JP2001335672A - Thermoplastic resin composition and molded article thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition capable of being formed into a molded article having excellent thermal resistance, scratch resistance and transparency. SOLUTION: This thermoplastic resin composition comprises (A) 98 to 55 wt.% of at least one modified inter-polymer obtained by grafting a radically polymerizable monomer having a reactive polar group and (B) 2 to 45 wt.% of a compound having a reactive polar group, wherein the modified inter- polymer (A) is a graft-modified substantially random inter-polymer consisting of (1) 1 to 99 mol% of a polymer unit derived from an aromatic vinyl or vinylidene monomer and/or a hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer, and (2) 99 to 1 mol% of a polymer unit derived from ethylene or α-olefin having 3 to 20 carbons or their combination.

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 and a molded article thereof, and more particularly, to a method for preparing a graft modified product of an interpolymer, for example, a graft modified product of an ethylene-styrene copolymer, using a reactive polar group. The present invention relates to a thermoplastic resin composition capable of providing a molded article having excellent heat resistance, scratch resistance and transparency by blending with a compound having a compound such as a polyamide resin to form an alloy, and a molded article thereof.

[0002]

Technical background of the invention WO99 / 20686 discloses that
1-99.9% by weight of an ethylene-styrene copolymer (ESI) and another polymer such as a polyamide resin 0-99.
Disclosed are thermoplastic resin compositions comprising, by weight, 0.01% to 99% by weight of one or more conductive additives and / or one or more additives. However, in this composition, the compatibility between the ethylene-styrene copolymer (ESI) and the polyamide resin is not sufficient, and the heat resistance, scratch resistance and transparency of a molded article obtained from this composition are as follows: It was not always enough for some applications. In addition,
This publication does not disclose a modified ethylene-styrene copolymer blend.

[0003] WO 99/46326 and WO 99/46327 disclose that ethylene-styrene copolymer (ESI) contains 20 to 99% by weight of at least 1%.
A thermoplastic resin composition comprising 80 to 1% by weight of a kind of engineering plastic such as a polyamide resin and a molded article comprising the composition are disclosed. However, even in the compositions described in these publications, the compatibility between the ethylene-styrene copolymer (ESI) and the polyamide resin is not sufficient, and the heat resistance of molded articles obtained from these compositions is also low. , Scratch resistance and transparency were not always sufficient for some applications. In addition,
These publications disclose olefin elastomers and functional group-containing polyolefins as other polymers to be blended, but do not disclose modified ethylene-styrene copolymers.

[0004] Therefore, the emergence of a thermoplastic resin composition and a molded article thereof capable of preparing a molded article excellent in heat resistance, scratch resistance and transparency using a polymer excellent in compatibility with a polyamide resin is desired. It is rare.

[0005]

An object of the present invention is to solve the problems associated with the prior art as described above, and to use a compound having a reactive polar group, particularly a polymer having excellent compatibility with a polyamide resin, An object of the present invention is to provide a thermoplastic resin composition capable of preparing a molded article having excellent heat resistance, scratch resistance and transparency, and a molded article thereof.

[0006]

SUMMARY OF THE INVENTION The thermoplastic resin composition according to the present invention comprises:
(A) 98 to 55% by weight of at least one substantially random interpolymer graft-modified with a radically polymerizable monomer having a reactive polar group, and (B)
2 to 45% by weight of a compound having a reactive polar group, wherein the modified interpolymer (A) comprises (1) (a) at least one kind of aromatic vinyl or vinylidene monomer, or (b) At least one hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer, or (c) a combination of at least one aromatic vinyl or vinylidene monomer with at least one hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer (2) ethylene, or at least one carbon atom having 3 carbon atoms
It is characterized in that it is a graft modification of a substantially random interpolymer consisting of 99 to 1 mol% of polymer units derived from ２０20 α-olefins or a combination thereof.

As the modified interpolymer (A), 1 to 99 mol% of a polymer unit derived from at least one kind of aromatic vinyl or vinylidene monomer;
A substantially random graft-modified interpolymer comprising 99 to 1 mol% of polymer units derived from at least one α-olefin having 3 to 20 carbon atoms, or the interpolymer (A), Substantially 1 to 99 mol% of polymer units derived from styrene and 99 to 1 mol% of polymer units derived from ethylene or a combination of ethylene and at least one α-olefin having 3 to 10 carbon atoms. A graft modification of a random interpolymer is preferably used.

Further, the modified interpolymer (A) includes: (1) (a) at least one kind of aromatic vinyl or vinylidene monomer, or (b) at least one kind of hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer. Or (c) 1-65 mol% of polymer units derived from a combination of at least one aromatic vinyl or vinylidene monomer and at least one hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer; and (2) Preference is also given to using a pseudo-random interpolymer graft modification of 35 to 99 mol% of polymer units derived from ethylene or ethylene and at least one α-olefin having 3 to 20 carbon atoms.

As the modified interpolymer (A), (1) 1 to 65 mol% of a polymer unit derived from at least one kind of a hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer, and (2) ethylene or ethylene and A pseudo-random interpolymer graft-modified product comprising 35 to 99 mol% of polymer units derived from at least one α-olefin having 3 to 20 carbon atoms is also preferably used.

[0010] Here, "pseudo" of a pseudo-random interpolymer means that there is no homopolymer segment composed of vinyl or vinylidene monomer in the interpolymer molecular structure as disclosed in JP-A-7-070223. Means that. That is, with a pseudo-random interpolymer, insertion of the vinyl or vinylidene monomer from head to head and head to tail does not occur.

In the thermoplastic resin composition according to the present invention, when a molded product is prepared, it is preferable that the haze value of the molded product measured at a thickness of 1 mm is 65% or less.
As the compound (B) having a reactive polar group, for example, a polyamide resin, particularly, nylon-6 is preferably used.

A molded article according to the present invention is characterized by comprising the above-mentioned thermoplastic resin composition according to the present invention. The molded body is usually formed by extrusion molding, rotational molding, calendar molding, injection molding, compression molding, or blow molding.

The thermoplastic resin composition according to the present invention is suitable for applications such as flooring materials, wallpaper materials, coating materials, decorative sheets, pipes, tubes, artificial leathers, sheets, agricultural films, wrap films, hoses and bottles. Used for

[0014]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the thermoplastic resin composition according to the present invention and its molded product will be described in detail.

[0015] The thermoplastic resin composition according to the present invention comprises a modified interpolymer (A) and a compound (B) having a reactive polar group. Modified Interpolymer (A) The modified interpolymer (A) used in the present invention is graft-modified with a radically polymerizable monomer having a reactive polar group.

The modified interpolymer (A) is used for graft modification, and a part of a substantially random interpolymer may be unmodified. Further, the modified interpolymer (A) may be prepared by a so-called master batch.

When the modified interpolymer (A) used in the present invention contains an unmodified interpolymer, the unmodified interpolymer is a total of 100 parts by weight of the graft-modified interpolymer and the unmodified interpolymer. To 99 parts by weight, usually 0 to 9 parts by weight
Desirably, the content is 5 parts by weight.

The interpolymer used in the preparation of the modified interpolymer (A) includes (1) (a) at least one kind of an aromatic vinyl or vinylidene monomer, or (b) a hindered aliphatic vinyl monomer or a hindered cyclic monomer. At least one selected from aliphatic vinyl monomers, hindered aliphatic vinylidene monomers and hindered cyclic aliphatic vinylidene monomers, or (c) at least one aromatic vinyl or vinylidene monomer, and hindered aliphatic vinyl monomers and hindered cycloaliphatic 1 to 99 mol% of a polymer unit derived from a combination of at least one selected from a vinyl monomer, a hindered aliphatic vinylidene monomer and a hindered cycloaliphatic vinylidene monomer, and (2) ethylene, At least one carbon atoms 3
A substantially random interpolymer consisting of from 99 to 1 mol% of polymer units derived from ２０20 α-olefins or a combination thereof.

The term "interpolymer" as used herein means a copolymer obtained by polymerizing at least two kinds of monomers to form an interpolymer. As used herein, “copolymer” means a polymer obtained by polymerizing at least two types of monomers to form a copolymer.

As used herein, an α-olefin comprises an aromatic vinyl monomer, an aromatic vinylidene monomer, a hindered aliphatic vinyl monomer, a hindered cycloaliphatic vinyl monomer, a hindered aliphatic vinylidene monomer or a hindered cycloaliphatic vinylidene monomer. "Substantially random" in a substantially random interpolymer refers to Academic of New York.
Press 1977 "POLYMER SE
QUEEN DEDERMINATION, Carb
on-13 NMR Method, pp. 71-78. C. As described by Randall, it means that the monomer distribution of the interpolymer can be described by "Bernuri's statistical model" or by "first or second order Marcobian statistical model".

Preferably, the substantially random interpolymer of ethylene and / or an α-olefin having 3 to 20 carbon atoms and an aromatic vinyl or vinylidene monomer is an aromatic vinyl or vinylidene monomer having more than 3 units. The block (for example, a styrene monomer having at least 4 repeating units derived from styrene) does not contain 15% or more of the total amount of the aromatic vinyl or vinylidene monomer. More preferably, the interpolymer is not characterized by a high degree of isotacticity or syndiotacticity. This is due to the fact that in the carbon-13 NMR spectrum of the substantially random interpolymer, the peak region corresponding to the main chain methylene and methine carbon showing either the mesodiad sequence or the racemic diad sequence is the sum of the main chain methylene and methine carbon. 7 in the peak area
Meaning should not exceed 5%.

Interpolymers suitable for preparing the thermoplastic compositions of the present invention include ethylene and / or one or more α-olefins, one or more aromatic vinyl or vinylidene monomers and / or one or more hindered Includes, but is not limited to, interpolymers obtained by polymerization with aliphatic or cycloaliphatic vinyl or vinylidene monomers.

Examples of preferred α-olefins include α-olefins having 3 to 20, preferably 3 to 12, and more preferably 3 to 8 carbon atoms. Among them, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene are particularly preferred. These α-olefins do not contain aromatic groups. Also, ethylene is particularly preferably used.

Examples of the aromatic vinyl or vinylidene monomer suitable for producing the interpolymer used in the present invention include monomers represented by the following formula.

[0025]

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In this formula, R ¹ is an atom or group selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom or a methyl group.

Each R ² is independently an atom or group selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom or a methyl group. Ar is a phenyl group or a phenyl group substituted with 1 to 5 substituents selected from the group consisting of a halogen atom, an alkyl group having 1 to 4 carbon atoms and a haloalkyl group having 1 to 4 carbon atoms.

N is an integer of 0 to 4, preferably 0
２2, most preferably 0. Specific examples of the aromatic monovinyl or monovinylidene monomer include styrene, vinyltoluene, α-methylstyrene, t-butylstyrene, and chlorostyrene, and all isomers thereof are also included. Particularly preferred aromatic monovinyl or monovinylidene monomers include styrene and its lower alkyl- or halogen-substituted derivatives. Preferred monomers include styrene, α-methylstyrene,
Lower alkyl (alkyl having 1 to 4 carbon atoms)-or phenyl-ring-substituted derivatives of styrene, such as ortho-, meta-, para-methylstyrene, ring-substituted styrene,
There is para-vinyl toluene or a mixture thereof. A more preferred aromatic monovinyl or monovinylidene monomer is styrene.

The term "hindered aliphatic or cycloaliphatic vinyl or vinylidene compound" means an addition-polymerizable vinyl or vinylidene monomer corresponding to the compound represented by the following formula.

[0030]

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In this formula, A ¹ has 20 carbon atoms.
The following are sterically bulky aliphatic or cycloaliphatic substituents. R ¹ is an atom or group selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom or a methyl group.

Each R ² is independently an atom or a group selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom or a methyl group. R ¹ and A ¹ may together form a ring system.

The term "sterically bulky" means that the monomer having the aliphatic or cycloaliphatic substituent cannot normally be subjected to addition polymerization with a standard Ziegler-Natta catalyst at a rate comparable to ethylene polymerization. I do.

Preferred hindered aliphatic or cycloaliphatic vinyl or vinylidene compounds are monomers in which one of the carbon atoms having an ethylenically unsaturated bond is tertiary or quaternary. Examples of these substituents include
There are cycloaliphatic groups such as cyclohexyl, cyclohexenyl, cyclooctenyl, or their cyclic alkyl or aryl substituted derivatives. The most preferred hindered aliphatic or cycloaliphatic vinyl or vinylidene compounds are cyclohexane and various isomeric vinyl-ring substituted derivatives of substituted cyclohexane, and 5-ethylidene-2.
-Norbornene. Particularly preferred are 1-, 3- and
4-vinylcyclohexene.

The ethylene and / or 1 used in the present invention
Interpolymers obtained by polymerizing the above α-olefin with one or more aromatic vinyl or vinylidene monomers and / or one or more hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers are substantially random polymers. These interpolymers usually contain at least one aromatic vinyl or vinylidene monomer and / or hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer from 1 to 99.
Mol%, preferably 1 to 65 mol%, more preferably 5 mol%.
５０50 mol%, and 99 to 1 mol%, preferably 35 to 99 mol%, more preferably 50 to 95 mol% of ethylene or at least one α-olefin having 3 to 20 carbon atoms or a combination thereof. I do.

Number average molecular weight (Mn) of interpolymer
Is usually 10,000 or more, preferably 20,000 to
1,000,000, more preferably 50,000-5
00,000.

By the way, during the production of a substantially random interpolymer, some amount of atactic aromatic vinyl or vinylidene homopolymer may be produced by homopolymerization of the aromatic vinyl or vinylidene monomer under heating. The presence of an aromatic vinyl or vinylidene homopolymer is generally not preferred for the purposes of the present invention and cannot be ignored. If desired, the aromatic vinyl or vinylidene homopolymer can be separated from the interpolymer by extraction techniques such as selective precipitation from solution using a non-solvent for either the interpolymer or the aromatic vinyl or vinylidene homopolymer. . For the purpose of the present invention, it is desirable that the amount of the aromatic vinyl or vinylidene homopolymer is not more than 20% by weight, preferably not more than 15% by weight of the total amount of the interpolymer.

A substantially random interpolymer is
James C.W. Stevens et al., July 3, 1990
No. 07 / 545,403 (EP-A-)
US Patent Application Serial No. 08 / 469,828, filed and granted on June 6, 1995.
(US Pat. No. 5,703,187). All of these disclosures in these U.S. applications are incorporated herein by reference. Preferred operating conditions for these polymerization reactions are as follows:
The temperature is between -30 and 200C. If the polymerization and unreacted monomer removal are performed at temperatures higher than the automatic polymerization temperature of the respective monomers, free radical polymerization may produce some amount of homopolymer polymerization products.

An example of a preferred catalyst and method for producing the substantially random interpolymer used in the present invention is 199 corresponding to EP-A-416,815.
US application 07 / 545,403 filed July 3, 009; E
May 20, 1991, corresponding to PA-514,828.
EP-A-5
U.S. application Ser. No. 07 / 876,268 filed on May 1, 1992 and U.S. Application No. 08 / 241,523 filed on May 12, 1994 corresponding to U.S. Pat.
0,993); U.S. Patent 5,055,438; 5,05.
7,475; 5,096,867; 5,064,80
2, 5,132,380; 5,189,192; 5,3
21,106; 5,347,024; 5,350,72
3, 5,374,696; 5,399,635 and 5,556,928. All of these disclosures are cited herein.

The substantially random α used in the present invention
-Olefin / aromatic vinyl or vinylidene interpolymers are also available from WO 95/32095 John.
C. To Bradfute et al. (WR Grace &
Co) described in WO 94/00500.
B. Pannell (Exxon Chemical P
attents, Inc. ), And "P
plastics Technology ", page 25 (1
(September 992), all of which are hereby incorporated by reference.

Also, Francis J. et al. Timer
US Application 08 / 708,809 filed Sep. 4, 1996 (US Pat. No. 5,879,149).
Also preferred are the substantially random interpolymers of at least one α-olefin / vinyl aromatic / vinyl aromatic / α-olefin tetrad disclosed in US Pat. These interpolymers have an additional signal with an intensity that is more than three times peak-to-peak noise. These signals are 43.75-44.25 ppm and 38.0-3.
Appears in the 8.5 ppm chemical shift range. In particular, peaks are observed at 44.1, 43.9 and 38.2 ppm. In the proton test NMR experiment, 43.75-4
The signal in the 4.25 ppm chemical shift region is methine carbon, and the signal in the 38.0-38.5 ppm region is methylene carbon.

The pseudo-random interpolymer comprising an aliphatic α-olefin and an aromatic monovinyl or monovinylidene compound used in the present invention is disclosed in US Pat. No. 5,545,403 filed on Jul. 3, 1990 (European Patent Publication No. No. 0416815).

These interpolymers are -30 to 2
It can be produced by carrying out the polymerization at a temperature of 50 ° C. in the presence of a catalyst as represented by the following formula and, if desired, preferably a cocatalyst.

[0044]

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Wherein each Cp is independently in each case a substituted cyclopentadienyl group π-bonded to M, E is a carbon or silicon atom, and M is A Group IV metal, preferably Zr or Hf, most preferably Zr, wherein each R is independently at each occurrence a hydrogen atom, or hydrocarbyl, silahydrocarbyl or hydrocarbylsilyl, up to 30 and preferably from 1 to 20; More preferably a group having from 1 to 10 carbon or silicon atoms, each R ′ is independently in each occurrence a hydrogen atom, a halogen atom, or hydrocarbyl, hydrocarbyloxy, silahydrocarbyl, hydrocarbylsilyl, A group having 30 or less, preferably 1 to 20, more preferably 1 to 10 carbon or silicon atoms Or two R 'groups together forms a C _1-10 hydrocarbyl substituted 1,3-butadiene, m is 1 or 2. Particularly preferred substituted cyclopentadienyl groups include groups represented by the following formula.

[0046]

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Here, each R is independently in each case a hydrogen atom or hydrocarbyl, silahydrocarbyl or hydrocarbylsilyl, and is not more than 30, preferably 1 to 20, more preferably 1 to 10 carbon or silicon atoms. Or two R groups are taken together to form a divalent derivative of these groups. Preferably, R is independently at each occurrence (including all isomers, if any), hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl or silyl, or (possibly Two) these R groups are taken together to form indenyl, fluorenyl,
It forms fused ring systems such as tetrahydroindenyl, tetrahydrofluorenyl or octahydrofluorenyl.

Specific examples of particularly preferred catalysts include racemic- (dimethylsilanediyl) -bis- (2-methyl-4-phenylindenyl) zirconium dichloride, racemic
(Dimethylsilanediyl) -bis- (2-methyl-4-phenylindenyl) zirconium 1,4-diphenyl-1,3-butadiene, racemic- (dimethylsilanediyl) -bis- (2-
Methyl-4-phenylindenyl) zirconium di-C
_1-4 alkyl, racemic- (dimethylsilanediyl) -bis- (2-methyl-4-phenylindenyl) zirconium di-C _1-4 alkyl, racemic- (dimethylsilanediyl) -bis- (2-methyl- 4-phenylindenyl) zirconium di-C _1-4 alkoxide, or a combination thereof.

Further, the following titanium-based constrained geometric catalyst (Tita
Specifically, as [nium-based constrained geometry catalysts], [N- (1,1-dimethylethyl) -1,1-dimethyl
-1-[(1,2,3,4,5-η) -1,5,6,7-tetrahydro-s-indacen-1-yl] silane aminato (2-)-N] titanium dimethyl; Indenyl) (t-butylamido) dimethyl-
Silane titanium dimethyl; ((3-t-butyl) (1,2,3,
4,5-η) -1-indenyl) (t-butylamido) dimethylsilanetitanium dimethyl; and (3-iso-propyl) (1,2,3,4,5-η) -1-indenyl) (t- Butylamido) dimethylsilane titanium dimethyl or a combination thereof.

Another type of the interpolymer used in the present invention
Is manufactured by Longo and Grassi. (Ma
cromol. Chem. , Vol. 191, 2387
-2396 (1990)), and D'Anniel.
lo etc. (Journal of Applied Po
lymer Science, Vol. 58, 1701
-1706 (1995)).
Is methylaluminoxane (MAO) and cyclopen
Tadienyl titanium trichloride (CpTiCl _Three)system
Of ethylene-styrene copolymer using various catalysts
I have. Xu and Lin (Polymer Pr)
eprints, Am. Chem. Soc. , Div.
Polym. Chem. ) Vol. 35, 686, 68
Page 7 (1994))_Two/ TiCl_Four/ Nd
Cl_Three/ Al (iBu)_ThreeUsing a catalyst, styrene and
A random copolymer with propylene is being prepared. Further
And Lu etc. (Journal of Applied
Polymer Science, Vol. 53, 14
53-1460 (1994))_Four/ Nd
Cl_Three/ MgCl_Two/ Al (Et)_ThreeEchile using catalyst
Reports the copolymerization of styrene and styrene.

[0051] Sernets and Mulhapt
aupt) (Macromol. Chem. Phys., v. 197, pp. 1071-108
3, 1997) is Me ₂ Si (Me ₄ Cp) (Nt-butyl) Ti
Cl ₂ / methylaluminoxane, describes the effects of the polymerization conditions in the copolymerization of styrene and ethylene using Ziegler-Natta catalysts.

The ethylene-styrene copolymer produced by the bridged metallocene catalyst is described in Arai, Toshiaki and Suzuki (Polymer Preprints, Am. Chem. Soc., Di.
v. Polym. Chem.) Vol. 38, p. 349, 350, 1997) and U.S. Pat. No. 5,652,315 (Mitsui Toatsu Chemical Co., Ltd.).

For a method for producing an interpolymer composed of α-olefin / aromatic vinyl monomer (for example, propylene / styrene or butene / styrene), see US Pat.
244,996 (Mitsui Petrochemical Co., Ltd.) or U.S. Pat. No. 5,652,315 (Mitsui Petrochemical Co., Ltd.), and German Patent Publication DE19711339.
A1 and U.S. Pat. No. 5,883,213 (Electrical Chemical Industry Co., Ltd.).

The method of preparing the interpolymer component disclosed above is incorporated herein by reference. Aria, Toru et al., Polymer Preprints Vol. 39, No.
The ethylene / styrene random copolymer disclosed in 1, March 1998 can also be used as a component of the present invention.

An example of a suitable catalyst and method for producing the pseudorandom interpolymer suitably used in the present invention is described in US Patent Application No. 5, filed July 3, 1990.
No. 45403 (EP-A-0416815)
US Patent Application No. 5 filed July 3, 1990.
No. 47718 (European Patent Publication No. 468,651)
U.S. Patent Application No. 702475 filed May 20, 1991 (European Patent Publication 514828).
No. 876,268, filed May 1, 1992 (EP-A-520732).
No. 8003 (U.S. Pat. No. 5,374,696), filed Jan. 21, 1993.
U.S. Patent Application No. 82197 filed June 24, 3 years
No. (corresponding to WO 95/00526), and U.S. Patent Applications Nos. 5055536, 5057475, 509686.
7, 5064802, 5132380 and 51891
No. 92, each of which is incorporated herein by reference.

The modified interpolymer (A) used in the present invention is obtained by graft-modifying the above interpolymer with a radically polymerizable monomer having a reactive polar group. The graft amount of the radical polymerizable monomer in the modified interpolymer (A) is 0.01% with respect to 100% by weight of the interpolymer before the graft modification.
%, Preferably 0.01 to 10% by weight, more preferably 0.1 to 2% by weight.

The radically polymerizable monomer having a reactive polar group used in the present invention is a monomer having at least one radically polymerizable double bond in the molecule, and is a hydroxyl-containing ethylenically unsaturated compound, At least one selected from a group-containing ethylenically unsaturated compound, an epoxy group-containing ethylenically unsaturated compound, an aromatic vinyl compound, an unsaturated carboxylic acid and its derivatives, a vinyl ester compound, a nitrile group-containing unsaturated compound, and vinyl chloride. .

Specific examples of the hydroxyl group-containing ethylenically unsaturated compound include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy
-3-phenoxy-propyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, tetramethylol (Meth) acrylic acid esters such as ethane mono (meth) acrylate, butanediol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, and 2- (6-hydroxyhexanoyloxy) ethyl acrylate; 10-undecene-1- All, 1-octen-3-ol, 2-methanol norbornene, hydroxystyrene,
Hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N-methylolacrylamide, 2- (meth) acryloyloxyethyl acid phosphate,
Glycerin monoallyl ether, allyl alcohol, allyloxyethanol, 2-butene-1,4-diol, glycerin monoalcohol and the like can be mentioned.

The above-mentioned amino group-containing ethylenically unsaturated compound is a compound having an ethylenic double bond and an amino group. As such a compound, at least one of an amino group and a substituted amino group represented by the following formula is used. And a vinyl monomer having the same.

[0060]

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In the formula, R ³ represents a hydrogen atom, a methyl group or an ethyl group, and R ⁴ represents a hydrogen atom and a carbon atom number of 1 to 1.
It is an alkyl group having 12, preferably 1 to 8, or a cycloalkyl group having 6 to 12, preferably 6 to 8 carbon atoms. The above alkyl group and cycloalkyl group may further have a substituent.

Specific examples of the amino group-containing ethylenically unsaturated compound include aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate,
Alkyl or methacrylic acid alkyl ester derivatives such as dimethylaminoethyl methacrylate, aminopropyl (meth) acrylate, phenylaminoethyl methacrylate and cyclohexylaminoethyl methacrylate; N-vinyldiethylamine and N-acetylvinylamine Vinylamine derivatives; allylamine derivatives such as allylamine, methacrylamine, N-methylacrylamine, N, N-dimethylacrylamide and N, N-dimethylaminopropylacrylamide; acrylamide derivatives such as acrylamide and N-methylacrylamide Aminostyrenes such as p-aminostyrene; 6-
Aminohexyl succinimide, 2-aminoethyl succinimide and the like are used.

The above-mentioned epoxy group-containing ethylenically unsaturated compound is a monomer having at least one polymerizable unsaturated bond and at least one epoxy group in one molecule. ,
Specifically, glycidyl acrylate, glycidyl methacrylate; mono and diglycidyl esters of maleic acid, mono and diglycidyl esters of fumaric acid, mono and diglycidyl esters of crotonic acid, mono and diglycidyl esters of tetrahydrophthalic acid, itaconic acid Mono- and glycidyl esters of butenetricarboxylic acid, mono- and diglycidyl esters of citraconic acid, endo-cis-
Mono- and diglycidyl esters of bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (Nadic acid ^™ ),
End - cis - bicyclo [2.2.1] hept-5-ene-2-mono- and diglycidyl esters of methyl-2,3-dicarboxylic acid (methylnadic acid ^TM), a dicarboxylic acid such as mono- and glycidyl esters of allyl succinic acid Mono- and alkyl glycidyl esters (alkyl groups having 1 to 12 carbon atoms in the case of monoglycidyl esters); alkyl glycidyl esters of p-styrenecarboxylic acid, allyl glycidyl ether, 2-methylallyl glycidyl ether,
Styrene-p-glycidyl ether, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1
-Pentene, 3,4-epoxy-3-methyl-1-pentene, 5,6-
Epoxy-1-hexene, vinylcyclohexene monoxide and the like can be exemplified.

The aromatic vinyl compound includes a compound represented by the following formula.

[0065]

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In the above formula, R ⁵ and R ⁶ may be the same or different from each other and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, specifically, a methyl group, an ethyl group, Propyl and isopropyl groups can be mentioned.

R ⁷ represents a hydrocarbon group having 1 to 3 carbon atoms or a halogen atom, specifically, a methyl group, an ethyl group, a propyl group and an isopropyl group, a chlorine atom, a bromine atom and an iodine atom. And the like.

N is usually from 0 to 5, preferably from 1 to 5.
Represents an integer of 5. Specific examples of such an aromatic vinyl compound include styrene, α-methylstyrene, and o-methylstyrene.
Methylstyrene, p-methylstyrene, m-methylstyrene, p-chlorostyrene, m-chlorostyrene, p-chloromethylstyrene, 4-vinylpyridine, 2-vinylpyridine,
5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine, 2-isopropenylpyridine, 2-vinylquinoline, 3-
Vinyl isoquinoline, N-vinyl carbazole, N-vinyl pyrrolidone and the like can be mentioned.

Specific examples of the unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, and nadic acid. ^TM (endocis-bicyclo [2,2,
1] Hept-5-ene-2,3-dicarboxylic acid), bicyclo [2,
2,1] hept-2-ene-5,6-dicarboxylic acid.

Examples of unsaturated carboxylic acid derivatives include acid halide compounds, amide compounds, imide compounds, acid anhydrides and ester compounds of the above unsaturated carboxylic acids. Specifically, maleenyl chloride, maleenyl imide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic anhydride, Dimethyl maleate, monomethyl maleate, dimethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citrate, dimethyl tetrahydrophthalate, bicyclo [2,2,1] hept-2-ene-5,6 -Dimethyl dicarboxylate, glycidyl maleate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, aminoethyl methacrylate and aminopropyl methacrylate.

Of these, (meth) acrylic acid, maleic anhydride, hydroxyethyl (meth) acrylate, glycidyl methacrylate, and aminopropyl methacrylate are preferred.

Specific examples of the vinyl ester compound include vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, and stearic acid. Vinyl, vinyl benzoate, pt-butyl vinyl benzoate, vinyl salicylate, vinyl cyclohexanecarboxylate and the like can be mentioned.

Specific examples of the above-mentioned unsaturated compound containing a nitrile group include acrylonitrile, methacrylonitrile, fumaronitrile, allyl cyanide, cyanoethyl acrylate and the like.

Among these radically polymerizable monomers, maleic anhydride, (meth) acrylic acid, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, aminoethyl (meth) acrylate, (meth) acryl It is preferable to use propylaminoethyl acrylate, glycidyl (meth) acrylate, styrene, methyl (meth) acrylate, ethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) acrylamide, and (meth) acrylonitrile. .

The graft modification of the above interpolymer with a radical polymerizable monomer can be carried out using a conventionally known graft polymerization method. For example, there is a method in which the interpolymer is melted and an unsaturated carboxylic acid or the like is added to perform graft polymerization, or a method in which the interpolymer is dissolved in a solvent and a radical polymerizable monomer is added to perform the graft polymerization.

In these methods, when the graft polymerization is carried out in the presence of a radical initiator, the radical polymerizable monomer can be efficiently graft-polymerized.
In this case, the radical initiator is the above-mentioned interpolymer 1
It is usually used in an amount of 0.001 to 1 part by weight based on 00 parts by weight.

As such a radical initiator, an organic peroxide, an azo compound or the like is used. Specific examples of such a radical initiator include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (peroxidebenzoate) hexyne-
3,1,4-bis (t-butylperoxyisopropyl) benzene, lauroyl peroxide, t-butylperacetate, 2,5-dimethyl-2,5-di- (t-butylperoxide)
Hexin-3,2,5-dimethyl-2,5-di (t-butyl peroxide) hexane, t-butyl perbenzoate, t-butyl perphenyl acetate, t-butyl perisobutyrate, t-butyl per-sec- Octoate, t-butyl perpivalate, cumyl perpivalate, t-butyl perdiethyl acetate; azobisisobutyronitrile, dimethylazoisobutyrate, and the like.

Of these, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 2,5-dimethyl-2,5
-Dialkyl peroxides such as di (t-butylperoxy) hexane and 1,4-bis (t-butylperoxyisopropyl) benzene are preferably used.

The reaction temperature of the graft polymerization reaction using a radical initiator as described above or the graft polymerization reaction carried out without using a radical initiator is usually 60 to 30.
The temperature is set at 0 ° C, preferably within the range of 80 to 230 ° C.

In the present invention, the radical polymerizable monomer is used in an amount of 0.01 to 30% by weight, preferably 0.01 to 30% by weight, based on 100% by weight of the interpolymer.
It can be added in an amount of 10% by weight, more preferably 0.1 to 2% by weight.

In the present invention, the modified interpolymer (A) is preferably 98 to 55% by weight, more preferably 98 to 55% by weight, based on 100% by weight of the total of the modified interpolymer (A) and the compound (B) having a reactive polar group. Is 98-56% by weight,
More preferably, it is used in a ratio of 98 to 60% by weight. When the modified interpolymer (A) is used in the above ratio, a thermoplastic resin composition capable of preparing a molded article having excellent heat resistance, scratch resistance and transparency can be obtained.

Compound (B) having a reactive polar group The compound (B) having a reactive polar group used in the present invention includes, for example, polyamines such as hexamethylenediamine; terephthalic acid, pyromellitic acid, and trimellitate Carboxylic acids such as acids and derivatives thereof; polyisocyanate compounds; polyglycols; polyepoxy compounds;
Ring opening compounds such as lactones and lactams; low molecular weight compounds such as phenols; thermoplastic resins such as polyamide, polyester, polyacetal and thermoplastic polyurethane; unsaturated polyester resins; epoxy resins; phenolic resins; .

The polyamide resin is obtained by using ring-opening polymerization or polycondensation of polymerizable aminocarboxylic acids or their lactams, dicarboxylic acids, diamines and the like as raw materials.

Specific examples of the aminocarboxylic acids include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like. These amino acids can be used as a mixture of two or more.

Examples of the lactam include valerolactam, caprolactam, enantholactam, capryllactam, laurolactam and the like. Of these, use of caprolactam and laurolactam is preferred. Most preferred is the use of caprolactam. In addition, these lactams can also be used in a mixture of two or more.

Specific examples of the dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, and tridecanedioic acid. acid,
Aliphatic dicarboxylic acids such as tetradecandioic acid, pentadecandioic acid and octadecandioic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; phthalic acid, isophthalic acid;
And aromatic dicarboxylic acids such as terephthalic acid and naphthalenedicarboxylic acid. In addition, these dicarboxylic acids can be used in a mixture of two or more.

Specific examples of the diamines include 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 2-methyl-1,5-diaminopentane (MDP),
1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17
-Aliphatic diamines such as diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane and 1,20-diaminoeicosane; alicyclics such as cyclohexanediamine and bis- (4-aminohexyl) methane Diamine;
And aromatic diamines such as xylylenediamine. These diamines can also be used in a mixture of two or more.

The polyamide resin can be used alone or as a mixture. As the polyamide resin, specifically, nylon-6, nylon-66, nylon-
Examples thereof include aliphatic amide resins such as 10, nylon-12, and nylon-46, and aromatic amide resins produced from an aromatic dicarboxylic acid and an aliphatic diamine.
Among them, nylon-6 is particularly preferred.

In the present invention, the molecular weight of the polyamide resin is not particularly limited, but is 1 g / 100% in 23% sulfuric acid and 98% sulfuric acid.
The relative viscosity measured in ml concentration is preferably 2.0 to 4.0, more preferably 2.1 to 3.8, and particularly preferably 2.2 to 3.6. 2.0
If less than the above, mechanical properties may be reduced, while
If it exceeds 4.0, the fluidity during molding tends to decrease.

As the polyamide resin, a resin whose terminal is blocked by a carboxylic acid compound or an amine compound can be used, if necessary. When the terminal is blocked by a monocarboxylic acid and / or a monoamine, the concentration of the terminal amino group and the terminal carboxyl group of the obtained polyamide resin (hereinafter simply referred to as “terminal group concentration”) is lower than that before the terminal blocking. descend. On the other hand, when the terminal is blocked with a dicarboxylic acid or a diamine, the ratio of the terminal amino group concentration to the terminal carboxyl group concentration changes while the terminal group concentration does not change.

Specific examples of the carboxylic acid compound used for terminal blocking of the polyamide resin include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, undecanoic acid, lauric acid, and tridecanoic acid. Aliphatic monocarboxylic acids such as myristic acid, myristoleic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and arachiic acid; cycloaliphatic monocarboxylic acids such as cyclohexanecarboxylic acid and methylcyclohexanecarboxylic acid; benzoic acid; Aromatic monocarboxylic acids such as toluic acid, ethylbenzoic acid and phenylacetic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecane diacid Acid, tridecandioic acid, tetradecandioic acid, pentadecandioic acid Aliphatic dicarboxylic acids such as octadecanedioic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, and aromatic dicarboxylic acids such as naphthalene dicarboxylic acid.

Specific examples of the amine compound used for blocking the terminal of the polyamide resin include butylamine, pentylamine, hexylamine, peptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine and tridecyl. Amines, tetradecylamine, pentadecylamine,
Aliphatic monoamines such as hexadecylamine, octadecylamine, nonadecylamine and icosylamine; alicyclic monoamines such as cyclohexylamine and methylcyclohexylamine; aromatic monoamines such as benzylamine and β-phenylethylamine; 1,4-diaminobutane; ,Five-
Diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane , 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentatecan, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-
Aliphatic diamines such as diaminononadecane and 1,20-diaminoeicosane; alicyclic diamines such as cyclohexanediamine and bis- (4-aminohexyl) methane; and aromatic diamines such as xylylenediamine.

Specific examples of the polyacetal resin include polyformaldehyde (polyoxymethylene),
Examples thereof include polyacetaldehyde, polypropionaldehyde, and polybutyraldehyde. Among them, polyformaldehyde is particularly preferred.

The thermoplastic polyurethane resin includes:
Examples thereof include polyester-based polyurethane resins and polyether-based polyurethane resins. In the present invention, the compound (B) having a reactive polar group is 2-45% by weight based on 100% by weight of the total of the modified interpolymer (A) and the compound (B) having a reactive polar group. , Preferably 2 to 44% by weight, more preferably 2 to 44% by weight.
It is used in a proportion of 40% by weight.

Thermoplastic Resin Composition The thermoplastic resin composition according to the present invention contains the above-mentioned modified interpolymer (A) and the compound (B) having a reactive polar group in the above-mentioned specific ratio. I have.

In the thermoplastic resin composition according to the present invention, in addition to the above-mentioned modified interpolymer (A) and the compound (B) having a reactive polar group, an antioxidant and an ultraviolet absorbing Additives such as agents, weather stabilizers, heat stabilizers, antistatic agents, flame retardants, pigments, dyes, and fillers can be blended within a range that does not impair the object of the present invention.

Further, the thermoplastic resin composition according to the present invention may be blended with another polymer as long as the object of the present invention is not impaired. Examples of the filler include carbon black, asbestos, talc, silica, silica alumina and the like.

The thermoplastic resin composition according to the present invention comprises the above-mentioned modified interpolymer (A), a compound (B) having a reactive polar group, and additives optionally blended. By melt-mixing according to a conventionally known method.

That is, in the thermoplastic resin composition according to the present invention, the above-mentioned components are simultaneously or sequentially charged and mixed in, for example, a Henschel mixer, a V-type blender, a tumbler mixer, a ribbon blender, and the like. It is obtained by melt-kneading with a single-screw extruder, a multi-screw extruder, a kneader, a Banbury mixer or the like.

Among them, multi-screw extruders, kneaders,
When a device having excellent kneading performance such as a Banbury mixer is used, a high-quality thermoplastic resin composition in which each component is more uniformly dispersed can be obtained.

At any of these stages, the above additives, such as antioxidants, can be added as necessary. The thermoplastic resin composition according to the present invention obtained as described above preferably has a haze value of 65% or less when the molded article is prepared at a thickness of 1 mm when the molded article is prepared.

The thermoplastic resin composition according to the present invention obtained as described above can be used as a floor material, a wallpaper material, a coating material, a decorative sheet, a pipe, a tube, an artificial leather, a sheet, an agricultural film, a wrap film, a hose. And bottles.

Molded article The molded article according to the present invention can be produced by using the thermoplastic resin composition according to the present invention obtained as described above and various conventionally known melt molding methods, for example, extrusion molding, rotational molding, calendering. It can be formed into various shapes by methods such as molding, injection molding, compression molding, and blow molding.

[0104]

The thermoplastic resin composition according to the present invention contains a modified interpolymer (A) having excellent compatibility with the compound (B) having a reactive polar group at a specific ratio, and is alloyed. Therefore, a molded article excellent in heat resistance, scratch resistance and transparency can be prepared.

Since the molded article according to the present invention is prepared from such a thermoplastic resin composition, it is excellent in heat resistance, scratch resistance and transparency.

[0106]

EXAMPLES Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

The Martens hardness (indicator of scratch resistance), the tensile heat resistance temperature (indicator of heat resistance) and the haze (indicator of transparency) in Examples and the like of the present invention are as follows:
It was measured according to the following test method. (1) Martens hardness (scratch resistance) Using a Martens hardness and scratch hardness tester manufactured by Tokyo Ikki Co., Ltd., a load of 20 g of a scratch indenter was applied to a 3 mm-thick test piece to determine the groove width generated when the sample was scratched. It measured and calculated the reciprocal, and made the value into Martens hardness (1 / mm). (2) Film tensile heat resistance temperature (heat resistance) A press sheet having a length of 64 mm, a width of 13 mm, and a thickness of 0.2 mm is suspended in a nitrogen circulation high-temperature tank, a load of 10 g is applied thereto, and the temperature is raised at a rate of 5 ° C / min. The temperature rose. The temperature at which the press sheet stretched and fractured was defined as the film tensile heat resistance temperature (° C.). (3) Haze (Transparency) The haze (transparency) was measured with a digital turbidimeter “NDH-20D” manufactured by Nippon Denshoku Industries Co., Ltd. using a test piece having a thickness of 1 mm.

The ethylene-styrene copolymer (interpolymer), the maleic anhydride graft-modified ethylene-styrene copolymer (interpolymer) and the polyamide resin used in the examples and the like are as follows. (1) Ethylene-styrene copolymer (interpolymer) (ESI-70) Styrene content: 69.8% by weight (= 38.4 mol%) MI (ASTM D 1238, 190 ° C, 2.16 kg load): 1. 0g /
10 minutes (2) Ethylene-styrene copolymer (interpolymer) (ESI-30) Styrene content: 30% by weight (= 10.3 mol%) MI (ASTM D 1238, 190 ° C, 2.16 kg load): 1. 0g /
10 minutes (3) Modified ethylene-styrene copolymer (interpolymer) (M-ESI-1) Styrene content: 69.8% by weight (= 38.4 mol%) MI (ASTM D 1238, 190 ° C, 2.16 kg) Load): 1.5 g /
10 minutes Maleic anhydride (MAH) graft amount: 0.2% by weight (4) Modified ethylene-styrene copolymer (interpolymer) (M-ESI-2) Styrene content: 69.8% by weight (38.4 mol) %) MI (ASTM D 1238, 190 ° C, 2.16 kg load): 6.0 g /
10 minutes Maleic anhydride (MAH) graft amount: 1% by weight (5) Polyamide resin Nylon-6 (Ny-6): trade name C, manufactured by Toray Industries, Inc.
M1007

[0109]

Example 1 Modified ethylene-styrene copolymer (ME)
SI-1) 70 parts by weight and nylon-6 (Ny-6) 3
0 parts by weight was melt-kneaded at a resin temperature of 190 ° C. using a small Banbury mixer.

Then, using the obtained melt-kneaded material, press molding was performed at 190 ° C. to obtain a molded product according to the above test method. With respect to the obtained molded body, the tests for the Martens hardness, the tensile heat resistance temperature of the film, and the haze were performed according to the above-mentioned methods.

The results are shown in Table 1.

[0112]

Example 2 Ethylene-styrene copolymer (ESI-7
0) 35 parts by weight, modified ethylene-styrene copolymer (M-ESI-1) 35 parts by weight, and nylon-6 (Ny-
6) 30 parts by weight using a small Banbury mixer,
Melt kneading was performed at a resin temperature of 190 ° C.

Next, press molding was performed at 190 ° C. using the obtained melt-kneaded product to obtain a molded product according to the above-mentioned test method. With respect to the obtained molded body, the tests for the Martens hardness, the tensile heat resistance temperature of the film, and the haze were performed according to the above-mentioned methods.

The results are shown in Table 1.

[0115]

Example 3 Ethylene-styrene copolymer (ESI-7)
0) 63 parts by weight, modified ethylene-styrene copolymer (M-ESI-2) 7 parts by weight, nylon-6 (Ny-
6) 30 parts by weight using a small Banbury mixer,
Melt kneading was performed at a resin temperature of 190 ° C.

Next, using the obtained melt-kneaded material, press molding was performed at 190 ° C. to obtain a molded article according to the above test method. With respect to the obtained molded body, the tests for the Martens hardness, the tensile heat resistance temperature of the film, and the haze were performed according to the above-mentioned methods.

Table 1 shows the results.

[0118]

Example 4 Modified ethylene-styrene copolymer (ME)
SI-2) 70 parts by weight and nylon-6 (Ny-6) 3
0 parts by weight was melt-kneaded at a resin temperature of 190 ° C. using a small Banbury mixer.

Next, using the obtained melt-kneaded material, press molding was performed at 190 ° C. to obtain a molded article according to the above test method. With respect to the obtained molded body, the tests for the Martens hardness, the tensile heat resistance temperature of the film, and the haze were performed according to the above-mentioned methods.

The results are shown in Table 1.

[0121]

Comparative Example 1 Ethylene-styrene copolymer (ESI-7
Press molding was performed at 190 ° C. by using the above method (0) to obtain a molded body according to the above test method. With respect to the obtained molded body, the tests for the Martens hardness, the tensile heat resistance temperature of the film, and the haze were performed according to the above-mentioned methods.

The results are shown in Table 1.

[0123]

Comparative Example 2 Ethylene-styrene copolymer (ESI-3
Press molding was performed at 190 ° C. by using the above method (0) to obtain a molded body according to the above test method. With respect to the obtained molded body, the tests for the Martens hardness, the tensile heat resistance temperature of the film, and the haze were performed according to the above-mentioned methods.

The results are shown in Table 1.

[0125]

Comparative Example 3 Ethylene-styrene copolymer (ESI-7
0) 70 parts by weight and 30 parts by weight of nylon-6 (Ny-6) were mixed at a resin temperature of 19 using a small Banbury mixer.
The mixture was melt-kneaded at 0 ° C.

Next, press molding was performed at 190 ° C. using the obtained melt-kneaded product to obtain a molded product according to the above-mentioned test method. With respect to the obtained molded body, the tests for the Martens hardness, the tensile heat resistance temperature of the film, and the haze were performed according to the above-mentioned methods.

Table 1 shows the results.

[0128]

Comparative Example 4 Ethylene-styrene copolymer (ESI-3
0) 70 parts by weight and 30 parts by weight of nylon-6 (Ny-6) were mixed at a resin temperature of 19 using a small Banbury mixer.
The mixture was melt-kneaded at 0 ° C.

Next, using the obtained melt-kneaded product, press molding was performed at 190 ° C. to obtain a molded product according to the above-mentioned test method. With respect to the obtained molded body, the tests for the Martens hardness, the tensile heat resistance temperature of the film, and the haze were performed according to the above-mentioned methods.

The results are shown in Table 1.

[0131]

[Table 1]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI theme coat ゛ (reference) C08L 77/00 C08L 77/00 77/02 77/02 F term (reference) 4F071 AA14X AA15X AA21X AA22X AA54 AA77 AH01 AH03 AH04 BA01 BB03 BB04 BB05 BB06 BC01 BC04 4J002 BN031 BN051 BN061 BN201 CL002 CL012 GA01 GG00 GL00 GM00 4J026 AA11 AA12 AA13 AA14 AA16 AA17 AA21 BA01 BA06 BA12 DB19 BA20 BA25

Claims (9)

[Claims] (A) 98-55% by weight of at least one substantially random interpolymer graft-modified with a radically polymerizable monomer having a reactive polar group, and (B) a reactive polar polymer Wherein the modified interpolymer (A) comprises (1) (a) at least one aromatic vinyl or vinylidene monomer, or (b) at least one Hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer, or (c) derived from a combination of at least one aromatic vinyl or vinylidene monomer with at least one hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer 1 to 99 mol% of polymer units, and (2) ethylene or at least Number one carbon atom of the 3
A thermoplastic resin composition characterized by being a substantially random graft-modified interpolymer comprising 99 to 1 mol% of polymer units derived from -20 or more α-olefins or a combination thereof. 2. The modified interpolymer (A) comprises 1 to 99 mol% of polymer units derived from at least one aromatic vinyl or vinylidene monomer, and at least one α-C 3 to C 20 carbon atom. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is a substantially random graft-modified interpolymer comprising 99 to 1 mol% of a polymer unit derived from an olefin. 3. The modified interpolymer (A) is composed of 1 to 99 mol% of a polymer unit derived from styrene and ethylene or a combination of ethylene and at least one α-olefin having 3 to 10 carbon atoms. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is a graft modification product of a substantially random interpolymer composed of 99 to 1 mol% of a derived polymer unit. 4. The modified interpolymer (A) comprises: (1) (a) at least one aromatic vinyl or vinylidene monomer, or (b) at least one hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer. Or (c) 1-65 mol% of polymer units derived from a combination of at least one aromatic vinyl or vinylidene monomer and at least one hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer; and (2) A) pseudo-random interpolymer graft modified product comprising 35 to 99 mol% of polymer units derived from ethylene or ethylene and at least one α-olefin having 3 to 20 carbon atoms. Item 10. The thermoplastic resin composition according to Item 1. 5. The modified interpolymer (A) comprises: (1) 1 to 65 mol% of a polymer unit derived from at least one kind of hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer; and (2) ethylene or 3. A graft-modified pseudo-random interpolymer comprising 35 to 99 mol% of polymer units derived from ethylene and at least one α-olefin having 3 to 20 carbon atoms. The thermoplastic resin composition according to the above. 6. The composition according to claim 1, wherein a molded article is prepared
The thermoplastic resin composition according to any one of claims 1 to 5, wherein a haze value of the molded body measured at a thickness of 1 mm is 65% or less. 7. The compound (B) having a reactive polar group
Is a polyamide resin. The thermoplastic resin composition according to claim 1, wherein 8. The thermoplastic resin composition according to claim 7, wherein said polyamide resin is nylon-6. 9. A molded article comprising the thermoplastic resin composition according to claim 1.