JPH0532902A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition having excellent impact characteristics and appearance and simultaneously reduced in coloring and free from release by blending a thermoplastic resin with an olefin-based polymer, styrene-based polymer and specific formamide group-containing copolymer. CONSTITUTION:The objective resin composition obtained by blending 100 pts.wt. total amount of (A) 5-95wt.% thermoplastic resin having a functional group capable of reacting with an amino group and (B) 95-5wt.% olefin-based polymer and/styrene-based polymer with (C) 0.05-20 pts.wt. copolymer (salt) consisting of 20-99.8mol% recurring units expressed by formula I, 50-0mol% recurring units expressed by formula II and 30-0.2mol% total amount of recurring units expressed by formula III, recurring units expressed by formula IV and formula V (R<1>, R<2>, R<5>, R<6> and R<7> are H, alkyl, aryl, etc.; R<3> and R<4> are H, halogen, etc.; R<8> is direct bond, methylene, etc.; R<9> and R<10> are H, alkyl, etc.; R<11> is alkylene, etc.; R<12> is alkyl, etc.; (n) is l-10; X<1> and X<2> are NH2 or NH-CHO) and having excellent weather resistance and solvent resistance.

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 more specifically, it is prepared by blending two or more specific thermoplastic resins with a novel formamide group-containing copolymer. The present invention relates to a thermoplastic resin composition which is excellent in both surface impact strength, Izod impact strength, appearance and hue while improving the properties.

[0002]

2. Description of the Related Art Generally, engineering plastics have mechanical properties,
Although it has excellent thermal characteristics and has made remarkable progress in recent years, it is inferior to other general-purpose resins in terms of molding processing characteristics and cost. Therefore, research has been conducted to solve these problems and to bring out the accompanying characteristics by blending or alloying an olefin resin or a styrene resin that is excellent in fluidity and is advantageous in terms of price. It is being actively conducted. However, in a simple blend, a plurality of different resins do not mix with each other, and as a result, physical properties, particularly impact properties are significantly deteriorated, causing problems such as peeling and poor appearance.

As a method for solving these problems, development of a compatibilizing agent for improving the miscibility of resins has been carried out in parallel with the improvement of the molding processing method. Examples of such techniques include a method of modifying a resin, a method of adding a copolymer, a method of reacting in an extruder with a resin having reactivity or a reactive reagent, and a method of using them in combination. There is. Specifically, for polycarbonate,
For example, as disclosed in JP-A-59-223749, a method has been proposed in which a polypropylene modified with maleic anhydride is added to improve compatibility and suppress surface peeling. However, with this method, the impact strength is remarkably reduced, the properties of the polycarbonate are lost, and the effect of suppressing peeling is not sufficient. In addition, JP-A-63-21
5714, 63-15749 and 63.
JP-A-215750 discloses a method of improving the compatibility by mixing a reactive polycarbonate modified product and a reactive polypropylene modified product with polycarbonate and polypropylene and allowing them to react with each other. However, even this method has not sufficiently solved the problems of reduction in impact strength and peeling.

Further, in JP-A-2-36248, by adding a polymer having an amino group to a blend of polycarbonate, polyamide, polyester, polyether and polyolefin, and further adding polyurethane as necessary, Attempts have been made to improve peeling and Izod impact strength. The purpose of these modifications is to skillfully combine the advantages of each other to provide new and distinctive materials. However, the miscibility is insufficient in any of the above-mentioned methods, and the problems caused by the above-mentioned blends have not yet been sufficiently solved. It is hard to say that the resin product surface is peeled off or the appearance is poor, but it is considered that the impact properties are insufficient. For example, impact characteristics are generally evaluated by the Izod impact test, but even if the Izod impact strength is large, the surface impact characteristics useful in practical use are often poor, and it is a material with truly excellent impact characteristics. Therefore, it is necessary that the Izod impact strength and the surface impact property are both excellent.

The inventors of the present invention have previously proposed a method for improving the drawbacks of the conventional known technology (Japanese Patent Application No. 3-088).
5738). That is, carbonate bond, ester bond,
By adding a polymer having an amino group having a small gel component to a blend of a resin having an amide bond or an ether bond and an olefin and / or a styrene resin,
It was proposed that the miscibility between resins is enhanced, the peeling of the surface is prevented, and a resin composition having an excellent appearance and good Izod impact strength and surface impact properties can be obtained. However, this method has a problem that the resulting composition is colored.

[0006]

DISCLOSURE OF THE INVENTION As a result of earnest studies in view of such a background, the present inventors have found that a thermoplastic resin such as engineering plastic and an olefin polymer and / or
Alternatively, by melt-kneading a styrene-based polymer and a novel copolymer having a formamide group, a resin composition which is excellent in impact properties (particularly surface impact properties) and appearance and which is less colored and does not peel off is obtained. It was found that it can be obtained. The present invention has been completed based on such findings.

That is, the present invention comprises [A] 5 to 95% by weight of a thermoplastic resin having a functional group capable of reacting with an amino group and [B] an olefin polymer and / or styrene polymer of 95 to 5% by weight. 100 parts by weight in total and [C] in the molecule, repeating unit I represented by general formula (I) I 20 to 99.8 mol%, repeating unit II represented by general formula (II) 50 to 0 mol%, general formula ( Repeating unit III represented by III), the general formula (I
The total amount of the repeating unit IV represented by V) and the repeating unit V represented by the general formula (V) is 30 to 0.2 mol% (provided that the repeating unit III is 0.2 mol% or more).

[0008]

[Chemical 4]

[0009]

[Chemical 5]

[0010]

[Chemical 6]

(Wherein R ¹ , R ² , R ⁵ , R ⁶ and R ⁷
Are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms,
C3-C8 cycloalkyl group, C6-C10 aryl group, C2-C4 alkenyl group, C1-C4
Alkoxy group, C1-18 alkoxycarbonyl group, C1-17 alkylcarboxyl group, C1-6 alkylcarbonyl group, C6-8 arylcarbonyl group, halogen atom or nitrile group R ³ and R ⁴ are each independently a hydrogen atom and a carbon number of 1 to
4 represents an alkyl group, an alkenyl group having 2 to 4 carbon atoms or a halogen atom, R ⁸ does not exist or represents a methylene group or an ethylene group, and R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a carbon number of 1 indicates 6 alkyl group or an aryl group having 6 to 8 carbon atoms, R ¹¹ is an alkylene group having 1 to 12 carbon atoms, cycloalkylene group having 5 to 17 carbon atoms,
An arylene group having 6 to 12 carbon atoms, an arylalkylene group having 7 to 12 carbon atoms or a polyoxyalkylene group having 4 to 30 carbon atoms is shown, and R ¹² is a hydrogen atom or 1 carbon atom.
10 represents an alkyl group. n shows the integer of 1-10. Note that R ^{1 to} R ¹² may be the same or different for each repeating unit. Further, X ¹ and X ² each independently represent NH ₂ or NH—CHO. The present invention provides a thermoplastic resin composition containing, as a main component, 0.05 to 20 parts by weight of a copolymer containing).

The composition of the present invention comprises [A],
It is composed of the components [B] and [C]. Here, the component [A] may have a functional group that reacts with an amino group. That is, it is considered that the formamide group contained in the component [C] causes a carbon monoxide reaction due to the heat during the melt-kneading, and the formamide-containing copolymer is changed to an amino group-containing copolymer. Therefore, any component having a functional group capable of reacting with an amino group, which is considered to be produced from the component [C], can be used as the component [A] in the present invention. Further, during melt-kneading, the component [C] becomes an amino group having high reactivity and reacts rapidly with the component [A], and thus it is considered that side reactions such as coloring are unlikely to occur. Therefore, it is considered that the coloring is less than in the case of using the (polymer) reagent having an amino group at the time of melt kneading. Specific functional groups capable of reacting with an amino group include carboxylic acids, other organic acids, their esters and salts, or groups consisting of acid anhydrides and their salts, as well as hydroxyl groups, thiols, oxazoline groups, epoxy groups and isocyanato groups. There are nate groups, amide bonds, carbonate bonds, urethane bonds, urea bonds, ether bonds, etc. Among them, the thermoplastic resin having at least one bond selected from carbonate bond, ester bond, amide bond and ether bond is preferably used as the component [A].

A typical example of the thermoplastic resin having a carbonate bond used as the component [A] is a polycarbonate resin, which may be an aliphatic or aromatic polycarbonate resin. The molecular weight is not particularly limited, but in consideration of the moldability and physical properties of the obtained composition, the number average molecular weight is 10,000 to 100,000,
It is preferably 10,000 to 40,000. The terminal group of this polycarbonate resin may be a usual monovalent phenol terminal (phenol, halogen-substituted phenol, alkyl-substituted phenol (cumylphenol, octylphenol), and various other substituted phenols). Further, a polycarbonate resin in which the above-mentioned functional group or bond reactive with an amino group is introduced in the form of graft, block, random copolymer or at the molecular end may be used. Further, an elastomer, a filler, various additives and the like may be added during or after the polymerization for the purpose of modification or reinforcement. Such a polycarbonate resin can be manufactured by various known methods. For example, various methods such as phosgene method, transesterification method, and melt polymerization method can be applied.

There are various types of the above polycarbonate resin, for example, the general formula (VI)

[0015]

[Chemical 7]

It is a polymer having a repeating unit represented by: Here, Z represents a mere bond or is an alkylene having 1 to 8 carbon atoms, an alkylidene having 2 to 8 carbon atoms, a cycloalkylene having 5 to 15 carbon atoms, a cycloalkylidene having 5 to 15 carbon atoms, SO ₂ , SO, O, CO or formula

[0017]

[Chemical 8]

It means a group represented by: Y represents a hydrogen, chlorine or bromine atom or a saturated alkyl group having 1 to 8 carbon atoms, and a and b represent a number of 0 to 4.

This polycarbonate resin is prepared by, for example, a solvent method, that is, a reaction between a dihydric phenol and a carbonate precursor such as phosgene in the presence of a known acid acceptor and a molecular weight modifier in a solvent such as methylene chloride, or a dihydric phenol. And a carbonate precursor such as diphenyl carbonate.
Here, as the dihydric phenol that can be preferably used, there are bisphenols, and 2,2-bis (4-hydroxyphenyl) propane [commonly called bisphenol A] is particularly preferable. Further, a part or all of bisphenol A may be replaced with another dihydric phenol. Examples of dihydric phenols other than bisphenol A include hydroquinone; 4,4′-dihydroxydiphenyl; bis (4-hydroxyphenyl) alkane; bis (4-hydroxyphenyl) cycloalkane; bis (4-hydroxyphenyl) sulfide; bis (4-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) sulfoxide; compounds such as bis (4-hydroxyphenyl) ether or bis (3,5-dibromo-4-hydroxyphenyl) propane; bis (3,5 -Dichloro-4
Mention may be made of halogenated bisphenols such as -hydroxyphenyl) propane. These dihydric phenols may be homopolymers of dihydric phenols or copolymers or blends of two or more. Further, the polycarbonate resin may be a thermoplastic random branched polycarbonate obtained by reacting a polyfunctional aromatic compound with a dihydric phenol and / or a carbonate precursor. As the thermoplastic resin having a carbonate bond other than the above-mentioned polycarbonate resin, there are polyarylate resin, polyester polycarbonate resin and the like, which are preferably used.

The resin used as the component [A] may be a resin having a carbonate bond, or a thermoplastic resin having an ester bond, that is, a polyester resin. The type of the polyester resin is not particularly limited, and various types can be used. Either an aliphatic or aromatic polyester resin may be used, but the latter is preferred from the viewpoint of physical properties. The molecular weight may be appropriately selected depending on the purpose of use and the like, but normally the intrinsic viscosity is 0.2 to 2.0 dl / g, preferably 0.5 to
It is 1.2 dl / g. Further, the terminal of this polyester resin may be a carboxylic acid terminal or an alcoholic hydroxyl group terminal, and the ratio thereof is not particularly limited, but it is 9/1 to 1/9.
Is preferred. Further, it may be a polyester resin in which the above-mentioned functional group or bond having reactivity with an amino group is introduced in the form of graft, block, random copolymer or at the molecular end. In addition, elastomers, fillers, various additives and the like may be added during or after the polymerization for the purpose of modification or reinforcement, and a polyester containing two or more dicarboxylic acid components within a range not impairing the physical properties. It does not matter if it is resin. Such polyester resin can be produced by various known methods, and various kinds thereof can be mentioned.

Specific examples of the polyester resin that can be used in the present invention include polyethylene terephthalate (PET) and polybutylene terephthalate (PB).
T), polycyclohexadimethylene terephthalate (P
CT), polyarylate, etc., and polyethylene terephthalate is particularly preferable. The polyethylene terephthalate may be a polyester composed of an aromatic dicarboxylic acid component containing terephthalic acid as a main component and a glycol component containing ethylene glycol as a main component, or a polyester obtained by copolymerizing another dicarboxylic acid component and a glycol component. Good.

The resin used as the component [A] may be a thermoplastic resin having an amide bond, that is, a polyamide resin. The type of this polyamide resin is not particularly limited, and various types can be used. It may be an aliphatic or aromatic polyamide resin. The molecular weight is not particularly limited, but considering the moldability and physical properties of the composition to be obtained, the number average molecular weight is 4,000 to 50,000, preferably 5,000 to 30,000. Furthermore, a functional group or a bond reactive with the above-mentioned amino group,
It may be a polyamide resin in the form of graft, block, random copolymer or introduced at the molecular end. In addition, elastomers, fillers, and various additives may be added during or after the polymerization for the purpose of modification and reinforcement. Such a polyamide resin can be manufactured by various known methods. For example, it can be produced by ring-opening (co) polymerization or (co) polycondensation of a lactam having three or more members, polymerizable ω-amino acid, dibasic acid and diamine, and more specifically, ε -(Co) polymerization of caprolactam, aminocaproic acid, 11-aminoundecanoic acid or the like, or diamines such as hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, metaxylylenediamine and terephthalic acid, isophthalic acid, (Co) polycondensation with a dicarboxylic acid such as adipic acid, sebacic acid, dodecane dibasic acid or glutaric acid may be used.

Various kinds of polyamide resins can be used as the above-mentioned polyamide resin.
Nylon 6 (Polyamide 6); Nylon 6,6; Nylon 6,10; Nylon 11; Nylon 12; Nylon 6,12; Nylon 6,6 and other aliphatic polyamides, Nylon 6/6, 6; Nylon 6/6, 10; Nylon 6
/ 6,12, etc., aliphatic copolyamides, polyhexamethylenediamine terephthalamide, polyhexamethylenediamine isophthalamide, xylene group-containing polyamides (eg, nylon-MXD (meta-xylylenediamine)) and other aromatic polyamides. . Furthermore, polyester amide, polyether amide, polyester ether amide and the like can be mentioned. Of these, nylon 6 and nylon 6,6 are particularly preferable.

The resin used as the component [A] may be a thermoplastic resin having an ether bond, that is, a polyether resin. The type of this polyether resin is not particularly limited, and various types can be used. It may be an aliphatic or aromatic polyether resin. The molecular weight is not particularly limited, but considering the moldability and physical properties of the resulting composition, the number average molecular weight is 30,000 to 300,000, preferably 50,000 to 100,000. Further, it may be a polyether resin in which the above-mentioned functional group or bond having reactivity with an amino group is introduced in the form of graft, block, random copolymer or at the molecular end. In addition, elastomers, fillers, various additives, and the like may be added during or after the polymerization for the purpose of modification or reinforcement, and may contain a copolymerization component.

As the above-mentioned polyether resin, there are various ones. For example, polyacetal containing polyoxymethylene (POM) or other polyacetal homopolymer or polyether unit component such as trioxane-ethylene oxide copolymer. Copolymer, polyphenylene ether (PPE), polyether sulfone (PES) in which ether groups and sulfone groups are mixed, polyether ketone (PEK) in which ether groups and carbonyl groups are mixed, and polyphenylene sulfide (PK) having thioether groups
It can be roughly classified into PS) and polysulfone (PSO). Among them, polyacetal (polyoxymethylene (POM)) and polyphenylene ether (PPE)
Is preferred. Here, the polyacetal homopolymer is a polymer having an oxymethylene unit as a molecular main chain, and can be produced by homopolymerizing formaldehyde or trioxane. On the other hand, the polyacetal copolymer is one in which oxyalkylene units such as oxyethylene units, oxypropylene units, and oxytetramethylene units, and oxyphenylethylene units are randomly mixed in the chain consisting of the oxymethylene units. It can be produced by copolymerizing formaldehyde or trioxane with a cyclic ether such as ethylene oxide.

In the thermoplastic resin composition of the present invention, [A]
The above-mentioned resins may be used alone or as a mixture of two or more kinds as a component. On the other hand, as the component [B], an olefin polymer, a styrene polymer or a mixture thereof may be used. Here, the olefin polymer is not particularly limited as long as it is a resin containing a polyolefin component, and various kinds can be used. As a specific polyolefin resin, polyethylene (linear low-density polyethylene (L
LDPE), low density polyethylene (LDPE), ultra low density polyethylene (VLDPE), high density polyethylene (HDPE)), polypropylene, polybutene, polyisobutene, ethylene-propylene copolymer, ethylene-propylene copolymer rubber (EPR) , Ethylene-butene copolymer (EBM), EPDM, ethylene-propylene-butene copolymer, ethylene-butylene copolymer and other ethylene-α-olefin copolymers, propylene-butene copolymer and other propylene and others Of α-olefins, and various ethylene-based copolymers (ethylene-
Vinyl acetate copolymer (EVA), ethylene-vinyl alcohol copolymer (EVOH), ethylene-maleic anhydride copolymer, ethylene-alkyl (meth) acrylate copolymer, etc.) and poly (4-methyl-1-) Penten)
Etc., or mixtures thereof. The term "copolymer" as used herein includes random, block, random block copolymer, and further graft copolymer. The molecular weight of the olefin polymer may be appropriately selected according to various situations, but the number average molecular weight is usually 0.550,000 to 300,000, preferably 10,000 to 200,000.

The styrene-based polymer as the component [B] may be of various types as long as it contains a styrene component such as styrene, α-methylstyrene and p-methylstyrene, and is not particularly limited. However, for example, general-purpose polystyrene (GPPS), high-impact polystyrene (HIP)
S), syndiotactic polystyrene (SPS), styrene-maleic acid copolymer (SMA), styrene-maleimide copolymer, rubber-reinforced SMA, MS resin, AS resin, ABS resin (high heat-resistant ABS resin, AAS resin, AE
(Including S resin) and the like, and further examples include SEBS resin, SEPS resin, SEP resin and derivatives thereof which are so-called styrene thermoplastic elastomers.
The molecular weight of the styrene-based polymer may be appropriately selected according to various situations, but the number average molecular weight is usually 20,000 to 300,000, preferably 30,000 to 200,000.

In the composition of the present invention, the ratio of the components [A] and [B] is [A]: [B] = 5 to 95: 9.
5 to 5 (% by weight), preferably 30 to 95:70 to 5
(% By weight). Here, the mixing ratio of the components [A] and [B] deviates from the above range, and if the amount of the component [A] is too large, the moldability is deteriorated. If the amount of the component [B] is too large, the mechanical strength such as rigidity is deteriorated. Inconvenience of shortage occurs.

Further, the composition of the present invention comprises the above [A],
A copolymer having a formamide group, which is the component [C], is contained together with the component [B]. This formamide group-containing copolymer has the repeating unit I represented by the general formula (I):
Repeating unit II represented by general formula (II), repeating unit III represented by general formula (III), repeating unit IV represented by general formula (IV)
And a novel copolymer having a repeating unit V represented by the general formula (V) (however, for repeating units II, IV and V,
Not required. ) Is a random, block or graft copolymer of these repeating units. As described above, the content ratio of each repeating unit in this copolymer is 2 to 99.8 mol% of repeating unit I, preferably to the total amount of repeating units I, II, III, IV and V. Is 60.0
99.5 mol%, repeating unit II 5 to 0.0 mol%, preferably 40.0 to 0.0 mol%, repeating unit III, repeating unit IV
And the total amount of the repeating unit V is 30 to 0.2 mol% (however, the repeating unit III is 0.2 mol% or more.
And V may be zero. ), Preferably III.
0-0.5 mol%, IV 19.5-0.0 mol%, V 19.5
~ 0.0 mol%. Here, if the content ratio of the total amount of repeating units III, IV, and V is less than 0.2 mol%, the addition effect is not exhibited, while if it exceeds 30 mol%, the dispersion of the component [C] becomes poor. As a result, the physical properties of the resulting composition, particularly the surface impact strength, deteriorate. The formamide group-containing copolymer as the component [C] basically comprises the above repeating units I to V, but it may contain a small amount of other repeating units.

The component (C) is not particularly limited in its molecular weight, but usually has a viscosity average molecular weight of 3,000 to 3,000.
It is 500,000. This was obtained by dissolving the amino group-containing copolymer at 10% by weight in a good solvent such as toluene, xylene, cumene, tetralin, 1,3-dimethyl-2-imidazolidinone, dimethylsulfoxide, acetone, and methylethylketone. This corresponds to a viscosity in the range of 10 to 50,000 cps. The copolymer as the component [C] is characterized in that it has a formamide group on the side chain of the repeating unit III through an imide group. Further, this copolymer has a formamide group of sulfuric acid, benzenesulfonic acid,
Form salts by combining with sulfonic acids such as toluene sulfonic acid and naphthalene sulfonic acid, halogeno acids such as hydrochloric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, nitric acid, boric acid, phosphoric acid, etc. Also includes those that have been done.

The repeating unit I is represented by the general formula (I).
R in the formula¹And R ²Each independently (
Mari, R¹And R²May be the same or different)
Child, an alkyl group having 1 to 10 carbon atoms (preferably 1 carbon atom)
~ 4 alkyl group), C3-8 cycloalkyl group
(Preferably a cycloalkyl group having 3 to 6 carbon atoms), carbon
An aryl group having 6 to 10 carbon atoms (preferably an aryl group having 6 to 9 carbon atoms)
Reel group), C2-C4 alkenyl group, C1-C1
4 alkoxy groups, C1-C18 alkoxycarbo
Nyl group (preferably an alkoxycarbonyl group having 1 to 8 carbon atoms)
Group), an alkylcarboxyl group having 1 to 17 carbon atoms (preferred
More preferably, an alkylcarboxyl group having 1 to 3 carbon atoms), charcoal
Alkyl or arylcarbonyl groups of prime number 1 to 6 (preferred
More preferably, an alkylcarbonyl group having 1 to 4 carbon atoms), carbon
Number 6 to 8 alkyl carboxyl group, halogen atom (preferred
It preferably represents chlorine, bromine) or a nitrile group. Na
Oh, R ¹And R²Are the same for each repeating unit
Or it may be different. That is, the above general formula (I) is
One of the return units I is ethylene unit (R¹And R²Together with water
And another one of the repeating units I is propylene unit
Rank (R¹Is hydrogen, R²Is also a methyl group)
To do.

The repeating unit II is represented by the general formula (II).
However, in the formula, R³And R ^FourAre each independently hydrogen
Atoms, alkyl groups having 1 to 4 carbon atoms (methyl group, ethyl group
Etc.), alkenyl groups having 2 to 4 carbon atoms (vinyl group, allyl)
Group) or halogen atom (chlorine, bromine, etc.).
In addition, R³And R^FourAre the same for each repeating unit
It may or may not be the same as the above R¹And R²of
It is similar to the case. In addition, repeating units III, IV, V
Which are represented by the general formulas (III), (IV) and (V) respectively.
Yes, here R^Five~ R⁷Is the R¹, R²As well as each
Each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (preferably
Or an alkyl group having 1 to 4 carbon atoms) or an alkyl group having 2 to 4 carbon atoms.
Lucenyl group (vinyl group, allyl group, etc.), C3-8
Cycloalkyl group (preferably cycloalkyl having 3 to 6 carbon atoms)
Alkyl group), an aryl group having 6 to 10 carbon atoms (preferably
An aryl group having 6 to 9 carbon atoms), an alkoxy group having 1 to 4 carbon atoms
Si group, an alkoxycarbonyl group having 1 to 18 carbon atoms (preferably
Or C1-8 alkoxycarbonyl group), carbon
Number 1 to 17 alkylcarboxyl group (preferably carbon
C1-C6 alkyl carboxyl group), C1-C6
Alkylcarbonyl group, arylcarbo having 6 to 8 carbon atoms
Nyl group (preferably alkylcarbonyl having 1 to 4 carbon atoms)
Group), a halogen atom (preferably chlorine, bromine) or
Indicates a nitrile group. Also, R⁸Does not exist (ie simple
Or a methylene group or an ethylene group
Show, R⁹And R^TenAre each independently a hydrogen atom and 1 to 1 carbon atoms.
An alkyl group of 6 (preferably an alkyl group having 1 to 2 carbon atoms)
Group) or an aryl group having 6 to 8 carbon atoms, R¹¹Is
An alkylene group having 1 to 12 carbon atoms (preferably methylene,
Ethylene, propylene, tetramethylene, hexamethylene
Alkylene groups having 1 to 8 carbon atoms such as benzene, and 5 to 17 carbon atoms
A cycloalkylene group of (preferably cyclohexylene,
C6-10 carbon atoms such as methylenecyclohexylmethylene
Cycloalkylene group), an arylene group having 6 to 12 carbon atoms
(Preferably phenylene, oxydiphenylene, etc.), charcoal
An arylalkylene group having a prime number of 7 to 12 (preferably xyloxy)
Arylalkylene group having 8 to 10 carbon atoms such as rylene)
Rui is a polyoxyalkylene group having 4 to 30 carbon atoms (poly
C4-C1 such as oxmethylene and polyoxypropylene
5 polyoxyalkylene group), R¹²Is a hydrogen atom
Alternatively, an alkyl group having 1 to 10 carbon atoms (preferably carbon
The alkyl groups of the numbers 1 to 8 are shown. These R^Five~ R
¹²Are the same or different in each repeating unit
Also, the above R ¹And R²As in
It In addition, n is an integer of 1 to 10 (preferably 1 to 3)
Show. Here, when n is multiple, that is, 2 or more, the number of n
Each R that exists only⁹, R^Ten, R¹¹Are the same but different
It may be one. Also, X in the repeating unit V¹And X²Is
Both are NH₂And / or NH-CHO.

No particular limitation is imposed on the production of the copolymer as the component [C] of the present invention, and various methods can be used. However, according to the following methods (a) and (b), further It can be manufactured efficiently. That is, the repeating unit I represented by the general formula (I) is 20 to 99.8 mol%, the repeating unit II represented by the general formula (II) is 50 to 0.0 mol% and the compound is represented by the general formula (VII). Repeating unit VII 30-0.2 mol%

[0034]

[Chemical 9]

[In the formula, R ^{5 to} R ¹⁰ , R ¹² and n are the same as defined above. To the copolymer containing the following general formula (VIII) H ₂ N—R ¹¹ —NH ₂ ... (VIII) [wherein, R ¹¹ is the same as defined above]. ] The salt of the diamine represented by the following is reacted in the presence of formamides, and then contacted with a base for deoxidation, whereby efficient production can be carried out (method (a)). In the molecule, the repeating unit I represented by the general formula (I) is represented by I20 to 99.8 mol%, the repeating unit II represented by the general formula (II) is 50 to 0 mol%, and the repeating unit II is represented by the general formula (VII). A reaction product obtained by reacting a copolymer containing 30 to 0.2 mol% of a repeating unit VII, a diamine represented by the general formula (VIII), and one selected from formyl group-containing compounds, The reaction can also efficiently produce a copolymer containing a formamide group as the component [C] (method (b)).

First, a copolymer containing repeating units I, II and VII, which are raw materials for producing the formamide group-containing copolymer, is represented by the general formulas (I), (II) and (VII). It is produced by radical polymerization or ionic polymerization of a monomer giving the repeating unit. There are various specific examples of the monomer that gives the repeating unit I of the general formula (I). For example, ethylene,
Olefin such as propylene, 1-butene, 1-octene and isobutylene, cyclic olefin such as cyclopentene, cyclohexene and cyclooctene, styrenes such as styrene, α-methylstyrene, vinyltoluene and pt-butylstyrene (aromatic vinyl Compound), vinyl acetate,
Vinyl butyrate, vinyl stearate, and other vinyl esters, methyl vinyl ether, ethyl vinyl ether, and other vinyl ethers, vinyl chloride, vinylidene chloride, and other halogenoolefins, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, Hexyl (meth) acrylate, cyclohexyl (meth) acrylate, decyl (meth) acrylate,
There are acrylic acid or methacrylic acid esters such as octadecyl (meth) acrylate and methoxyethyl (meth) acrylate, nitriles such as acrylonitrile and methacrylonitrile, and vinyl ketones such as methyl vinyl ketone and phenyl vinyl ketone. Or two or more kinds can be used in combination. Among these, examples of preferable monomers include ethylene, propylene, styrene, methyl vinyl ether, isobutylene, vinyl acetate, and (meth) acrylic acid esters.

Specific examples of the monomer providing the repeating unit II of the general formula (II) include conjugated dienes such as butadiene, isoprene and chloroprene, which can be used alone or in combination of two or more kinds. Preferred monomers include butadiene and isoprene. The repeating unit VII of the general formula (VII) is obtained by copolymerizing the monomer giving the repeating unit I and the monomer giving the repeating unit II by a known method,
Using a known peroxide or initiator, maleic anhydride, methyl maleic anhydride, 1,2-dimethyl maleic acid, ethyl maleic anhydride, phenyl maleic anhydride,
It can be formed by grafting an unsaturated dicarboxylic acid anhydride such as itaconic anhydride. The preferred grafting monomer is maleic anhydride. here,
The grafting reaction proceeds by attaching a grafting monomer such as maleic anhydride to the portion of repeating unit I or II. As the raw material copolymer containing the repeating unit VII used in the present invention, a commercially available polymer grafted with the above unsaturated dicarboxylic acid anhydride (maleic acid-modified EPR, maleic acid-modified SEBS, etc.) is used. It is also possible to apply.

From the above, the copolymers containing the repeating units I, II and VII, which are the raw materials of the method of the present invention, will be exemplified.
Polyethylene, polypropylene, polyisoprene and its hydrogenated product, polybutadiene and its hydrogenated product, chloroprene rubber and its hydrogenated product, nitrile rubber and its hydrogenated product, ethylene-propylene copolymer, ethylene- (meth) acrylic acid ester Copolymer, styrene-isoprene copolymer and hydrogenated product thereof, styrene-
Polymers or copolymers such as butadiene copolymer and hydrogenated products thereof (note that in the case of the copolymer, it may be a random copolymer, a block copolymer, or an alternating copolymer) And a copolymer obtained by graft-reacting an anhydride of an unsaturated dicarboxylic acid such as maleic anhydride, methylmaleic anhydride, ethylmaleic anhydride, and itaconic anhydride. However, it should not be limited to these examples.

Further, according to the above method (a), the copolymer containing the repeating units I, II and VII produced as described above is treated with at least one selected from formamide, formic acid and derivatives thereof. The compound is reacted with a salt of a primary diamine represented by the general formula (VIII) in the presence of some formyl group-containing compound. The formyl group-containing compound used here is
As described above, formamide, formic acid or their derivatives, which are commercially available, can be used. As the derivative of this formamide, N-methylformamide; N-
Ethylformamide; N-butylformamide; N, N
-Dimethylformamide; N, N-diethylformamide; N-methylformanilide; nitrogen-substituted formamide such as N-ethylformanilide. Examples of formic acid derivatives include formic acid esters such as methyl formate, ethyl formate, propyl formate and butyl formate, and salts of formic acid such as sodium formate, potassium formate and ammonium formate. These formamides act not only as a solvent but also as a reaction reagent.

Specific examples of the diamine represented by the general formula (VIII) include ethylenediamine; 1,3-diaminopropane; 1,4-diaminobutane; 1,5-diaminopentane; hexamethylenediamine; 7-diaminoheptane; 1,8-diaminooctane; 1,9-diaminononane; 1,10-diaminodecane; 2,2,5-
Trimethylhexanediamine; linear or branched aliphatic alkylenediamines such as 2,2,4-trimethylhexanediamine, isophoronediamine; 1,3-bis (aminomethyl) cyclohexane; bis (4-aminocyclohexyl) methane; Bisaminomethylhexahydro-
4,7-Methaneindane; 1,4-Cyclohexanediamine; 1,3-Cyclohexanediamine; 2-Methylcyclohexanediamine; 4-Methylcyclohexanediamine; Fats such as bis (4-amino-3,5-dimethylcyclohexyl) methane Examples thereof include cyclic diamines, m-xylylenediamine; arylalkyldiamines such as p-xylylenediamine, polyoxypropylenediamine; and polyoxyalkylenediamines such as polyoxyethylenediamine. Of these, particularly preferred are aliphatic and alicyclic diamines. This diamine may be either a partially neutralized salt (mono salt) or a completely neutralized salt (di salt), but a method using a partially neutralized salt is preferable because of high reaction efficiency. The diamine is preferably used as a partially neutralized salt of an acid, and it is desirable to select such an acid having an acid strength larger than that of the carboxylic acid. Specific examples include sulfonic acids such as sulfuric acid, benzene sulfonic acid, toluene sulfonic acid, and naphthalene sulfonic acid, halogeno acids such as hydrochloric acid, hydrofluoric acid, hydrobromic acid, and hydroiodic acid, nitric acid, boric acid. , Phosphoric acid, etc. Of these, hydrochloric acid and toluenesulfonic acid are preferable.

In preparing the salt of the diamine, the molar ratio of the diamine to the acid is in the form of a salt corresponding to a degree of neutralization of 50 to 100% in terms of acid equivalent based on the total amino groups of the diamine. Used. If it is less than 50%, crosslinking and gelation cannot be avoided during the imidization reaction. On the other hand, if it exceeds 100%, the imidization reaction takes a long time, which is economically disadvantageous. The preferred range is 50-80%. The diamine salt can be easily prepared by a neutralization reaction between the corresponding diamine and the corresponding acid. For example, a diamine may be added dropwise to an alcohol solution of an acid, and if necessary, concentrated and recrystallized with alcohol to be isolated and used as a raw material.
Formyl group-containing compound or 1,3-dimethyl-2-imidazolidinone (DMI) which is an essential component of the present invention;
N-methyl-2-pyrrolidone; dimethyl sulfoxide (DMSO); dimethyl sulfone; dioxane; 1,2
-Dimethoxyethane; Hexamethylenephosphoric acid-triamide; Partially neutralized salt of diamine and acid may be formed in an aprotic polar solvent such as tetramethylurea and used for the reaction as it is. In terms of operation, it is more efficient and preferable to form a salt in the formyl group-containing compound and use it in the reaction as it is. In the method (a), the reaction product obtained as described above may then be brought into contact with a base to deoxidize it.

Another method that can be provided to obtain the copolymer of the component (C) is to react the reaction product obtained by reacting the diamine represented by the general formula (VIII) with the above-mentioned formyl group-containing compound. Used as a reagent, the repeating unit I, I
A method (b) in which the copolymer containing I and VII is imidized or simultaneously amidated is mentioned. This reaction reagent is 1 mole or more per 1 mole of the formyl group-containing compound,
Preferably 1.5 to 5 times as much diamine is distilled off at 60 to 180 ° C., more preferably 80 to 150 ° C. while distilling off water for formic acid and ammonia or amine for formamides for 2 to 5 hours. Or transamidation reaction is performed. Although it is possible to use this reaction product as it is as the next imidization or amidation reagent,
The reaction mixture usually contains unreacted diamine, and if used in the next imidization reaction as it is, it causes crosslinking and gelation, so the reaction mixture is heated under reduced pressure to distill off the unreacted diamine. , Or in the case of high boiling diamine,
It is preferable to use it after neutralizing once with hydrochloric acid or the like and removing it as a dihydrochloride of diamine by recrystallization.

The methods (a) and (b) are the same as those of the copolymers containing the above repeating units I, II and VII and having the general formula (VIII)
The reaction proceeds with a salt of a diamine represented by the formula (1) in the presence of a formyl group-containing compound, or by reacting the copolymer with a reaction product of a diamine and a formyl group-containing compound. Here, the imidization reaction can also be performed in a solventless molten state using a screw extruder or the like. In this case, in order to make the reaction uniform, it is desirable to use an inert solvent in addition to the formyl group-containing compound essential for the present invention. Solvents usable for such purpose include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, cymene, ethyltoluene, propylbenzene and diethylbenzene, methylcyclopentane, cyclohexane, ethylcyclopentane, methylcyclohexane, 1, Alicyclic hydrocarbons such as 1-dimethylcyclohexane and ethylcyclohexane, aliphatic hydrocarbons such as hexane, heptane, octane, decane, methylheptane, 3-ethylhexane and trimethylpentane, DMI,
Tetramethylurea, dimethyl sulfone, dioxane,
Aprotic polar solvents such as 1,2-dimethoxyethane, hexamethylenephosphoric triamide, DMSO and N-methyl-2-pyrrolidone can be mentioned. This method (a),
In (b), since reaction substrates having considerably different polarities are reacted with each other, it is generally preferable to use a nonpolar solvent and a polar solvent at the same time.

The amount of the above-mentioned solvent to be used is not particularly limited and may be appropriately selected depending on the situation, but it is usually a copolymer containing repeating units I, II and VII (ie, substituted or non-substituted) used as a raw material. It may be determined in a weight ratio of 0.3 to 20 times, preferably 1 to 10 times that of the polyfunctional copolymer having substituted succinic anhydride as a functional group. If the amount is less than 0.3 times, the dilution effect may not be sufficient, and the reaction mixture may have a high viscosity and may be difficult. On the other hand, if the amount is more than 20 times, the effect corresponding to the amount used is not particularly improved, which is economically disadvantageous.

The ratio of the reaction solvent and the formyl group-containing compound for the above dilution (reaction solvent / formyl group-containing compound) is 40/60 to 100/0 on a weight basis (100/0 is the case of the method (b)). ), Preferably from 50/50.
It is 95/5. When the reaction product of the diamine and the formyl group-containing compound is used as the substrate for the imidization and amidation reaction in the production of the copolymer of the component [C], it is not always necessary to use the formyl group-containing compound as the solvent. However, in other cases (that is, in method (a)), it is essential (however, not as a solvent but as a reaction substrate), and is used in the form of a mixed solvent with an inert solvent for dilution. As for the ratio, when the ratio of the formyl group-containing compound is increased according to the ratio of the functional groups of the raw materials used, the solubility of the substrate is better and the reaction rate tends to be higher. Method (a) above,
The imidization reaction and amidation reaction in (b) do not require a catalyst, but when used, they are trimethylamine, triethylamine, tributylamine, N, N-
Dimethylaniline, N, N-diethylaniline, 1,8
-Tertiary amines such as diazabicyclo (5.4.0) undecene-7 are preferred.

In the method of the present invention, the use ratio of the raw material copolymer, the diamine or its salt, and the formyl group-containing compound varies depending on the type and the situation of the raw material used and cannot be uniquely determined. Is a substituted or unsubstituted succinic anhydride group (that is, repeating unit VI
I) 1.0 to 10 times, preferably 1.05 times, based on the unneutralized amino group or unreacted amino group of the diamine, relative to 1 mol.
~ 5.0 times. If it is less than 1.0 times, there will be succinic anhydride groups that remain without being imidized or amidated even after the completion of the reaction, and in the method (a), the primary amino acid regenerated in the deoxidation step. There is a possibility that a group reacts with the succinic anhydride group to cause gelation due to amide cross-linking, thereby overturning the effect of the present invention. On the other hand, when the molar ratio exceeds 10 times,
Although the imidization or amidation reaction itself has the advantage of proceeding rapidly, it is unavoidable from the economic disadvantage of requiring a large amount of reaction reagents.

The reaction temperature and the reaction time in the above methods (a) and (b) vary depending on the solvent used and the presence or absence of a catalyst, but are usually 100 to 250 ° C., preferably 110 to 10.
It is 1 to 20 hours at 200 degreeC. If the reaction temperature is less than 100 ° C, there is a disadvantage that the reaction takes a long time, and if it exceeds 250 ° C, the reaction product may be colored and the introduced formamide group may be thermally decomposed.

Therefore, when the above reaction is carried out without a catalyst, the reaction is carried out at a relatively low temperature, or when the molar ratio of the reaction reagent to the raw material copolymer is small, the general formula (III ) And (IV), i.e. the production of repeating units III and IV is high and the production of formula (V), i.e. repeating unit V, is substantially negligible or very small. On the contrary, the production ratio of the repeating unit V tends to increase under the conditions of using the catalyst, or under the conditions of high temperature or high reaction reagent molar ratio to the raw material copolymer. Regarding the ratio of formamide group to amino group, when a reaction product of a diamine and a formyl group-containing compound is used as an imidizing or amidating reagent,
A copolymer of substantially 100% formamide group is obtained, and when a salt of diamine is used, a copolymer in which formamide group and amino group are mixed is obtained, and the ratio is such that the reaction temperature is higher and the reaction time is longer. The higher the rate, the higher the production rate of formamide groups.

Thus, under the above reaction conditions, the ratio of ((III) + (IV)) / (V) is 100/0 to 30.
/ 70, the ratio of formamide group / amino group is 100/0
˜30 / 70 copolymer is obtained. The above composition of the copolymer which is the [C] component of the present invention has, for example, a chemical shift of 176 to 180 pp obtained by measuring a nuclear magnetic resonance ( ¹³ C-NMR) spectrum using isotope carbon.
Carbonyl carbon (W) of the imide ring appearing near m, 17
It can be known from the peak intensity ratio of the amide carbonyl carbon (Y) appearing around 2 to 174 ppm and the formamide group carbonyl carbon (Z) appearing near 162 ppm.

In the method (a), the order of charging the reaction raw materials is not particularly limited, and the reaction raw materials can be carried out in various modes. Usually, the formyl group-containing compound (or a compound obtained by dissolving the compound in another solvent) is used. In (), the powder or solution of the diamine and acid salt is added and dissolved, and then the copolymer containing repeating units I, II and VII is gradually added, or vice versa. The charging during this period may be carried out under heating of the solvent (or the compound containing a formyl group) under reflux. Also, in the method (b), the order of charging the reaction raw materials is not particularly limited, and the reaction raw materials can be carried out in various modes. Usually, a copolymer containing repeating units I, II and VII is used as a solvent. After uniform dissolution, the reaction product obtained by reacting the diamine and the formyl group-containing compound is gradually added, or the reverse order is taken. The charging during this period may be performed under heating with reflux of the solvent. Since the imidation or amidation reaction of the raw material copolymer and the salt of diamine and the formyl group-containing compound, or the reaction product of the diamine and the formyl group-containing compound proceeds while generating water, the generated water is It will azeotrope with the solvent used. Therefore, the reaction can be efficiently progressed by removing the azeotropic water from the reaction system by means of a Dean-Stark water diverter or the like.
Completion of the imidization or amidation reaction means that azeotropic water is no longer observed, and that the absorption intensity of carbonyl of imide around 1700 cm ^-1 is no longer found by measuring the infrared absorption spectrum of a part of the reaction mixture. It can be confirmed by the fact that it is no longer accepted.

The reaction mixture thus obtained contains a salt of the copolymer which is the component [C] of the present invention in which the formamide group and the primary amino group are bound via an imide bond or an amide bond. This reaction mixture as it is or after being thrown into a non-solvent such as methanol, isopropanol, isobutanol, hexane, or water as necessary to pulverize it, an aqueous solution of a base, or a methanol / water mixed solution of a base as required. It can be deoxidized by contact with and converted into a free amine. Specific examples of the base used for deoxidation include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate,
Any water-soluble base such as sodium bicarbonate, potassium bicarbonate, ammonia, methylamine, ethylamine, trimethylamine, triethylamine may be used. Of these, sodium hydroxide, sodium carbonate, and sodium bicarbonate are preferable for economic reasons. According to the method (b), since the salt of the copolymer is not formed, the deoxidation step as described above is unnecessary. Purification of a copolymer containing only formamide groups can be easily carried out by adding the reaction mixture to the above-mentioned methanol, isopropanol, isobutanol, hexane, water, etc. and recovering the obtained precipitate as a powder.

The resin composition of the present invention comprises the component [A],
The main component is the component [B] and the component [C], and the proportion thereof is 5 to 95% by weight of the component [A] with respect to the total amount of the components [A] and [B]. Preferably 3
0 to 95% by weight, and the component [B] is 95 to 5% by weight, preferably 70 to 5% by weight. If the ratio of the components [A] and [B] is out of the above range, there are disadvantages that the moldability is deteriorated and the mechanical strength such as rigidity is lowered. The component [C] is selected in the range of 0.05 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total amount of the components [A] and [B]. If the blending ratio of the component [C] is less than 0.05 part by weight, the effect of improving various physical properties such as surface impact strength of the resulting composition is not sufficient,
Further, even if it exceeds 20 parts by weight, the effect corresponding to the blending amount is not improved, which is economically disadvantageous and the balance of physical properties is deteriorated.

The resin composition of the present invention comprises the above [A],
It is mainly composed of the components [B] and [C], but may further contain other additives (reinforcing agents such as glass fiber and carbon fiber, inorganic fillers, heat stabilizers, antioxidants, etc.) as required. Agents, light stabilizers, flame retardants, weathering agents, plasticizers, antistatic agents, release agents, foaming agents, etc.) can also be added. In preparing the resin composition of the present invention, the above-mentioned components are added to a single screw extruder, a twin screw extruder, a Banbury mixer,
A kneading machine such as a kneading roll, a Brabender, a kneader, or a mixer such as a Henschel mixer may be used and kneading may be performed in a heating and melting state. Further, in this case, the kneading order is not particularly limited and may be appropriately performed. The kneading temperature differs depending on the types of components used, the amount to be mixed, the physical properties of the composition to be produced, and the like, and cannot be uniquely determined, but it is usually 180 to 340.
It may be selected in the range of ° C. In order to prepare the resin composition of the present invention, the components [A], [B] and [C] may be appropriately combined and kneaded, but when the compatibility between the components is taken into consideration, for example, [B] When the component is an olefin polymer, the [C] component is also preferably an olefin formamide group-containing compound (for example, a formamide group-containing compound of an ethylene / ethyl acrylate / maleic anhydride copolymer), and [B] When the component] is a styrene-based polymer, the component [C] is also preferably a styrene-based formamide group-containing compound (for example, a formamide group-containing compound of a styrene / maleic anhydride copolymer).

[0054]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. Reference Example 1 (Preparation of partially neutralized p-toluenesulfonic acid salt of ethylenediamine) A flask having an internal volume of 1 liter equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser was charged with 30 parts of methanol.
0 ml and p-toluenesulfonic acid monohydrate 9
5 g (0.5 mol) was charged and dissolved. While cooling in an ice bath, a solution prepared by dissolving 150 g (2.5 mol) of ethylenediamine in 300 ml of methanol was heated at a temperature of 10 to 2
The solution was added dropwise at such a rate that 0 ° C was maintained. After the dropping, 70 ℃
The mixture was heated to 1, then depressurized to remove methanol and unreacted ethylenedimiane, and 132.7 g of a white solid was deposited. The obtained white solid was taken out, made into a slurry with 300 ml of toluene, filtered, and further washed twice with 100 ml of toluene, and the obtained white powder was dried under reduced pressure. The yield was 109.8g.
The neutralization equivalent of this white powder was measured by titration with 0.5N hydrochloric acid using bromophenol blue as an indicator. Table 1 shows the measured value of the neutralization equivalent and the degree of neutralization.

Reference Example 2 (Preparation of partially neutralized hydrochloric acid salt of ethylenediamine) Reference Example 1
A white powder of ethylenediamine monohydrochloride was obtained by the same procedure as in Reference Example 1, except that the same reaction vessel as in Example 1 was used and p-toluenesulfonic acid was replaced with a 35% aqueous hydrochloric acid solution.
Table 1 shows the measured value of the neutralization equivalent and the degree of neutralization.

Reference Example 3 (Preparation of partially neutralized p-toluenesulfonic acid salt of hexamethylenediamine) 95 g (0.5 mol) of p-toluenesulfonic acid monohydrate was dissolved in 500 ml of DMF at room temperature. Next, 52.2 g of hexamethylenediamine (0.
45 mol) was gradually added and dissolved at a rate such that the temperature of the contents did not exceed 20 ° C. to prepare a DMF solution of a partially neutralized p-toluenesulfonic acid neutral salt of hexamethylenediamine. Table 1 shows the measured value of the neutralization equivalent per solid content and the value of the degree of neutralization.

Reference Examples 4 and 5 In the same manner as in Reference Example 3, p-toluenesulfonic acid salts of 1,3-bis (aminomethyl) cyclohexanediamine and m-xylylenediamine were prepared. The measured value of the neutralization equivalent and the value of the degree of neutralization obtained are shown in Table 1.

Reference Example 6 (Preparation of Reaction Product of Ethylenediamine and Formamide) 300 g of ethylenediamine (in the same reaction vessel as in Reference Example 1)
5.0 mol) and then 45 g of formamide (1.0
Mol) was gradually added dropwise at room temperature. After finishing the dropping, heat to 80
Reacted at ~ 120 ° C for 5 hours. During this period, generation of ammonia gas was observed. After the reaction, 61 ℃ / 88mmHg
Then, unreacted ethylenediamine was distilled off to obtain a residue.
The neutralization equivalents of this residue measured by neutralization titration are shown in Table 1.

Reference Example 7 (Preparation of Reaction Product of Hexamethylenediamine and DMF) In the same manner as in Reference Example 6, hexamethylenediamine and DMF.
Was reacted. The reaction mixture was mixed with ethanol / water (volume ratio 7
/ 3), neutralized with 35% hydrochloric acid, concentrated and recrystallized. Hexamethylenediamine hydrochloride was precipitated as needle crystals, which were removed by filtration and the filtrate was concentrated. Table 1 shows the neutralization equivalents of the concentrated residue by potentiometric titration.

Reference Example 8 In the same manner as in Reference Example 7, 1,3-bis (aminomethyl) cyclohexanediamine was reacted with DMF to obtain the reaction product. Table 1 shows the neutralization equivalents of the concentrated residue by potentiometric titration.

Reference Example 9 272 g (2.0 mol) of m-xylylenediamine and formic acid 2
3 g (0.5 mol) was reacted at 120 ° C. for 10 hours while distilling off water with a Dean-Stark water divider. The reaction product was treated in the same manner as in Reference Example 7 to obtain a reaction product of m-xylylenediamine and formic acid. The neutralization equivalents by potentiometric titration are shown in Table 1.

[0062]

[Table 1]

Reference Example 10 Preparation of Maleic Acid Grafted Polypropylene (Maleic Acid Modified Product: Male Modification-1) It was produced by referring to the method described in JP-B-56-9925. 100 parts by weight of a crystalline polypropylene powder having a weight average molecular weight (Mw) of 60000 and a number average molecular weight (Mn) of 24000 (unmodified: unmodified-1), 12 parts by weight of maleic anhydride and 4 parts by weight of dicumyl peroxide. Mix in advance, set the extruder with a screw diameter of 30 mm and L / D = 28 to a barrel temperature of 230 ° C., and rotate the screw at a speed of 60.
Extrusion reaction was carried out at rpm, and the extruded graft product was crushed and then immersed in acetone to extract and remove unreacted maleic anhydride, followed by drying to obtain a maleic anhydride grafted polypropylene resin (Mahen-1). . The amount of maleic anhydride grafted on this product was 4.5% by weight, and the molecular weight by gel permeation chromatography (GPC) was Mw = 15000 and Mn = 6500 in terms of polystyrene.

Reference Example 11 By the same method as in Reference Example 10, maleic anhydride graft copolymers (Mahen-2) to (Mahen-10) shown in Table 2 were obtained.

[0065]

[Table 2]

Reference Example 12 Preparation of Formamide Group-Containing Copolymer (Containing E-1) Xylene 6 was placed in a flask having an internal volume of 1 liter equipped with a thermometer, a stirrer, a dropping funnel, and a Dean-Stark water separator.
00 ml and 120 g of maleic anhydride-grafted polypropylene (Mahen-1) produced in Reference Example 10 were charged and heated, and dissolved at 140 ° C. under reflux of xylene. Next, 17.8 g of p-toluenesulfonate of ethylenediamine prepared in Reference Example 1 was added to this flask as DM.
What was melt | dissolved in F200 ml was dripped gradually over 3 hours. During this period, the reaction mixture was kept at the reflux temperature of xylene, and as a result of the imidization reaction, azeotropic water was removed out of the reaction system by a Dean-Stark water separator. After the reaction was continued for 14 hours from the start of the dropwise addition of the ethylenediamine salt, the mixture was cooled and the reaction mixture was put into 5 liters of methanol to collect the product as a precipitate. The precipitate was dissolved in toluene under heating, it was measured infrared absorption (IR) spectrum to prepare a toluene cast film, absorption based on imide ring 1768,1700cm ^-1, 1660cm ^-1 (shoulder), 1530 cm ^{- In} addition to the absorption of formamide group in ¹ , 1122, 1035, 1
Absorption based on p-toluenesulfonic acid was observed at 010,685,570 cm ^-1 , and the formamide group or the primary amino group was bonded to polypropylene through an imide bond in the form of p-toluenesulfonic acid. Was confirmed. The precipitate was further immersed in a water / methanol (volume ratio 1/1) solution containing 8.0 g of potassium carbonate overnight, and then filtered off,
After thoroughly washing with water and methanol, it was dried. Yield is 12
It was 1.1 g. The obtained copolymer was a pale yellowish white powder, which was dissolved in tetralin at 10% by weight at 100 ° C., and the viscosity was measured with a B-type viscometer at the same temperature.
It was s. Also, IR with xylene cast film
In the spectrum, 1122, 1035, 1010, 68
Absorption based on p- toluenesulfonic acid 5,570Cm ^-1 completely disappeared, absorption based on amino group to 3400 cm ^-1, 1768 cm ^-1, 1700 to absorption based on imide ring, 1660 (shoulder), 1530 cm ^The absorption based on the formamide group was observed at ^-1 . CDCl ₃
In the NMR spectrum measured in 176-180 p
The carbonyl carbon of the imide ring has a strength ratio of 2.00 in pm,
At 162 ppm, the carbonyl carbon of the formamide group was observed at an intensity ratio of 0.78. No spectrum showing the presence of an amino group was observed at 172 to 174 ppm. N
From the enhancement of the MR spectrum ((III) + (IV)) /
(V) = 100/0 NHCHO group / NH ₂ group = 78/22 was determined.

Reference Example 13 Preparation of Formamide Group-Containing Copolymer (Containing F-2) In the same reaction vessel as in Reference Example 12, hexamethylenediamine p-toluenesulfonate salt 10.8 prepared in Reference Example 3 was prepared.
50 g of DMF solution containing g and 150 ml of DMF were charged and heated to 80 ° C. In the above reaction vessel, a maleic anhydride modified product of the hydrogenated product of the styrene-butadiene copolymer produced in Reference Example 11 (Men-2) (Mw = 5)
60 g (0000, Mn = 48000, grafted amount of maleic anhydride 1%) was dissolved in 600 ml of xylene, and was gradually added dropwise from a dropping funnel. After the completion of the dropping, a part of the reaction mixture was sampled and the infrared absorption spectrum was examined. As a result, the absorption based on the succinic anhydride ring at 1780 cm ⁻¹ was completely disappeared. Heating and heating were continued, and since water azeotroped with reflux of xylene from around 140 ° C., this was continuously removed from the reaction system by a Dean-Stark water diverter. The reaction was continued at 140 ° C. for 8 hours, the reaction was terminated when the generation of new water was no longer observed, the reaction mixture was concentrated under reduced pressure to 400 ml, and water / 6.0 g of sodium carbonate was added. Methanol (volume ratio 1 /
1) The solution was poured into 5 liters to obtain a precipitate. The obtained precipitate was thoroughly washed with water and methanol and then dried. The yield was 59.1 g, which was a pale yellowish white color. The obtained copolymer was dissolved in xylene at 10% by weight, and the B-type viscosity was measured at 25 ° C., whereupon it was 790 cps. The infrared absorption spectrum of the xylene cast film was 3420c.
Absorption of amino group at m ^-1 (trace), 1775, 1702c
Absorption of imide ring at m ^-1 , 1665 (shoulder), 15
Absorption of formamide group was observed at 29 cm ^-1 and CDC
In the NMR spectrum measured in l _3, one hundred and seventy-six to eighteen
The carbonyl carbon of the imide ring has an intensity ratio of 2.00 at 0 ppm.
At 162 ppm, the carbonyl carbon of the formamide group was observed at an intensity ratio of 0.65. From this ((III) + (I
V)) / (V) = 100/0, NHCHO group / NH ₂ group = 65/35.

Reference Example 14 Preparation of Formamide Group-Containing Copolymer (Containing E-3) In the same reaction vessel as in Reference Example 12, the maleic anhydride-grafted ethylene-propylene copolymer prepared in Reference Example 11 (Macodi-3) was used. ) 90 g and 500 ml of cumene were charged and dissolved. After heating to 153 ° C. and refluxing cumene, 17.7 g of the hydrochloride of ethylenediamine prepared in Reference Example 2 was added to D
It was dissolved in 80 ml of MF and added dropwise. The reaction was carried out for 9 hours while removing azeotropic water with a Dean-Stark water separator. After completion of the reaction, the reaction mixture was poured into 5 liters of methanol to collect the product as a precipitate. This precipitate was mixed with methanol / water containing 10 g of sodium carbonate (volume: 1
1) overnight, filtered, thoroughly washed with water and methanol, and dried to obtain a white copolymer powder. Yield is 89.7g
Met. The B-type viscosity of the obtained copolymer dissolved in xylene at 10% by weight and measured at 25 ° C. was 350 cps. In the IR spectrum of the xylene cast film, absorption of an amino group at 3435 cm ⁻¹ , 1775,
Imide ring at 1700 cm ^-1 , 1670 (shoulder),
Absorption of formamide group and amide group was observed at 1529 cm ^-1 . In the NMR spectrum measured in CDCl ₃ , the carbonyl carbon of the imide ring has an intensity ratio of 2.00 at 176 to 180 ppm, and the carbonyl carbon of the formamide group has an intensity ratio of 1.09 at 162 ppm.
Carbonyl carbon of amide group was observed in pm with intensity ratio of 0.22 ((III) + (IV)) / (V) = 82/18, NH
It was determined that CHO group / NH ₂ group = 89/11.

Reference Example 15 Preparation of Formamide Group-Containing Copolymer (Containing E-4) In Reference Example 12, maleic anhydride grafted polypropylene was replaced with maleic anhydride grafted polyethylene (Men-6) of Reference Example 11 (120 g). Was used in place of the p-toluenesulfonic acid salt of ethylenediamine, and Reference Example 6
The reaction was performed in the same manner as in Reference Example 12 except that 45.5 g of the reaction product of ethylenediamine and formamide of Example 1 was used. The reaction mixture was poured into 5 liters of methanol, and the precipitate was washed with a sufficient amount of methanol and dried to obtain a white target copolymer in a yield of 134.3 g. This copolymer is tetralin /
10% by weight dissolved in DMI = 1/1 (volume ratio)
The B type viscosity measured at 0 ° C. was 45 cps. IR spectrum (KBr tablet method): 1780, 1772c
Absorption of imide ring at m ^-1 , 1670 (shoulder), 15
Absorption of formamide group was observed at 32 cm ^-1 . C
In the NMR spectrum measured in DCl ₃ , 176-
The carbonyl carbon of the imide ring has a strength ratio of 2.0 at 180 ppm.
At 0, the carbonyl carbon of formamide was observed at 162 ppm at an intensity ratio of 0.85. From this ((III) + (I
V)) / (V) = 100/0, NHCHO group / NH ₂ group = 85/15.

Reference Examples 16 to 21 Preparation of Formamide Group-Containing Copolymers (e.g., -5 to 10) The salts of Reference Examples 1 to 9 were used as the salt of diamine (or the reaction product of diamine and formyl group-containing compound). The procedure was carried out in the same manner as in Reference Examples 12 to 15, except that the maleic anhydride modified product described in Reference Example 11 was used as the raw material copolymer.
The results are shown in Table 3. The viscosity of the obtained copolymer was measured in the same manner as in Reference Example 1. The results are shown in Table 3.

[0071]

[Table 3]

[0072]

[Table 4]

[0073]

[Table 5]

[0074]

[Table 6]

[0075]

[Table 7]

[0076]

[Table 8]

[0077]

[Table 9]

Reference Example 17 The same procedure as in Reference Example 12 was carried out except that 200 ml of DMI was used instead of DNF. Soluble in xylene and 10% by weight in tetralin
Viscosity measured by B-type viscometer is 165 cps, IR spectrum (xylene cast film) is 3350 cm ^-1
Although a copolymer having (amino group), 1770 cm ^-1 and 1700 cm ^-1 (imide ring) was obtained, this product was a brown powder (amino group-containing modified product: A modification -1).

Examples 1 to 29 and Comparative Examples 1 to 30 Prescribed [A] and [B] components shown in Tables 4 and 5 below, and the above amino modified, modified or unmodified [C]. After dry blending the ingredients, dry thoroughly,
Using an NVC single-screw extruder (manufactured by Nakatani Machinery Co., Ltd.), kneading was sufficiently performed while venting was effective. Next, IS100
A test piece was molded using an EN injection molding machine (manufactured by Toshiba Machine). Using the obtained test piece, various physical properties were evaluated by the following methods. The obtained result is No. 6
Shown in the table.

(1) Izod impact test: JIS-K-
Compliant with 7110. [Conditions] Temperature = 23 ° C. and −30 ° C., notched, n =
5 (2) Surface impact test: An automatic falling weight impact test was performed to measure the fracture mode and fracture energy. [Method] The center of an 80 × 80 × 3 mm injection-molded plate was fixed to the center of the hole of a sample fixing plate (hole diameter: 2 inches), and the displacement curve for the force was calculated under the following conditions, and the force suddenly decreased. The area up to the displacement point was calculated and used as the breaking energy [J]. After the test, the fracture morphology was observed and the ductility (D) →
The evaluation was made as slightly ductile (D ′) → slightly brittle (B ′) → brittle (B). [Conditions] Temperature = -10 ° C., weight load = 3.75 kg, weight speed = 7.0 m / sec, n = 5. The testing machine used is RD
It was T5000 (manufactured by Rheometrics). (3) Peelability evaluation: According to a cross-cut peeling test. [Method] First, 100 squares of 1 mm square are cut into a 10 × 10 mm mass at the center of an 80 × 80 × 3 mm injection-molded plate (constant injection time and filling time) using a sharp cutter blade. I put it in. Next, attach the cellophane adhesive tape so that it is strongly pressed against the board, and stick it at 45 ° C.
It was peeled off rapidly while maintaining the angle of, and the residual rate of the cross was defined in the following form and evaluated. Test each sample 5 times,
They were averaged and evaluated by the average residual rate. (Remaining rate) = (Number of remaining 1 mm square cross-cuts) / 100 (4) Appearance: Visual defects such as flow marks, streak patterns, fluffiness, and silver were visually evaluated, and ○ (good), △
(Slightly bad), × (poor) was evaluated.

[0081]

[Table 10]

* 1 The terminal is rich in carboxylic acid, and the ratio of terminal carboxylic acid to amino group is 9: 1. * 2 Idemitsu Petrochemical Co., Ltd., trade name: Tafflon * 3 Idemitsu Petrochemical Co., Ltd., trade name: Tafflon * 4 Unitika Co., Ltd., trade name: U Polymer * 5 Mitsubishi Rayon Co., Ltd., Product name: Diamond Night * 6 Mitsubishi Rayon Co., Ltd. product name: Toughpet * 7 Ube Industries Co., Ltd. product name: Ube Nylon * 8 Ube Industries Co., Ltd. product name: Ube Nylon * 9 Toray ( Co., Ltd., trade name: Alamin * 10 Polyplastics Co., Ltd., trade name: Duracon * 11 Nippon GE Plastics Co., Ltd., trade name: Noryl

[0083]

[Table 11]

* 12 Idemitsu Petrochemical Co., Ltd., block polypropylene, trade name: Idemitsu Polypro * 13 Ube Industries, Ltd., block polypropylene, trade name: Ube Polypro * 14 Idemitsu Petrochemical Co., Ltd., homopolypropylene Product name: Idemitsu Polypro * 15 Idemitsu Petrochemical Co., Ltd. Product name: Idemitsu Polyethylene * 16 JSR Product name: JSR EP * 17 Idemitsu Petrochemical Co., Ltd. GPPS Product name: Idemitsu Styrol * 18 Idemitsu Petrochemical Co., Ltd., HIPS, Product name: Idemitsu Styrol * 19 JSR, Product name: JSR ABS * 20 JSR, Product name: JSR AS * 21 Idemitsu Petrochemical Co., Ltd., Product name: Moremax

[0085]

[Table 12]

[0086]

[Table 13]

[0087]

[Table 14]

[0088]

[Table 15]

[0089]

[Table 16]

[0090]

[Table 17]

[0091]

[Table 18]

[0092]

[Table 19]

[0093]

[Table 20]

[0094]

[Table 21]

[0095]

[Table 22]

[0096]

[Table 23]

* A Percentage based on the total of the components [A] and [B] * b Ratio of the total of the components [A] and [B] to 100 parts by weight * c Notched Izod impact strength (kgcm / cm) * d Visual observation * e 8 parts by weight of MBS elastomer (C223 / manufactured by Mitsubishi Rayon Co., Ltd.) was added to 100 parts by weight of the total amount of the components [A], [B] and [C]. * F In accordance with Example 12, MBS elastomer (C22
3 / Mitsubishi Rayon Co., Ltd. 8 parts by weight added * g Cross-cut peeling (number of peeled cross-cuts / 100 cross-cuts)
* H Visual observation * i ABS-1 and Ho-containing -7 were kneaded with NVC (220 ° C), then blended with PC-3 * j According to Example 9, ABS-1 and m-change. -2 and first.

[0098]

According to the present invention, a formamide group-containing copolymer having a small amount of gel component is blended in a mixed system of engineering plastics and general-purpose resins to enhance the miscibility of the two and to prevent peeling and poor appearance. It is possible to provide a resin composition which is excellent in impact strength, particularly surface impact strength and Izod impact strength, and has excellent weather resistance and solvent resistance without causing problems. Therefore, the resin composition of the present invention is expected to be widely and effectively used for automobile interior materials, OA equipment housing materials, home electric appliances and the like.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yasuhisa Sugita             1 Iezaki Oil, 1 Anezaki Coast, Ichihara City, Chiba Prefecture             Inside Chemical Co., Ltd. (72) Inventor Katsutoshi Ota             1 Iezaki Oil, 1 Anezaki Coast, Ichihara City, Chiba Prefecture             Inside Chemical Co., Ltd.

Claims (2)

[Claims] 1. A total of 100 wt% of [A] 5 to 95 wt% of a thermoplastic resin having a functional group that reacts with an amino group and [B] olefin polymer and / or styrene polymer of 95 to 5 wt%. Part and [C] in the molecule, repeating unit I represented by general formula (I) I 20 to 99.8 mol%, repeating unit II represented by general formula (II) 50 to 0 mol%, general formula (III) Repeating unit III represented, Repeating unit IV represented by general formula (IV)
And the total amount of repeating units V represented by the general formula (V) is 30 to
0.2 mol% (however, the repeating unit III is 0.2 mol% or more.) [Chemical 2] [Chemical 3] (In the formula, R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and 3 to 8 carbon atoms.
Cycloalkyl group, C6-10 aryl group, C2-4 alkenyl group, C1-4 alkoxy group, C1-18 alkoxycarbonyl group, C1-17 alkylcarboxyl Group, an alkylcarbonyl group having 1 to 6 carbon atoms, an arylcarbonyl group having 6 to 8 carbon atoms, a halogen atom or a nitrile group, and R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. , An alkenyl group having 2 to 4 carbon atoms or a halogen atom, R ⁸ does not exist or represents a methylene group or an ethylene group, and R ⁹ and R ¹⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Represents a group or an aryl group having 6 to 8 carbon atoms, R ¹¹ represents an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group having 5 to 17 carbon atoms, and 6 to 6 carbon atoms.
12 represents an arylene group, an arylalkylene group having 7 to 12 carbon atoms or a polyoxyalkylene group having 4 to 30 carbon atoms, and R ¹² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. n shows the integer of 1-10. In addition, R
^{1 to} R ¹² may be the same or different for each repeating unit. Further, X ¹ and X ² each independently represent NH ₂ or NH—CHO. A thermoplastic resin composition containing 0.05 to 20 parts by weight of a copolymer or a salt thereof as a main component. 2. The thermoplastic resin [A] having a functional group capable of reacting with an amino group comprises a carbonate bond, an ester bond,
The thermoplastic resin composition according to claim 1, which is a thermoplastic resin having at least one bond selected from an amide bond and an ether bond.