold with a shape of 100 mm × 200 mm × 3 mm,
The sample was injection-molded under the following conditions, and the molded product was visually judged.

Injection molding conditions Molding machine IS-90B (manufactured by Toshiba Machine Co., Ltd.) Injection pressure 1,000 kg / cm ² Molding temperature 230 to 290 ° C Mold temperature 70 to 90 ° C Good visual judgment in good order A four-level evaluation up to ○ △ x was used.

Examples 13 to 24, Comparative Examples 13 to 24 The same as Examples and Comparative Examples 1 to 12 except that the polyester resin (A2) was used as the thermoplastic resin.

Test / Measurement Method 1. Flexural Modulus Measured according to ASTM D-790. 2. Izod impact strength Measured according to JIS K-6758. 3. Deflection Temperature Under Load (HDT) Measured according to JIS K-7207. 4. Hydrolysis resistance A 40 mm × 50 mm sample piece was cut out from an injection-molded plate having a thickness of 3 mm, immersed in a 40 wt% NaOH aqueous solution at 90 ° C. for 72 hours, and the strain and the surface state were observed. As a visual judgment, a four-stage evaluation of ∘∘∘x was given in order of goodness. 5. Flow mark For a mold with a shape of 100 mm × 200 mm × 3 mm,
The sample was injection-molded under the following conditions, and the molded product was visually judged.

Conditions for injection molding Molding machine IS-90B (manufactured by Toshiba Machine Co., Ltd.) Injection pressure 1,000 kg / cm ² Molding temperature 230-290 ° C Mold temperature 70-90 ° C Good visual judgment in good order A four-level evaluation up to ○ △ x was used.

Examples 25 to 36, Comparative Examples 25 to 36 The same as Examples and Comparative Examples 1 to 12 except that (A3) polyoxymethylene resin was used as the thermoplastic resin.

Test / Measurement Method 1. Flexural Modulus Measured according to ASTM D-790. 2. Izod impact strength Measured according to JIS K-6758. 3. Deflection Temperature Under Load (HDT) Measured according to JIS K-7207. 4. Molding shrinkage For a mold with a shape of 100 mm × 200 mm × 3 mm,
The sample was injection molded under the following conditions, and the dimension of the molded product in the MD direction with respect to the mold was measured.

Injection molding conditions Molding machine IS-90B (manufactured by Toshiba Machine Co., Ltd.) Injection pressure 1,000 kg / cm ² Molding temperature 230-290 ° C Mold temperature 70-90 ° C

5. Flow mark For a mold with a shape of 100 mm × 200 mm × 3 mm,
The sample was injection-molded under the following conditions, and the molded product was visually judged.

Injection Molding Conditions Molding Machine IS-90B (manufactured by Toshiba Machine Co., Ltd.) Injection pressure 1,000 kg / cm ² Molding temperature 230-290 ° C. Mold temperature 70-90 ° C. A four-level evaluation up to ○ △ x was used.

Examples 37 to 48, Comparative Examples 37 to 48 The same as Examples and Comparative Examples 1 to 12 except that (A4) polycarbonate resin was used as the thermoplastic resin.

Test / Measurement Method 1. Flexural Modulus Measured according to ASTM D-790. 2. Izod impact strength Measured according to JIS K-6758. 3. Deflection Temperature Under Load (HDT) Measured according to JIS K-7207. 4. Solvent resistance It was immersed in 95 vol% acetone for 48 hours, and the molded product was judged visually. As a visual judgment, in good order ◎ ○ △ ×
Up to 4 grades. 5. Flow mark For a mold with a shape of 100 mm × 200 mm × 3 mm,
The sample was injection-molded under the following conditions, and the molded product was visually judged.

Injection molding conditions Molding machine IS-90B (manufactured by Toshiba Machine Co., Ltd.) Injection pressure 1,000 kg / cm ² Molding temperature 230-290 ° C Mold temperature 70-90 ° C

Examples 49 to 54, Comparative Examples 49 to 54 The same as in Examples and Comparative Examples 1 to 12 except that (A5) polyphenylene ether resin was used as the thermoplastic resin.

Test / Measurement Method 1. Flexural Modulus Measured according to ASTM D-790. 2. Izod impact strength Measured according to JIS K-6758. 3. Deflection Temperature Under Load (HDT) Measured according to JIS K-7207. 4. Solvent resistance It was immersed in 95 vol% acetone for 48 hours, and the molded product was judged visually. As a visual judgment, in good order ◎ ○ △ ×
Up to 4 grades. 5. Flow mark For a mold with a shape of 100 mm × 200 mm × 3 mm,
The sample was injection-molded under the following conditions, and the molded product was visually judged.

Conditions for injection molding Molding machine IS-90B (manufactured by Toshiba Machine Co., Ltd.) Injection pressure 1,000 kg / cm ² Molding temperature 230-290 ° C Mold temperature 70-90 ° C

[0123]

As described above, the modified thermoplastic resin composition obtained by the present invention comprises at least one type of thermoplastic resin selected from polyamide resins, polyester resins, polyoxymethylene resins and polycarbonate resins. A plastic resin and a polyolefin resin, a functional group in the presence of a dihydroaromatic compound or a polymer thereof as a modifier, an ether compound, a tetrahydroaromatic compound, a cyclopentane compound, and optionally a radical generator. By modifying with a compound containing, the thermoplastic resin itself retains its excellent mechanical strength, thermal properties and molding processability, while impact resistance and low water absorption for polyamide resins are maintained. Impact resistance, moldability, and hydrolysis resistance to polyester resins. It is possible to dramatically improve impact resistance, acid resistance, low specific gravity, and flame retardancy for resin, and solvent resistance and moldability for polycarbonate resin. The properties as a solubilizer and the like are remarkably excellent, and the paintability can be remarkably improved.

[0124]

[Table 1]

[0125]

[Table 2]

[0126]

[Table 3]

[0127]

[Table 4]

[0128]

[Table 5]

[0129]

[Table 6]

[0130]

[Table 7]

[0131]

[Table 8]

[0132]

[Table 9]

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08L 71/12 LQM 9167-4J LQP 9167-4J 77/00 LQS 9286-4J

Claims (2)

[Claims] 1. A thermoplastic resin composition comprising a melt-kneaded product of the following components (A) to (D). (A) At least one thermoplastic resin selected from polyamide-based resin (A1), polyester-based resin (A2), polyoxymethylene resin (A3), polycarbonate resin (A4), and polyphenylene ether resin (A5) (B) Polyolefin resin (C) At least one compound selected from the following (C1) to (C4) C1: Dihydroaromatic compound or polymer thereof C2: Ether compound C3: Tetrahydroaromatic compound C4: Cyclopentane compound (D) At least one compound containing the following functional groups (D1) to (D6) D1: Carbonyl group D2: Cyclic iminoether group D3: Epoxy group D4: Hydroxy group D5: Amino Group D6: Nitrile group 2. A method for producing a thermoplastic resin composition, which comprises melt-kneading the following components (A) to (D). (A) At least one thermoplastic resin selected from polyamide-based resin (A1), polyester-based resin (A2), polyoxymethylene resin (A3), polycarbonate resin (A4), and polyphenylene ether resin (A5) (B) polyolefin resin and (C) at least one compound selected from the following (C1) to (C4) C1: dihydroaromatic compound or polymer thereof C2: ether compound C3: tetrahydroaromatic system Compound C4: Cyclopentane compound (D) At least one compound containing the following functional groups (D1) to (D6) D1: Carbonyl group D2: Cyclic iminoether group D3: Epoxy group D4: Hydroxy group D5: Amino group D6: Nitrile group