JPS601255A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a thermoplastic resin compsn. having improved mechanical properties such as tensile strength, flexural strength, rigidity, etc., by blending an olefin polymer/polyamide copolymer with a polyamide. CONSTITUTION:5-95pts.wt. polyamide(A) such as nylon 6 or nylon 66, 0.1- 90pts.wt. olefin polymer/polyamide copolymer (B) such as a polybutadiene/nylon 6 copolymer and 0-95pts.wt. olefin polymer (C) such as an ethylene/propylene copolymer are melt-mixed together in such a quantity that the combined quantity of components A, B and C amounts to 100pts.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermoplastic resin composition with improved mechanical properties such as impact resistance by blending an olefin polymer/polyamide copolymer with a polyamide.

Polyamides such as poly-ε-caprolactam are used for fibers, electrical and electronic parts, etc., but they may not be able to meet the characteristics required for each molded product. For this reason, the balance of physical properties is adjusted by blending other polymers or adding inorganic fillers.

For example, attempts have been made to blend elastomers and polyolefins to improve the impact resistance of polyamide, but these polymers do not necessarily have good compatibility with polyamide, resulting in poor dispersibility. This tends to cause non-uniformity and separation between different phases, and the purpose of modification is often not achieved.

On the other hand, polyolefins are used in a wide range of fields because they are relatively inexpensive, chemically stable, have excellent moldability, and have low density. Furthermore, as the development of applications has progressed in recent years, the required performance has become stricter, and in order to cope with this, efforts are being made to further improve the physical properties by blending other polymers or adding inorganic fillers.

For example, attempts have been made to blend nylons such as poly-ε-caprolactam into polyolefins such as polyethylene, but for the same reasons as above, the purpose of the modification is often not realized.

The present inventors investigated methods of adding other polymers to polyamides such as poly-ε-caprolactam to improve their mechanical properties such as impact resistance and water resistance, and also added other polymers to polyolefins. As a result of investigating ways to improve mechanical properties such as tensile strength, bending strength, and rigidity by adding polyamide, we decided to use an olefin-based polymer/polyamide copolymer (B) that has an affinity for both polyamide and polyolefin. It has been found that these objectives can be achieved by doing so. In other words, the present inventors discovered that the olefin polymer/polyamide copolymer (B) has excellent dispersibility when blended with the polyamide (A) or the olefin polymer (0), and that this results in excellent dispersibility when blended with the polyamide (A). ) and the olefinic polymer (C) were found to have improved mechanical properties.

The present inventors also found that when this copolymer (E) was blended into a blend system containing polyamide (A) and olefin polymer (0), the polyamide (A) and olefin polymer (C) It was discovered that the compatibility between polyamide (A) and olefin polymer (0) was significantly improved.
found that the mechanical properties of blends of
This led to the present invention.

That is, the present invention comprises 5 to 95 parts by weight of polyamide (A), olefin polymer/polyamide copolymer (B)
0.1 to 90 parts by weight, and 0 to 95 parts by weight of olefin polymer (C) (A) + (B)
+(0) (total of 100 parts by weight).

The polyamide (A) used in the composition of the invention is of sufficient molecular weight to produce molded articles and is produced by known methods. Such methods include, for example, polycondensation of organic dicarboxylic acids or derivatives thereof with organic diamines, ring-opening polymerization of lactams, and polycondensation of aminocarboxylic acids. The polycondensation reaction between an organic dicarboxylic acid and an organic diamine is usually carried out by mixing the two in equimolar amounts.

However, if necessary, a diamine can be used in the polyamide so that the amino group ends are in excess of the carboxyl group ends, or conversely, a dicarboxylic acid can be used so that the carboxyl groups are in excess. These polyamides can also be produced from the amine and acid-forming derivatives and amine-forming derivatives, such as esters, acid chlorides, amine salts, and the like. Typical dicarboxylic acids used to produce polyamides include aliphatic dicarboxylic acids such as succinic acid, adipic acid, pimelic acid, superric acid, sebacic acid and dodecanoic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. , terephthalic acid, isophthalic acid, aromatic dicarboxylic acids such as naphthalene dicarboxylic acid, and the like.

On the other hand, typical diamines include aliphatic diamines such as ethylene diamine, tetramethylene diamine, hexamethylene diamine, octamethylene diamine, decamethylene diamine, and dodecamethylene diamine, and fatty acids such as diaminocyclohexane, diaminomethylcyclohexane, piperazine, and isophorone diamine. Examples include aromatic diamines such as cyclic diamines, p-phenylene diamines, m-phenylene diamines, and xylylene diamines.

Examples of the lactam include ε-caprolactam, enantlactam, undecanolactam, and laurinlactam.

Also, as an aminocarboxylic acid, monoaminocaproic acid,
Examples include 11-aminoundecanoic acid and 12-aminododecanoic acid.

Examples of polyamides made from organic dicarboxylic acids and organic diamines include polyhexamethylene adipamide (nylon 6.6), polyhexamethylene azelamide (nylon 6.9), and polyhexamethylene adipamide (nylon 6.9). Nylon 6, IO) and polyhexamethylene dodecanoamide (Nylon 6.12), polybis(4-aminocyclohexyltumethanandodecanoamide 1), which are also produced by ring-opening polymerization of lactams or polycondensation of aminocarboxylic acids. Examples of polyamides include poly-ε-caprolactam (nylon 6) and polylaurinlactam (nylon 1).
2) or poly-11-aminoundecanoic acid (nylon 11). A copolymer polyamide produced by combining at least two or more of the diamines, dicarboxylic acids, lactams, and aminocarboxylic acids used to produce the above-mentioned polyamides, such as adipic acid, isophthalic acid, and hexamethylene. It is also possible to use polymers made from diamines. It is also possible to use blends of polyamides, such as mixtures of nylon 6.6 and nylon 6.6. The polyamide used in the present invention is preferably polyhexamethylene adipamide (nylon 6.6), polyhexamethylene adipamide (nylon 6.10), polyε-caprolactam (nylon 6), polylaurin lactam (nylon 12), and poly-11-aminoundecanoic acid (
Nylon 11), etc.

The olefin polymer/polyamide copolymer (B) used in the composition of the present invention is a copolymer having an olefin polymer segment and a polyamide segment. Examples of the olefinic polymer segment include those having the same repeating unit as the polymer exemplified later as olefinic polymer (0) that may be used as a component of the composition of the present invention. in this case,
The type of segment of the olefinic polymer does not necessarily have to be the same as the type of the olefinic polymer (C) that may be used in combination with the composition of the present invention, but it is preferable that they are compatible with each other. Among these, α-olefin-based elastic polymers or diene-based polymers are preferred, and hydrogenated diene polymers are particularly preferred.

Examples of the polyamide segment constituting the copolymer (B) include those having the same repeating units as the polymer exemplified as the polyamide straight A).

These polyamide segments do not need to be the same as those used for polyamide (A), as long as they have affinity with the polyamide used for polyamide (A). However, when it is the same as that used for polyamide (A), it has particularly excellent compatibility with copolymer (B).

The olefin polymer segment and the polyamide segment of the copolymer (B) are a block copolymer or a graft copolymer connected to each other via a divalent group. The connecting portion of each segment is preferably an ester bond.

The copolymer (B) used in the present invention can be produced by various methods.

For example, the applicant filed a patent application (title of the invention: method for producing a polyamide copolymer) on May 201, 1981, or patent application (2) (title of the invention) filed on May 2, 1980. :Production method of copolymerized polyamide).

As a preferable manufacturing method, the following general formula (1) or (
1 - a -z (1) (However, in the formula, Y is oxygen, sulfur or -N-, and R
is a divalent hydrocarbon group or a divalent hydrocarbon group having an ether or thioether bond in the main chain, m is zero or 1, and n is zero (p is a positive integer from 4 to 15). There is a method for producing the copolymer (B) by ring-opening polymerization of lactams in the presence of an olefinic polymer having a group represented by , ) at its terminal and/or side chain G.

In this production method, in order to introduce the group represented by the general formula (1) into the olefinic polymer, one type selected from the group consisting of hydroxyl group, thiol group, and amide group is usually introduced at the terminal or side chain. The dicarboxylic acid civalide or acyl civalide represented by the following general formula (wherein, X is a halogen, and the others are the same as general formula (1)) is added to the above-mentioned olefinic polymer into which a polar group has been introduced. ,
Alternatively, a method may be used in which a compound selected from dicarboxylic acid monohalide monolactam amide or acyl lactam monohalide is reacted.

Another method is to introduce an acyl halide by reacting the olefinic polymer into which the above polar group has been introduced with a compound selected from dicarboxylic acid cybarides or acyl cybaride compounds among the compounds represented by the above general formula (■). There is a method of introducing a group represented by the above general formula (1) by reacting a lactam after the reaction.

In order to introduce a group represented by general formula (1) into an olefinic polymer, a method of reacting a halogenating agent such as thionyl chloride with a polyolefin having a carboxyl group at the terminal and/or side chain, or a method of introducing a group represented by general formula (1) using this method. There is a method in which the acyl halide group is further reacted with a lactam.

In these methods, an olefin polymer having one or more types of polar groups selected from the group consisting of hydroxyl group, thiol group, carboxyl group, and amino group at the terminal or side chain is added to the olefin polymer by a conventionally known method. Manufactured by introducing

The olefin polymer used as a raw material has the same repeating units as the polymer later exemplified as olefin poly Y-(0), such as ethylene, propylene, 1-butene, 4-methyl-1 − α of pentene etc. −
Homopolymers of olefins or copolymers of two or more types are also exemplified, but diene polymers and hydrides thereof are particularly preferably used in the present invention.

As the diene polymer segment used in the copolymer (B) of the present invention, polymers selected from polybutadiene, polyisoprene, and hydrides thereof are particularly suitable.

Various conventionally known methods can be employed to introduce a hydroxyl group, thiol group, carboxyl group or amino group into the terminal and/or side chain of the diene polymer.

As the diene polymer that is the raw material for introducing these various polar groups or hydrogenating, polybutadiene polymers or copolymers having a hydroxyl group or carboxyl group at the end, and their hydrogenated products can be used. For example, N15so PB-G-, 1000 Nippon Soda 2000 tt -3000 G knee 1000 tt 〃 G knee 2000 G knee 5000 a-+oo.

〃 0 knee 100 D tt Poly-BD Urf Co. Butarez l (T Philip Co. Hycar B
Commercially available products such as TB Gudrich, Telogen HT, General Tire, etc. can also be used.

Preferred examples of olefinic polymers having polar groups at the terminal and/or side chains used in these production methods have a molecular weight of about 500 to about 400,000, particularly preferably about 500 to about 500,000, and have a polarity. Group concentration in olefin polymer is 0.0025 meq
/g to 7meq/P%, particularly preferably 0.00
35 mθq/g to 4 meq/g.

In a further preferred embodiment, the olefin polymer is a diene polymer or a hydride thereof, has a molecular weight of about 300 to about 400,000, particularly preferably about 500 to about 300,000, and has a polar group at both or one end. is a diene polymer or hydrogenated diene polymer into which is introduced.

Among the compounds represented by the above general formula (1) that can be used to prepare raw materials for these production methods, the following compounds are exemplified as dicarboxylic acid cybarides or acyl cybarides in which two of the compounds are halogens like X.

Examples of dicarboxylic acid halides include oxalic acid dichloride, oxalic acid dichloride, malonic acid dichloride,
Malonic acid dichloride, succinic acid dichloride, glitaric acid dichloride, adipic acid dichloride, sebacic acid dichloride, cyclohexanedicarboxylic acid dichloride, terephthalic acid dichloride, isophthalic acid dichloride, phthalic acid dichloride, xylene dicarboxylic acid dichloride, 2,6-naphthalenedicarboxylic acid dichloride , bis(4-carboxyphenyl) ether dichloride, and phosgene as an example of the acyl halide.

(However, p is an integer of 4 to 16) Among the dicarboxylic acid monohalide monolactam amide or acyl lactam monohalide compounds, those in which p is 5 to 11 are preferable, and in particular, when n is 5, ε- Dicarboxylic acid monohalide lactamamide or acyllactam monohalide compounds derived from caprolactam are preferred.

More specifically, such compounds include the following.

Reacting one or more of these dicarboxylic acid cybaride or acyl civalide, or carboxylic acid monohalide monolactamamide or acyllactam monohalide, which are compounds represented by the general formula (■), with an olefinic polymer containing a polar group, After reacting one or more compounds selected from dicarboxylic acid cybalides or acyl cybalides with an olefinic polymer having a polar group to introduce an acyl halide, a lactam such as ε-caprolactam is further reacted to form the terminal with the general formula (1)
The reaction for introducing the group represented by is carried out in the presence or absence of an organic diluent such as a solvent.

However, if an organic diluent is used, it must be substantially anhydrous and must have no active element atoms or electron groups that would react with the acyl halide group.

The reaction of introducing an acyl halide group among the groups represented by general formula (1) by reacting an olefinic polymer having a carboxyl group at the terminal and/or side chain with a halogenating agent such as thionyl chloride is usually carried out by organic dilution. carried out in the presence of an agent.

1. In these production methods, the polyolefin having an acyl halide group introduced in the above reaction is further reacted with a lactam, and about 50% of the polar groups introduced into the olefin polymer, especially about It is desirable to convert 50% or more into a group represented by the general formula (1) or (river). If it is less than 50%, there are some unsatisfactory points such as low efficiency of copolymerization with lactams.

Copolymer (B) can also be obtained by copolymerizing lactams using an alkali catalyst in the presence of an olefinic polymer such as a hydrogenated diene polymer into which a group represented by formula (1) or (I) is introduced. It can be produced by linking segments of an olefinic polymer and polyamide chains.

Lactams include compounds represented by the general formula (IV) [where p is an integer of 4 to 13], of which ε-caprolactam is preferably used.

Further, as the alkali catalyst, catalysts conventionally used for anionic polymerization of lactams can be used, such as alkali metals such as lithium, sodium, potassium, etc. as exemplified in Japanese Patent Publication No. 43-19033, Alkaline earth metals such as magnesium, calcium, strontium, barium, etc. or hydrides thereof can be used.

As a method for producing the olefin polymer/polyamide copolymer (B), an olefin polymer having a carboxyl group, a carboxylic acid derivative group, or an amine 7 group at the terminal and/or side chain, and an amide that can react with the functional group are used. Also exemplified is a method of reacting with a polyamide or an oligomer thereof having a terminal group of 7 groups, a carboxyl group, or a carboxylic acid derivative group.

The olefinic polymer having the functional group is the same as that exemplified above, and in this production method, the diene polymer having the functional group and its hydride are particularly preferably used.

In this production method, diene polymers having a carboxyl group, a carboxylic acid derivative group, or an amide group at the terminal and/or side chain and their hydrides are more preferably diene polymers having a carboxyl group at the terminal and/or a hydride thereof. It is its hydride.

Furthermore, preferable examples of diene polymers having a carboxyl group at the terminal or their hydrides have a molecular weight of about 300 to about + o o, o o O, particularly preferably about 500 to about 50,000, and a carboxyl group , the hydride width of the diene-containing polymer having carboxyl groups from about 0.02 mθq/g to about 7 meq/g
, particularly in the range of about 0.04 meq/g to about 4 meq/g.

Examples of the structural units of the polyamide having the functional group include the same polyamides as those exemplified above, and can be produced by known methods.

Such methods include, for example, polycondensation of lactams, polycondensation of amino acids, or polycondensation of dicarboxylic acids and diamines, and these polycondensation reactions are carried out in the presence of an excess of dicarboxylic acids, dicarboxylic acid derivatives, or diamines. . These excess dicarboxylic acids, dicarboxylic acid derivatives, or diamines act as chain limiters;
By appropriately selecting the amount of the dicarboxylic acid derivative or diamine, the length of the polymer chain, that is, the average molecular weight of the polyamide can be adjusted.

Among the compounds used as chain limiters, diamines include aliphatic, alicyclic and aromatic diamines, such as ethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, cyclohexanediamine, piperazine, isophoronediamine, p-phenylene. Examples include diamine, m-phenylenediamine, and p-xylylenediamine. The dicarboxylic acids which can also be used as chain limiters are aliphatic, cycloaliphatic and aromatic dicarboxylic acids, such as adipic acid, pimelic acid, sebacic acid, dodecanoic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid and the like.

Further, dicarboxylic acid derivatives used as chain limiters include esters and acid chlorides of the above dicarboxylic acids. The polycondensation reaction is usually carried out in the melt without a solvent, but it can also be carried out at the interface by dissolving the dicarboxylic acid chloride and the diamine in an organic solvent or in two or more solvents that are immiscible with each other. It is possible. Further, excess dicarboxylic acid, dicarboxylic acid derivative, or diamine as a chain limiter can be added at the beginning, middle, or final stage of the reaction. It is also possible to produce a polyamide having the functional group at the terminal end by adding a chain limiter to a high molecular weight polyamide and carrying out the reaction.

These polyamides having amino groups, carboxyl groups, or carboxylic acid-derived groups at the terminals used in this production method are preferably polyhexamethylene adipamide (
Nylon 6.6), polyhexamethylene adipamide (Nylon 6.10), poly ε-caprolactam (Nylon 6), poly ω-laurin lactam (Nylon 12) and poly-11-aminoundecanoic acid (Nylon 11). Preferably, the molecular weight is about 10 to about 1.
0[1,I][lO.

Especially preferably about 500 to about 50,000
belongs to.

An olefin polymer having a carboxyl group, a carboxylic acid derivative group, or an amino group at the end and/or a side chain, and a polyamide having an amine 7 group, a carboxyl group, or a carboxylic acid derivative group at the end that can form an amide bond with the functional group. are melt-mixed under heating to obtain a copolymer in which olefin polymer segments and polyamide segments are connected by amide bonds.

Melt mixing under heating can be carried out in the presence of an organic diluent, but is usually carried out in its absence.

The copolymer (B) used in the present invention is usually used after separating and removing the unreacted polyolefin and polyamides that did not contribute to the copolymerization, but it contains some unreacted materials. It can also be used in this manner.

In the copolymer (B) used in the present invention, the polyolefin chain (a) and the polyamide chain (b) are a-b, b-a-b.
There are not only structures such as +a-b+j (
A block copolymer or graft copolymer having a structure in which j is any positive integer, each a and each may be the same or different, and each of which may be the same or different. are also exemplified, each chain has an ester bond,
They are linked by a thioester bond, amide bond, urethane bond, urea bond, or imide bond.

Furthermore, in the copolymer (B) used in the present invention, the ratio (M 17M 2 ) of the weight of the olefin polymer (Ml) to the total weight of the polyamide chains (M2) is about 2/9.
A range of 8 to about 9715, more preferably about 3/97 to about 9515, is preferred.

When the weight ratio (M1/M2) is smaller than 2/98, the compatibility between the copolymer (B) and the olefin polymer (C) deteriorates.

Moreover, if the weight ratio exceeds 9775, the compatibility with the polyamide (A) will deteriorate, which is not preferable.

A particularly preferred embodiment of the olefin polymer/polyamide copolymer (B) is one in which the olefin polymer segment has a molecular weight of about 500 to about 400,000, particularly about 500 to about 30 [1,000]. , a polyamide chain is connected to one end or both ends of the olefinic polymer segment in the long chain, and the total molecular weight of the polyamides is about 30.0 to about 100.0.
00, particularly in the range of about 500 to about 50,000.

In addition, such a copolymer CB) is often soluble in a solvent with m-cresol/toluene = 171 (wt ratio),
In that case, [η]j is preferably about 0.6 to about 5.0.

Examples of the copolymer (B) include polybutadiene-nylon 6 copolymer, polyisoprene-nylon 6 copolymer, hydrogenated polybutadiene-nylon 6 copolymer, hydrogenated polyisoprene-nylon 6 copolymer, and hydrogenated polyisoprene-nylon 6 copolymer. Polybutadiene-nylon 66 copolymer, hydrogenated polybutadiene-nylon 12 copolymer, hydrogenated polybutadiene-nylon 11 copolymer, ethylene-propylene copolymer-nylon 6 copolymer, polypropylene-nylon 6 copolymer, etc. Can be mentioned.

The olefinic polymer (0) that may constitute the composition of the co-invention includes α-olefin homopolymers, 2
α = niolefin block copolymers, random copolymers, graft copolymers, block copolymers containing α-olefin as a main component and other polar vinyl monomers and diene monomers as copolymerization components, random copolymers, etc. There are polymers, graft copolymers and diene polymers.

Among these, α-olefin elastic polymers are amorphous or low-crystalline elastic polymers whose main component is α-olefin component units, and are composed only of two or more α-olefin component units. However, there is no problem even if a small amount of diene component units are contained in addition to the α-olefin component.

The content of α-olefin component units constituting the base α-olefin elastic polymer is usually 80 mol% or more, preferably 85 mol% or more, and the content of the diene component is usually 0 to 20 mol%. %, preferably in the range of 0 to 15 mol %. Other physical properties of the base α-olefin elastomer include a degree of crystallinity which is usually 20% or less, preferably in the range of 19 to 1%, and a melt flow rate [MFR19o=c] at 190°C. Usually 0.01
to 50g/I 0m1n.

It is preferably in the range of 0.05 to 20 g/lomtn, and the glass transition temperature is usually -10°C or lower, preferably -20°C or lower. Here, the constituent α-olefin component units include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-
Examples include dodecene, and diene component units include 1,4-hexadiene, dicyclopentadiene,
Examples include non-conjugated diene components such as 5-ethylidene-2-norbornene and 2,5-turbonasien, and conjugated diene components such as butadiene, isoprene and piperylene. Examples of the base α-olefin elastic polymer include ethylene-in-brepyrene copolymer, ethylene-+-butene copolymer, ethylene/4-methyl-1-pentene copolymer, and ethylene/1-hexene copolymer. ,ethylene·
1-octene copolymer, ethylene/1-decene copolymer, propylene/ethylene copolymer, propylene/1-butene copolymer, propylene/4-methyl-1-pentene copolymer, propylene-1-octene copolymers, α-olefin elastic copolymers such as propylene/1-decene copolymers, propylene/1-dodecene copolymers, ethylene/propylene/1°4-hexadiene copolymers, ethylene/propylene/di Cyclopentadiene copolymer, ethylene/propylene/5-ethylidene-2-norbornene copolymer, ethylene/propylene/2,5-norbornene copolymer, ethylene/1-butene/dicyclopentadiene copolymer, ethylene・1-butene・1,4-hexane copolymer, ethylene・1-butene・5-ethylidene-
Examples include α-olefin/non-conjugated diene elastic copolymers such as 2-norbornene copolymers.

Among these α-olefin polymers, ethylene/propylene copolymer, ethylene/1-butene copolymer, and propylene/ethylene copolymer are particularly preferably used.

In addition, a modified α-olefin polymer obtained by modifying part or all of an α-olefin elastic polymer with an unsaturated carboxylic acid or a derivative thereof can also be used as an a-olefin polymer or the α-olefin polymer as exemplified above. Can be used with olefinic polymers.

Such modified α-olefin elastomeric polymers are usually prepared by adding unsaturated carboxylic acid or its derivative component units to about 100 parts by weight of a base α-olefin elastomer containing α-olefin component units as a main component. It is graft copolymerized in a proportion of about 0.01 to about 10 parts by weight,
Further, its crystallinity is usually within a range of about 20% or less. These polymers have a melt flow rate at 190°C (M F R1q.°C) of about 0.01 to about 50
It is preferable to use a range G of 710 min,
Further, about 0.00 parts of unsaturated carboxylic acid or its derivative component is added to 100 parts by weight of the base α-olefin elastic polymer containing α-olefin component units as a main component.
05 l/l, the crystallinity is in the range of 19% or less, and 19
Melt flow rate at 0°C (M F R19
°・C] is 0.05 and 1 to 20 g/I Omin
). Furthermore, other physical properties of the modified α-olefin elastic polymer include molecular weight distribution (100 W
/flash n) is usually in the range of 1.5 to 1 to 50, preferably 2 to 50, and the glass transition temperature is usually -10°C.
The temperature is preferably below -20'C.

When the grafting ratio of the unsaturated carboxylic acid or its derivative component unit in the modified α-olefin elastomer is greater than 10 parts by weight, the degree of crosslinking of the graft modified product increases, and even when blended with polyamide, the composition The effect of improving the impact resistance of objects tends to be reduced. When the melt flow rate at 190°C of the homogeneous α-olefin elastic polymer becomes smaller than 0.01 g/10 min, the melt viscosity of the polyamide composition decreases, and
When g is larger than 710 min, the effect of improving impact resistance tends to decrease.

The α-olefin crystalline polymer, which is another example of the olefin polymer (0), is a crystalline polymer mainly composed of α-olefin component units, and includes one or more α-olefin units. It may be composed only of olefin component units, or may contain a small amount of polar vinyl monomer component units in addition to α-olefin component units. The content of α-olefin component units constituting the base α-olefin crystalline polymer is usually 60 mol% or more, preferably 70 mol% or more, and if polar vinyl monomer component units are included, the The content is usually 0 to 4
0 mol%, preferably in the range of 0 to 60 mol%. Regarding the physical properties of the α-olefin crystalline polymer, the degree of crystallinity is usually 30% or more, preferably in the range of 88 to 35%, and the melt flow rate at 190'C (M F
p190'c) is usually 0.01 to 50g/
I 0m1n, preferably 0.05 to 20 g/
The melting point is usually in the range of 60 to 3
00°C1 is preferably in the range of 8o to 280°C. Here, the constituent α-olefin component units include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, -1-octene, 1-decene, 1-dodecene. Examples of the polar vinyl monomer component unit include vinyl acetate, acrylic acid, methacrylic acid, acrylic ester, methacrylic ester, various metal salts of acrylic acid, various metal salts of methacrylic acid, etc. Examples of these α-olefin crystalline polymers include polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene/propylene copolymer, and ethylene e1-butene copolymer. Polymerization K, ethylene/1-pentene copolymer, ethylene/4-methyl-1
-Pentene copolymer, ethylene/1-octene copolymer, ethylene/1-decene copolymer, ethylene/1-dodecene copolymer, ethylene/vinyl acetate copolymer, ethylene/(methyl methanoacrylate copolymer) Coalescence, ethylene (
Examples include meth)acrylic acid copolymers and ethylene/(methanoacrylate copolymers).

Furthermore, a modified α-olefin crystalline polymer obtained by further modifying part or all of an α-olefin crystalline polymer with an unsaturated carboxylic acid or a derivative thereof is also an α-olefin polymer. It can be used as a polymer or together with the above-mentioned α-olefin crystalline polymer.

The modified α-olefin crystalline polymer is usually grafted in an amount of about 0.01 to 10 parts by weight based on 100 parts by weight of the base α-olefin crystalline polymer containing 1α-olefin component units as a main component. copolymerized, and its crystallinity is usually in the range of 30% or more, and its crystallinity is 190% or more.
Melt flow rate at °C) (M F R19o
= c) is usually about 0.91 to 50 g710 min
within the range of Furthermore, a base α-olefin crystalline polymer 1 containing α-olefin component units as a main component
0.05 to about 7 parts by weight, the degree of crystallinity is in the range of about 88 to about 55%, and the melt flow rate at 190°C [ MFR19o=c] is preferably in the range of about 0.05 to about 20 g/I Omin. Other physical properties of the modified α-olefin crystalline polymer include a molecular weight distribution (Mw/Mn) of 1.5 to 50;
In particular, it is preferably in the range of 2 to 60°C, and the melting point is usually 60 to 600°C, particularly 80 to 280°C.
Preferably, it is in the range of °C.

The modified α-olefin crystalline polymer can be obtained by reacting the base α-olefin crystalline polymer with the unsaturated carboxylic acid or its derivative described later by the method described later. The unsaturated carboxylic acid or its derivative component unit of the graft monomer component constituting the modified α-olefin elastic polymer and the modified α-olefin crystalline polymer includes, for example, acrylic acid, methacrylic acid, α-
Ethyl acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endocys-bicyclo [2°2.1
]Hept-5-ene-2,5-dicarboxylic acid (nadic acid ■), methyl-endocys-bicyclo(2,2,1)
Unsaturated dicarboxylic acids such as hept-5-ene-2,5-dicarboxylic acid (methylnadic acid [F]), acids of the unsaturated dicarboxylic acids! 1 derivatives of unsaturated dicarboxylic acids such as amide, imide, acid anhydride, and ester, specifically, maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, Examples include glycidyl maleate.

Among these, unsaturated dicarboxylic acids or their acid anhydrides are preferred, and maleic acid, nadic acid, and their acid anhydrides are particularly preferred.

The graft monomer selected from the unsaturated carboxylic acids or derivatives thereof is combined with an a-olefin elastomer or an α-
Various conventionally known methods can be employed to produce the modified α-olefin elastic polymer or modified α-olefin crystalline polymer by graft copolymerization with the olefin crystalline polymer. For example, the α-olefin crystalline polymer or the α-olefin crystalline polymer is melted and a graft monomer is added thereto for graft copolymerization, or the α-olefin crystalline polymer is dissolved in a solvent and a graft monomer is added thereto for graft copolymerization. There is a way. In any case, in order to efficiently graft copolymerize the graft monomer, it is preferable to carry out the reaction in the presence of a radical initiator. The grafting reaction is usually carried out at a temperature of 60 to 550°C. The proportion of the radical initiator used is usually in the range of about 0.01 to 20 parts by weight per 100 parts by weight of the α-olefin elastic polymer or α-olefin crystalline polymer. As the radical initiator, organic peroxides, organic bere esters, azo compounds, etc. can be used.

In the thermoplastic resin composition of the present invention, when the unmodified or modified α-olefin elastomeric polymer and the unmodified or modified α-olefin crystalline polymer are blended together, the temperature of both is 190°C. Usually the value of is 0.01
It is desirable to adjust it to a range of 100 to 100.

Other preferred examples of the olefin polymer (C) include diene polymers and hydrides thereof. Such diene polymers include, for example, 1,6-butadiene,
There are polymers obtained by polymerizing at least one type of diene monomer such as 1,5-pentadiene, chlorobrene, and isoprene, and if necessary, other copolymerized monomers such as styrene, α-methylstyrene, - or p-vinyltoluene, vinylxylene, acrylonitrile, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate,
Also included are diene polymers obtained by copolymerizing a vinyl monomer such as vinylpyridine in a proportion of about 40 mol% or less, preferably about 10 mol% or less of the constituent monomers.

Diene polymers include polymers using catalysts such as radicals, cations, anions, and coordinating anions, and can be used without particular limitation in the present invention. For example, it can be prepared by a living anion polymerization method using an initiator such as organic lithium, or by radical polymerization using a peroxide as an initiator.

In addition, linear or branched polymers are prepared by coupling the same or different living polymers together using a polyfunctional coupling agent such as methyl chloride, xylylene dibromide, terephthalic acid dichloride, silicon tetrachloride, etc. in the presence of the initiator. Although radial diene polymers are also exemplified, linear polymers are usually used.

In addition, it is desirable to use the diene polymer after hydrogenation, and it is preferable that the average degree of unsaturation is reduced to about 50% or less of the original value. % or less is preferable.

To hydrogenate the diene polymer, methods well known to those skilled in the art can be employed.

As the diene polymer segment used in the copolymer of the present invention, polymers selected from polybutadiene, polyisoprene, and hydrides thereof are particularly suitable.

The composition of the present invention contains 5 to 95 parts by weight of polyamide (A) and 0 parts by weight of olefinic polymer/polyamide copolymer (B).
．． 1 to 90 parts by weight and olefinic poly T-(0
)0 to 95 parts by weight (A) +(B)+((
total of 100 parts by weight.

Among the resin components, polyamide (for a composition containing Shu as the main component, 55 to 95 parts by weight of polyamide (A), olefin polymer/polyamide copolymer (B)
Oj to 90 parts by weight and olefinic polymer (a
) o to 45 parts by weight (approx. AJ1CB), +
(Total of 100 parts by weight of (7)) is preferred.

In a composition containing polyamide (A) as the main component among the resin components, in an embodiment in which only the copolymer (B) is blended, properties such as impact strength and elongation properties of polyamide (Shu) are improved. In an embodiment in which the olefin polymer (C) is blended with the polymer (B), polyamide (
The compatibility between A) and the olefin polymer (0) is improved, and impact strength, elongation properties, water resistance, etc. are improved.

On the other hand, among the resin components, polyamide (N5 to 45
Parts by weight, olefin polymer/polyamide copolymer (
BJO, I to 90 parts by weight and olefin polymer (0) 55 to 95 parts by weight (A) +
Particularly preferred are compositions consisting of (B) + (0) in total of 100 gw.

In a composition containing the olefin polymer (0) as a main component, the tensile strength and rigidity of the olefin polymer (0) can be improved.

In addition to the above-mentioned essential components, the thermoplastic resin composition of the present invention may optionally contain antioxidants, ultraviolet absorbers, photoprotectants,
It is also possible to incorporate phosphite stabilizers, peroxide decomposers, basic adjuvants, nucleating agents, plasticizers, lubricants, antistatic agents, flame retardants, pigments, dyes, and the like. In addition, the composition of the present invention may contain other polymers within a range that does not impair its physical properties.
For example, polyester of polyethylene terephthalate, polycarbonate, polyacetal, polysulfone,
Polyphenylene oxide, fluororesin, silicone resin, epoxy resin, etc. can also be blended.

It may be preferable to use a filler in combination with the composition of the present invention, and fillers include carbon black, carbon fiber, asbestos, glass fiber, potassium titanate whisker, ceramic fiber, mica, kaolin, talc,
Inorganic fillers such as silica and silica alumina, fluororesin fibers such as Teflon, wholly aromatic polyamide resin fibers such as Kevlar, and organic fillers such as phenol resin fibers are suitable.

When blending these fillers, the above (A) + (
B)+(a) It is preferable to blend the filler in a ratio of about 1 to about 200 parts by weight, particularly about 2 to about 150 parts by weight, relative to 00 parts by weight.

The thermoplastic resin compositions of the present invention are prepared by melt-mixing in a variety of ways. For example, two optional components may be premixed and then mixed with the remaining other components, or two essential components and other remaining components that may be added as needed may be mixed at the same time. Moreover, the above-mentioned additives, such as antioxidants, can be added at any of these stages as necessary.

The thermoplastic resin composition of the present invention can be molded into various shapes by various conventionally known melt molding methods depending on the intended use.

Examples include injection molding, extrusion molding, compression molding, foam molding, and casting molding.
Used for a wide range of applications including electrical parts and packaging materials.

Next, the present invention will be explained in more detail with reference to Examples.

In the examples, thermoplastic resin compositions and evaluations were performed in the following manner.

Molding: The dried thermoplastic resin composition is molded using a press molding machine (molding temperature: 260°C) in a nitrogen atmosphere.
+ sCmx o, o 5c1n (D and 15m x 1
5zX O, 2c11 (if) (7) Shape: iplanarchy) was produced. The thermoplastic resin composition blended with glass fiber was molded using an injection molding machine (S-35 manufactured by Toshiba Machinery Co., Ltd.).
F) was used to prepare a 2 mm thick J Engineering S2 dumbbell test piece and a notched Izot test piece under the following conditions: resin temperature 230°C, mold temperature 40°C, curing time 50 seconds (7).

Tensile test: A dumbbell test piece with a length of 5 m and a width of 0.5 m in the parallel part punched out from the sheet in (1), or a J-Ko S2 dumbbell test piece molded with an injection molding machine, was tested using an Instron tensile tester model. 1122 under the conditions of 26°C, cross rad speed of 50 mm, and 7 minutes.

Izot impact strength: (Measured at 26°C using a sample of 10 sheets or two stacked Izot test pieces molded with an injection molding machine by the method of J.K.S.K. 7NO.

Compatibility: Microtome (MT 2 manufactured by Ipansopal)
After cutting the sheet of (1) using B), the microstructure of the cross section of the sample was photographed using a scanning electron microscope (JSM-2583 manufactured by JEOL Ltd.). From this photograph, the average diameter of the olefin polymer or polyamide particles dispersed in the sample was measured.

In addition, in the Examples, the analysis of the olefin polymer/polyamide copolymer and the polyamide as its raw material was performed by the following method.

Glass transition point Tg: Measured using a dynamic mechanical analyzer (DMA) model 981 manufactured by DuPont.

Melting point Tm: Measured using a differential scanning calorimeter model DSO-2 manufactured by PerkinElmer.

Composition ratio of copolymer: Calculated by quantifying the weight of nitrogen contained in the copolymer using elemental analysis.

Molecular weight of copolymer: The copolymer was reacted with trifluoroacetic anhydride in chloroform to trifluoroacetylate, and measured by GPO using THF solvent.

Intrinsic viscosity of the copolymer was measured in m-cresol/toluene (1/1 wt ratio) solution at 2'50°C.

Molecular weight of polyamide: Calculated by quantifying the terminal amide 7 groups and carboxyl groups. The amino group makes the polyamide m-
Dissolved in cresol and used thymol blue as an indicator.
．． It was determined using a 1N p-toluenesulfonic acid m-cresol solution.

After dissolving the polyamide in benzyl alcohol, the carboxyl group was removed using phenolphthalein as an indicator.
．． It was titrated with a 1N NaOH/benzyl alcohol solution.

Example 1 (Production of olefin polymer/polyamide copolymer (B)) 400 me of toluene was charged into a three-bottle flask equipped with a condenser, a dropping funnel, and a stirrer, and hydrogenated polybutadiene (Nippon Soda Co., Ltd.) having dihydroxyl groups at both ends was charged. Co., Ltd., product name Nl5
64 g (16 mmol) mm of SO-FB, GI-3000, number average molecular weight calculated from KOH value: 4000)
did. Terephthalic acid dichloride 52.48g (+60
mmol) and piperidine 27.84 g (352 mmol)
1) was dissolved in 200+J of toluene, and the solution was added dropwise to a flask using a dropping funnel, and reacted at room temperature for 2 hours with strong stirring. Then ε-ca'prolactam was added to 3
Add 9.77 g (652 mmol) to the reaction system,
The reaction was further carried out at room temperature for 12 hours.

A purification operation was performed to remove the pyridine hydrochloride and the reaction product of terephthalic acid dichloride and ε-caprolactam contained in the reaction solution. That is, the reaction solution was filtered to remove insoluble portions, and then washed with water. Next, the polymer obtained by concentration was further dissolved in hexane, and the hexane-soluble portion was dried under reduced pressure. 18 g (4 mmol) of this product and ε-
54 g (478 mmol) of caprolactam and 4 oom6 of decalin were charged into a three-hole flask equipped with a condenser and a stirrer and stirred until uniform. Next, add 0.096 g of sodium hydride oil dispersion (Na
After that, the temperature of the reactor was raised to +50°C and the reaction was carried out for 2 hours. The produced polymer was precipitated in a large excess of acetone and thoroughly washed. The yield of crude polymer was 65%. The unreacted hydrogenated polybutadiene component and polyamide homopolymer component contained in this crude polymer were extracted with toluene and formic acid, respectively, to isolate only the copolymer. The ratio of copolymer to crude polymer was 80%.

As a result of GPO measurement, the number average molecular weight of the copolymer, M
n is 13000 in terms of hydrogenated polybutadiene, Mw/M
n (Mw; weight average molecular weight) was 1.95. As a result of investigating the composition of this copolymer by elemental analysis, the weight composition ratio of the polyamide component and hydrogenated polybutadiene component was 5.
It was 274B. The Tm of this copolymer is 211°C
1 Tg was -23°C.

(Production of thermoplastic resin composition Nylon 6 (manufactured by Toshiku Co., Ltd., cM1021XF) 154
．． 6 parts, ethylene/propylene copolymer (ethylene composition: 81+1101%, intrinsic viscosity (decalin 135°C):
After tri-blending 45.4 parts of 2j 9 aff/g) and 20 parts of the above olefin polymer/polyamide copolymer, a 20 mmφ vent type extruder (L/D
= 28, using a dalmage type screw under nitrogen atmosphere, resin temperature 220°C, 1 screw rotation speed 50
Melt blending was carried out under the conditions of rpm. Table 1 shows the results of measuring the physical properties.

Example 2 In Example 1, when producing the thermoplastic resin composition, propylene/propylene copolymer was used instead of ethylene/propylene copolymer.
Ethylene copolymer (propylene composition: 59 mo1%, intrinsic viscosity (decalin 135°C): 2.90 till/
A blend sample was prepared in the same manner as in Example 1 except that g) was used. Table 1 shows the results of measuring the physical properties.

Examples 5 to 6 When producing an olefin polymer-polyamide copolymer, the same reaction as in Example 1 was carried out by changing the charging ratio of hydrogenated polybutadiene having ε-caprolactam groups at both ends and ε-caprolactam, Copolymers having various compositions as shown in Table 1 were produced. Using these copolymers, the first
Compositions were prepared with blend ratios as shown in the table. The results of measuring physical properties are also shown in Table 1.

Example 7 (Production of olefin polymer/polyamide copolymer) Anhydrous benzene 700 was placed in a reactor equipped with a cooler and a stirrer.
mff, add 150g of isoprene and mix vigorously with S.
A hexane solution containing 0.64 g of θC-butyllithium was added dropwise, and the mixture was reacted for 5 hours at room temperature under an argon atmosphere. Next, the reactor was cooled in a water bath, 16 g of ethylene oxide was added dropwise, and the reaction was continued at 5°C for 2 hours and then at room temperature for 12 hours. The reaction solution was precipitated into a large excess of methanol,
Polyisoprene with hydroxyl groups at the ends was isolated. THF
As a result of measuring GI)O using a solvent, the number average molecular weight was approximately IC100O in terms of polyisoprene. 50 g of this polyisoprene 1 700 mL of cyclohexane 15 g of palladium on a carbon carrier (5% palladium supported) was charged into an autoclave, and heated at a hydrogen pressure of 100 kg/- for 14 hours.
The reaction was carried out at 0°C% for 4 hours. The reaction solution was passed through the mouth and washed with water, and then precipitated in methanol to obtain hydrogenated polyisoprene having hydroxyl groups at the terminals. The iodine value of this hydrogenated polyisoprene was 11.

In Example 1, the reaction was carried out under the same conditions as in Example 1, except that the thus synthesized hydrogenated polyisoprene having hydroxyl groups at the ends was used instead of hydrogenated polybutadiene Gny 3000 having hydroxyl groups at both ends. Ta. A blend sample was prepared under the same conditions as in Example 1, except that the hydrogenated polyisoprene-polyamide copolymer produced by the above method was used instead of the hydrogenated polybutadiene-polyamide copolymer in Example 1. Table 1 shows the results of measuring the physical properties.

Example 8 570 g of 6-aminocaproic acid and 60.76 g of hexamethylene diamine were introduced into a stirred reactor. The reaction mixture was heated to 200-260'C for 5 hours and then for a further 4 hours at 260'C under a vacuum of 1 mmHH to obtain a polyamide with amide 7 groups at the end with an average molecular weight of 150o. Polyamide 2 with an amino group at the end
6.3 g (+8 mmol) and hydrogenated polybutadiene having a carboxyl group at the end (manufactured by Nippon Soda Co., Ltd., trade name Nl5SO-PBO, number average molecule ffi calculated from 1000° acid value: 2300) 41.9ε (18 mm)
ol) was introduced into a stirred reactor. The reaction mixture was placed under nitrogen atmosphere and heated until the temperature reached 260°C. The mixture was then placed under high vacuum (0.7 mmHg) and the reaction continued for 7 hours with stirring. By continuing the reaction for 7 hours, a very viscous melt was produced. The melt was cooled and powdered. Unreacted hydrogenated polybutadiene and polyamide contained in this crudely produced polymer were extracted with toluene and formic acid, respectively, to isolate only the copolymerized polyamide. The ratio of the copolyamide to the crude polymer was 50%. Through elemental analysis,
As a result of examining the composition of this copolymer, the weight composition ratio of the hydrogenated polybutadiene component and the polyamide component was 60/40. Also, the intrinsic viscosity is 1, Oa#/g-melting point is 197
°C, Tg was -25°C.

Compositions having the blend ratios shown in Table 2 were prepared in the same manner as in Example 1 using the olefin polymer/polyamide copolymer produced by the above method.

The results of measuring the physical properties are shown in Table 2.

Examples 9 to 10 In Example 8, polyamides having amide 7 groups at various molecular weights were produced by changing the charging ratio of 6-aminocaproic acid and hexamethylene diamine. Using these polyamides and hydrogenated polybutadiene (ax-1000) having a carboxyl group at the terminal, the same reaction as in Example 8 was carried out to produce an olefin polymer/polyamide copolymer having the composition shown in Table 2. These copolymers were used to prepare compositions having the blend ratios shown in Table 2. The results of measuring the physical properties are also shown in Table 2G.

Example 11 Nylon 6 resin (aM1021xF) 1s 26 parts, ethylene propylene copolymer 174 parts, olefin polymer polyamide copolymer used in Example 10 150
707 parts of glass fiber (manufactured by Nitto Boseki KK, Tep Trust Strand O36PK-251) having an average length of 6 mm were melt-mixed under the same conditions as in Example 1. Table 2 shows the results of measuring the physical properties of Comparative Examples 1 to 5.
Compositions having blend ratios shown in Table 5 were prepared using propylene copolymers or propylene/ethylene copolymers. Table 5 shows the results of measuring the physical properties.

Continuation of page 1 0 shots by Takashi Nagai 2-3-19 Minamiei, Otake City 0 shots clearer Hidehiko Hashimoto Waki 2-chome, Waki-machi, Kuga-gun, Yamaro Prefecture 4 number 8 , 0 shots clear person Takayuki Nakano Misono-chome 2-3, Otake City

Claims (1)

[Claims] (1) 5 to 95 parts by weight of polyamide (A), 0.1 to 90 parts by weight of olefin polymer/polyamide copolymer (B), and 0 to 95 parts by weight of olefin polymer (0) (A) + (B) ) + (a)
A thermoplastic resin composition comprising a total of 100 parts by weight.