JPH09124936A - Polyesteramide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyesteramide resin composition which can be made high-molecular weight without reducing block polymerization capability, is excellent in chemical resistance and processability, and is excellent particularly in flexibility, mechanical characteristics, durability and mold release properties. SOLUTION: A higher fatty acid salt or polycarbodiimide is added in an amount of 0.1-20 pts.wt. to 100 pts.wt. polyesteramide obtained by incorporating 1-30 pts.wt. diisocyanate into 100 pts.wt. polyesteramide oligomer which is produced from a dicarboxylic acid represented by the formula HOOC-R<1> -COOH (wherein R<1> is a 2-8C alkylene), a diol represented by the formula HO-R<2> -OH (wherein R<2> is a 2-6C alkylene) and a polyamide having a reduced viscosity (1g/dl solution in 98% sulfuric acid, at 20 deg.C) of 0.5-7.0dl/g and which has a content of the polyamide of 3-30wt.% and an intrinsic viscosity (in orthochlorophenol, at 30 deg.C) of 0.1-0.5dl/g.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyesteramide resin composition having excellent mechanical properties, flexibility, releasability and durability in a temperature range from room temperature to a practically high temperature.

[0002]

2. Description of the Related Art In various industrial fields including manufacturing fields of automobiles and the like, there is a strong need for materials having excellent oil resistance, chemical resistance, flexibility and flexibility. In particular, there is a strong demand for hoses and tube materials with excellent oil resistance and gasoline resistance. For such applications, conventionally, vulcanized rubber such as NBR,
Plasticized nylon is used.

However, in recent years, since environmental problems have been emphasized, demands for recycling of materials have increased, and use of materials that cannot be recycled has been avoided.
As a result, the use of vulcanized rubber has come to be restricted. Further, vulcanized rubber has many disadvantages in terms of environmental problems even in the manufacturing process thereof.

On the other hand, plasticized nylon is a material in which flexibility is imparted to nylon, as disclosed in, for example, JP-A-60-173047, but it is used in a solvent having a strong affinity with a plasticizer. Physical properties may change due to the extraction of the plasticizer at. Further, there is a certain limit in the plasticization of nylon, and there is a drawback that it cannot sufficiently meet the required flexibility. Furthermore, since the glass transition temperature is high, low temperature properties such as low temperature impact resistance and elongation at low temperature are insufficient.

Polyether amides and polyester amides have been proposed as flexible nylon materials for compensating the above-mentioned drawbacks. Of these, regarding polyether amide,
For example, Japanese Patent Application Laid-Open No. 61-247732 discloses a method for producing a polyetheramide by polymerizing caprolactam in the presence of a polyether segment having a molecular weight of 800 to 5000. However, according to this method, since the polyether segment is introduced in a considerable ratio, the chemical resistance originally possessed by nylon is deteriorated, and it cannot be used for applications in which chemical resistance is essential. In addition, heat deterioration resistance is low and it cannot withstand continuous use at 150 ° C.

[0006] On the other hand, polyesteramide has excellent chemical resistance unlike polyetheramide and is more flexible than plasticized nylon. Among them, polyester amide having a polyester portion obtained from a dicarboxylic acid and a diol as a soft segment is preferable in terms of characteristics.

As a method for producing such a polyesteramide, for example, Japanese Patent Publication No. 61-36858 discloses that
A method of mixing a saturated dimeric fatty acid, a diol and a diamine for simultaneous reaction is disclosed. However, this method has drawbacks such as the need to use saturated dimer fatty acid and long reaction time. Also,
Japanese Patent Publication No. 46-2268 discloses 2,2-dimethyl-
A method of making a polyesteramide copolymer from a polyester formed from 1,3-propanediol and an aliphatic dicarboxylic acid and a polyamide is disclosed.
However, in this method, in order to obtain a polyester amide having a high molecular weight, it takes a long time for the polymerization, and the block property is lowered, so that only the one having poor mechanical properties can be obtained.

Further, in Japanese Patent Laid-Open No. 6-65537,
A technique for improving releasability by adding a silicone compound to a urethane polymer is disclosed.
This method cannot be used universally because the silicone compound is expensive.

Further, Japanese Patent Publication No. 1-50340 discloses that
Disclosed are hindered phenol compounds and phosphite compounds that serve as stabilizers for stabilizing the heat resistance of polyester compositions. However, although these stabilizers show some improvement in heat resistance, they cannot exhibit sufficient physical properties in weather resistance including water resistance.

[0010]

SUMMARY OF THE INVENTION In view of the above, the present invention is capable of increasing the molecular weight without deteriorating the block property, is excellent in chemical resistance and molding processability, and is particularly flexible,
It is an object of the present invention to provide a polyesteramide resin composition having excellent mechanical properties as well as excellent durability and releasability.

[0011]

The gist of the present invention is (A)
Formula ^{(1) HOOC-R 1 -COOH} (1) ( wherein, R ¹ represents an alkylene group having 2 to 8 carbon atoms)
A dicarboxylic acid represented by the general formula (2) HO—R ² —OH (2) (wherein R ² represents an alkylene group having 2 to 6 carbon atoms).
And a reduced viscosity (1 g / dL98
% Sulfuric acid solution, 20 ° C.) is 0.5 to 7.0 dL / g, and the polyamide content is 3 to
100 parts by weight of a polyesteramide oligomer having an intrinsic viscosity of 30% by weight and an intrinsic viscosity (in orthochlorophenol at 30 ° C.) of 0.1 to 0.5 dL / g, and (B).
100 parts by weight of polyester amide consisting of 1 to 30 parts by weight of diisocyanate, 0.1 to 2 parts of higher fatty acid salt
The polyesteramide resin composition itself contains 0 part by weight.

The gist of the present invention is also to provide a polycarbodiimide 0.1 having an average of 1 to 20 carbodiimide groups per molecule per 100 parts by weight of the above polyesteramide.
There is also a polyesteramide resin composition itself containing about 20 parts by weight. Hereinafter, the present invention will be described in detail.

The polyesteramide used in the present invention comprises (A) polyesteramide oligomer and (B) diisocyanate. The above-mentioned (A) polyesteramide oligomer has the general formula (1) HOOC-R ¹ -COOH (1) (wherein R ¹ represents an alkylene group having 2 to 8 carbon atoms).
At least one of the dicarboxylic acids (A-1) represented by formula (2) HO—R ² —OH (2) (wherein R ² represents an alkylene group having 2 to 6 carbon atoms).
At least one of the diols (A-2) represented by
And polyamide (A-3).

The dicarboxylic acid (A-1) represented by the above general formula (1) is not particularly limited, and examples thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, Azelaic acid, sebacic acid, etc. are mentioned. In the present invention, as the dicarboxylic acid component, various other dicarboxylic acids such as dimer acid can be used in combination as long as the physical properties of the molded product obtained from the produced polyesteramide are not impaired. The amount of the other dicarboxylic acid component blended is preferably 5 to 20% by weight based on the total amount of the dicarboxylic acid component combined with the dicarboxylic acid (A-1) represented by the general formula (1).

The diol represented by the above general formula (2) (A
-2) is not particularly limited, and examples thereof include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5. -Pentanediol, 1,6-hexanediol and the like can be mentioned. Of these, branched diols such as 1,2-propanediol and neopentyl glycol are preferable because they improve the flexibility of the polyesteramide.

In the present invention, as the diol-containing component, glycol, polyalkylene oxide or the like may be appropriately used in combination as long as the physical properties of the molded product obtained from the produced polyesteramide are not impaired. The blending amount of these is such that the diol represented by the general formula (2) (A
It is preferably 5 to 20% by weight based on the total amount of diol components combined with -2). The glycol is not particularly limited, and examples thereof include 1,7-heptanediol,
1,8-octanediol, 1,9-nonanediol,
1,10-decanediol, cyclopentane-1,2-
Diol, cyclohexane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4
-Diol, cyclohexane-1,4-dimethanol and the like. The polyalkylene oxide is not particularly limited, and examples thereof include polyethylene oxide, polypropylene oxide, polytetramethylene oxide, polyhexamethylene oxide and the like.

In the present invention, at least one of the dicarboxylic acids (A-1) represented by the general formula (1) and the general formula (2) are used as the components constituting the (A) polyesteramide oligomer. At least one of the diols (A-2) represented by the formula (1) is used. In this case, the dicarboxylic acid (A-1) represented by the general formula (1) and the general formula (2) represented by the general formula (2) are used. Diol (A
In the case where neither of -2) has an alkyl chain in the side chain, it is preferable to use two or more of any one of these components. There is only one dicarboxylic acid (A-1) represented by the above general formula (1) having no alkyl chain in the side chain, and represented by the above general formula (2) having no alkyl chain in the side chain. When only one diol (A-2) is used, the crystallinity of the produced polyesteramide oligomer becomes high, and as a result, the polyesteramide obtained using this produced polyesteramide oligomer as a constituent component has high hardness, The rubber elasticity is inferior, which is not preferable.

The dicarboxylic acid (A-1) represented by the general formula (1) and the diol (A represented by the general formula (2).
-2), in the case of using two or more of any one of the components, the dicarboxylic acid (A-1) represented by the general formula (1) or the diol (A represented by the general formula (2). -2), at least one of the two or more of the two or more used is at least one of the dicarboxylic acid (A-1) represented by the general formula (1) and the general formula (2). The ratio of the diol (A-2) represented by
It is preferably from 0 to 70% by weight. When it is less than 30% by weight or more than 70% by weight, the crystallinity of the produced polyesteramide oligomer is slightly high, and as a result,
The obtained polyesteramide has a high hardness and is inferior in rubber elasticity.

In the polyesteramide oligomer (A), the dicarboxylic acid (A-1) represented by the general formula (1) and the other dicarboxylic acid optionally used in combination are used as the dicarboxylic acid component. The diol (A-2) represented by the general formula (2) and the glycol, polyalkylene oxide, etc., which are optionally used in combination, are used as a diol component, and each is used as a polyester-forming component.

In the polyester-forming component, the dicarboxylic acid component and the diol component are 1.2 to 3 of the diol component with respect to 1 mol of the dicarboxylic acid component.
It is preferable to charge it in a molar manner. If the amount of the diol component is less than 1.2 mols relative to 1 mol of the dicarboxylic acid component, the esterification reaction does not proceed efficiently, and if it exceeds 3 mols, an excess of the diol component is used, resulting in cost reduction. It is disadvantageous, and the cleavage reaction of the polyamide is likely to occur due to the excess diol component, so that the block property is lowered and the heat resistance is lowered.

The above polyamide (A-3) which is the third component in the above (A) polyesteramide oligomer.
Has an amide bond in the polymer main chain,
Dicarboxylic acid (A-1) which is a constituent component of polyester
And a diol (A-2) and can be heated and melted, and the reduced viscosity thereof is 0.5 to 7.0 dL /
g (1 g / dL 98% sulfuric acid solution, 20 ° C.). If the reduced viscosity is less than 0.5 dL / g, the mechanical strength of the resulting resin composition at high temperature will be insufficient, and if it exceeds 7.0 dL / g, the solubility will decrease and synthesis will be difficult. Is limited to the above range. Preferably 2.0 to 7.0 dL / g
It is. It is preferable that the polyamide (A-3) has a swelling degree with respect to a toluene / isooctane = 1/1 (weight ratio) mixed solution of 5.0% or less in terms of weight change rate. The polyamide (A-3) has a molecular weight of about 1000-
What is 60000 is preferable, and it is 2000-5000.
A value of 0 is more preferable.

The polyamide (A-3) is not particularly limited, and examples thereof include 4-nylon, 6-nylon, 6,
6-nylon, 11-nylon, 12-nylon, 6,
Aliphatic nylons such as 10-nylon, 6,12-nylon; isophthalic acid, terephthalic acid, metaxylylenediamine, 2,2-bis (paraaminocyclohexyl) propane, 4,4'-diaminodicyclohexylmethane,
2,2,4-trimethylhexamethylenediamine, 2,
Examples thereof include polyamides obtained by polycondensing monomers such as 4,4-trimethylhexamethylenediamine and the like aromatic compounds, alicyclic compounds, and side chain-substituted aliphatic compounds.

The content of the polyamide (A-3) in the (A) polyester amide oligomer is 3 to 30% by weight.
It is. If it is less than 3% by weight, the mechanical strength of the molded product obtained by using the produced polyesteramide is insufficient,
If it exceeds 30% by weight, the hard segment content increases and the composition becomes hard and a polyesteramide having good rubber elasticity cannot be obtained. Therefore, the content is limited to the above range. It is preferably 5 to 18% by weight.

The polyesteramide oligomer (A) can be synthesized by any method, for example, polymerization of the dicarboxylic acid component and the diol component in the presence of the polyamide (A-3). You can The above-mentioned polymerization is usually carried out by advancing an esterification reaction as a first step and advancing a polycondensation reaction as a second step. In this case, the esterification reaction is preferably carried out in a state of a transparent homogeneous solution by dissolving the polyamide (A-3) in the polyester forming component. The reaction does not proceed efficiently in a heterogeneous state. The melting temperature is preferably 150 to 230 ° C. If it is less than 150 ° C, it is difficult to dissolve the
If it exceeds ℃, decomposition reaction occurs.

The above polycondensation reaction is carried out under reduced pressure, preferably 1
It is preferably performed at 180 to 260 ° C. at 0 mmHg or less. If it is lower than 180 ° C., the reaction rate is low and the polymerization viscosity becomes high, so that efficient polymerization is difficult, and if it exceeds 260 ° C., a decomposition reaction and coloration occur.

In the above polycondensation reaction, a catalyst generally used in the production of polyester can be used. As such, for example, lithium, sodium, potassium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tungsten,
Metals such as tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese and zirconium; organometallic compounds thereof, organic acid salts, metal alkoxides, metal oxides and the like can be mentioned. Among these, calcium acetate, diacyl stannous, tetraacyl stannic acid, dibutyltin oxide, dibutyltin dilaurate, dimethyltin malate, tin dioctanoate, tin tetraacetate, triisobutylaluminum, tetrabutyl titanate, tetrapropoxy titanate, titanium ( (Oxy) acetyl acetate, germanium dioxide, tungstic acid, antimony trioxide and the like are preferable. These catalysts may be used alone or in combination of two or more kinds.

The intrinsic viscosity of the above (A) polyesteramide oligomer (in orthochlorophenol, 30 ° C.) is
It is 0.1 to 0.5 dL / g. When it is less than 0.1 dL / g, the amount of diisocyanate for obtaining a high molecular weight polyesteramide increases, and the hardness of the obtained polyesteramide increases, resulting in poor rubber elasticity. When it exceeds, it is difficult to quantitatively proceed the chain extension reaction of the polyesteramide because the reactivity with the diisocyanate is poor, and it is not possible to suppress the simultaneous crosslinking reaction, and the resulting polyesteramide has poor fluidity. Therefore, it is limited to the above range. It is preferably 0.2 to 0.4 dL / g.

The polyesteramide used in the present invention is obtained by subjecting the hydroxyl groups at both terminals of the thus obtained (A) polyesteramide oligomer to the chain extension reaction of the isocyanate group of the (B) diisocyanate. Obtainable. The (B) diisocyanate is not particularly limited as long as it is a compound having two isocyanate groups in the same molecule, and within the range of keeping the fluidity of the produced polyesteramide, three such as triphenylmethanetriisocyanate are used. The compounds having an isocyanate group described above can also be used in combination.

The above-mentioned (B) diisocyanate is not particularly limited, and examples thereof include aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, phenylene diisocyanate and naphthalene diisocyanate; 1,2-ethylene diisocyanate, 1,3 -Propylene diisocyanate, 1,4-
Aliphatic diisocyanates such as butane diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate and the like can be mentioned.

In the present invention, the compounding amount of the (B) diisocyanate is 1 to 30 parts by weight based on 100 parts by weight of the (A) polyesteramide oligomer. 1
When it is less than parts by weight, it is difficult to obtain a polyesteramide having a high molecular weight, and it is not possible to obtain a polyesteramide having sufficient strength, and when it exceeds 30 parts by weight, excess isocyanate groups cause intermolecular crosslinking reaction. Occurs, and the resulting polyesteramide has poor fluidity, and thus is limited to the above range. It is preferably 2 to 15 parts by weight. In the present invention, the blending amount of the above (B) diisocyanate is
Further, with respect to 1 mol of the (A) polyesteramide oligomer, 0.9 to 1.2 of the (B) diisocyanate is used.
The amount is preferably mol, and more preferably 0.95 to 1.1 mol.

The above polyesteramide can be obtained by adding and mixing the above (B) diisocyanate to the above (A) polyesteramide oligomer and reacting. The above-mentioned (B) diisocyanate in the present invention can be added and mixed by using a kneader such as a kneader or an extruder. In this case, the kneading temperature is 60 to 240 ° C.
Is preferred. When the temperature is lower than 60 ° C, it is difficult to obtain a high molecular weight polyesteramide because the reactivity is low,
It is not possible to obtain polyesteramide with sufficient strength,
If it exceeds 240 ° C, the polyesteramide and diisocyanate are decomposed, and the polyesteramide having sufficient strength cannot be obtained. Preferably it is 100-200 degreeC.

In the present invention, a catalyst can be used when the above (A) polyesteramide oligomer and the above (B) diisocyanate are reacted. As the catalyst, diacyl stannous, tetraacyl stannic, dibutyltin oxide, dibutyltin dilaurate, dimethyltin malate, tin dioctanoate, tin tetraacetate,
Examples thereof include triethyleneamine, diethyleneamine, triethylamine, metal salts of naphthenic acid, metal salts of octylic acid, triisobutylaluminum, tetrabutyltitanate, calcium acetate, germanium dioxide, and antimony trioxide. Two or more of the above catalysts can be used in combination.

In the present invention, a higher fatty acid salt is added to the above polyesteramide to obtain the polyesteramide resin composition of the present invention. The higher fatty acid salt can remarkably improve the releasability of the polyester amide and prevent the distortion of the resulting molded article. The higher fatty acid salt is not particularly limited, and examples thereof include sodium stearate, magnesium stearate, calcium stearate, zinc stearate, barium stearate, sodium palmitate, and the like. The amount of the higher fatty acid salt added is 0.1 to 20 parts by weight based on 100 parts by weight of the polyesteramide. When the amount is less than 0.1 parts by weight, the resulting polyesteramide resin composition has poor releasability, and a molded product obtained by using the resin is distorted.
If it exceeds 0 parts by weight, the mechanical strength of the obtained molded product will be insufficient, so the content is limited to the above range. Preferably 1 to 1
0 parts by weight.

The above-mentioned higher fatty acid salt can be added during or after the production of the above polyesteramide. When the polyester amide is added at the time of formation, it can be added by adding the (B) diisocyanate to the (A) polyester amide oligomer, mixing and reacting, and further adding.

If desired, a stabilizer may be further added to the polyesteramide resin composition of the present invention. Examples of the stabilizer include 1,3,5-trimethyl-
2,4,6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 3,9-bis {2- [3
-(3-t-Butyl-4-hydroxy-5-methylphenyl) -propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5.
5] Hindered phenolic antioxidants such as undecane; tris (2,4-di-t-butylphenyl) phosphite, trilaurylphosphite, 2-t-butyl-
α- (3-t-butyl-4-hydroxyphenyl) -p
-Cumenylbis (p-nonylphenyl) phosphite,
Dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, pentaerystyryltetrakis (3-laurylthiopropionate), ditridecyl-3,3'-thiodipropionate And the like.

The polyesteramide resin composition of the present invention may be added to the polyester amide resin composition at the time of production or after the production so long as the practicality is not impaired.
Additives such as fibers, inorganic fillers, flame retardants, ultraviolet absorbers, antistatic agents, and inorganic substances may be added. Examples of the fibers include glass fibers, carbon fibers, boron fibers, silicon carbide fibers, alumina fibers, amorphous fibers, inorganic fibers such as silicon / titanium / carbon fibers; organic fibers such as aramid fibers. Examples of the inorganic filler include calcium carbonate, titanium oxide, mica, talc and the like. Examples of the flame retardant include hexabromocyclododecane, tris- (2,3-dichloropropyl) phosphate, pentabromophenyl allyl ether, and the like.

Examples of the ultraviolet absorber include p-
t-butylphenyl salicylate, 2-hydroxy-4
-Methoxybenzophenone, 2-hydroxy-4-methoxy2-carboxybenzophenone, 2,4,5-trihydroxybutyrophenone and the like can be mentioned. Examples of the antistatic agent include N, N-bis (hydroxyethyl) alkylamine, alkylallyl sulfonate, and alkyl sulfanate. Examples of the inorganic material include barium sulfate, alumina, silicon oxide and the like.

The polyesteramide resin composition of the present invention can be used by mixing it with other thermoplastic resins, rubber components and the like to modify its properties. As the thermoplastic resin, for example, polyolefin, modified polyolefin, polystyrene, polyvinyl chloride, polyamide,
Examples thereof include polycarbonate, polysulfone, polyester and the like. Examples of the rubber component include natural rubber, styrene-butadiene copolymer, polybutadiene,
Polyisoprene, acrylonitrile-butadiene copolymer, ethylene-propylene copolymer (EPM, EPD
M), polychloroprene, butyl rubber, acrylic rubber,
Examples thereof include silicone rubber, urethane rubber, olefin-based thermoplastic elastomer, styrene-based thermoplastic elastomer, vinyl chloride-based thermoplastic elastomer, ester-based thermoplastic elastomer, and amide-based thermoplastic elastomer.

In another embodiment of the present invention, a polycarbodiimide is added to the above polyesteramide in place of the higher fatty acid salt, or optionally together with the higher fatty acid salt, to obtain the polyesteramide resin composition of the present invention. be able to. The above-mentioned polycarbodiimide can improve the heat deterioration resistance and water deterioration resistance of the above polyesteramide, and can improve the durability of the resulting molded article. As the polycarbodiimide, one having an average of 1 to 20 carbodiimide groups in one molecule is used. When the number of carbodiimide groups is less than 1 on average in one molecule, the resulting molded product has insufficient heat deterioration resistance and water deterioration resistance, and the reaction proceeds during compounding and kneading in excess of 20 and fluidity becomes poor. As a result, a good molded product cannot be obtained.
It is limited to the above range. The average of 1 to 1 molecule is preferable.
There are ten.

Examples of the polycarbodiimide include poly (1,3,5-triisopropylphenylene-
2,4-carbodiimide), poly (1,3-diisopropylphenylene-2,4-carbodiimide) and the like.

The amount of the polycarbodiimide added is 0.1 to 20 parts by weight based on 100 parts by weight of the polyesteramide.
Parts by weight. If it is less than 0.1 part by weight, the effect of adding polycarbodiimide will not be exhibited, and if it exceeds 20 parts by weight, the reaction will proceed during kneading to lower the fluidity, and the mechanical strength of the obtained molded article will be poor. Since it is sufficient, it is limited to the above range. The addition amount is appropriately varied within the above range depending on the number of carbodiimide groups present in one molecule of polycarbodiimide used, but preferably 1 to 1
0 parts by weight.

The polyesteramide resin composition of the present invention can be formed into a molded body by a commonly used molding method such as press molding, extrusion molding, injection molding and blow molding. In this case, the molding temperature varies depending on the melting point of the polyesteramide resin composition and the molding method, but is generally 130 to 280 ° C. If it is lower than 130 ° C.,
Since the polyesteramide resin composition has low fluidity, a uniform molded product cannot be obtained. When the temperature exceeds 280 ° C., the polyesteramide resin composition is decomposed and a molded product having sufficient strength cannot be obtained.

The polyesteramide resin composition of the present invention can be suitably applied to the fields of automobile parts, electric and electronic parts, industrial parts, sports goods, medical goods and the like. Examples of the above-mentioned automobile parts include boots such as constant velocity joint boots and rack and opinion boots; ball joint seals; safety belt parts; bumper facias; emblems;

Examples of the electric and electronic parts are:
Examples include electric wire coating materials, gears, rubber switches, membrane switches, tact switches, O-rings, and the like. Examples of the industrial parts include hydraulic hoses, coil tubes, sealing materials, packings, V belts, rolls, vibration damping materials, shock absorbers, couplings, diaphragms, and the like. Examples of the sporting goods include shoe soles, balls for ball games, and the like. Examples of the medical supplies include medical tubes, blood transfusion packs, catheters and the like. In addition to the above applications, it can be suitably used as an elastic fiber, an elastic sheet, a composite sheet, a hot melt adhesive, a material for alloying with other resins, and the like.

[0045]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 146 parts by weight of adipic acid, 108 parts by weight of butylene glycol, 125 parts by weight of neopentyl glycol (butylene glycol / neopentyl glycol = 50/50 (molar ratio), adipic acid component / diol component during charging = 1
/2.4 (molar ratio)), 6-nylon (T
850, 98% sulfuric acid, reduced viscosity at 20 ℃ 3.5dL
/ G) 20 parts by weight, 0.25 parts by weight of tetrabutyl titanate as a catalyst, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-) as a stabilizer.
(Hydroxybenzyl) benzene 0.4 part by weight, tris (2,4-di-t-butylphenyl) phosphite 0.1 part by weight.
4 parts by weight was added, and the reaction system was heated to 200 ° C. under nitrogen. After 10 minutes, the nylon dissolved and became a clear solution. The mixture was kept at this temperature for 1 hour to carry out an esterification reaction. The progress of the esterification reaction was confirmed by measuring the amount of distilled water. After the progress of the esterification reaction, the temperature was raised to 240 ° C. in 20 minutes, and the pressure was reduced. Polymerization system is 1
In 0 minutes, the degree of pressure reduction reached 1 mmHg or less. In this state 2
As a result of the 0 minute polycondensation reaction, 227 parts by weight of a transparent resin was obtained.

The intrinsic viscosity of the obtained polyesteramide oligomer was [η] = 0.18 dL / g (in orthochlorophenol, 30 ° C.). Hereinafter, this is referred to as "polyesteramide oligomer (I)". 100 parts by weight of polyesteramide oligomer (I), 4,
12 parts by weight of 4'-diphenylmethane diisocyanate was added to 18 parts using a Brabender Plastograph extruder.
Knead at 0 ° C for 5 minutes and then add magnesium stearate 2
A part by weight was added, and the mixture was kneaded for 1 minute and then extruded to obtain a polyesteramide resin composition. Using the obtained polyesteramide resin composition, a No. 3 dumbbell test piece was prepared by injection molding (injection pressure 1500 kgf / cm ² , mold temperature 70 ° C., cylinder temperature 200 ° C.). Using the obtained test piece, room temperature (23 ° C) and 150
The physical properties at ° C were measured for the following items. The results are shown in Table 1.

Evaluation method 1. Intrinsic viscosity [η] Using an Ubbelohde viscosity tube, 3
It was measured at 0 ° C. 2. Surface hardness According to ASTM D2240, the surface hardness was measured with a D type durometer or an A type durometer. 3. Melting point Using a differential scanning calorimeter (DSC), measurement was performed at a temperature rising rate of 10 ° C / min. 4. Tensile Breaking Strength and Tensile Breaking Elongation A No. 3 dumbbell produced according to JIS K 6301 was measured at room temperature (23 ° C.) and 150 ° C. 5. Polyamide content of polyesteramide oligomer (% by weight) Calculated from the weight of polyamide at the time of charging relative to the weight of the produced polyesteramide oligomer. 6. Confirmation of Presence or Absence of Distortion of Molded Body The releasability of the molded body from the mold was evaluated by the presence or absence of distortion of the obtained molded body.

Example 2 6-nylon A1050 (manufactured by Unitika, 98) instead of 20 parts by weight of 6-nylon (T850, manufactured by Toyobo Co., Ltd.)
% Reduced sulfuric acid at 20 ° C., 6.2 dL / g) 30 parts by weight, and the polycondensation reaction time after reaching a degree of reduced pressure of 1 mmHg or less was 30 minutes. In the same manner as the polyesteramide oligomer (I) of Example 1, 237 parts by weight of resin was obtained. The intrinsic viscosity of the obtained polyesteramide oligomer is [η] = 0.32 dL
/ G (in orthochlorophenol, 30 ° C.).
Hereinafter, this product is referred to as "polyester amide oligomer (I
I) ”. Polyesteramide oligomer (II)
100 parts by weight and 7,4 parts by weight of 4,4′-diphenylmethane diisocyanate were kneaded using a Brabender Plastograph extruder at 160 ° C. for 10 minutes, and further 10 parts by weight of calcium stearate were added and kneaded for 2 minutes.
Extruded to obtain a polyesteramide resin composition. Test pieces were prepared from the obtained polyesteramide resin composition in the same manner as in Example 1, and the physical properties were measured. The results are shown in Table 1.

Example 3 58.4 parts by weight of adipic acid, 104.5 parts by weight of suberic acid (adipic acid / suberic acid = 40/60 (molar ratio)), 130 parts by weight of butylene glycol, and 1,2-propanediol 73 Parts by weight (butylene glycol / 1,
2-Propanediol = 60/40 (molar ratio), adipic acid component / diol component at the time of charging = 1 / 2.4 (molar ratio)), Toyobo Co., Ltd. 6-nylon (T850, 98%)
40 parts by weight of reduced viscosity at 20 ° C. in sulfuric acid of 3.5 dL / g), 0.25 parts by weight of tetrabutyl titanate as a catalyst, and 1,3,5-trimethyl-2,4,6 as a stabilizer.
0.4 parts by weight of tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris (2,4-di-
0.4 parts by weight of (t-butylphenyl) phosphite was added, and the reaction system was heated to 200 ° C. under nitrogen. After 10 minutes, the nylon dissolved and became a clear solution. The mixture was kept at this temperature for 1 hour to carry out an esterification reaction. The progress of the esterification reaction was confirmed by measuring the amount of distilled water. After the progress of the esterification reaction, the temperature was raised to 240 ° C. in 20 minutes, and the pressure was reduced. Polymerization system is 1mmH in 10 minutes
g or less. As a result of carrying out a polycondensation reaction for 30 minutes in this state, 251 parts by weight of a transparent resin was obtained.

The intrinsic viscosity of the obtained polyesteramide oligomer was [η] = 0.30 dL / g (in orthochlorophenol, 30 ° C.). Hereinafter, this is referred to as "polyesteramide oligomer (III)".
100 parts by weight of the polyesteramide oligomer (III) and 7 parts by weight of 4,4'-diphenylmethane diisocyanate were added using a Brabender Plastograph extruder.
The mixture was kneaded at 180 ° C. for 10 minutes, 0.2 parts by weight of sodium stearate was further added, and the mixture was kneaded for 1 minute and then extruded to obtain a polyesteramide resin composition. Test pieces were prepared from the obtained polyesteramide resin composition in the same manner as in Example 1, and the physical properties were measured. The results are shown in Table 1.

Example 4 6-nylon A1050 (manufactured by Unitika, 98) instead of 20 parts by weight of 6-nylon (T850, manufactured by Toyobo Co., Ltd.)
% Sulfuric acid at 20 ° C., a reduced viscosity of 6.2 dL / g) of 65 parts by weight, and a polycondensation reaction time of 40 minutes after reaching a degree of reduced pressure of 1 mmHg or less were carried out. 272 parts by weight of resin were obtained in the same manner as the polyesteramide oligomer (I) of Example 1. The intrinsic viscosity of the obtained polyesteramide oligomer is [η] = 0.40 dL
/ G (in orthochlorophenol, 30 ° C.).
Hereinafter, this product is referred to as "polyester amide oligomer (I
V) ”. Polyesteramide oligomer (IV)
100 parts by weight and 4.5 parts by weight of 4,4'-diphenylmethane diisocyanate were kneaded for 2 minutes at 195 ° C using a Brabender Plastograph extruder, and then 5 parts by weight of magnesium stearate were added and kneaded for 2 minutes. After that, it was extruded to obtain a polyesteramide resin composition.
Test pieces were prepared from the obtained polyesteramide resin composition in the same manner as in Example 1, and the physical properties were measured. The results are shown in Table 1.

Example 5 100 parts by weight of polyesteramide oligomer (IV),
4,4'-Diphenylmethane diisocyanate 1.95
Using a Brabender Plastograph extruder, 1 part by weight was kneaded at 180 ° C. for 5 minutes, 4 parts by weight of calcium stearate was further added, and the mixture was kneaded for 5 minutes and extruded to obtain a polyesteramide resin composition. Test pieces were prepared from the obtained polyesteramide resin composition in the same manner as in Example 1, and the physical properties were measured. The results are shown in Table 1.

Example 6 100 parts by weight of polyesteramide oligomer (I),
17 parts by weight of 4,4'-diphenylmethane diisocyanate was added to 1 by using a Brabender Plastograph extruder.
After kneading at 80 ° C. for 5 minutes, 0.6 part by weight of magnesium stearate was further added and kneading for 3 minutes, and then extruded to obtain a polyesteramide resin composition. Test pieces were prepared from the obtained polyesteramide resin composition in the same manner as in Example 1, and the physical properties were measured. The results are shown in Table 1.

Example 7 Polyesteramide oligomer except that 182 parts by weight of 1,2-propanediol was used as the diol component in place of butylene glycol and neopentyl glycol in the synthesis of the polyesteramide oligomer of Example 1. 206 parts by weight of a polyesteramide oligomer was synthesized under the same composition and conditions as (I). The intrinsic viscosity of the obtained polyesteramide oligomer is [η]
= 0.19 dL / g (in orthochlorophenol, 30
° C). Hereinafter, this is referred to as "polyesteramide oligomer (V)". A polyesteramide oligomer (V) was used in place of the polyesteramide oligomer (I), kneaded under the same composition and conditions as in Example 1, and extruded to obtain a polyesteramide resin composition.
Test pieces were prepared from the obtained polyesteramide resin composition in the same manner as in Example 1, and the physical properties were measured. The results are shown in Table 1.

Example 8 146 parts by weight of adipic acid, 216 parts by weight of butylene glycol (adipic acid component / diol component at the time of preparation = 1 /
2.4 (molar ratio), Toyobo Co., Ltd. 6-nylon (T8
Reduced viscosity at 20 ° C in 50, 98% sulfuric acid 3.5 dL /
g) 30 parts by weight, 0.25 parts by weight of tetrabutyl titanate as a catalyst, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-) as a stabilizer.
(Hydroxybenzyl) benzene 0.4 part by weight, tris (2,4-di-t-butylphenyl) phosphite 0.1 part by weight.
4 parts by weight was added, and the reaction system was heated to 200 ° C. under nitrogen. After 10 minutes, the nylon dissolved and became a clear solution. The mixture was kept at this temperature for 1 hour to carry out an esterification reaction. The progress of the esterification reaction was confirmed by measuring the amount of distilled water. After the progress of the esterification reaction, the temperature was raised to 240 ° C. in 20 minutes, and the pressure was reduced. Polymerization system is 1
In 0 minutes, the degree of pressure reduction reached 1 mmHg or less. 3 in this state
As a result of the 0 minute polycondensation reaction, 230 parts by weight of a transparent resin was obtained. The intrinsic viscosity of the obtained polyesteramide oligomer was [η] = 0.31 dL / g (in orthochlorophenol, 30 ° C.). Hereinafter, this is referred to as "polyesteramide oligomer (VI)". 100 parts by weight of polyesteramide oligomer (VI),
7 parts by weight of 4,4'-diphenylmethane diisocyanate was added to 18 parts using a Brabender Plastograph extruder.
The mixture was kneaded at 0 ° C. for 5 minutes, 0.3 part by weight of calcium stearate was further added, and the mixture was kneaded for 1 minute and then extruded to obtain a polyesteramide resin composition. Test pieces were prepared from the obtained polyesteramide resin composition in the same manner as in Example 1, and the physical properties were measured. The results are shown in Table 1.

Comparative Example 1 6-nylon manufactured by Toyobo Co., Ltd. (T850 in 98% sulfuric acid,
2 parts by weight of reduced viscosity of 3.5 dL / g at 20 ° C.,
209 parts by weight of a transparent resin was obtained in the same manner as in Example 1 except that the polycondensation reaction time after reaching a reduced pressure of 1 mmHg or less was 5 minutes. The intrinsic viscosity of the obtained polyesteramide oligomer is [η] = 0.08 dL /
g (in orthochlorophenol, 30 ° C.). Hereinafter, this product is referred to as "polyester amide oligomer (VI
I) ”. Polyester amide oligomer (VI
I) 100 parts by weight and 32 parts by weight of 4,4′-diphenylmethane diisocyanate were kneaded at 180 ° C. for 5 minutes using a Brabender Plastograph extruder, and then 5 parts by weight of magnesium stearate were added and kneaded for 2 minutes. After that, it was extruded to obtain a polyesteramide resin composition.
Test pieces were prepared from the obtained polyesteramide resin composition in the same manner as in Example 1, and the physical properties were measured. The results are shown in Table 1.

Comparative Example 2 6-nylon manufactured by Toyobo Co., Ltd. (T850, in 98% sulfuric acid,
The same procedure as in Example 1 was repeated except that 100 parts by weight of reduced viscosity at 20 ° C. of 3.5 dL / g) was used and the polycondensation reaction time after the pressure reduction degree of 1 mmHg or less was 90 minutes.
307 parts by weight of transparent resin were obtained. The intrinsic viscosity of the obtained polyesteramide oligomer is [η] = 0.78.
It was dL / g (in orthochlorophenol, 30 ° C.). Hereinafter, this is referred to as "polyesteramide oligomer (VIII)". 100 parts by weight of polyesteramide oligomer (VIII) and 0.5 parts by weight of 4,4′-diphenylmethane diisocyanate were kneaded at 180 ° C. for 5 minutes using a Brabender Plastograph extruder,
Further, 2 parts by weight of calcium stearate was added, and the mixture was kneaded for 2 minutes and then extruded to obtain a polyesteramide resin composition. Test pieces were prepared from the obtained polyesteramide resin composition in the same manner as in Example 1, and the physical properties were measured. The results are shown in Table 1.

Comparative Example 3 A polyesteramide resin composition was produced in the same manner as in Example 1 except that the polyesteramide oligomer (I) was used and magnesium stearate was not added. Test pieces were prepared from the obtained polyesteramide resin composition in the same manner as in Example 1, and the physical properties were measured. The results are shown in Table 1.

Comparative Example 4 A polyesteramide resin composition was produced in the same manner as in Example 1 except that the polyesteramide oligomer (I) was used and 21 parts by weight of magnesium stearate was added. Test pieces were prepared from the obtained polyesteramide resin composition in the same manner as in Example 1, and the physical properties were measured.
The results are shown in Table 1.

Example 9 100 parts by weight of polyesteramide oligomer (I),
12 parts by weight of 4,4'-diphenylmethane diisocyanate was added to 1 part using a Brabender Plastograph extruder.
The mixture was kneaded at 80 ° C. for 5 minutes, and then poly (1,3,5-triisopropylphenylene-2,
4-carbodiimide) (Stavaxol P-100, manufactured by Sumitomo Bayer Urethane Co., Ltd.) (2 parts by weight) was added, and the mixture was kneaded for 1 minute and then extruded to obtain a polyesteramide resin composition. Test pieces were prepared from the obtained polyesteramide resin composition in the same manner as in Example 1, and the physical properties of the items shown in Table 2 were measured. However, among the items shown in Table 2, the heat deterioration resistance test and the water resistance test were evaluated by the following methods. The results are shown in Table 2.

Evaluation method 7. Heat deterioration test After standing in a gear oven at 120 ° C for 300 hours,
The No. 3 dumbbell produced according to JIS K 6301 was measured for elongation at break at room temperature (23 ° C.) to calculate the elongation retention rate. 8. Water resistance test JIS K 6301 was immersed in hot water at 70 ° C for 14 days.
The No. 3 dumbbell produced according to the above was measured for breaking elongation at room temperature (23 ° C.) to calculate the elongation retention rate.

Example 10 100 parts by weight of polyesteramide oligomer (II),
7 parts by weight of 4,4'-diphenylmethane diisocyanate was added to 16 parts using a Brabender Plastograph extruder.
HMV-8C, which was kneaded at 0 ° C. for 10 minutes and further contained as polycarbodiimide 8 carbodiimide groups in one molecule.
10 parts by weight of A (manufactured by Nisshinbo Co., Ltd.) was added and kneaded for 2 minutes, and then extruded to obtain a polyesteramide resin composition.
Test pieces were prepared from the obtained polyesteramide resin composition in the same manner as in Example 9, and the physical properties were measured. The results are shown in Table 2.

Example 11 100 parts by weight of polyesteramide oligomer (III) and 7 parts by weight of 4,4'-diphenylmethane diisocyanate were added using a Brabender Plastograph extruder.
The mixture was kneaded at 180 ° C. for 10 minutes, and further, as a polycarbodiimide, HMV-containing 8 carbodiimide groups in one molecule.
After adding 0.2 parts by weight of 8CA (manufactured by Nisshinbo Co., Ltd.) and kneading for 1 minute, it was extruded to obtain a polyesteramide resin composition. Test pieces were prepared from the obtained polyesteramide resin composition in the same manner as in Example 9, and the physical properties were measured. The results are shown in Table 2.

Example 12 100 parts by weight of polyesteramide oligomer (IV),
4.5 parts by weight of 4,4'-diphenylmethane diisocyanate were added using a Brabender Plastograph extruder.
Kneading at 195 ° C. for 2 minutes, and further, as polycarbodiimide, HMV-8 containing 8 carbodiimide groups in one molecule.
After adding 5 parts by weight of CA (manufactured by Nisshinbo Co., Ltd.) and kneading for 2 minutes, it was extruded to obtain a polyesteramide resin composition.
Test pieces were prepared from the obtained polyesteramide resin composition in the same manner as in Example 9, and the physical properties were measured. The results are shown in Table 2.

Example 13 100 parts by weight of polyesteramide oligomer (IV),
4,4'-Diphenylmethane diisocyanate 1.95
A part by weight is kneaded for 5 minutes at 180 ° C. using a Brabender Plastograph extruder, and further, an HMV containing 8 carbodiimide groups in one molecule as polycarbodiimide.
4 parts by weight of -8CA (manufactured by Nisshinbo Co., Ltd.) was added, kneaded for 5 minutes, and extruded to obtain a polyesteramide resin composition.
Test pieces were prepared from the obtained polyesteramide resin composition in the same manner as in Example 9, and the physical properties were measured. The results are shown in Table 2.

Example 14 100 parts by weight of polyesteramide oligomer (I),
17 parts by weight of 4,4'-diphenylmethane diisocyanate was added to 1 by using a Brabender Plastograph extruder.
HMV-8C, which was kneaded at 80 ° C. for 5 minutes and further contained as polycarbodiimide 8 carbodiimide groups in one molecule.
0.6 part by weight of A (manufactured by Nisshinbo Co., Ltd.) was added and kneaded for 3 minutes, and then extruded to obtain a polyesteramide resin composition.
Test pieces were prepared from the obtained polyesteramide resin composition in the same manner as in Example 9, and the physical properties were measured. The results are shown in Table 2.

Example 15 Polyesteramide oligomer (V) was used in place of polyesteramide oligomer (I), kneaded under the same composition and conditions as in Example 9, and extruded to obtain a polyesteramide resin composition. Test pieces were prepared from the obtained polyesteramide resin composition in the same manner as in Example 9, and the physical properties were measured. The results are shown in Table 2.

Comparative Example 5 100 parts by weight of polyesteramide oligomer (VII), 32,4'-diphenylmethane diisocyanate 32
A part by weight is kneaded for 5 minutes at 180 ° C. using a Brabender Plastograph extruder, and further, an HMV containing 8 carbodiimide groups in one molecule as polycarbodiimide.
After adding 5 parts by weight of -8CA (manufactured by Nisshinbo Co., Ltd.) and kneading for 2 minutes, the mixture was extruded to obtain a polyesteramide resin composition. Test pieces were prepared from the obtained polyesteramide resin composition in the same manner as in Example 9, and the physical properties were measured. The results are shown in Table 2.

Comparative Example 6 100 parts by weight of polyesteramide oligomer (VIII), 4,4'-diphenylmethane diisocyanate
5 parts by weight of the mixture was kneaded at 180 ° C. for 5 minutes using a Brabender Plastograph extruder, and further poly (1,3,5-triisopropylphenylene-2,4-carbodiimide) (stabacol P- 1
00, manufactured by Sumitomo Bayer Urethane Co., Ltd.)
After kneading for 2 minutes, it was extruded to obtain a polyesteramide resin composition. Test pieces were prepared from the obtained polyesteramide resin composition in the same manner as in Example 9, and the physical properties were measured. The results are shown in Table 2.

Comparative Example 7 Poly (amide amide oligomer) (I) was used to prepare poly (1,3,5-triisopropylphenylene-2,4-).
A polyesteramide resin composition was produced in the same manner as in Example 9 except that carbodiimide) was not added. Test pieces were prepared from the obtained polyesteramide resin composition in the same manner as in Example 9, and the physical properties were measured. The results are shown in Table 2.

Comparative Example 8 Using the polyesteramide oligomer (I), poly (1,3,5-triisopropylphenylene-2,4-
A polyesteramide resin composition was produced in the same manner as in Example 9 except that 21 parts by weight of carbodiimide) was added. Test pieces were prepared from the obtained polyesteramide resin composition in the same manner as in Example 9, and the physical properties were measured.
The results are shown in Table 2.

[0073]

[Table 1]

[0074]

[Table 2]

From the results shown in Table 1, the polyesteramide resin composition of the present invention in which a higher fatty acid salt is blended has a room temperature to 15
The mold releasability can be improved without lowering the mechanical strength and flexibility at a practically high temperature of about 0 ° C. In particular, Examples 1 to 4, 7 and 8 are excellent in mechanical properties. It turned out that

From the results shown in Table 2, it was found that the polyesteramide resin composition of the present invention containing polycarbodiimide has both excellent mechanical properties and durability.

[0077]

EFFECT OF THE INVENTION Since the polyesteramide resin composition of the present invention has the above-mentioned constitution, it can be made into a high molecular weight without deteriorating the blocking property, and it is excellent in flexibility and mechanical properties and is durable. It is possible to obtain a molded product having excellent releasability.

Claims (2)

[Claims] 1. (A) General formula (1) HOOC-R ¹ —COOH (1) (wherein R ¹ represents an alkylene group having 2 to 8 carbon atoms).
A dicarboxylic acid represented by the general formula (2) HO—R ² —OH (2) (wherein R ² represents an alkylene group having 2 to 6 carbon atoms).
And a reduced viscosity (1 g / dL98
% Sulfuric acid solution, 20 ° C.) is 0.5 to 7.0 dL / g, and the polyamide content is 3 to
100 parts by weight of a polyesteramide oligomer having an intrinsic viscosity of 30% by weight and an intrinsic viscosity (in orthochlorophenol at 30 ° C.) of 0.1 to 0.5 dL / g, and (B).
100 parts by weight of polyester amide consisting of 1 to 30 parts by weight of diisocyanate, 0.1 to 2 parts of higher fatty acid salt
A polyesteramide resin composition comprising 0 part by weight. 2. (A) General formula (1) HOOC-R ¹ —COOH (1) (In the formula, R ¹ represents an alkylene group having 2 to 8 carbon atoms.)
A dicarboxylic acid represented by the general formula (2) HO—R ² —OH (2) (wherein R ² represents an alkylene group having 2 to 6 carbon atoms).
And a reduced viscosity (1 g / dL98
% Sulfuric acid solution, 20 ° C.) is 0.5 to 7.0 dL / g, and the polyamide content is 3 to
100 parts by weight of a polyesteramide oligomer having an intrinsic viscosity of 30% by weight and an intrinsic viscosity (in orthochlorophenol at 30 ° C.) of 0.1 to 0.5 dL / g, and (B).
An average of 1 to 20 in one molecule per 100 parts by weight of polyester amide consisting of 1 to 30 parts by weight of diisocyanate
Polycarbodiimide having one carbodiimide group.
A polyesteramide resin composition comprising 1 to 20 parts by weight.