JPH0428743A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition having excellent mechanical properties and improved heat resistance, comprising a polymer to be processed in a molten state, capable of forming an anisotropic melt, a polyolefin-based polymer and an epoxy group-containing copolymer. CONSTITUTION:The objective composition comprising (A) 3-60wt.% polymer which is a polyester preferably having a structural unit shown by formula I or formula II and formula III or formula I, formula II and formula III, is capable of forming an anisotropic melt and of being processed in a molten state, (B) 97-40wt.% polyolefin-based polymer modified with an unsaturated carboxylic acid (derivative) and (C) 0.1-30 pts.wt. based on 100 pts.wt. total amounts of the components A and B of an epoxy group-containing copolymer composed of a combination of preferably ethylene, an unsaturated epoxy compound, etc., and having improved moldability and excellent surface appearance.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a resin composition having good moldability and excellent surface appearance, as well as excellent heat resistance and mechanical properties.

[Conventional technology]

In recent years, demands for higher performance plastics have been increasing. Polyolefins have excellent moldability, toughness, water resistance, organic solvent resistance, chemical resistance, etc., and are low in specific gravity and inexpensive, so they have been widely used in various molded products, films, sheets, etc.

However, polyolefins generally do not have very high heat resistance or rigidity, and it is desirable to further improve these properties in order to develop new uses. As a method for improving this, it is known to blend reinforcing materials such as calcium carbonate and glass fibers, but this increases the specific gravity of the material, which reduces the lightweight advantage of plastics and worsens the appearance of the molded product. It has the following drawback. Furthermore, during molding, the molding machine is subject to severe wear and tear, which poses many practical problems.

On the other hand, as a polymer that forms an anisotropic melt, for example, a liquid crystal polymer obtained by copolymerizing parahydroxybenzoic acid with polyethylene terephthalate (Japanese Patent Laid-Open No. 49-7239
3), a liquid crystal polymer copolymerized with para-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid (Japanese Unexamined Patent Publication No. 5)
4-77691) and a liquid crystal polymer obtained by copolymerizing parahydroxybenzoic acid with 4,4'-dihydroxybiphenyl, terephthalic acid, and isophthalic acid (Japanese Patent Publication No. 57
-24407) etc. are known. These liquid crystal polymers have excellent heat resistance, rigidity, and dimensional stability, but
Because it is expensive, its range of use is limited.

Regarding blends of such liquid crystal polymers with various thermoplastic resins, see J. Kiss, Polymer Engineering and Science, Vol. 27 (1987), 41.
It is reported on page O. However, although the mechanical properties of this blend have been improved to some extent, they are insufficient for practical use.

[Problem to be solved by the invention]

In view of the above-mentioned current situation, the present invention combines the respective advantages of polyolefin and liquid crystal polymer, compensates for the disadvantages,
The object of the present invention is to obtain a resin composition having excellent heat resistance and mechanical properties.

[Means to solve the problem]

The present inventors have discovered that polyolefin-liquid crystal poly? - As a result of intensive studies to improve the heat resistance and mechanical properties of compounds, the present invention was achieved.

That is, the present invention comprises 1 to 95 wt% of a melt processable polymer (A) capable of forming an anisotropic melt, 99 to Swt% of a polyolefin polymer (B) modified with an unsaturated carboxylic acid or a derivative thereof, and Total of (A) and (B) 1
00 parts by weight, epoxy group-containing copolymer (C) o
, 1 to 30 parts by weight.

The melt-processable polymer (A) capable of forming an anisotropic melt in the present invention has a flow temperature of 160
C. to 350.degree. C., preferably 165 to 325.degree. C., more preferably 170 to 270.degree.

Flow temperature: Using a capillary rheometer with a nozzle with an inner diameter of 1 mm and a length of 10 mm, when extruding a heated melt through the nozzle at a heating rate of 4°C/min under a load of 100 kg/cnf, The temperature at which the viscosity is 48,000 poise.

The melt-processable polymer has the following repeating structural unit (
III), or (I) and (II), or (I)
, (n) and (III) are preferred.

fC-R, -C+
(I) -eO-R2-0te(n) -eo-R, -C+ or -fO-RvO-C-R -Ctera (III) Indicates more than one type of group.

The above groups are shown below.

represents one or more groups.

However, in any of R,, R2, and Rs, some of the hydrogen atoms in the benzene ring of the aromatic hydrocarbon are halogen atoms,
It may be substituted with an aryl group, a C4-CIQ alkyl group, or an alkoxy group. ) Specific examples of dicarboxylic acids that provide the repeating structural unit (I) include terephthalic acid, methoxyterephthalic acid, ethoxyterephthalic acid,
Fluoroterephthalic acid, chloroterephthalic acid, bromo terephthalic acid, methyl terephthalic acid, isophthalic acid, methoxyisophthalic acid, biphenyl-4,4°-dicarboxylic acid, diphenyl ether-4,4′-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid acid, naphthalene-1,5
-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, etc., but two or more of these may be used in combination.

Specific examples of the dioxy compound providing the repeating structural unit (If) include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1. 6-hexanediol, 1,12-dodecanediol, cyclohexane-1,4-diol, cyclohexane-1,3-
Diol, cyclohexane-1,2-diol, 1,4
-dioxymethyl-cyclohexane, 4,4-dihydroxybiphenyl, hydroquinone, resorcinol, methylhydroquinone, t-butylhydroquinone, chlorohydroquinone, phenylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, etc. Use a mixture of two or more of these.
Good too.

Furthermore, examples of the oxycarboxylic acid providing the repeating structural unit (III) include parahydroxybenzoic acid, 4-hydroxy-3-chlorobenzoic acid, 4-hydroxy-3-methylbenzoic acid, metahydroxybenzoic acid, and 4-hydroxybenzoic acid. Examples include 3,5-dimethylbenzoic acid, 2-oxy-6-naphthoic acid, ■-oxy-5-naphthoic acid, l-hydroxy-4-naphthoic acid, polyethylene terephthalate, polybutylene terephthalate, and two or more of these. May be used in combination.

There is no particular restriction on the ratio of repeating structural units in the liquid crystal polyester, but repeating structural units (I) and (II)
and (In) dicarboxylic acid residue (I)
and dioxy residue (II) is 20 to 90 mol% of the total, preferably 30 to 80 mol%, and oxycarboxylic acid residue (I [I) is 80 to 10 mol% of the total, preferably 1 It is preferably 70 to 20 mol%.

Furthermore, it is also possible to copolymerize a diamino compound, an oxyamino compound, or an aminocarboxylic acid with the above structural unit. Specific examples of these include meta or para-phenylenecyamine, meta or para-aminophenol,
Examples include para-aminobenzoic acid. Two or more of these may be used in combination.

The polyester consisting of the above-mentioned structural units must form an anisotropic melt, and preferably exhibits optical anisotropy at a temperature of 350°C or lower.

The polyester can be produced in the presence or absence of a catalyst according to conventionally known polyester polymerization methods, and although there are no particular limitations, the following method can be mentioned as a typical example.

(1) Acetic acid depolycondensation of an aromatic dicarboxylic acid such as parahydroxybenzoic acid and an acylated product of an aromatic dihydroxy compound such as 4,4'-dihydroxybiphenyl with acetic anhydride and an aromatic dicarboxylic acid such as terephthalic acid. A method of manufacturing by reaction.

(2) Produced by phenol-free polycondensation reaction from phenyl esters of aromatic oxycarboxylic acids such as hydroxybenzoic acid and aromatic dicarboxylic acids such as terephthalic acid and aromatic dihydroxy compounds such as 4,4''-dihydroxybiphenyl. Method.

(3) A method of producing by method (1) in the presence of a polyester made from a divalent aliphatic diol such as ethylene glycol and an aromatic dicarboxylic acid such as terephthalic acid.

(4) A method for producing by deacetic acid polycondensation reaction of an acylated aromatic oxycarboxylic acid such as hydroxybenzoic acid with acetic anhydride.

Further, the polyolefin polymer (B) modified with an unsaturated carboxylic acid or a derivative thereof in the present invention includes the following. That is, in the presence or absence of a radical initiator, a polyolefin contains (a) a carbon-carbon double bond or a carbon-carbon triple bond and (b) a carboxylic acid group, an acid anhydride group, or an acid amide group in the molecule. basis,
It is a modified polyolefin obtained by modifying with a compound simultaneously having one or more groups selected from imide groups, epoxy groups, and carboxylic acid ester groups.

Specific examples of the modifier having the above-mentioned functional groups include maleic anhydride, maleic acid, fumaric acid, maleimide, maleic acid hydrazide, a reaction product of maleic anhydride and diamine, etc. (wherein R is an aliphatic or aromatic methylnadic anhydride, dichloromaleic anhydride, maleic acid amide, soybean oil, tung oil, castor oil, linseed oil, hempseed oil, cottonseed oil, sesame oil, rapeseed oil, peanut oil, etc. oil, natural oils and fats such as camellia oil, olive oil, coconut oil, and sardine oil, epoxidized natural oils and fats such as epoxidized soybean oil, acrylic acid, butenoic acid, crotonic acid, vinyl acetic acid, methacrylic acid, pentenoic acid, ankeric acid, Tiburic acid, 2-pentenoic acid, 3-pentenoic acid, α-ethyl acrylic acid, β-methylcrotonic acid, 4-pentenoic acid,
2-hexenoic acid, 2-methyl-2-pentenoic acid, 3-methyl-2-pentenoic acid, α-ethylcrotonic acid, 2,2
-dimethyl-3-butenoic acid, 2-heptenoic acid, 2-octenoic acid, 4-decenoic acid, 9-undecenoic acid, 10-undecenoic acid, 4-dodecenic acid, 5-dodecenic acid, 4-tetradecenic acid, 9-tetradecene acid, 9-hexadecenoic acid,
2-octadecenoic acid, 9-octadecenoic acid, icosenoic acid, tocosenoic acid, erucic acid, tetracosenoic acid, mycolipenic acid, 2,4-pentadienoic acid, 2,4-hexanoic acid, diallylacetic acid, geranic acid, 2,4- Decadienoic acid, 2,4-dodecadienoic acid, 9,12-hexadecadienoic acid, 9,12 octadecanoic acid, hexadecatrienoic acid, linoleic acid, lylunic acid, octadecatrienoic acid, icosadienoic acid, icosatrienoic acid, ico Satetraenoic acid, ricinoleic acid, eleostearic acid, oleic acid, icosapentaenoic acid, erucic acid, docosadienoic acid, docosatrienoic acid, docosatetraenoic acid, docosapentaenoic acid, tetracosenoic acid, hexanoic acid,
Unsaturated carboxylic acids such as hexacosenoic acid, oftacosenoic acid, and traacontenoic acid, or esters of these unsaturated carboxylic acids, such as alkyl esters such as methyl, ethyl, butyl, aryl esters such as phenyl,
Examples include glycidyl esters such as glycidyl acrylate and glycidyl methacrylate, acid amides, and anhydrides. One or more types of these may be used.

Among these, particularly preferred compounds are maleic anhydride, maleic acid, and nadic anhydride. Further, in the present invention, it is also possible to use the above-mentioned modifier together with a vinyl compound such as styrene or p-oxystyrene.

The amount of the above modifier used is generally 10% of the polyolefin.
0.01 to 30 parts by weight, preferably 0.05 to 20 parts by weight, more preferably 0.1 to IO
Parts by weight range. When modifying a polyolefin with the modifier described above, a radical generator can also be used depending on the case.

Examples of the radical generator used include known organic peroxides and diazo compounds, and preferred specific examples include benzoyl peroxide, dicumyl peroxide,
Di-tert-butyl peroxide, tert-butylcumyl peroxide, tert-butyl hydroperoxide, 1,3-bis(tert-butylperoxyisopropyl)benzenecumene hydroperoxide, azobisisobutyronitrile, etc. It will be done.

The amount of radical generator used is generally polyolefin 1
00 parts by weight, the range is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight.

In the modified polyolefin of the present invention, the modifier and the polyolefin may be chemically reacted, or physical interaction (for example, physical adsorption to the polyolefin) may occur.
It may be.

The method for producing the modified polyolefin in the present invention is not particularly limited, and known methods can be used. For example, (1) A method in which the polyolefin and the above-mentioned modifier are uniformly mixed in the form of pellets, powder, or pieces using a high-speed stirrer or the like, and then melt-kneaded and blended.

(2) A method in which the above-mentioned modifier is added to a solution in which polyolefin is dissolved or swollen, the solution is dissolved or swollen, and the solution is heated while stirring.

Here, in the method (1), there are no particular restrictions on the temperature and time of melt-kneading. The temperature may vary slightly depending on the type and amount of the modifier, but is generally 120 to 350°C.
is within the range of As the melt-kneading device, any method may be used as long as it can handle a viscous material, and either a batch method or a continuous method can be used. Specific examples thereof include, for example, a single-screw or multi-screw extruder, a Banbury mixer, a roll, a kneader, and the like.

Further, the solvent used in the method (2) is not particularly limited as long as it can dissolve or swell the polyolefin. Further, a mixed solvent may be used as long as it can be dissolved or swelled.

There are no particular restrictions on the temperature and time for blending, and generally a temperature of 20 to 250°C and a time of 1 minute to 10 hours are appropriate.

In addition, the polyolefin used in the present invention is a crystalline or non-quality olefin polymer, and specifically,
For example, polypropylene, high density polyethylene, low density polyethylene, linear low density polyethylene, propylene-ethylene copolymer, ethylene-butene-1-copolymer, ethylene-pentene copolymer, ethylene-hexene copolymer, A polymer of the olefin itself, such as poly-4-methylpentene-1, or a predominant amount of the olefin and a vinyl monomer copolymerizable with it (e.g., acrylic esters, methacrylic esters, vinyl acetate, styrene, acrylonitrile) , glycidyl (meth)acrylate, etc.)
Examples include copolymers with Copolymerization can be random copolymerization, block copolymerization, or graft copolymerization. These can be used alone or as a mixture of two or more. Among these polyolefins, polyethylene and polypropylene are preferred, and particularly preferred are polypropylene and propylene-ethylene random copolymers and block copolymers.

These polyolefins can be prepared by methods known to those skilled in the art, for example in the ``Encyclopedia of Polymer Science and Technology'' (ENCYCLOPED).
rA OF POLYMER5CIENCE ANDT
ECHNOLOGY) Volume 6, page 275 (published in 1967) and Volume 11, page 597 (published in 1969) [John Wiley & Sons, Inc.]
& 5ons, Inc.)].

When using a modified polyolefin in the present invention, it is preferable to prepare the modified polyolefin in advance and then mix it with other components to produce the resin composition of the present invention. It is also possible to prepare a resin composition by mixing them all at once.

The epoxy group-containing copolymer (C) in the present invention is a copolymer consisting of an unsaturated epoxy compound and an ethylenically unsaturated compound.

There is no particular restriction on the composition ratio of the epoxy group-containing copolymer (C), but the unsaturated epoxy compound is 0.1 to 50 parts by weight per 100 parts by weight of ethylene and ethylenically unsaturated compounds other than ethylene. , preferably 1 to 30 parts by weight.

Furthermore, two or more of these epoxy group-containing copolymers may be used in combination.

The unsaturated epoxy compound is a compound having an epoxy group and an unsaturated group copolymerized with an ethylenically unsaturated compound in the molecule.

Examples include unsaturated glycidyl esters, unsaturated glycidyl ethers, and the like represented by (1) and (2) below.

(R is a hydrocarbon group having 2 to 18 carbon atoms and having an ethylenically unsaturated bond.) (R is a hydrocarbon group having 2 to 18 carbon atoms having an ethylenically unsaturated bond, and X is -CH2- 1 or specifically glycine acrylate, glycidyl methacrylate,
Examples include itaconic acid lysicyl esters, allyl glycidyl ether, 2-methylallyl glycidyl ether, and styrene-p-grindyl ether. Among these, glycidyl methacrylate is particularly preferably used.

Ethylenically unsaturated compounds are olefins, having 2 or more carbon atoms.
Vinyl esters of 6 saturated carboxylic acids, carbon number 1-8
Examples include esters of saturated alcohol components and acrylic acid or methacrylic acid, maleic esters, methacrylic esters, fumaric esters, vinyl halides, styrenes, nitriles, vinyl ethers, and acrylamides. .

Specifically, ethylene, propylene, butene-1, vinyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate, diethyl maleate, diethyl fumarate,
Examples include vinyl chloride, vinylidene chloride, styrene, acrylonitrile, isobutyl vinyl ether, and acrylamide.

These are generally used as binary copolymers with unsaturated epoxy compounds or as terpolymers containing ethylene and unsaturated epoxy compounds.

Epoxy group-containing copolymers can be made in a variety of ways.

Both a random copolymerization method in which the unsaturated epoxy compound is introduced into the main chain of the copolymer and a graft copolymerization method in which the unsaturated epoxy compound is introduced as a side chain of the copolymer can be used. Specifically, the production method involves mixing an unsaturated epoxy compound and ethylene in the presence of a radical generator,
A method of copolymerizing in the presence or absence of an appropriate solvent or chain transfer agent at 0 to 4,000 atmospheres and 100 to 300 °C, mixing polypropylene with an unsaturated epoxy compound and a radical generator, and extruding or a method of copolymerizing an unsaturated epoxy compound and an ethylenically unsaturated compound in an inert medium such as water or an organic solvent in the presence of a radical generator.

In practicing the present invention, it is also possible to add auxiliary agents to the present resin composition. Specific examples of auxiliary agents include glass fiber, silica alumina fiber, alumina fiber, carbon fiber,
Reinforcing agents such as potassium titanate fibers and high modulus polyamide fibers, carbon black, silica, titania, talc,
Inorganic and organic fillers such as calcium carbonate, magnesium sulfate, and wollastonite, plasticizers, lubricants, and stabilizers such as triphenyl phosphate and phthalate esters;
Examples include antimony trioxide, halogen compounds, flame retardants such as phosphate esters, dyes, and pigments.

In the present invention, a meltable polymer (
The amounts used of A) and polyolefin (B) modified with carboxylic acid and its derivatives are 1 to 95 wt%, respectively.
, 99 to 5 wt%, but the blending ratio is appropriately selected depending on the purpose of use.

For example, in order to improve the strength of polyolefin, mechanical strength such as elastic modulus, thermal properties such as heat denaturation temperature, processing fluidity, etc., (A) should be 1 to 70 wt%, preferably 3
~60wt%, more preferably 5~55wt%, (B
) is 99 to 30 wt%, preferably 97 to 40 wt%,
More preferably, it is 95 to 45 wt%, and (A) is 1
If it is less than 70 wt%, it will not be very effective in improving the physical properties of the polyolefin (and if it exceeds 70 wt%, the inherent properties of the polyolefin resin will not be expressed.

In addition, it has the original properties of an anisotropic melt, and has a molding shrinkage rate,
In order to reduce anisotropy such as mechanical strength, (A)
is 40 to 95 wt%, preferably 50 to 90 wt%, and (B) is 60 to 5 wt%, preferably 50 to 10 wt%.
It is wt%.

The amount of the epoxy group-containing copolymer (C) is 0.1 to 30 parts by weight, preferably 0.1 to 30 parts by weight, relative to a total of 100 parts by weight of the above-mentioned anisotropic melt (A) and modified polyolefin polymer (B).
The amount is 5 to 20 parts by weight, more preferably 1 to 10 parts by weight.

If the epoxy group-containing copolymer (C) is less than 0.1 part by weight, the reaction with the modified polyolefin polymer will not proceed sufficiently, and if it exceeds 30 parts by weight, it will gel during melt-kneading.
The appearance of the injection molded product will be significantly damaged.

There are no particular limitations on the method for producing the resin composition of the present invention,
Commonly known methods can be used.

Although methods of mixing in a molten state and evaporating the solvent or precipitating in a non-solvent are also effective, from an industrial standpoint, a method of kneading in a molten state is actually used. For melt-kneading, commonly used kneading devices such as single-screw or twin-screw extruders and various types of kneaders can be used. In particular, a twin-screw high kneader is preferred.

When kneading, it is preferable that each resin component is uniformly mixed in advance in the form of powder or pellets using a device such as a tumbler or a Henschel mixer.
If necessary, a method may be used in which mixing is omitted and the components are individually supplied in fixed amounts to the kneading device.

In addition, by melt-kneading, modified polyolefin polymer (
In order to promote the reaction between B) and the epoxy group-containing copolymer (C), it is preferable to add triphenylphosphine, tertiary amine, etc.

The kneaded resin composition is molded by injection molding, extrusion molding, and various other molding methods, but the present invention also provides a method in which the resin composition is tri-blended during injection molding or extrusion molding, without undergoing a kneading process in advance. It also includes a method of directly kneading the molded product to obtain a molded product.

〔Effect of the invention〕

The present invention has made it possible to produce a resin composition that has excellent mechanical properties and good heat resistance.

〔Example〕

The present invention will be explained below with reference to Examples, but these are merely illustrative and the present invention is not limited thereto.

In addition, the tensile test, bending test, and load deflection temperature test in the examples were conducted in accordance with JIS K7113 and JIS K7113, respectively.
K7203 and JIS K7207i: Measurements were made based on this.

Reference example 1 Polypropylene (manufactured by Sumitomo Chemical Co., Ltd. (Kiki; Sumitomo Noblen@D-501 melt index 0.4 g/10 minutes)
After adding 100 g of maleic anhydride, 50 g of styrene and 20 g of dicumyl peroxide to 10 kg and mixing well, the
The mixture was melt-kneaded at a temperature of 0°C and pelletized.

(Hereinafter, abbreviated as M-PP) Reference Example 2 170 g of nadic anhydride, 80 g of styrene, and 20 g of dicumyl peroxide were added to 10 kg of polypropylene, and mixed well with a Henschel mixer to obtain a pellet in the same manner as in Reference Example 1. (Hereinafter, abbreviated as N-PP) Reference Example 3 (Production of LC-1) LC-1 is Example 1 of JP-A No. 62-285916
Manufactured by the method disclosed in . That is, terephthalic acid and ethylene glycol are esterified by a conventional method,
An esterified product with an esterification reaction rate of 95% was obtained. This esterified product was charged into a polycondensation reactor, and 3 x 10-" mol of antimony trioxide was added per 1 mol of the acid component, and the polycondensation reaction was carried out under reduced pressure at 270°C with stirring for 3 hours. This molten state of polyester, a mole of bara hydroxybenzoic acid equal to the polyester, and acetic anhydride in an amount equivalent to 1.2 times that of the bara hydroxybenzoic acid were mixed, and the mixture was stirred at 270°C under a nitrogen atmosphere to form a uniform molten state. A mixture was formed.The pressure of this reaction mixture was gradually reduced, and finally a polycondensation reaction was carried out at 1.0 torr for 6 hours.

The obtained polymer is called LC-1.

Reference Example 4 (Manufacture of LC-2) Hydroxybenzoic acid 7 was added to a polymerization tank that had an anchor-type stirring blade and had a small clearance between the tank wall and the stirring blade.
56 g (5,48 mol), 453 g (2 mol) of terephthalic acid
, 73 mol), 4,4'-dihydroxydiphenyl 5
08g (2.73 mol), 169g of polyethylene terephthalate (PET RT-560 manufactured by Toyobo ■) (equivalent to 10% by weight of the final polymer) and acetic anhydride 1
337 g (13.1 mol) was charged, heated to 150° C. over 1 hour while stirring under a nitrogen atmosphere, and refluxed at this temperature for 3 hours. Thereafter, acetic acid was distilled off while raising the temperature, and finally polymerization was carried out at 330°C for 12 hours under high shear.
After that, it was gradually cooled and continued to be stirred vigorously until it reached 200℃.
The polymer was taken out of the tank.

After pulverizing this polymer, it was transferred to an aluminum rotary oven, the entire system was rotated under a nitrogen stream, and the temperature was gradually raised to 320°C over 6 hours while thoroughly stirring the powder.
After processing at 320°C for 3 hours, it was cooled and the powder was taken out at 200°C. The obtained polymer is called LC-2.

Reference Example 5 (Production of LC-3) Based on Example 1 of Japanese Patent Publication No. 57-24407, 517.5 g (3.75 mol) of parahydroquine benzoic acid
, 155.7 g (0.94 mol) of terephthalic acid, 51.8 g (0.31 mol) of isophthalic acid, 4.4°-
232.5 g (1.25 mol) of dihydroxydiphenyl and 688.5 g (6.75 mol) of acetic anhydride were charged into a polymerization tank and polymerized. The obtained polymer was subjected to LC-3
That's what it means.

Reference Example 6 (Manufacture of LC-4) It was manufactured based on the method disclosed in Example 1 of JP-A-54-77691. That is, 675 g (3.75 mol) of acetoquine benzoic acid, 6-acetoquine 2-
287 g (1.25 mol) of naphthoic acid was charged into a polymerization tank and stirred at 250°C for 3 hours and at 280°C for 1 hour and 30 minutes under an argon stream. Next, the polymerization temperature was raised to 320° C. and held for 30 minutes to perform acetic acid depolycondensation reaction.

Next, the argon flow was stopped, and the pressure was gradually reduced to about 0. A pressure of lmmHg was maintained for 30 minutes to obtain a polymer. This polymer was crushed, transferred to an aluminum rotary oven, and dried in air at 150°C for 1 hour. The obtained polymer is called LC-4.

Reference Example 7 Ethylene/methyl acrylate/glycidyl methacrylate terpolymer [ethylene/methyl acrylate/glycidyl methacrylate = 35/63/2] was prepared according to the method described in Example 5 of JP-A-61-127709.
(Weight ratio), 190°C 12, M under 16kg load
I = 8.7 g/10 minutes] was obtained. (hereinafter E-MAG
Reference Example 8 JP-A-47-23490, JP-A-48-1138
Based on the method described in Publication No. 8, ethylene/glycidyl methacrylate copolymer [ethylene/glycidyl methacrylate-h-88/12 (weight ratio)] was mixed with 1,400 g
Copolymerization was carried out under conditions of ~1.600 atm and 180 to 200°C. (hereinafter referred to as E-GMA) Reference Example 9 Produced with reference to the method described in Japanese Patent Publication No. 55-12449. Ethylene-vinyl acetate copolymer pellets were mixed with glycidyl methacrylate in which dicumyl peroxide had been dissolved in advance, and extruded using a 30 mm diameter twin-screw extruder with a vent at a tip temperature of 170°C to obtain ethylene/vinyl acetate/glycidyl methacrylate = 90/ Glycidyl methacrylate grafted ethylene-vinyl acetate copolymer pellets having a weight ratio of 6/4 were obtained. (hereinafter referred to as GMA-g-EVA)
Example 1 800 g of M-PP shown in Reference Example 1, LC-1200 g shown in Reference Example 3, and E-GMA described in Reference Example 8
Mix 30g with a Henschel mixer, mix 200~2
Pellets were obtained by extrusion using a 30 mm twin screw extruder at a temperature of 50°C. In addition, the cylinder diameter 2 made by Nisshin Jushi Kogyo ■
A test piece was obtained using a 2 mm injection molding machine, and various physical properties were measured. The results are shown in Table 1.

Example 2 600g of M-PP and LC-2400 described in Reference Example 4
g Furthermore, 50 g of E-MA-GMA obtained in Reference Example 7
Pellets were obtained using a twin-screw extruder at a temperature of 240 g to 300° C., molded products were made using an injection molding machine, and various physical properties were measured. The results are shown in Table 1.

Example 3 N-PP 700 described in Reference Example 2 instead of M-PP
g, LC-2300 g, and E-GMA 20 g were blended, and various physical properties of the molded product were measured according to Example 2.

The results are shown in Table 1.

Example 4 N-PP 900g, LC-3100 described in Reference Example 5
GMA-g-EVA 100 shown in g and Reference Example 9
g. Mix, obtain pellets using a twin-screw extruder at a temperature of 270 to 320°C, and make a molded product using an injection molding machine.
Various physical properties were measured. The results are shown in Table 1.

Example 5 M-PP 800g, LC-4200 described in Reference Example 6
Example 4
Various physical properties of the molded product were measured according to the following. The results are shown in Table 1.

Comparative Example 1 Pellets were obtained according to Example 1 except that E-GM and A were not used, test pieces were obtained using an injection molding machine, and various physical properties were measured. The results are shown in Table 1.

\、 \ \ \ \ \ hand Continued Supplementary Positive book (spontaneous) August 22, 1991 Day l.

Case Description Patent Application No. 134-28 of 1990 Address 4-5-33 Kitahama, Chuo-ku, Osaka Name Sumitomo Chemical Co., Ltd. Representative Hideo Mori 4゜ Agent Address 4-5-33 Kitahama, Chuo-ku, Osaka Contact number: (06) 220-3404 5. The "Claims" and "Detailed Description of the Invention" columns of the specification to be amended.

6. Contents of amendment (The scope of the 11th patent claim is amended as shown in the attached sheet.

(2) “1 to 95 wt%j” in line 8 of page 6 of the specification
~60wt%”.

(31, page 6, line 1O (7) r99~5 wt%J
is corrected to "97-4°wt%".

(4) →○−R, −C÷ or →○−Rr−0−C−R, −C+−−−−(m) J on page 7, lines 9 to IO
is corrected to r 11 (−0−R, −C+ −−−−, −be l1r)”.

(5) Insert "and naphthalene ring" next to "benzene ring" on page 8, line 8.

(6) “l-Hydroxy-4-
Next to "naphthoic acid", "nato is mentioned, and as a polyester consisting of repeating structural units (1) and (I[)" is inserted.

(7) From page 23, line 15 to page 24, line 9, ``In the present invention, it becomes impossible to express...''.

"In the present invention, the amounts used of the meltable polymer (A) capable of forming an anisotropic melt and the polyolefin polymer (B) modified with an unsaturated carboxylic acid or its derivative are based on the amount of the polyolefin." In order to improve mechanical strength such as strength and elastic modulus, thermal properties such as heat distortion temperature, processing fluidity, etc., (A) is contained in an amount of 3 to 60 wt%, more preferably 5 to 60 wt%.
55 wt%, and (B) is preferably 97 to 40 wt%, more preferably 95 to 45 wt%. If (A) is less than awt%, it will not be very effective in improving the physical properties of polyolefin.
If it exceeds 60 wt%, the inherent properties of the polyolefin polymer cannot be expressed. ” is corrected.

(8) On page 24, lines 10 to 14, “In addition, the anisotropic melt...
It is. ” to be deleted.

Claims (1) A melt-processable polymer capable of forming an anisotropic melt (A)
) 3 to 60 wt%, polyolefin polymer modified with unsaturated carboxylic acid or its derivative (B) 97 to 4o
A thermoplastic resin composition containing 0.1 to 30 parts by weight of an epoxy group-containing copolymer (C) based on 100 parts by weight of (A) and (B) in total.

(2) The melt-processable polymer (A) is a polyester consisting of the following repeating structural unit (III), or (I) and (II), or (I), (It), and (I[). Item 1. Thermoplastic resin composition according to item 1.

+ORs　Oji (I[) Indicates more than one species.

The above groups are shown below.

represents one or more groups.

However, in all of RI, Rt, and Rs, some of the hydrogen atoms in the benzene ring and naphthalene ring of the aromatic hydrocarbon are halogen atoms and aryl groups.

It may be substituted with a C8-C1 alkyl group or an alkoxy group. ) (3) The polyolefin polymer (B) contains (a
) a carbon-carbon double bond or a carbon-carbon triple bond; and (b) one or more groups selected from a carboxylic acid group, an acid anhydride group, an acid amide group, an imide group, an epoxy group, or a carboxylic acid ester group. 2. The thermoplastic resin composition according to claim 1, which is a modified polyolefin obtained by modifying a polyolefin with a compound simultaneously contained in the presence or absence of a radical initiator.

(4) The epoxy group-containing copolymer (C) is ethylene and an unsaturated epoxy compound, or an ethylenically unsaturated compound other than ethylene and an unsaturated epoxy compound, or ethylene, an ethylenically unsaturated compound other than ethylene, and unsaturated The thermoplastic resin composition according to claim 1, which is a polymer consisting of one or more combinations selected from the group of monomer combinations consisting of epoxy compounds.

that's all

Claims (1)

[Scope of Claims] (1) Melt processable polymer (A
) 1 to 95 wt%, polyolefin polymer modified with unsaturated carboxylic acid or its derivative (B) 99 to 5 w
t% and a thermoplastic resin composition containing 0.1 to 30 parts by weight of an epoxy group-containing copolymer (C) based on 100 parts by weight in total of (A) and (B). (2) The melt-processable polymer (A) has the following repeating structural unit (III), or (I) and (II), or (
The thermoplastic resin composition according to claim 1, which is a polyester consisting of I), (II) and (III). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼or▲Mathematical formulas, chemical formulas, tables, etc. There is▼...(III) (In the formula, R_1 is ▲a mathematical formula, a chemical formula, a table, etc.▼, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
Shows one or more groups selected from ▼. In the formula, R_2 can be ▲a mathematical formula, a chemical formula, a table, etc.▼, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
Shows one or more groups selected from ▼. In the formula, R_3 has a ▲ mathematical formula, chemical formula, table, etc. ▼, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ indicates one or more groups selected from. However, in any of R_1, R_2, and R_3, some of the hydrogen atoms in the benzene ring of the aromatic hydrocarbon may be substituted with a halogen atom, an aryl group, an alkyl group or an alkoxy group of C_1 to C_1_0. ) (3) The polyolefin polymer (B) contains (a) carbon-
A compound having at the same time a carbon double bond or a carbon-carbon triple bond and (b) one or more groups selected from a carboxylic acid group, an acid anhydride group, an acid amide group, an imide group, an epoxy group, or a carboxylic acid ester group. The thermoplastic resin composition according to claim 1, which is a modified polyolefin obtained by modifying a polyolefin in the presence or absence of a radical initiator. (4) The epoxy group-containing copolymer (C) is ethylene and an unsaturated epoxy compound, or an ethylenically unsaturated compound other than ethylene and an unsaturated epoxy compound, or ethylene, an ethylenically unsaturated compound other than ethylene, and unsaturated The thermoplastic resin composition according to claim 1, which is a polymer consisting of one or more combinations selected from the group of monomer combinations consisting of epoxy compounds.