JPH07286079A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin compsn. capable of forming a molded product, excellent in impact resistance and rigidity. CONSTITUTION:A thermoplastic resin compsn. comprises 20-70wt.% component (A) and 80-30wt.% component, (B). The component (A) is a metal salt of a copolymer of 70-99.9 wt.%, 2-8C alpha-olefin with 30-0.1 wt. % alpha,beta-unsatd. carboxylic acid or anhydride thereof having a hydrogen atom as the substituent, at the alphaposition thereof wherein the amt. of carboxyl groups neutralized with a metal is 0.01 to 2.5 mol per kg of the copolymer. The component (B) is a basic nitrogen-contg. copolymer of a vinyl monomer having a heterocyclic structure contg. basic nitrogen with other vinyl monomer wherein the amt. of the constituent, units of the vinyl monomer having the heterocyclic structure contg. basic nitrogen is 0.01 to 4.8mol per kg of the copolymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition which gives molded articles such as sheets, containers and housings having excellent impact resistance and elasticity.

[0002]

2. Description of the Related Art For improving impact resistance of polyolefin, ethylene / α, β-unsaturated carboxylic acid copolymer or its metal salt (a) 1 to 70% by weight, and (A) vinyl having amino group Amino group-containing copolymer (b) 99 comprising 0.01 to 40% by weight of a monomer and 99.9 to 60% by weight of a vinyl monomer selected from styrene, acrylonitrile and alkyl (meth) acrylate. ~ 30% by weight
A thermoplastic resin composition containing is known (JP-A-60-58450).

As a vinyl monomer having an amino group,
Examples thereof include aminoethyl acrylate, aminopropyl methacrylate, phenylaminopropyl methacrylate, N-acetylvinylamine and methallylamine. This resin composition has improved tensile strength and elongation, but its impact resistance is not sufficient for practical use.

Further, JP-A-5-194800 discloses an ethylene / methacrylate polymer (Na salt, Zn salt) 1
The Young's modulus of a compression molded product of a resin composition containing 5 to 100% by weight and a styrene-4-vinylpyridine copolymer of 85 to 0% by weight is disclosed. Although this product also has improved tensile strength and elongation, it cannot be said that the impact resistance is practically sufficient.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a thermoplastic resin composition which gives a molded product excellent in impact resistance and flexural rigidity without lowering tensile properties.

[0006]

The present invention provides the component (A):
70 to 99.9% by weight of α-olefin having 2 to 8 carbon atoms
And a metal salt of a copolymer of α, β-unsaturated carboxylic acid having a substituent at the α-position being hydrogen or 30 to 0.1% by weight of an anhydride thereof, the amount of which may vary depending on the metal in 1 kg of the copolymer. A metal salt of a copolymer in which the amount of carboxylated groups is 0.01 to 2.5 mol.
20 to 70% by weight of component (B): a copolymer of a vinyl monomer having a heterocyclic structure containing basic nitrogen and another vinyl monomer,
The amount of structural units based on a vinyl monomer having a heterocyclic structure containing basic nitrogen in 1 kg of the copolymer is 0.01
To 4.8 mol basic nitrogen-containing copolymer
Provided is a thermoplastic resin composition containing 80 to 30% by weight of the above component (A) and component (B).

[0007]

As the component (A), a metal salt of a copolymer using an α, β-unsaturated carboxylic acid such as acrylic acid having no substituent at the α-position or maleic anhydride or its anhydride as a raw material, Further, by using as the component (B) a copolymer having a heterocyclic structure in which basic nitrogen forms part of the cyclic structure, when this resin composition is melt-kneaded, it is neutralized by the metal of the component (A). Coordination bonds between the carboxyl group and the nitrogen of the heterocyclic structure of the component (B) are intermolecularly bonded to give a molded article excellent in impact resistance and rigidity.

(Detailed Description of the Invention) (A) Metal Salt of Copolymer The metal salt of the copolymer of the component (A) has an α of 2 to 8 carbon atoms.
-70 to 99.9% by weight of an olefin, 30 to 0.1% by weight of an α, β-unsaturated carboxylic acid having an α-position substituent of hydrogen or an anhydride thereof, and optionally other olefin or co- 30 to 100 mol% of the carboxyl groups (including acid anhydride groups) of the copolymer obtained by copolymerizing 0 to 30% by weight of the polymerizable monomer is a metal such as Na, Zn, K or Al. Neutralized, the amount of carboxyl groups neutralized by the metal in 1 kg of the metal salt of the copolymer is 0.
01 to 2.5 mol.

As the α-olefin having 2 to 8 carbon atoms, ethylene, propylene, butene-1, hexene-
1, octene-1 and the like. Among them, ethylene is preferable from the viewpoint of impact resistance. Other olefins include linear or branched α-olefins having 9 to 22 carbon atoms such as vinylcyclohexane, alkyl-substituted vinylcyclohexane, and vinylcyclopentane; cyclic internal olefins such as cyclobutane, cyclohexene, and cyclopentane. Cyclopentadiene, cyclopentene, cyclohexene, vinylcyclohexane, styrene, vinylnaphthalene, allylbenzene, butadiene, 1,4-hexadiene, 3-methyl-1-butene, 4-methyl-1-pentene, indene and other monoolefins and diene Ring closure or Diels-Alder from olefins
der) addition reaction such as reaction, ring expansion reaction and, if necessary, a bicyclo ring structure obtained by hydrogenation reaction,
External olefins and internal olefins having a tricyclo ring structure or a bridged polycyclic structure can be used.

Further, α, β-, in which the substituent at the α-position is hydrogen
Specific examples of the unsaturated carboxylic acid or its anhydride include:
Acrylic acid, maleic acid, itaconic acid, maleic anhydride and the like can be mentioned. Among them, from the viewpoint of easy copolymerization with α-olefin and a copolymer having a higher level of mechanical properties, Acrylic acid and maleic anhydride are preferred, with acrylic acid being most preferred.

Vinyl monomers other than α-olefin and α, β-unsaturated carboxylic acid or acid anhydride which are optionally copolymerized include vinyl acetate, methyl acrylate, propyl acrylate, butyl acrylate and acryl. 2-ethylhexyl acid, ethyl methacrylate, butyl methacrylate and the like can be mentioned. Specific examples of the bonding mode of these structural units of the copolymer of the component (A) include random, graft, block and the like, and any of them can be used, but random from the viewpoint of obtaining a higher level of impact strength. , And grafting is more preferable.

The amount of the structural unit based on the α-olefin in the metal salt (A) of the copolymer is 70 to 99.9% by weight, preferably 80 to 99% by weight, particularly preferably 88 to 98%.
% By weight. If it exceeds 99.9% by weight, the impact strength of the molded product obtained from the resin composition tends to be low, and if it is less than 70% by weight, the moldability of the resin composition becomes difficult.

Further, α, β-, in which the substituent at the α-position is hydrogen
The ratio of the structural unit based on the metal salt of unsaturated carboxylic acid or its anhydride to 1 kg of the copolymer is 0.01 to
The amount is 2.5 mol, preferably 0.3 to 1.5 mol, particularly preferably 0.5 to 1.3 mol. If the amount of the structural unit per 1 kg of the metal salt (A) of the copolymer exceeds 4 mol, the moldability of the resin composition becomes difficult, and if it is less than 0.01 mol, the impact strength of the obtained molded product is low.

The metal salt of the metal salt of the copolymer of the component (A) before being made into a metal salt is an α-olefin and an α, β-unsaturated carboxylic acid or its anhydride, and if necessary, other olefin or vinyl. In the presence of a radical generator such as an organic peroxide or an inorganic peroxide, an azo compound or oxygen, the monomer is 50 to
A method for producing a copolymer by contacting at 4000 atm and 40 to 300 ° C., a high pressure polyethylene or a transition metal catalyst such as Ziegler / Natta type, chromium type, rare earth metal type, so-called titanocene type, zirconocene type A copolymer of ethylene and the above-mentioned olefin, an α, β-unsaturated carboxylic acid or its anhydride in which the α-position substituent such as acrylic acid or maleic anhydride is hydrogen, and an organic solvent such as xylene. A method of producing by contacting in the presence or absence of a medium radical generator, or using a uniaxial or multiaxial melt-kneading device, with an ethylene resin in the presence or absence of the radical generator in a molten state Examples include a method of producing by contacting with an α, β-unsaturated carboxylic acid.

In order to partially or completely neutralize the carboxyl group or the acid anhydride group of the copolymer to obtain the metal salt of the copolymer as the component (A), for example, the copolymer may be used in various amounts in various amounts. Metal compounds such as Na ₂ CO ₃ , ZnCO ₃ , N
Using a uniaxial or biaxial melt-kneader with aOH, KOH, (CH ₃ COO) ₂ Zn, for example 150 to 35
A method of neutralizing by melt-kneading in the temperature range of 0 ° C., a method of contacting both in a mixed solvent of a hydrocarbon solvent and an aliphatic alcohol, and then removing the mixed solvent, and the like can be mentioned. To be

The metal elements constituting the metal compound used for neutralization include IA, IIA and I of the Periodic Table of Elements.
B and Group IIB metals, selected from manganese, lead, tin, antimony, aluminum and zirconium. These can be used alone or in combination. Of these, sodium and zinc are preferable, and zinc is the most preferable.

As the anion paired with the cation of these metals, hydroxide anion, carbonate anion, bicarbonate anion, acetate anion, propion oxide anion, or C3 Saturated or unsaturated fatty oxide anions in the range of 10 and the like can be mentioned.
Of these, more preferred are those selected from hydroxide anions, carbonate anions and acetate anions, more preferably carbonate anions and acetate anions, particularly preferably acetate anions. Ion.

Among various metal compounds composed of a combination of these metal cations and anions, preferred are sodium hydroxide, sodium acetate, sodium carbonate, zinc acetate, basic zinc carbonate (zinc carbonate and a small amount of zinc carbonate). (A mixture with zinc hydroxide), more preferably zinc acetate and basic zinc carbonate, particularly preferably zinc acetate. Further, these metal compounds may be hydrates or hydrated salts.

The degree of neutralization of carboxyl groups or acid anhydride groups of the copolymer is 2 with the total amount of these groups being 100 mol%.
It is 0% or more, more preferably 50% or more, further preferably 70% or more, and particularly preferably 100%. When the degree of neutralization is less than 20%, the resulting molded article has low impact strength. The amount of the metal salt used for neutralization is calculated from the product of the stoichiometric amount and the degree of neutralization with respect to the total amount of carboxyl groups contained in the copolymer before being neutralized.

The measurement of the molecular weight of the metal salt (A) of the copolymer is difficult because the intermolecular or intramolecular interaction is extremely strong. That is, from a copolymer or a metal salt (A) of a copolymer before being neutralized by a metal, a polymer equivalent to the copolymer, that is, a metal salt (A) of the copolymer is chemically synthesized. Similarly, in a polymer in which a portion of a carboxylic acid metal salt is converted to a carboxyl group, intermolecular or intramolecular interaction based on the carboxyl group is extremely strong, and therefore there are many points in which it is difficult to measure the molecular weight. For example, when the molecular weight of a polymer having a carboxyl group is measured by gel permeation chromatography (GPC), association of the carboxyl group portion and adsorption into the column for GPC measurement occur, and the measurement tends to be difficult. For this reason, it is necessary to convert the functional group into a functional group such as methyl ester, which is unlikely to cause association or adsorption of the carboxyl group portion, and then perform measurement. Therefore, it is convenient that the molecular weight of the metal salt (A) of the copolymer is quantified with respect to the methyl esterified product of the copolymer before neutralization and calculated from this. The methyl esterified product of this copolymer is obtained by the following method. That is, in a Teflon pressure crucible (UNI-SEAL, UNI-SEAL, internal volume 23 ml), an α-olefin and α, β-unsaturated carboxylic acid (including anhydride) copolymer 60 mg, hexane 10 ml, methanol 0 .5
ml and trimethylsilyldiazomethane [10% hexane solution, manufactured by Tokyo Kasei Co., Ltd.] are added, and heated at 140 ° C. for 3 hours to perform methyl esterification. The reaction solution is evaporated to dryness to obtain an esterified product, which is formed into a film by compression molding, and its infrared absorption spectrum is measured. Since no absorption peak derived from a carboxyl group is seen, it is not esterified. Make sure that no carboxyl groups remain.

The molecular weight and molecular weight distribution curve of the methyl esterified product of the copolymer thus obtained can be determined by a general GPC measuring method for polyethylene. The molecular weight of the methyl esterified product of the copolymer is determined by the following GPC measurement. The measuring device is
Waters GPC / ALC150C and Showa Denko KK column (AD80M / S) three in series, and Foxboro infrared absorption detector (MILAN-
1A, detection wavelength 3.42 micrometers) was used. The measurement conditions are a temperature of 140 ° C., a flow rate of 1 ml / min, a measurement sample solution concentration of 2 mg / ml, and a sample solution injection amount of 20.
0 ml, the measuring solvent is orthodichlorobenzene (Wako Pure Chemical Industries, Ltd.).

To convert the molecular weight, monodisperse polystyrene (manufactured by Tosoh Corp.) is used to prepare a general-purpose calibration curve (universal calibration curve) according to a conventional method, and the molecular weight is converted to that of linear polyethylene. It was done by the method. Changes in the relationship between intrinsic viscosity and molecular weight due to carboxylic acid methyl ester moieties and long chain branching are not considered. The following viscosity equation is used to convert the molecular weight.

[0023]

## EQU1 ## Polystyrene: [η] = 1.079 × 10 ^-4 × M ^0.723 Polyethylene: [η] = 3.915 × 10 ^-4 × M ^0.733

The average molecular weight of the copolymer is such that the weight average molecular weight (Mw) measured by the above method is 30,000-
1,000,000, preferably 80,000-20
50,000 g, particularly preferably 100,000 to
It is 150,000. If it exceeds 1,000,000, fluidity is poor in terms of molding processability. When it is less than 30,000, the resulting molded article has low impact strength. Also,
Regarding the molecular weight distribution, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.5 to 5.
The range is 0, preferably 3 to 10, and particularly preferably 4 to 9. If Mw / Mn exceeds 50, the resulting molded article has a low impact strength and tends to be insufficient in practical use. If it is less than 1.5, the molding processability is difficult.

(B) Basic Nitrogen-Containing Copolymer The basic nitrogen-containing non-crystalline copolymer having a basic nitrogen-containing heterocyclic structure of the component (B) is a heterocycle containing a basic nitrogen in its molecular structure. A copolymer of a vinyl monomer having a ring structure and another vinyl monomer, which is based on a vinyl monomer having a heterocyclic structure containing a basic nitrogen in 1 kg of the copolymer. It is a copolymer having a unit amount of 0.01 to 4.8 mol.

The heterocyclic structure containing a basic nitrogen is an aromatic monocycle, a condensed ring, a monocycle having a saturated or partial carbon-carbon double bond or a carbon-nitrogen double bond, a bicyclo ring, A structure having a nitrogen atom in the cyclic structure such as adamantane or a complex ring or a bridged ring and a molecular structure, and this nitrogen shows basicity, and the number of nitrogen atoms constituting the ring is one. There may be one or more. A cyclic structure containing a plurality of basic nitrogens is also regarded as a cyclic structure containing one unit of basic nitrogen. Further, in the case where a plurality of ring structures are combined and joined, for example, in the case of a condensed ring or a bridged ring structure such as bicyclo or tricyclo, in the case where a plurality of basic nitrogen atoms are contained in the joined heterocyclic structure, Together they are considered as a cyclic structure containing one unit of basic nitrogen.

Specific examples of the heterocyclic structure include pyridine, imidazole, thiazole, carbazole, thiazole, pyrrole, 3-pyrroline, pyrimidine, purine,
Examples thereof include pyrazole, pyrazoline, pyridazine, indole, pyrrolidinopyridine, acridine, phenazine, bipyridyl, pyrazine and the like, and substituted structures thereof.
Among these, from the viewpoint of a resin composition that gives a molded article exhibiting higher impact strength, those in which a nitrogen atom forms part of a cyclic structure are preferable, and the nitrogen atom is a 5-membered, 6-membered or 7-membered, aromatic. Those having a ring structure or a part of a cyclic structure having at least a part thereof conjugated are more preferable, and those having a nitrogen atom of 5 or 6 members and a part of an aromatic ring structure are further preferable.

Examples of the vinyl monomer having a structure in which the basic nitrogen atom forms a part of a cyclic structure include 4-vinylpyridine, 3-vinylpyridine, 2-vinylpyridine,
N-vinyl imidazole, 2-, 3- or 5-vinyl imidazole, N-vinyl carbazole, 1-, 2-,
3- or 4-vinylcarbazole, 2-, 4- or 5-vinylthiazole, 4-methyl-5-vinylthiazole, 1-, 2- or 3-vinylpyrrole, 1, -2
-Or 3-vinyl-3-pyrroline, 2-, 4- or 5-vinylpyrimidine, vinyl-substituted purine, 2- or 3-vinylpyridazine, 1-, 2-, 3-, 4-, 5-
-, Or 6-vinylindole, 1-, 4-, 5-,
6- or 7-vinyl indoline, 2- or 3-indolyl methacrylate, 2- or 3-vinyl-4-pyrrolidinopyridine, 2-, 3- or 4- (2-pyridinyl) styrene, 2-, 3- Or 4- (3-pyridinyl) styrene, 2-, 3- or 4- (4-pyridinyl) styrene, 1-, 2-, 3-, 4- or 9-vinylacridine, 1- or 2-vinylphenazine, 1
-, 2-, 3-, 4-, 6-, 7-, 8-, 9- or 10-vinylphenanthridine, 2-, 3-, 4-, 5
-, 6-, 8-, 9- or 10-vinyl-1,7-phenanthrrolidine, vinyl-substituted 1,7-phenanthrrolidine, 2-, 3- or 4-vinyl-1,10-phene Nantholidine, 1-, 2-, 3- or 5-vinyl-
4,7-phenanthrrolidine, 3-, 4-, 5- or 6-vinylbipyridyl, 2-, 3-, 4-, 5-, 6
-, 7- or 8-vinylquinoline, 1-, 3-, 4
-, 5-, 6-, 7- or 8-vinylisoquinoline,
2-, 5- or 6-vinylquinoxaline, 2, 4
-, 5-, 6-, 7- or 8-vinylquinazoline, 2
-, 4-, 5- or 6-vinyl 3- (pyrrolo-1-ylmethyl) pyridine, 3- (2- or 3-vinylpyrrolo-1-ylmethyl) pyridine, 2-, 3-, 4-, 5
-, 6- or 7-vinyl-7-azaindole, 2-
Vinylpyrazine, N-vinylpiperidine, 2- or 3-piperidinyl methacrylate, 2-piperazinyl methacrylate, 2- or 3-morpholinyl methacrylate,
2- or 3-pyrrolidinyl methacrylate, 2-, 3- or 4-vinyl-1-azaviciro [2.
2.2] Octyl and the like can be mentioned.

Among these, 4-vinylpyridine, 2-vinylpyridine, N-vinylimidazole, 2-vinylimidazole, N-vinylpyrrole, 2- or 3-vinyl, from the viewpoint of obtaining a molded article having good impact strength. Pyrrole, 2-vinyl-3-pyrroline, 2-vinylpyrimidine, 2-vinylpurine, 2-vinylpyrazole, 2-
Vinylpyrazoline, 2-vinylpyridazine, 2-vinylpyrrolidinopyridine, 4-vinylacridine, 4-vinylphenazine, 4-vinylbipyridyl, preferably selected from the group consisting of, particularly 4-vinylpyridine,
More preferred is one selected from the group consisting of 2-vinylpyridine and N-vinylimidazole, and the best one is 4-
It is vinyl pyridine.

The constituent unit based on the vinyl monomer having a basic nitrogen-containing cyclic structure which constitutes the copolymer (B) is a copolymer 1.
The proportion in kg is in the range of 0.01 mol to 4.8 mol, preferably 0.08 mol to 2.1 mol, and most preferably 0.12 mol to 1.7 mol. If it is less than 0.01 mol, the impact strength of the obtained molded article will be low. 4.8
If it exceeds the molar amount, molding processability will be difficult.

Among the vinyl monomers for producing the copolymer (B), the vinyl monomer having a basic nitrogen-containing cyclic structure is
It is used in a proportion of 0.11 to 50% by weight, preferably 0.6 to 30% by weight, particularly preferably 1.4 to 15% by weight. If it is less than 0.11% by weight, the resulting molded article has low impact resistance, and if it exceeds 50% by weight, injection moldability and extrusion moldability are poor.

In the case of using a copolymer having a functional group having a basic nitrogen but not having a cyclic structure,
When using a copolymer having a functional group in which the basic nitrogen atom is not included in the cyclic structure even though it has a cyclic structure, or when electron absorption such as a carbonyl group is present on the nitrogen atom even though it has a cyclic structure Those having an amide or imide structure to which a volatile substituent is bonded give only a molded product having insufficient impact strength.

Other vinyl monomers (b) to be copolymerized with the vinyl monomer (a) having a heterocyclic structure containing basic nitrogen include styrene, o-, m- or p-vinyltoluene. , Styrene-based monomers such as p-, t-butylstyrene, vinylxylene, α-methylstyrene and vinylnaphthalene, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth ) Cyclohexyl acrylate, methacrylic acid such as norbornyl (meth) acrylate, and acrylic acid having 1 or more carbon atoms 20
The following linear, branched or cyclic alkyl esters,
Aralkyl ester, substituted or unsubstituted aromatic ester, unsaturated nitrile such as acrylonitrile, methacrylonitrile, maleimide, N-phenylmaleimide, N-
(O-, m-, or p-toluyl) maleimide, N-
Substituted groups such as methylmaleimide, N-ethylmaleimide, N-butylmaleimide, and N-hexylmaleimide are saturated straight-chain, branched or cyclic aliphatic or alicyclic groups and aromatics having 1 to 20 carbon atoms. Examples thereof include substituted or unsubstituted maleimides substituted with a group.

Of these, styrene-based monomers are preferable because they improve the moldability of the resin composition and increase the rigidity of the resulting molded article. The amount of the other vinyl monomer used is 50 to 99.89% by weight, preferably 70 to 99.4.
%, Particularly preferably 85 to 98.6% by weight. If it exceeds 99.89% by weight, the impact strength of the molded product obtained from the resin composition is low, and if it is less than 50% by weight, molding processability becomes difficult.

The preferred component (B) is the following (a),
It has a weight average molecular weight of 50,000 to 150,000 obtained by copolymerizing the vinyl monomers of the components (b) and (c). (A) Vinyl monomer having a heterocyclic structure containing a basic nitrogen selected from 4-vinylpyridine, 2-vinylpyridine and N-vinylimidazole 0.11 to 50% by weight (b) Styrene-based monomer 50 to 99.89% by weight (c) 0 to 40% by weight of a vinyl monomer selected from acrylonitrile, methacrylonitrile and N-substituted maleimide.

The basic nitrogen-containing copolymer as the component (B) is polymerized by a polymerization method such as addition polymerization, condensation polymerization, ring-opening polymerization, polyaddition, addition condensation, emulsion polymerization, suspension polymerization and bulk polymerization. Alternatively, the basic nitrogen-containing copolymer (B) as the component (B) can be produced by modification after the polymerization. If necessary, a molecular weight modifier and a chain transfer agent may be used.

Various types of copolymers such as random copolymers, graft copolymers and block copolymers can be used. Particularly, in the case of random copolymers, basic nitrogen functional groups can be used. The groups are dispersed throughout the polymer chain of the copolymer (B), and the interaction with the metal ions in the component (A) is dispersed throughout the resin, giving a molded article having higher rigidity and impact resistance. A resin composition is obtained.

The amount of structural units (copolymerization ratio) occupied by each of the monomers (a), (b) and (c) constituting the copolymer (B) is determined by elemental analysis, nuclear magnetic resonance spectroscopy or It can be determined by infrared spectroscopy.

Specific examples of the copolymer (B) include styrene-4-vinylpyridine copolymer, styrene-2-vinylpyridine copolymer, styrene-N-vinylimidazole copolymer and styrene-N-. Vinylcarbazole copolymer, styrene-4-methyl-5-vinylthiazole copolymer, styrene-2-vinylpyrazine copolymer, styrene-acrylonitrile-4-vinylpyridine copolymer, styrene-acrylonitrile-2-vinylpyridine Copolymer, styrene-acrylonitrile-N-vinylimidazole copolymer, styrene-acrylonitrile-N
-Vinylcarbazole copolymer, styrene-acrylonitrile-4-methyl-5-vinylthiazole copolymer,
Styrene-acrylonitrile-2-vinylpyrazine copolymer, styrene-methylmethacrylate-4-vinylpyridine copolymer, styrene-methylmethacrylate-2-vinylpyridine copolymer, styrene-methylmethacrylate-N-vinylimidazole Copolymer, styrene-methyl methacrylate-N-vinyl carbazole copolymer, styrene-methyl methacrylate-4-methyl-5-vinyl thiazole copolymer, styrene-methyl methacrylate-2
-Vinylpyrazine copolymer, styrene-N-phenylmaleimide-4-vinylpyridine copolymer, styrene-N
-Phenylmaleimide-2-vinylpyridine copolymer,
Styrene-N-phenylmaleimide-N-vinylimidazole copolymer, styrene-N-phenylmaleimide-
Examples thereof include N-vinylcarbazole copolymer, styrene-N-phenylmaleimide-4-methyl-5-vinylthiazole copolymer, styrene-N-phenylmaleimido-2-vinylpyrazine copolymer and the like. Among these, styrene-4-vinylpyridine copolymer, styrene-2-
Vinyl pyridine copolymer, styrene-N-vinyl imidazole copolymer, styrene-acrylonitrile-4-vinyl pyridine copolymer, styrene-acrylonitrile-
4-vinylpyridine copolymer, styrene-N-phenylmaleimide-2-vinylpyridine copolymer, styrene-
N-phenylmaleimide-4-vinylpyridine copolymer is preferred.

The weight average molecular weight (Mw) of the component (B) copolymer is 50,000 to 1,500,000, preferably 200,000 to 1,000,000, and more preferably 250,000 to 900. 1,000. 1,5
In the range of more than 0,000, problems in molding processability tend to occur, and in the range of less than 50,000, the impact strength of the obtained molded article is low. Regarding the molecular weight distribution,
The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1 to 50. From the viewpoint of obtaining a molded product having a high level of impact strength, the range is more preferably 1 to 10, and particularly preferably 1.5 to 4.5. The weight average molecular weight of the copolymer as the component (B) is determined by the following gel permeation chromatography (GP
It is obtained as a polystyrene reduced molecular weight according to C).

The measuring device is 600E manufactured by Waters Co.
Using Showa Denko KK column (AD80M / S, 2 in series) and Waters UV absorption detector (4
90E, measurement wavelength 260 nm) is used. Regarding the measurement conditions, the temperature is 35 ° C., the solvent flow rate is 1 ml / min,
The measurement sample solution concentration is 2 mg / ml, the sample solution injection amount is 50 microliters, and the measurement solvent is chloroform (Wako Pure Chemical Industries, Ltd. liquid chromatography grade). At the time of measurement, in order to prevent the influence of adsorption of a polymer sample containing a polar functional group on the column, 100 ppm of 1,8-diazabicyclo [5.
4.0] -7-Undecene is added.

Conversion to polystyrene-converted molecular weight is performed using monodisperse polystyrene [manufactured by Tosoh Corporation] and using a calibration curve prepared according to a conventional method.

Composition The proportion of the metal salt of the copolymer of the component (A) in the thermoplastic resin composition of the present invention is 20 to 70% by weight, preferably 35 to 60% by weight, and the component (B). The proportion of the basic nitrogen-containing copolymer of is 80 to 30% by weight, preferably 65 to 40% by weight.

In the composition, when the amount of the component (A) is less than 20% by weight, the impact strength of the obtained molded article becomes low, and when it exceeds 70% by weight, the rigidity of the molded article becomes low. Further, when the amount of the component (B) in the composition exceeds 80% by weight, the impact strength level of the obtained molded article becomes unsatisfactory for practical use, and 30% by weight
If it is less than this, the rigidity becomes unsatisfactory for practical use.

Optional Components This resin composition contains up to 40% by weight of other thermoplastic resins such as low density polyethylene, high density polyethylene, ethylene / vinyl acetate copolymer, and a density of 0.88-
0.945 g / cm ³ linear polyethylene, polypropylene, polyethylene terephthalate, polyphenylene ether, polyphenylene sulfide, nylon 6, nylon 66, nylon 6,10, nylon 6,12, polybutylene terephthalate, polycarbonate, etc. Good.

Further, with respect to 100 parts by weight of the resin component in the resin composition, a resin stabilizer such as a sterically hindered phenol-based, thioether-based, phosphorus-based, hindered amine-based, acetophenone-based resin stabilizer, etc., to the extent that the object of the present invention is not impaired. 0.05 to
3 parts by weight, 35 parts by weight or less of a filler or a plasticizer, a coloring agent,
You may mix | blend an antistatic agent, a mold release agent, a flame retardant, etc. in a ratio of 5 weight part or less.

The method for blending the respective components of the resin composition is a solution mixing method, that is, after dissolving the respective components separately or simultaneously in a common solvent for both components, contacting with a poor solvent for both components to cause precipitation, It can be obtained by a method of obtaining a blend by removing the solvent, a melt kneading method, that is, a method of contacting, mixing and kneading both components in a molten state with a uniaxial multiaxial batch type or continuous type melt kneader. However, the melt-kneading method which does not require the use of a common solvent is easy to carry out.

In carrying out the melt kneading method, if necessary, powdery, granular or lumpy components are uniformly dispersed by a Henschel mixer, a super mixer, a ribbon blender, a V blender or the like, and then the biaxial melting is carried out. Kneader, uniaxial melt kneader, roll, Banbury mixer, plastomill, brabender plastograph,
Melt kneading can be performed using a kneader or the like. The melt-kneading temperature is usually appropriately selected within the range of 150 ° C to 350 ° C. The thermoplastic resin composition prepared as described above can be extruded in a strand form from a die to form a cutting pellet form or a lump form, and is crushed as necessary for molding.

Since the thermoplastic resin composition of the present invention has good mechanical properties, particularly impact resistance, rigidity and tensile properties, it is used as interior / exterior parts for automobiles, interior / exterior parts for electric equipment, and so-called office automation equipment. It can be used for parts such as. It can also be used as an intermediate layer in multilayer molding using various different resins. As the molding method, various molding methods generally applied to thermoplastic resins, that is, injection molding, extrusion molding, blow molding, and press molding can be used.

[0050]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. Metal salt of ethylene / α, β-unsaturated carboxylic acid copolymer
Preparation Example Example 1 Commercially available Mitsubishi Petrochemical Co., Ltd. ethylene - acrylic acid random copolymer "Yukaron EAA A210K" [trade name; M
FR 3 g / 10 minutes, ethylene content 93% by weight, acrylic acid content 7% by weight, number average molecular weight (Mn) 19,400,
Weight average molecular weight 126,000, Q value (Mw / Mn)
6.5] 40 g and 3.852 g of a stoichiometric amount of zinc acetate dihydrate necessary for 100% neutralization were set on a Toyo Seiki Seisakusho Labo Plusromill at a set temperature of 200 ° C. and a rotor speed of 1
Neutralize by kneading for 7 minutes at 80 rpm,
A zinc salt of an ethylene-acrylic acid copolymer (A1) was produced. The kneading was performed under a nitrogen stream. After the completion of the kneading, the sample was pulverized with a pulverizer, the degree of neutralization was 100%, and the amount of the zinc salt of the copolymer was 0.88 mol based on zinc acrylate in 1 kg of the metal salt (A1) of the copolymer. A powder was obtained.

Example 2 (for comparison) Ethylene-acrylic acid copolymer "Yukaron EAA A2"
Instead of 10K ”, ethylene-methacrylic acid copolymer“ Nucrel 0903HC ”(trade name) manufactured by Mitsui DuPont Polychemical Co., Ltd. having the physical properties shown in Table 1 was used, and the results are shown in the same table as in Example 1. A zinc salt (A2) of a physical property ethylene-methacrylic acid copolymer was produced.

Example 3 As an ethylene-acrylic acid copolymer, shown in Table 1 is an ethylene-acrylic acid copolymer "Yukaron-" manufactured by Mitsubishi Petrochemical Co., Ltd.
EAA A500W "(trade name) was used in the same manner as in Example 1 except that zinc salt of ethylene-acrylic acid copolymer (A
3) was produced.

[0053]

[Table 1]

Production Example of Basic Nitrogen-Containing Copolymer (B) Monomers shown in Table 2 used for production, that is, styrene (S
T), acrylonitrile (AN), N-phenylmaleimide (PMI), 4-methyl-5-vinylthiazole (MVT), N-vinylimidazole (NVI), paraaminostyrene (PAS), methacrylate N, N-dimethylamino. As the ethyl (DAM), a reagent special grade of Wako Pure Chemical Industries, Ltd. was used. 4-vinylpyridine (4VP), 2-
As vinyl pyridine (2VP), a special grade reagent of Tokyo Chemical Industry Co., Ltd. was used. The vinyl monomer used for the polymerization was purified by distillation or recrystallization before the polymerization.

Example 4 Production Example of Styrene-4-vinylpyridine (ST-4VP) Copolymer Sodium dodecylsulfate (2 as a surfactant for emulsification)
A mixture of styrene (400 g) and 4-vinylpyridine (38 g) was added to 1 liter of distilled water in which 5.6 g) was dissolved and stirred, and an initiator (potassium persulfate 1 0.6 g) was added, and the mixture was stirred under a nitrogen stream at 55 ± 7 ° C. for 6 hours. Dodecyl thiol (0.87 g) as a chain transfer agent was divided into three equal parts and added to the reaction system at 0, 1.5 hours and 3.5 hours after the initiation of polymerization.

After completion of the reaction, the reaction mixture was cooled to room temperature and a poor solvent such as methanol-acetone mixture (3: 1) was added.
(Volume ratio) to cause precipitation and further wash with a large excess amount of methanol four times, and then the residual solvent is removed by filtration and drying under reduced pressure, and styrene-4-vinylpyridine (ST
-4VP) copolymer (B1) 402g was obtained. This had Mn of 171,000, Mw of 773,000, and the amount of structural units based on 4-vinylpyridine per 0.1 kg of the copolymer was 0.17 mol.

Examples 5 to 8 Styrene-4-vinylpyridine having the physical properties shown in the table was copolymerized in the same manner as in Example 4 except that the copolymerization ratio of styrene and 4-vinylpyridine was changed as shown in Table 2. (ST-
4VP) copolymers (B2, B3, B4 and B5) were prepared.

Examples 9 to 17 Copolymerization was carried out in the same or similar manner as in Example 4 by changing the kind and amount of the monomers used and the scale of the reaction system, and shown in Table 2 or Table 3. B6-B11
And B14 ST-2VP copolymer, ST-MVT copolymer, ST-AN-4VP copolymer, ST-PMI-
4VP copolymer, ST-4VP copolymer, ST-NVI
A copolymer was produced.

Also, the ST-DAM manufactured for the comparative example is used.
Copolymer (B12) and ST-PAS copolymer (B1
3) was obtained by polymerizing in a xylene solvent with 2,2'-azo (bisisobutyronitrile) or benzoyl peroxide as an initiator at 50 ° C to 60 ° C for 7 hours. The copolymerization composition of each component was determined by elemental analysis, nuclear magnetic resonance spectroscopy or infrared spectroscopy. The copolymerization composition and the measured molecular weight of each component are shown in Tables 2 and 3.

[0060]

[Table 2]

[0061]

[Table 3]

Example 1 47 parts by weight of zinc salt of ethylene-acrylic acid copolymer of A1 and styrene-4-vinylpyridine copolymer 5 of B1
3 parts by weight and 4-methyl-2,6-di-t as a stabilizer
After dry blending 0.15 part by weight of butylphenol and 0.15 part by weight of Irganox 1010 (trade name) manufactured by Ciba-Geigy Co., Ltd., using a Toyo Seiki Seisakusho Labo Plastomill, a set temperature of 200 ° C. and a rotor rotation speed of 180
Kneading was performed under the condition of rpm. After the completion of kneading, the sample was crushed with a crusher to obtain a powder.

Using a hydraulic compression molding machine manufactured by Toyo Seiki Seisakusho, this powder was preheated at 200 ° C. for 3 minutes and 19.6 MPa.
After press-molding for 3 minutes at 25 ℃, 22.1MP
A test piece sheet having a thickness of 2 mm for Izod impact test and storage elastic modulus measurement was obtained by pressurizing and cooling at a for 5 minutes.

Method for evaluating physical properties of molded article (1) Izod impact strength As an index of impact strength, Izod impact strength was measured. According to the test piece size ISOR-180, the above-mentioned thickness 2
mm test pieces were cut from 3 mm compression molded sheets, and three sheets were stacked to form Nichiban Co., Ltd. adhesive tape "Cellotape" (trade name)
After fixing it with, and cutting the notch, it was conditioned for 4 days in an atmosphere with a temperature of 23 ± 2 ° C and a humidity of 50 ± 5%, using an Izod impact tester manufactured by Toyo Seiki Co., Ltd. It was measured.

(2) Storage elastic modulus The storage elastic modulus was measured as a measure of rigidity. 47m long
A test piece of m, width 5 mm, and thickness 2 mm was compression-molded under the above-mentioned conditions, and using a solid viscoelasticity analyzer RSA2 type manufactured by Rheometrics, a storage elastic modulus (E) at 30 ° C. at a frequency of 1 hertz by three-point support. ′) Was measured.

(3) Evaluation of mixed state After cutting out a part of the above test piece and performing ion etching, a scanning electron microscope (S-240 manufactured by Hitachi, Ltd.)
The fine dispersion structure was observed in 0). Figure 1 (100
0 times).

In FIG. 1, a component that looks black (A-
1) and the white-appearing component (B-1) have a continuous structure. From this fact, the resin composition according to the present invention has a polymer and a component (B-
Polymers having an affinity for 2) such as polystyrene, polyphenylene ether, polyphenylene sulfide, nylon 6, nylon 6,6, nylon 6,12, polyethylene terephthalate, polybutylene terephthalate,
It can be understood that it is useful as a compatibilizing agent for ABS, polyethylene and the like. Further, it is presumed that the coextruded product of the layer of these polymers and the layer obtained from the resin composition of the present invention has good adhesiveness.

Examples 2 to 11 Sheets were obtained and evaluated in the same manner as in Example 1 except that the type of resin to be blended was changed as shown in Table 4, Table 5 or Table 6. The results are shown in the table.

[0069]

[Table 4]

[0070]

[Table 5]

[0071]

[Table 6]

The correlation between the Izod impact strength and the composition ratio of the molded articles obtained in Examples 4, 10 and 11 and Comparative Examples 1, 6 and 12 is shown in FIG.

[0073]

EFFECTS OF THE INVENTION From the comparison between Example 1 and Comparative Example 1 and Example 2 and Comparative Example 2, the α, β-unsaturated carboxylic acid of the present invention in which the substituent at the α-position is hydrogen is hydrogen. The resin composition containing the zinc salt (A) of the copolymer (ethylene-acrylic acid copolymer) with acrylic acid which is styrene and the styrene-4-vinylpyridine copolymer (B) is shown in Comparative Examples. Compared with a resin composition containing a zinc salt of an ethylene-methacrylic acid copolymer and a copolymer containing basic nitrogen, the impact strength is remarkably high, and the elastic modulus is also at a high level. However, they have a good balance of mechanical properties, which are said to be difficult to achieve at the same time.

From the comparison between Examples 1, 2, 3 and 4 and Comparative Examples 6 and 7, the resin composition of the present invention shows that the component (B)
As a resin composition using a nitrogen-containing copolymer obtained by copolymerizing DAM or PAS having a structure in which a nitrogen atom is not included in the cyclic structure as a basic nitrogen-containing functional group, the impact strength level is significantly higher, and It gives a molded product with an excellent level of rigidity.

From the comparison between Examples 2, 6, 7 and 8 and Comparative Example 8, the resin composition of the present invention has an imide structure in which a carbonyl group which is an electron-withdrawing substituent is directly bonded to a nitrogen atom. As compared with the resin composition of Comparative Example 8 which uses a copolymer obtained by copolymerizing PMI, a molded product having a significantly high impact strength level is provided.

[Brief description of drawings]

FIG. 1 is a diagram showing a dispersed structure of a molded sheet obtained in Example 1.

FIG. 2 is a diagram showing a correlation between a component ratio of a resin forming a sheet and Izod impact strength.

Claims (3)

[Claims] 1. Component (A): an α, β-unsaturated carboxylic acid having 70 to 99.9% by weight of an α-olefin having 2 to 8 carbon atoms and an α-position substituent being hydrogen, or an anhydride thereof. 30 ~
Copolymer 1 is a metal salt of a copolymer with 0.1% by weight.
Metal salt of copolymer in which the amount of carboxyl groups neutralized by the metal in 0.01 kg is 0.01 to 2.5 mol.
20 to 70% by weight of component (B): a copolymer of a vinyl monomer having a heterocyclic structure containing basic nitrogen and another vinyl monomer,
The amount of structural units based on a vinyl monomer having a heterocyclic structure containing basic nitrogen in 1 kg of the copolymer is 0.01
To 4.8 mol basic nitrogen-containing copolymer
80 to 30% by weight A thermoplastic resin composition containing the component (A) and the component (B). 2. The thermoplastic resin composition according to claim 1, wherein the metal salt of the copolymer as the component (A) is a zinc salt of an ethylene / acrylic acid copolymer. 3. The basic nitrogen-containing copolymer as the component (B) has a heterocyclic structure containing a basic nitrogen selected from (a) 4-vinylpyridine, 2-vinylpyridine and N-vinylimidazole. Vinyl monomer 0.11 to 50% by weight (b) Styrene-based monomer 50 to 99.89% by weight (c) Vinyl monomer selected from acrylonitrile, methacrylonitrile and N-substituted maleimide 0 to 40 The weight average molecular weight obtained by copolymerizing 50% by weight is 50,000 to 1
The thermoplastic resin composition according to claim 2, which is a copolymer having a molecular weight of 50,000.