JPS63170010A - Amide resin molded product and its manufacture - Google Patents

Abstract

PURPOSE:To reduce deterioration in rigidity and a dimensional change due to suction of water by improving mechanical physical properties, by a method wherein a molding composition containing a mixture of a polyamides, polyphenylene ether and a benzene sulfonamide derivative which are soluble in molten omega-lactam is injected or cast into a molding mold at a temperature of the melting point of the omega-lactam or higher. CONSTITUTION:Three ingredients such as polyamides, polyphenylene ether and benzene suflonamides soluble into omega-lactam which is in a molten state are mixed up beforehand under a molten state. Then a molding composition obtained by incorporating a polymerization catalyst, a polymerization auxiliary catalyst and the foregoing mixture with the omega-lactam is injected or cast into a molding mold at a temperature of the melting point of the omega-lactam or higher. Then polymerization reaction within the mold progresses swiftly, a cast material is cured or solidified in a short period of time (about 2-4 minutes) and the polymerization reaction is completed. Then the mold is cooled and a molded product is taken out of the mold. In addition, omega-enanthic lactam, an alkali metal and toluene di-isocyanate are used respectively for the omega-lactam, polymeri zation catalyst and polymerization auxiliary catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to an amide resin molded article and a method for producing the same. More specifically, it relates to a reaction injection molded product of amide resin and a method for producing the same, and a molded product with excellent mechanical properties, little dimensional change due to water absorption, and excellent surface appearance, and a method for producing the same. be.

"Prior Art" In recent years, so-called reaction injection molding has been developed as a method for obtaining molded products by injecting or injecting highly reactive liquid raw materials into a molding mold, and then causing a polymerization reaction of the liquid raw materials after being injected into the mold. (
Reaction InjectionMolcli
ng, hereinafter simply referred to as "RIM". ) technology has been proposed,
Attention has been paid.

The above RIM technology was previously put to practical use in the field of manufacturing molded products from polyurethane and has made great progress, but recently it has also been applied to materials such as amide i resin, unsaturated polyester resin, and epoxy resin. became. Among these, amide resins have excellent toughness, heat resistance, electrical properties, friction resistance, wear characteristics, etc. Furthermore, because the raw material composition has good fluidity, it can be molded at low injection pressure. It has the advantages of being able to be molded from thin to thick molded products at will, having good transferability on the mold surface, and producing little heat during polymerization, making it easy to carry out the polymerization reaction. Attention has been paid.

However, amide resins have a drawback that, because they have high water absorption, the rigidity of molded products tends to decrease and dimensional changes tend to occur. As a method for improving these drawbacks, a method has been proposed in which a certain type of block copolymer is added to the amide resin (see Japanese Patent Publication No. 40120/1983). However, according to this method, the rigidity of the outside is seriously reduced, which is not preferable. Another method to improve the above drawbacks is to add fillers to amide resins.
When using this method, it is possible to improve the rigidity reduction and dimensional change of the molded product due to water absorption, but the impact resistance at low temperatures is not improved.

"Problems to be Solved by the Invention" The present invention provides an amide resin molded product obtained by RIM technology using ω-lactam as a raw material, which eliminates the above-mentioned drawbacks, and a method for producing the same. With the goal. That is, the present invention aims to provide an amide resin molded product that (1) has excellent mechanical properties, (2) has little decrease in rigidity and dimensional change due to water absorption, and (3) has an excellent surface appearance, and a method for producing the same. purpose.

1.Means for Solving Problem 1" However, the gist of the first invention of the present invention is that ω-
A molding composition comprising a lactam, a polymerization catalyst, a polymerization cocatalyst, and a mixture of polyamides, polyphenylene ethers, and benzenesulfonamide derivatives soluble in the omega-lactam in a molten state is heated at a temperature equal to or higher than the melting point of the omega-lactam. The present invention relates to an amide resin molded article, which is characterized by being molded by injection or injection into a mold.

The gist of the second aspect of the present invention is to mix the components of polyamides, polyphenylene ethers, and benzenesulfonamide derivatives that are soluble in omega-lactam in a molten state, and to mix this mixture in a molten state. omega-lactam melt containing a polymerization catalyst (hereinafter referred to as "component system (A)")
That's what it means. ), an omega-lactam melt containing a polymerization cocatalyst (
Hereinafter, this will be referred to as "component system (B)." ), mixed at a temperature higher than the melting point of the ω-lactam, and injected or injected into a mold to form a molded product. Exists.

The present invention will be explained in detail below.

The amide resin molded article according to the present invention is a mixture of three types: an ω-lactam, a polymerization catalyst, a polymerization co-catalyst, a polyamide soluble in the molten ω-lactam, a polyphenylene ether, and a benzenesulfonamide derivative. M7JL for molding containing: Uses objects as raw materials.

41 Specific examples of ω-lactams used in the present invention include γ-lactams.
-butyrolactam, δ-valerolactam, ε-caprolactam, ω-enantholactam, ω-cabryl lactam, ω-unde'h/lactam, ω-laurinlactam, and the like. These ω-lactams may be used alone or in combination of two or more.

The polymerization catalyst used in the present invention may be any compound selected from those used in known anionic polymerization of ω-lactams.

Specific examples include alkali metals, alkaline earth metals, their hydrides, oxides, hydroxides, carbonates, alkyl compounds, aryl compounds, alkoxides, Grignard compounds, and ω- Examples include reaction products with lactams, such as sodium salts, potassium salts, and magnesium halide salts of ω-lactams. The amount of polymerization catalyst used is based on the total ω-lactam.
0.01-V-15, or 20 mole % or more.

The polymerization cocatalyst used in the present invention may also be any compound selected from those used in the known anionic polymerization of ω-lactams. Specific examples include toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, polymethylene polyphenyl polyisocyanate,
Isocyanates such as diisocyanate modified with carbodiimide, hexamethylene-1,6-biscarbamide, caprolactam, N,N'-diphenyl-p-phenylenebiscarbamid caprolactam, N,N'-diphenyl-P-phenylenebis Carbamide lactams such as carbamide and pyrrolidone, tele7 taloyl chloride,
Acid halides such as adipic acid chloride and sebacic acid chloride, adipoylbiscaprolactam, adipoylbispyrrolidone, tele7taloylbiscaprolactum, tele7taloylbisvirolidone, iso7taloylbiscaprolactam, iso7ta polyacyllactams such as loyl bispyrrolidone, or of formula E (where A is halogen or lene), a is an integer of 1, 2 or 3, and b is an integer of 1 or more. is an integer, R8 is an alkyl group, an aralkyl group, an alkyloxy group, an aryloxy group, a halogen group, or an aralkyloxy group, and R7 is an integer selected from a hydrocarbon group and a hydrocarbon having an ether bond. is a group with higher valence, and Z is a polyvalent hydroxyl group, amine 7
or an acyllactam functional material selected from the group consisting of those having a structure derived from a compound having a group, a mercapto group, or an epoxy group. ] etc.

Examples of compounds having polyvalent hydroxyl groups include alkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, tetramethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1,3-propanediol, 1,3 -Hexanediol, butylene glycol, 1g 4-butanediol, dicyclopentadiene glycol, heptaethylene glycol and isopropylidene bis(P-phenyleneoxypropanol-2)
, polyols other than alkylene glycols such as glycerol, pentaerythritol, 1,2,6-hexanetriol and 1-trimethylolpropane, polymeric polyols such as polyethylene glycol, polypropylene glycol, polyoxypropylene diol, and triols, polytetramethylene glycol , castor oil, polybutadiene glycol, polyester glycol, poly(ε-caprolactone) diol, and a number of compounds containing substituents other than hydroxy groups, such as 2,4-dichlorobutylene glycol.

Examples of compounds having polyvalent mercapto groups include hydroxyethylthioglycolate, ethylene glycol bis(thio-glycolate), pentaerythritol tetrakis-(thioglycolate), and thioglycol. Examples of compounds having groups include hexamethylenediamine, tolylenediamine, 2,4-diethyltolylenediamine, polyoxyethylenediamine,
Polyoxypropylene diamines and triamines, polyoxypropylene diamines, copolyamides with 7-amino terminal groups, etc. are mentioned, and compounds with polyvalent epoxy groups include resorcinol digrecidyl ether, digrecidyl ether of bisphenol A, etc. Examples include glycidyl ether, vinyl cyclohexane dioxide, butanediol glycidyl ether, polyglycidyl esters of polycarboxylic acids, epoxidized polyolefin and glycidyl ether resins, and epoxy/Bottsk resins.

Furthermore, in the present invention, compounds that do not substantially inhibit the polymerization reaction, such as plasticizers, blowing agents, dyes and pigments, antioxidants, internal mold release agents, etc., may be added.

Polyamides soluble in omega-lactam in a molten state include the following four monomer groups constituting polyamides: (a) dicarboxylic acids, (b) diamines, and (c)
(d) aminocarboxylic acids and (d) lactams.

These polyamides function to improve the impact resistance of molded articles, reduce water absorption, and improve rigidity reduction due to water absorption.

As (a) dicarboxylic acids which are one of the monomer groups,
Adipic acid, sebacic acid, corkic acid, geltaric acid, azelaic acid, β-methyladipic acid, terephthalic acid, isophthalic acid, decamethylene dicarboxylic acid, dodecamethylene dicarboxylic acid, 1,10-decanedicarboxylic acid, pimelic acid, etc. It will be done. Among this group (a), adipic acid and sebacic acid are preferred.

(b) Examples of the cyamines include ethylenecyamine, tetramethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, metaxylenediamine, and paraxylenediamine. Among this group (b), hexamethylene diamine is preferred.

As (c) aminocarboxylic acid as a monomer group, 6
-7-minocabronic acid, 7-amino/enanthic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 17-aminoundecanoic acid, and the like. - (d) Lactams include ε-caprolactam, enantlactam, caprylolactam, ε-undecanolactam, ω-laurinlactam, decyllactam, anddecyllactam, and the like.

A copolymer composed of at least three types of monomer acids selected from at least three groups among the four groups (a) to (d) above is produced by a known method for producing polyamides. , can be easily manufactured.

The amount of the above-mentioned polyamides incorporated into the molded product is not preferable because if it is too small, the object of the present invention will not be achieved.
On the other hand, if the amount is too high, the viscosity of the component system used for molding increases too much, making molding impossible.

The preferred blending amount in the molded article is from 0.1 to 40% by weight, particularly preferably from 5 to 35% by weight.

Polyphenylene ether soluble in omega-lactam in a molten state functions to improve the impact resistance of the molded article, reduce water absorption, and improve stiffness reduction due to water absorption. This polyphenylene ether has the following general formula (1), that is, [in the formula (I), R,, R2, R3 and R4 are
It means a substituent selected from the group consisting of hydrogen, halogen, alkyl group, substituted alkyl group, cyano group, alkoxy group, phenoxy group, nitro group, amino group and sulfo group, and n means an integer. Examples include a single polymer (homopolymer)* or a copolymer having the unit represented by 1.

Specific examples of polymers having units satisfying the above general formula (I) include poly(2,6-dimethyl-1t4-phenylene) ether, poly(2,6-dinityl-1,4-phenylene) ether, and poly(2,6-dimethyl-1t4-phenylene) ether. ,6-dichloro-1,4-7
(22lene) ether, poly(2,6-dipromo) 1.4
-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2-chloro-6-methyl-1,4-phenylene) ether, poly(
2-methyl-6-isopropyl-1,4-phenylene)
Ether, poly(2,6-di-n-propyl-1,4-
phenylene) ether, poly(2-chloro-6-bromo-1,4-7-dinilene) ether, poly(2-)ro-6-ethyl-1,4-phenylene) ether, poly(2-chloro-6-ethyl-1,4-phenylene) ether,
-Methyl-1,4-7dinilene) ether, poly(2-
chloro-1,4-phenylene) ether, poly(2-phenyl-1,4-7enylene) ether, poly(2-methyl-6-phenyl-1,4-phenylene) ether,
Examples include poly(2-bromo-6-phenyl-1°4-phenylene) ether, and styrene compound kraft copolymers of these polyphenylene ethers. Examples of styrene compounds that can be grafted include styrene, α-methylstyrene, methylstyrene, dimethylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene.

Examples of compounds that can be copolymerized with the compound having the unit represented by the above general formula (1) include 0-cresol and the like in addition to the above-mentioned styrene compounds.

The amount of the above polyphenylene ether added to the molded product is
If the amount is too small, the object of the present invention will not be achieved, which is undesirable. On the other hand, if it is too large, the viscosity of the component system to be molded will increase too much, making molding impossible, which is not preferred. The preferred blending amount in the molded article is from 0.1 to 40% by weight, particularly preferably from 5 to 30% by weight.

The benzenesulfonamide derivative that is soluble in omega-lactam in a molten state is produced when the polyamides soluble in omega-lactam in a molten state and the polyphenylene ethers are mixed, and the latter is added to the former in the form of fine particles. It serves the function of helping to disperse the

Usable benzenesulfonamide derivatives include the following general formula (n), that is, [In the formula (■), R5 and R6 are hydrogen, an alkyl group, a cycloalkyl group, an alkenyl group, an alkyl group, an aralkyl group , means a substituent selected from the group consisting of araalkenyl group or aromatic group, R7,
R, R9, RIG and R1+ mean a substituent selected from the group consisting of hydrogen, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an alkoxyalkyl group, an aralkyl group, an aralkenyl group, or an aromatic group. do. ].

Specific examples of the benzenesulfonamide derivative represented by the above general formula (II) include N-methylbenzenesulfonamide, N-ethylbenzenesulfonamide, N-propylbenzenesulfonamide, N-butylbenzenesulfonamide, and N-octylbenzenesulfonamide. benzenesulfonamide,
N-cyclohexylbenzenesulfonamide, N-methyl-N-butylbenzenesulfonamide, N-cyclohexyl-p-)luenesulfonamide, N-benzyl-
Examples include p-methoxybenzenesulfonamide, N7znylbenzenesulfonamide, N-cyclohexenylbenzenesulfonamide, N-butyl-p-methoxyethylbenzenesulfonamide, N-butyl-pphenylbenzenesulfonamide, and the like.

The amount of the benzenesulfonamide derivative represented by the above general formula (IT) is the total amount of polyamides soluble in ω-lactam in a molten state and polyphenylene ether soluble in ω-lactam in a molten state. 0.1 against
It is preferable to select it in the range of 10% by weight.

An amide resin molded product according to the present invention! ! In addition, polyamides soluble in the omega-lactam in the molten state;
It is preferable to mix the three components, polyphenylene ether and benzenesulfonamides, which are soluble in the omega-lactam in a molten state, in advance in a molten state. To mix, predetermined amounts of the three components are weighed out and prepared into a tri-blend using a tumbler, Henschel mixer, etc., and then this tri-blend is brought to a molten state using a Prabengu, Banbury, extruder, etc., and kneaded. This cross-mixing results in a mixture in which polyphenylene ether is dispersed in fine particles in the polyamide. According to experiments conducted by the present inventors, it has been found that the mixture of polyamides and polyphenylene ether is preferably introduced in a weight ratio of 70 to 35 for the former and 30 to 65 for the latter. According to the experiments of the present inventors, poly7 dispersed in polyamides
It was found that the smaller the particle size of enylene ether, the better the appearance of the molded product. The thickness is preferably 50μ or less, particularly preferably 10μ or less.

Next, a method for producing an amide resin molded article according to the present invention will be explained. First, a polymerization catalyst is added to ω-lactam, and ω
- Prepare a molten ω-lactam containing a polymerization catalyst (6) called component system (A) by heating to a temperature above the melting point of the lactam (e.g. 70°C or above when the ω-lactam is ε-caprolactam). do.

Similarly, a polymerization cocatalyst is added to the ω-lactam and heated above the melting point of the ω-lactam to prepare a molten ω-lactam containing the polymerization cocatalyst (referred to as component system (B)).

Then, the mixture prepared by the above method is blended into at least one of component system (A) and component system (B).

The blending amount of the mixture can be selected in the range of 1 to 50% by weight, when the total amount of component system (A), component system (B), and mixture is 100% by weight. Among these, it is preferable to select a value in the range of 5 to 40%. If necessary, other additives such as a crosslinking agent, a modifier, a plasticizer, a coloring agent, an antioxidant, etc. are added to the component system (A) or the component system (B) to prepare a molding composition. In addition, the above mixture can be used as component system (A)
and component system ('B), the distribution ratio is determined by the type of ω-lactam, component system (A) and component system ('B).
It is determined each time depending on the viscosity of B).

Subsequently, component system (A) and component system (B) in a molten state are mixed at a constant ratio, and the resulting mixture of molding compositions is injected or injected into a mold.

In this case, the mixing ratio of component system (A) and component system (B) is:
Depending on the purpose of the molded product and the properties to be provided, the component system (A)
/component system (B) volume ratio is preferably selected in the range of 571 to 115. To mix two-component systems, fluid mixing devices such as impingement mixers called mixing heads, static mixers or dynamic mixers can be used.

The temperature of the mold when manufacturing molded products is 100-200℃
, preferably maintained within the range of 120 to 160°C. When the temperature of the molding mold is maintained within the above range, the polymerization reaction within the mold will proceed rapidly and will occur within a short period of time (usually within 2 to 4 minutes) after the molding composition mixture is injected into the mold. )
The injected material hardens or solidifies to complete the polymerization reaction. After the polymerization reaction is completed, the mold is cooled and the product taken out from the mold is the desired amide resin molded product.

The amide resin molded products according to the present invention include vehicle parts such as outer panels of automobiles and snowmobiles, steering wheels, dash panels, instrument panels, cowl panels, cowl grilles, armrests, and bumpers;
Computer, word processor, typewriter
housings and carrying cases for OA equipment such as; parts and housings for home appliances such as televisions and audio equipment; insulation materials for other types of electrical equipment, furniture parts, agricultural machinery parts, plastic pallets, plastic sheets, etc. can be given. These examples are not intended to limit the invention.

"Effects of the Invention" 20. The present invention has been described above, and has the following particularly remarkable effects, and its industrial utility value is extremely large.

(1) The amide resin molded article according to the present invention has excellent mechanical properties because it contains polyamides and polyphenylene ether that are soluble in omega-lactam in a molten state.

(2) Since the amide resin molded article according to the present invention contains polyamides and polyphenylene ether that are soluble in omega-lactam in a molten state, its water absorption is reduced, and therefore, the rigidity is reduced due to moisture absorption and water absorption There is little dimensional change due to

"Examples" Next, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

The polyamides soluble in omega-lactam in a molten state used in the following examples are as follows.

・Nylon ■ A copolymer containing five monomer components: ω-caprolactam, hexamethylene diamine, adipic acid, heptatumesic acid, and lauryllactam. When expressed as polyamide, it is nylon 6, nylon 66: nylon 610: nylon 6.
The composition ratio of No. 12 is 5:45:45:5 and the average molecular weight is about 70,000.

・Nylon■ It is a copolymer containing four monomer components of ω-caprolactam, hexamethylene diamine, adipic acid, and ε-aminolauryllactam, and when expressed as a polyamide, the composition ratio of nylon 66 and nylon 12 is 2. :2
:3 and its average molecular weight is approximately 80,000.

・Nylon■ It is a polycondensate of terephthalic acid, isophthalic acid, and hexamethylene diamine in a weight ratio of 33:17:50, and "n-cresol and chloroform are mixed in a weight ratio of 1:4. The number average molecular weight measured by GPC (gel permeation chromatography) using a mixed solution as a solvent is io, ooo.

・Nylon■ It is a polycondensate of terephthalic acid, isophthalic acid, and 4.4'-diaminocyclohexylmethane in a weight ratio of 33:17:50, and the number average molecular weight measured by the same method as above is 15.000. Of things.

Further, the water absorption expansion coefficient, flexural modulus, appearance, etc. of the obtained molded article were measured according to the following methods. Furthermore, the particle size of poly7enylene ether in the mixture was measured by the method described below.

・Water absorption expansion rate 15cm long from a completely dry plate-shaped molded product.

A test piece with a width of 2 cm was cut out, and the length L) was accurately measured. This test piece was left in an atmosphere of 50° C. and 95% relative humidity for 48 hours, and immediately after being taken out, the length 1) was measured and calculated using the following formula.

・Bending elastic modulus Cut out a dry test piece from a flat plate-shaped molded product, and
Leave it in an atmosphere of 3°C and 50% relative humidity for 24 hours,
Measured according to ASTM D-790.

- The appearance of the molded product was mainly evaluated by visual observation, but in some cases, it was additionally evaluated using a surface roughness meter (Model 5E-3A manufactured by Koita Research Institute). The display criteria for the results are: ◎: Best, ○: Good, Δ: Fair,
×: 4 levels of not acceptable.

・The average particle size mixture of polyphenylene ether in the mixture + 'lk is dissolved in methanol for nylon I and nylon, and in n-methylpyrrolidone for nylon and nylon, and the poly-7-nylene ether particles are suspended. A suspension was prepared, and the average particle diameter of the suspension was measured using an Itaba centrifugal automatic particle size distribution analyzer (manufactured by Itaba Seisakusho, CAPA-5000).

Experimental Example 1 130 parts by weight of nylon, poly(2,6-cymethyl-1.
30 parts by weight of 4-phenylene) ether and 3 parts by weight of N-butylbenzenesulfonamide were each weighed and mixed to obtain a triblend.

Use this triblend with Brabender ν1.22
Mixture I was obtained by kneading for 3 minutes at a temperature of 0°C.

The average particle size of the polyphenylene ether in mixture I is 1
．． It was 8μ.

Next, component system (A) and component system (B) having the following compositions were prepared in flasks with capacities of 11 and 500 ml, respectively,
The temperature was maintained at 100°C.

Component system (A) ε-caprolactam 450 parts by weight Bromomagnesium caprolactam 50 Component system (B) ε-caprolactam 122 parts by weight Iso7taloyl biscaprolactam 2.6 Mixture T
35 parts by weight Subsequently, 30 parts by weight of the component system <A) and 90 parts by weight of the component system (B) were weighed into a beaker, mixed with a stirrer, and immediately after that, the vertical 3001 was heated to 135° C. with an electric heater. ,'Wi200
+n+n, into a flat molding mold having a cavity of 2.5 tIrn in depth, and held at 135° C. for 3 minutes.

The mold was then cooled, opened, and the molded product was taken out to produce the desired amide resin molded product.

The measurement results of the physical properties, appearance, etc. of the obtained molded product are
Shown in Table 1.

Experimental Example 2/4 In the preparation example of Mixture I of Experimental Example 1, nylon ■ (Experimental Example 2) and nylon ■ (Experimental Example 3) were used in place of nylon ■.
, 1. Mixture ■ (Experimental Example 2), Mixture ■ (Experimental Example 3), and Mixture ■ (Experimental Example 4) were prepared using Nylon (Experimental Example 4).

The average particle diameters of the polyphenylene ether dispersed in the resulting 3 g mixture were 2.0 μ (mixture ■) and 1 μ, respectively.
．． They were 8μ (mixture ■) and 2.1μ (mixture ■).

Next, in the example described in Experimental Example 1, the procedure was the same as in the same example, except that mixture ■, mixture ■, or mixture ■ was used instead of mixture I blended in component system (B). A molded article was manufactured.

The measurement results of physical properties, appearance, etc. of the molded products obtained are
Shown in Table 1.

Experimental Example 5-u8 In the preparation example of mixture T of Experimental Example 1, poly(2,6-
poly(2,6-di-propyl-1,4-phenylene) instead of dimethyl-1,4-phenylene)ether
Ether (Experimental Example 5), poly(2-methyl-6-chloro-1=4-7 enylene) ether (Experimental Example 6), poly(2-methyl-6-chloroethyl-1t 4-7 x
Nylene) ether (Example 79*) Four mixtures were prepared using a copolymer of 2,6-dimethyl-1,4-phenol and O-cresol (Example 8).

Next, in the example described in Experimental Example 1, instead of Mixture I blended into component system (B), the four types of mixtures prepared by the above method were separately blended, and the four types of amide type A resin molded product was manufactured.

The measurement results of physical properties, appearance, etc. of the molded products obtained are
Shown in Table 1.

Experimental Example 9 In the example described in Experimental Example 1, a molded article was produced using the same procedure as in the same example, except that the mixture (2) was not added to the component system (B) during molding.

The measurement results of physical properties, appearance, etc. of the molded products obtained are
Shown in Table 1.

Experimental Example 10 In the example described in Experimental Example 1, the composition of the component system (B) was changed as follows, and a molded article was manufactured by the same procedure as in the same example.

Component system (B) ε-caprolactam 80 parts by weight Polymerization promoter I 35 〃Mixture■
35 Polymerization co-catalyst (2) is a compound represented by the following formula (where n is an integer of 2 or more, and Z is polybutadiene with a molecular weight of about 5,000).

The measurement results of physical properties, appearance, etc. of the molded products obtained are
Shown in Table 1.

Experimental Examples 11 to 13 In the example described in Experimental Example 10, when preparing mixture I, N-butylbenzenesulfonamide V was replaced with N-
Methyl-N-butylbenzenesulfonamide (Experimental Example 1
1), N-cyclohexyl-1)-toluenesulfonamide (Experimental Example 12) or N-benzyl-p-methoxybenzenesulfonamide (Experimental Example 13) was prepared in the same manner as in the same example. A mixture of seeds was obtained.

The average particle size of the poly7-ethylene ether dispersed in the three types of mixtures obtained was 2.0 μm (Experimental Example 110.
They were 8 μ (Experimental Example 12) and 1.6 μ (Experimental Example 13).

Next, a molded article was manufactured in the same manner as in the example described in Experimental Example 10.

The measurement results of physical properties, appearance, etc. of the molded products obtained are
Shown in Table 1.

Experimental Example 14 In the example described in Experimental Example 10, a mixture was obtained in the same manner as on the same side except that N-butylbenzenesulfonamide was not added.

The polyphenylene ether dispersed in the resulting mixture did not form fine particles and had a large average particle size of 70 μm.

Next, a molded article was produced in the same manner as described in Experimental Example 10, except that the mixture prepared by the above method was used in place of the mixture (2) blended into the component system (B).

The measurement results of the physical properties, appearance, etc. of the obtained molded product are
Shown in Table 1.

Experimental Example 15 Nylon I 60 parts by weight, poly(2,6-cymethyl-1
*4-7 x Nilene) 10 parts by weight of ether and N
-3 parts by weight of butylbenzenesulfonamide were each weighed and mixed to obtain a triblend product.

This tri-blend was mixed with Brabender at 220%
Mixture X was obtained by kneading for 3 minutes at a temperature of .degree.

The average particle size of polyphenylene ether in mixture X is 1
．． It was 1μ.

Next, component system (A) and component system (B) with the following compositions.
were prepared, respectively, and molded articles were manufactured in the same manner as in Experimental Example 1.

Component system (A) ε-caprolactam 283 parts by weight Bromomagnesium caprolactam 17 Mixture X
200 // Component system (B) ε-caprolactam 210 parts by weight Polymerization cocatalyst ■ 90 〃Mixture X
200// Table 1 shows the measurement results of the physical properties, appearance, etc. of the obtained molded product.

Experimental Example 16 Component system (A) and component system (B) having the following compositions were prepared in the same manner as in Experimental Example 1, and an attempt was made to mold them, but component system (B) did not melt; It was not possible to produce a molded product.

Component system (A) ε-caprolactam 233 parts by weight Bromomagnesium caprolactam 17 Mixture X
250 // Component system (B) ε-caprolactam 160 parts by weight Iso7taloyl biscaprolactam 90 Mixture X
250//This example shows that component system (B) does not melt because the amount of nylon I derived from mixture X is too large relative to the amount of ω-lactam component in the molding composition.

Experimental Example 17 Weighed and mixed 24 parts by weight of 1% nylon, 36 parts by weight of poly(2,6-dimethyl-1?4-7xnylene)ether, and 5 parts by weight of N-butylbenzenesulfonamide, and mixed them to form a triblend. I got something.

This triblend was mixed with Brabender for 22 hours.
Mixture M was obtained by kneading for 3 minutes at a temperature of 0°C.

Next, component system (A) and component system (B) with the following compositions.
were prepared, respectively, and molded articles were manufactured in the same manner as in Experimental Example 1.

Component system (A) ε-caprolactam 225 parts by weight Bromomagnesium caprolactam 15 Mixture XI
260//Component system (B) ε-cabrolacta, mu 71 parts by weight Iso7
Taloylbiscaprolactam 2.6 Mixture T1
86//The measurement results of the physical properties, appearance, etc. of the obtained molded product are shown in Table @i.

Experimental Example 18 In the example described in Experimental Example 17, component system (A) and component system (B) were mixed in the following proportions, prepared in the same procedure as in Experimental Example 1, and attempted to be molded. The product could not be melted properly and a molded article could not be manufactured.

Component system (A) ε-caprolactam 200 parts by weight Bromomagnesium caprolactam 15 Mixture version
285 〃Component system (B) ε-caprolactam 65 parts by weight Iso7taloyl biscaprolactam 2.6 〃Mixture M
92 This example shows that molding cannot be performed because the amount of polyphenylene ether derived from mixture M with respect to the entire molding composition exceeds 30% by weight.

Experimental Example 19 18 parts by weight of nylon ■, poly(2,6-cymethyl-1.
6 parts by weight of N-butylbenzenesulfonamide were weighed and mixed to obtain a triblend. This triblend was kneaded using a Brabender at a temperature of 220°C to obtain a mixture (2).

Mixture (2) was used in place of mixture (2) in component system (A) and component M (B) of Experimental Example 17, and a molded article was attempted to be produced in the same manner as on the same side.

However, mixture (1) could not be dissolved in ε-caprolactam.

In this example, the weight ratio of nylon 1 to polyphenylene ether in mixture M is 30:7, and the preferred range of polyphenylene ether in the mixture is 65.
This indicates that molding is not possible because it exceeds the following range.

From Table 1, the following is clear.

(1) Amide resin molded product according to the present invention (Experimental Examples 1 to 8)
．． Nos. 10 to 13.15 and 17) have low moisture absorption and expansion coefficients due to water absorption, high bending elasticity, and excellent appearance.

(2) On the other hand, amide resin molded products that do not contain the essential components of the present invention (Experimental Examples 9 and 14) have a higher expansion rate due to moisture absorption and water absorption than molded products that contain the three components. is larger or has an inferior appearance.

Claims (2)

[Claims] (1) A molding composition containing an ω-lactam, a polymerization catalyst, a polymerization cocatalyst, and a mixture of polyamides, polyphenylene ethers, and benzene sulfonamide derivatives that are soluble in the ω-lactam in a molten state. An amide resin molded article, characterized in that it is molded by injection or injection into a mold at a temperature equal to or higher than the melting point of the amide resin. (2) In producing amide resin molded products, the components of polyamides, polyphenylene ethers, and benzenesulfonamide derivatives that are soluble in omega-lactam in a molten state are mixed in a molten state, and this mixture is polymerized. omega-lactam melt containing a catalyst (hereinafter referred to as "component system (A)")
That's what it means. ), an omega-lactam melt containing a polymerization cocatalyst (
Hereinafter, this will be referred to as "component system (B)." ), the mixture is mixed at a temperature equal to or higher than the melting point of the ω-lactam, and the mixture is injected or injected into a mold to form a molded product.