JPH0745570B2 - Amide-based resin molded article and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to an amide-based resin molded product and a method for producing the same. More specifically, it relates to a reaction injection molded product of an amide-based resin and a method for producing the same, which is excellent in mechanical properties at room temperature and low temperature, has less rigidity reduction and dimensional change due to water absorption, and has excellent surface appearance. ,
The present invention relates to a manufacturing method thereof.

"Prior art" In recent years, a so-called reaction injection molding is a method of injecting or injecting a highly reactive liquid material into a molding die, injecting it into the mold, and then performing a polymerization reaction of the liquid material to obtain a molded article. (Reaction Injection Molding, hereinafter simply referred to as "RIM".) Technology has been proposed and is drawing attention.

The above RIM technology has been put to practical use in the field of producing molded articles from polyurethane, and has made great progress, but recently, it is also applied to materials such as amide resins, unsaturated polyester resins, and epoxy resins. became. Among them, amide resins are excellent in toughness, heat resistance, electrical properties, friction resistance, wear characteristics, etc. Further, because the raw material composition has good fluidity, it can be molded at a low injection pressure. . Since it has the advantages that it can be used to mold thin to thick molded products as desired, it has good transferability on the mold surface, and that it can easily carry out the polymerization reaction because it generates less heat during polymerization, so it is of interest as a material for RIM. Has been done.

However, amide-based resins have insufficient impact resistance at low temperatures, and have high water absorption, resulting in a decrease in rigidity of molded products, significant dimensional changes, and even heat resistance when baking coating is performed. It has the drawback of being scarce. As a method for improving such a defect, a method of adding a certain block copolymer to an amide resin has been proposed (see Japanese Patent Publication No. 54-40120). However, this method is not preferable because the impact resistance at low temperature is improved, but the rigidity is remarkably reduced. As another method for improving the above-mentioned drawbacks, there is a method of adding a filler to an amide-based resin. With this method, the rigidity of a molded article due to water absorption can be reduced, dimensional change and heat resistance can be improved, but resistance to low temperature Impact resistance is not improved.

"Problems to be Solved by the Invention" The present invention provides an amide-based resin molded article obtained by RIM technology using ω-lactam as a raw material, in which the above-mentioned drawbacks are eliminated, and a method for producing the same. With the goal. That is, the present invention is (1) excellent in mechanical properties at normal temperature and low temperature, (2) less decreased in rigidity and dimensional change due to water absorption, and (3) sufficiently heat-resistant even during baking coating, (4) ) It is an object of the present invention to provide an amide resin molded product having an excellent surface appearance and a method for producing the same.

"Means for Solving the Problems" The gist of the first invention of the present invention is ω-
A mixture containing a lactam, a polymerization catalyst, a polymerization co-catalyst, a modified polyolefin and an aromatic polyamide soluble in ω-lactam in a molten state is injected or injected into a molding die at a temperature equal to or higher than the melting point of ω-lactam. The present invention resides in an amide-based resin molded product characterized by being a molded product.

The gist of the second invention of the present invention is that the ω-lactam melt containing the polymerization catalyst (hereinafter referred to as "component system (A)"), the ω-lactam melt containing the polymerization promoter (hereinafter " Component system (referred to as component (B)) is blended with a modified polyolefin in advance and dispersed in a molten ω-lactam-soluble aromatic polyamide, and the components (A) and (B) are added. A method for producing an amide-based resin molded article, which comprises mixing the components and injecting or injecting them into a molding die to obtain a molded article.

Hereinafter, the present invention will be described in detail.

The symmetrical amide resin molded article of the present invention contains a mixture of a modified polyolefin and an aromatic polyamide soluble in ω-lactam in a molten state, and is a reaction product of ω-lactam, a polymerization catalyst and a polymerization promoter. Consists of.

Specific examples of the ω-lactam used in the present invention include γ
-Butyrolactam, δ-valerolactam, ε-caprolactam, ω-enanthlactam, ω-capryllactam, ω-undecanolactam, ω-laurinlactam and the like. These ω-lactams may be used alone or in combination of two or more kinds.

The polymerization catalyst used in the present invention may be any compound selected from those used in the known anionic polymerization of ω-lactam. As a concrete example,
Alkali metals, alkaline earth metals, their hydrides,
Oxides, hydroxides, carbonates, alkyl compounds, aryl compounds, alkoxides, Grignard compounds, and reaction products of the above metals or metal compounds with ω-lactam, for example, sodium salt, potassium salt of ω-lactam,
Examples include magnesium halide salts. The amount of the polymerization catalyst used is in the range of 0.01 to 20 mol% or more based on the total ω-lactam.

The polymerization co-catalyst used in the present invention may be any compound selected from those used in known anionic polymerization of ω-lactam. Specific examples thereof include, for example, 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-phenylenebiscarbamide, carbamidelactams such as pyrrolidone, terephthaloyl chloride, adipic acid chloride, sebacic acid chloride, etc. Acid halides of
Polyacyl lactams such as adipoylbiscaprolactam, adipoylbispyrrolidone, terephthaloylbiscaprolactam, terephthaloylbispyrrolidone, isophthaloylbiscaprolactam, isophthaloylbispyrrolidone, or formula [Wherein A is halogen, or (Where Y is C ₃ -C ₁₁ alkylene) and a
Is an integer of 1, 2 or 3, b is an integer of 1 or more, R ₁ is an alkyl group, an aralkyl group, an alkyloxy group, an aryloxy group, a halogen group or an aralkyloxy group, R ₂ is a divalent or higher valent group selected from a hydrocarbon group and a hydrocarbon having an ether bond, and Z has a structure derived from a compound having a polyvalent hydroxyl group, an amino group, a mercapto group or an epoxy group. An acid halide functional material selected from the group consisting of
Or a lactam functional substance. ], Etc.

Examples of compounds having a polyvalent hydroxyl group 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,
1,4-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 diols, and triols, polytetramethylene glycol, castor oil, polybutadiene glycol, polyester glycols, poly (ε-caprolactone) diol, and other than hydroxy groups. There are numerous compounds containing substituents such as 2,4-dichlorobutylene glycol.

Examples of compounds having a polyvalent mercapto group include hydroxyethyl thioglycolate, ethylene glycol bis (thio-glycolate), pentaerythritol tetrakis (thioglycolate) and thioglycol, which have a polyvalent amino group. Examples of the compound include hexamethylenediamine, tolylenediamine, 2,4-diethyltolylenediamine, polyoxyethylenediamine, polyoxypropylenediamine and triamine, polyoxypropylenediamine, and a copolyamide having an amino group as an end group. As the compound having a polyvalent epoxy group, resorcinol digrecidyl ether,
Diglycidyl ether of bisphenol A, vinylcyclohexane dioxide, butanediol glycidyl ether, polyglycidyl ester of polycarboxylic acid, epoxidized polyolefin and glycidyl ether resin,
Epoxy novolac resin etc.

Further, in the present invention, a compound that does not substantially inhibit the polymerization reaction, such as a plasticizer, a foaming agent, a dye / pigment, an antioxidant, an internal release agent, etc., may be added.

In the present invention, the modified polyolefin imparts impact resistance at a low temperature to the molded product, reduces the water absorption of the molded product, and absorbs water together with the ω-lactam-soluble aromatic polyamide in the molten state described later. It has the function of improving rigidity and improving dimensional change.

As the modified polyolefin, ethylene, propylene,
Α-olefins such as butene-1, isoprene, and isobutylene, and copolymers that may contain dienes such as butadiene, hexadiene, norbornadiene in some cases, and 0.01 to 1.0% by weight of maleic anhydride is grafted. I can give you something. Further, it is a copolymer of ethylene and an α, β-unsaturated carboxylic acid such as acrylic acid or methacrylic acid, wherein the carboxylic acid contained in the copolymer is 0 to
There are also those in which 100 mol% is neutralized with a metal ion such as sodium, lithium, potassium, calcium or zinc. These may be used alone or in combination of two or more.

The ω-lactam soluble aromatic polyamide in the molten state is a polycondensate of dicarboxylic acids and diamines, and at least one of dicarboxylic acids or diamines contains an aromatic group. The polycondensation product is The condensate obtained by combining such compounds is
It is soluble in ω-lactam in a molten state, and has the function of improving the mechanical properties of an amide-based resin molded product at low temperatures, preventing deterioration of physical properties due to water absorption, and improving heat resistance.

Examples of dicarboxylic acids include terephthalic acid, isophthalic acid, methylterephthalic acid, methylisophthalic acid, dimethylterephthalic acid, dimethylisophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, bis (carboxyphenyl) propane and diphenyletherdicarboxylic acid. Of these, terephthalic acid and isophthalic acid are preferable.

Examples of the diamines include ethylenediamine, tetramethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, metaxylenediamine, paraxylenediamine, bis- (3-methyl-4-diamine).
Aminocyclohexyl) methane, 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and the like. Of these, hexamethylenediamine, 4,4'-diaminodicyclohexylmethane and bis- (3-methyl-4-aminocyclohexyl) methane are preferable.

The aromatic polyamide is a polycondensate of dicarboxylic acids and diamines, and it is preferable that at least one of the dicarboxylic acids and diamines contains an aromatic group. Such an aromatic polyamide is selected by combining the above dicarboxylic acid and the above diamine,
It can be manufactured by a conventionally known method. In order to produce the amide-based resin molded product according to the present invention, the modified polyolefin is previously blended and dispersed in the aromatic polyamide. The amount of the modified polyolefin to be added to the aromatic polyamide can be selected in the range of 1 to 50% by weight when the total amount of both is 100% by weight. When the amount of the modified polyolefin is 50% by weight or more, the aromatic polyamide is not soluble in the melted ω-lactam, which is not preferable. In the above range, the amount of modified polyolefin is preferably selected in the range of 15 to 40% by weight.

In order to disperse the modified polyolefin in the aromatic polyamide, a predetermined amount of both is applied, dry blended to obtain a mixture, and then the mixture is subjected to high shearing force and kneaded in a molten state. A twin-screw extruder may be used for this purpose, for example. In order to effectively achieve the object of the present invention, according to the experiments of the inventors, the modified polyolefin dispersed in the aromatic polyamide has a particle size of
It has been found that the range of 0.1 to 3 μm is preferable.

Next, a method for producing the amide resin molded product according to the present invention will be described. First, a polymerization catalyst was added to ω-lactam, and ω
-Heating above the melting point of the lactam (for example, 70 ° C or higher when the ω-lactam is ε-caprolamtam) to prepare a molten ω-lactam containing the polymerization catalyst (referred to as component system (A)). To do. Similarly, a polymerization promoter is added to the ω-lactam, and the mixture is heated to a temperature equal to or higher than the melting point of the ω-lactam, and a melted product of the ω-lactam containing the polymerization catalyst (referred to as component system (B)).
To prepare.

Next, the modified polyolefin is blended with at least one of the component system (A) and the component system (B), and the dispersed aromatic polyamide which is soluble in ω-lactam is blended. The blending amount of the aromatic polyamide in which the modified polyolefin is dispersed is 1 to 50 when the total amount of the component system (A), the component system (B) and the aromatic polyamide in which the modified polyolefin is dispersed is 100% by weight. It can be selected in the range of weight%. Above all, it is preferable to select in the range of 15 to 40% by weight. In the component system (A) or the component system (B), if necessary, other additives such as a crosslinking agent, a modifier, a plasticizer,
A colorant, an antioxidant and the like are mixed to obtain a molding composition.
When the aromatic polyamide in which the modified polyolefin is dispersed is blended in both the component system (A) and the component system (B), the distribution ratio is ω-lactam type, component system (A) and component system. It is determined each time depending on the viscosity of (B).

Then, the component system (A) and the component system (B) in a molten state are mixed at a constant ratio, and the obtained mixture of the molding composition is injected or injected into a molding die. In this case, the mixing ratio of the component system (A) and the component system (B) is 5 / 1-volume ratio of the component system (A) / component system (B) depending on the use of the molded article and the property to be provided. It is good to choose in the range of 1/5. To mix the two-component system, a fluid mixer such as a mixing mixer called a mixing head, a static mixer or a dynamic mixer can be used.

The temperature of the mold for producing the molded product is preferably maintained in the range of 100 to 200 ° C, preferably 120 to 160 ° C. When the temperature of the molding die is maintained in the above range, the polymerization reaction in the die rapidly progresses, and after the mixture of the molding composition is injected into the die, a short time (usually within 2 to 4 minutes). At), the injectate hardens or solidifies, ending the polymerization reaction. After completion of the polymerization reaction, the mold was cooled and taken out from the mold is the desired amide-based resin molded product.

The component system (A) and the component system (B) are preferably subjected to operations such as heating, mixing, and injection while sealing with an inert gas.
The inert gas used for the seal is partly contained in the molten material and also contained in the molded product, which helps prevent sinking of the molded product and improves the appearance of the molded product.

The amide-based resin molded article according to the present invention includes vehicle parts such as automobiles, snowmobile outer panels, steering wheels, dash panels, instrumental panels, cowl panels, cowl grills, armrests and bumpers;
Housing for OA equipment such as computers, word processors, typewriters, carrying cases; parts for electric home appliances such as televisions and audio equipment, housings; insulation materials for various other electric equipment, furniture parts, agricultural machine parts, plastics Examples include pallets and plastic sheets. These examples are not meant to limit the invention.

"Effects of the Invention" As described above, the present invention has particularly remarkable effects as described below, and its industrial utility value is extremely large.

(1) According to the method of the present invention, at least one of the component system (A) and the component system (B) is blended with an aromatic polyamide soluble in ω-lactam in a molten state in which a modified polyolefin is dispersed in advance. However, this was compounded ω
-The lactam melt has good flowability and excellent stability, so it is easy to handle and easy to inject into the mold during molding.

(2) Since the amide-based resin molded article according to the present invention contains the modified polyolefin and the aromatic polyamide soluble in the melted ω-lactam, it has excellent mechanical properties at room temperature and at low temperature. It also has excellent impact resistance.

(3) Since the amide-based resin molded article according to the present invention contains the modified polyolefin and the aromatic polyamide that is soluble in the ω-lactam in the molten state, the water absorption is reduced, and therefore the rigidity is reduced due to absorption. And there is little dimensional change due to water absorption.

(4) Since the amide-based resin molded article according to the present invention contains an aromatic polyamide that is soluble in ω-lactam in a molten state, it has excellent heat resistance during baking coating.

(5) The amide resin molded article according to the present invention is less likely to cause pinholes, voids, agglomeration of bubbles, etc. on the surface of the molded article,
The resulting molded article does not have irregularities and has an excellent appearance.

"Examples" Next, the present invention will be described based on Examples and Comparative Examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

The aromatic polyamides (hereinafter simply referred to as "aromatic nylon-
APO ". ) Is as follows.

Aromatic Nylon-APO I: ethylene, propylene and 1,4-butadiene copolymer of ethylene, propylene and 1,4-butadiene in a weight ratio of 91: 15: 4 (20% crystallinity, melt index (MI) of 5 g / 10 minutes (190 ° C.)), modified polyolefin pellets grafted with 0.4% by weight of maleic anhydride, and terephthalic acid, isophthalic acid and hexamethylenediamine in a weight ratio of 33: Aromatic polyamide pellets that were polycondensed at a ratio of 17:50 and had a number average molecular weight of about 10,000 measured by GPC using a mixed solution of m-cresol / chloroform in a ratio of 1 to 4 (weight ratio) as a solvent. And were weighed in a weight ratio of 30:70, and mixed with a blender.

The obtained mixture was mixed with a 50 mm twin screw extruder (Toshiba Machinery Co., Ltd., T
EM-50), the cylinder temperature was set to 190 ° C, 200 ° C, 210 ° C, 220 ° C from the hopper side to the die side, and the mixture was kneaded and pelletized under the screw rotation speed of 220 rpm. The average particle diameter of the modified polyolefin dispersed in is 0.3 μm.

Aromatic Nylon-APO II: Ethylene, butene-1 and 1,4-butadiene in a weight ratio of 81: 14: 5 ethylene, butene-1 and 1,4-butadiene copolymer (crystallinity 20 %, MI is 4g / 10 minutes (190
C.)) and 0.4% by weight of maleic anhydride grafted modified polyolefin pellets, terephthalic acid, isophthalic acid and 4,4′-diaminodicyclohexylmethane in a weight ratio of 33:17:50. Polycondensed with a number average molecular weight of about 1.
30% by weight of 50,000 aromatic polyamide pellets
Weighed in a ratio of 70 and mixed in a blender.

The obtained mixture was kneaded into pellets by using a 50 mm twin-screw extruder in the same manner as in the case of aromatic nylon-APO I. The average particle size of the modified polyolefin dispersed in the aromatic polyamide is 0.3 μm.

-Aromatic Nylon-APO III: In the combination of Aromatic Nylon-APO I, except that the modified polyolefin / aromatic nylon was replaced with a weight ratio of 40/60, the aromatic nylon-APO III was prepared in the same manner as in the case of the same combination preparation. APO III was prepared.

The average particle size of the modified polyolefin dispersed in the aromatic polyamide is 0.5 μm.

Aromatic Nylon-APO IV: ethylene, propylene and 1,4-butadiene copolymer of ethylene, propylene and 1,4-butadiene in a weight ratio of 91: 15: 4 (crystallinity 20%, melt index (MI) of 5 g / 10 minutes (190 ° C)), pellets of modified polyolefin grafted with 0.4% by weight of maleic anhydride, terephthalic acid, isophthalic acid and bis- (3-
Methyl-4-aminocyclohexyl) methane was polycondensed at a weight ratio of 33:17:50 by a GPC method using a m-cresol / chloroform 1 to 4 (weight ratio) mixture as a solvent. An aromatic polyamide pellet having a measured number average molecular weight of about 10,000 was weighed in a weight ratio of 30:70, and mixed with a blender.

The obtained mixture was mixed with a 50 mm twin screw extruder (Toshiba Machinery Co., Ltd., T
EM-50), the cylinder temperature was set 210 ° C, 250 ° C, 270 ° C, 270 ° C from the hopper side to the die side, and the mixture was kneaded and pelletized under the screw rotation speed of 220 rpm. The average particle diameter of the modified polyolefin dispersed in is 0.3 μm.

Aromatic nylon-APO V: ethylene, butene-1 and 1,4-butadiene in a weight ratio of 81: 14: 5 a copolymer of ethylene, butene-1 and 1,4-butadiene (crystallinity 20 %, MI is 4g / 10 minutes (190
C.)) and 0.4% by weight of maleic anhydride grafted modified polyolefin pellets, terephthalic acid, isophthalic and bis- (3-methyl-4-aminocyclohexyl) methane, hexamethylenediamine, in a weight ratio. It was polycondensed at a ratio of 33: 17: 25: 25.
Aromatic polyamide pellets having a number average molecular weight of about 15,000 measured in the same manner as the previous one were weighed in a weight ratio of 30:70, and mixed with a blender.

The obtained mixture was kneaded into pellets by using a 50 mm twin-screw extruder in the same manner as in the case of aromatic nylon-APO I. The average particle size of the modified polyolefin dispersed in the aromatic polyamide is 0.3 μm.

Further, in the following examples, low temperature impact resistance (DuPont impact value), bending rigidity (bending modulus), water absorption expansion coefficient, heat resistance (heat sag), porosity, and
The appearance and the like were evaluated as follows.

◎ Low temperature impact resistance (DuPont impact value) A test piece was cut out from the flat plate-shaped molded product obtained in the Examples or Comparative Examples, and the test piece was saturated with water in an atmosphere of 23 ° C and 50% relative humidity. After absorbing moisture up to -30
After being left in a low temperature room at ℃ for 6 hours, the impact value was measured using a DuPont impact tester according to JIS K-5400. The diameter of the dart used at this time was 12.7 mm, and the diameter of the receiving hole of the test piece was 12.7 mm.

◎ Bending rigidity (bending modulus) When a molding composition is injected into a molding die from a flat molded article, a direction parallel to the flowing direction of the molding composition and a direction perpendicular to the flowing direction. Then, two kinds of test pieces were cut out. These test pieces were allowed to absorb moisture to a saturated amount in an atmosphere of 23 ° C. and 50% relative humidity, and then measured according to ASTM D-790.

◎ Water Absorption Expansion Rate A test piece with a length of 15 cm and a width of 2 cm was cut out from an absolutely dry plate-shaped molded product, 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 the length (l) immediately after being taken out was measured and calculated by the following formula.

◎ Heat resistance (heat sag) A 125 mm long, 20 mm wide test piece is cut out from a flat dry molded product, and one end of the test piece is fixed by a 25 mm fixing jig, leaving the remaining 10 cm in a protruding shape. The sagging degree (mm) of the free end of the test piece under the condition of a temperature of 160 ° C is determined by ASTM D 3769.
It was measured according to −81.

◎ Porosity Test pieces were cut out from a flat-plate molded product in an absolutely dry state, and JIS
The specific gravity was measured according to K-6911 and calculated by the following formula.

◎ Surface appearance The surface of the molded product was observed mainly with the naked eye, but the surface roughness was additionally evaluated using a surface roughness meter (Model SE-3A, manufactured by Kosaka Laboratory Ltd.).

The evaluation results are displayed in the following four levels.

⊚: excellent, ◯: good, Δ: acceptable, ×: not possible Example 1 The component system (A) and the component system (B) having the following compositions were prepared in respective component system holding tanks, and the component system (A ) 90
° C., while maintaining component and (B) to 130 ° C., was sealed with nitrogen gas at 1 kg / cm ² under stirring, respectively.

Component system (A) ε-caprolactam 27.3 wt% sodium pyrrolidone 0.7 〃 aromatic nylon-APO I 8 〃 Component system (B) ε-caprolactam 37.5 wt% terephthaloylbiscaprolactam 1.5 〃 aromatic nylon-APO I 25 〃 Next The component system (A) and the component system (B) have a cavity of 300 mm in length, 300 mm in width, and 3 mm in depth controlled by an electric heater at a temperature of 140 ° C. using a reaction injection molding machine. The molding composition was injected through the gate in the center of the and held for 2 minutes.

Then, the mold was cooled, the mold was opened, and the molded product was taken out to obtain the desired amide resin molded product.

Table 1 shows the results of measuring the physical properties of the obtained molded product.

Comparative Example 1 A molded article was obtained by the same procedure as in Example 1 except that the component system (A) and the component system (B) in the example described in Example 1 were changed to the following.

Component system (A) ε-caprolactam 35.3% by weight sodium pyrrolidone 0.3 〃 Component system (B) ε-caprolactam 52.5% by weight terephthaloylbiscaprolactam 1.5 〃 polypropylene glycol 10 〃 (molecular weight 2,000) Physical property measurement of the obtained molded product The results are shown in Table 1.

Example 2 In the example described in Example 1, a molded product was obtained by the same procedure as in the same example, except that the component system (A) and the component system (B) were changed to the following.

Component system (A) ε-caprolactam 25% by weight Bromomagnesium caprolactam 3 〃 aromatic nylon-APO I 8 〃 Component system (B) ε-caprolactam 37.5% by weight Isophthaloyl biscaprolactam 1.5 〃 aromatic nylon-APO I 25 〃 Table 1 shows the results of measuring the physical properties of the obtained molded product.

Example 3 In the example described in Example 1, a molded product was obtained by the same procedure as in the same row except that the component system (A) and the component system (B) were changed to the following, respectively.

Component system (A) ε-caprolactam 28% by weight Bromomagnesium caprolactam 3 〃 aromatic nylon-APO I 5% by weight Component system (B) ε-caprolactam 47.5% by weight Isophthaloylbiscaprolactam 1.5 〃 aromatic nylon-APO I 15 Table 1 shows the results of measuring the physical properties of the obtained molded products.

Example 4 A molded article was obtained by the same procedure as in the example except that the component system (A) and the component system (B) in the example described in Example 1 were changed to the following.

Component system (A) ε-caprolactam 23% by weight Bromomagnesium caprolactam 3 〃 aromatic nylon-APO I 10 〃 Component system (B) ε-caprolactam 32.5% by weight Isophthaloyl biscaprolactam 1.5 〃 aromatic nylon-APO I 30% by weight % Table 1 shows the results of measuring the physical properties of the obtained molded products.

Example 5 In the example described in Example 2, the aromatic nylon-APO I
A molded article was obtained by the same procedure as in the same example except that aromatic nylon-APO II was used instead of.

Table 1 shows the results of measuring the physical properties of the obtained molded product.

Example 6 In the example described in Example 1, a molded product was obtained in the same procedure as in the same example, except that the component system (A) and the component system (B) were changed to the following.

Component system (A) ε-caprolactam 25% by weight Bromomagnesium caprolactam 3 〃 Aromatic nylon-APO III 8 〃 Component system (B) ε-caprolactam 37.5% by weight Isophthaloylbiscaprolactam 1.5% by weight Aromatic nylon-APO III 25 Table 1 shows the results of measuring the physical properties of the obtained molded products.

Comparative Example 2 A molded article was obtained by the same procedure as in Example 1 except that the component system (A) and the component system (B) in the example described in Example 1 were changed to the following.

Component system (A) ε-caprolactam 47% by weight Bromomagnesium caprolactam 3 〃 Component system (B) ε-caprolactam 27.7% by weight Polymerization promoter (X) 22.3 〃 where the polymerization promoter (X) is represented by the following formula. It is a compound.

[However, Z is a polyether having a molecular weight of about 6,000, n is an integer of 2 or more, and its weighted average is 2.3. The results of measuring the physical properties of the obtained molded product are shown in Table 1.

Comparative Example 3 A molded product was obtained by the same procedure as in Example 1 except that the component system (A) and the component system (B) in the example described in Example 1 were changed to the following.

Component system (A) ε-caprolactam 38 wt% Bromomagnesium caprolactam 2 〃 Component system (B) ε-caprolactam 14.4 wt% Polymerization co-catalyst (X) 15.6 〃 Milled fiber 30 〃 Here, the milled fiber has a fiber diameter of 11 μm, The average fiber length is 150 μm, and the surface is surface-treated with γ-aminopropyltriethoxysilane.

Table 1 shows the results of measuring the physical properties of the obtained molded product.

Comparative Example 4 In the example described in Example 2, the aromatic nylon-APO I
In the same example, except that aromatic nylon (polyterephthalic acid, isophthalic acid and hexamethylenediamine in a weight ratio of 33:17:50 was polycondensed in the ratio of 33:17:50) was used instead of the modified polyolefin. A molded product was obtained by the same procedure as described above.

Table 1 shows the results of measuring the physical properties of the obtained molded product.

Comparative Example 5 In the example described in Example 2, the aromatic nylon-APO I
Instead of using ε-caprolactam, a molded product was obtained by the same procedure as in the same example.

Table 1 shows the results of measuring the physical properties of the obtained molded product.

The following is clear from Table 1.

(1) The amide-based resin molded article according to the present invention has an excellent impact resistance value at low temperature (see Examples 1 to 5 and Comparative Examples 1, 3, and 4).

(2) The amide-based resin molded article according to the present invention has excellent rigidity in a water-absorbed state (Examples 1 to 5, Comparative Example 1,
2, 3, 5).

(3) The amide-based resin molded product according to the present invention has a low absorption expansion coefficient and excellent dimensional stability (see Examples 1 to 5 and Comparative Examples 1, 2, 3, and 5).

(4) The amide resin molded product according to the present invention has excellent heat resistance.

(5) The amide-based resin molded product according to the present invention is excellent in surface appearance (see Examples 1 to 5 and Comparative Example 3).

(6) The amide-based resin molded product according to the present invention is excellent in all of the above properties, and the comparative example is not excellent in all of the above properties.

Example 7 In the example described in Example 1, the aromatic nylon-APO I
A molded article was obtained by the same procedure as in the same example except that aromatic nylon-APO IV was used instead.

Table 2 shows the results of measuring the physical properties of the obtained molded product.

Example 8 In the example described in Example 2, the aromatic nylon-APO I
A molded article was obtained by the same procedure as in the same example except that aromatic nylon-APO IV was used instead.

Table 2 shows the results of measuring the physical properties of the obtained molded product.

Example 9 In the example described in Example 2, the aromatic nylon-APO I
A molded article was obtained by the same procedure as in the same example except that aromatic nylon-APO V was used instead.

Table 2 shows the results of measuring the physical properties of the obtained molded product.

Comparative Example 6 In the example described in Example 8, the aromatic nylon-APO IV
Aromatic nylon (terephthalic acid, isophthalic acid and bis- (3-
A molded product was obtained by the same procedure as in the same example, except that three components of methyl-4aminocyclohexyl) methane were polycondensed at a weight ratio of 33:17:50).

Table 2 shows the results of measuring the physical properties of the obtained molded product.

From Table 2, the amide-based resin molded product according to the present invention is excellent in impact resistance, rigidity, heat resistance, etc., has a low expansion coefficient when absorbing water,
It is clear that the dimensional stability is excellent. The comparative examples are significantly inferior in impact resistance.

Claims (6)

[Claims] 1. A mixture containing an ω-lactam, a polymerization catalyst, a polymerization promoter, a modified polyolefin, and an aromatic polyamide soluble in a molten ω-lactam is molded at a temperature equal to or higher than the melting point of the ω-lactam. An amide-based resin molded product, which is molded by injection or injection into a mold. 2. The modified polyolefin contained in the amide-based resin molded product is 0.5 to 25% by weight based on the amide-based resin molded product, and the average particle diameter thereof is in the range of 0.1 to 3 μm. The amide-based resin molded product according to claim (1). 3. An aromatic amide is a polycondensation product of a dicarboxylic acid and a diamine, wherein at least one of the dicarboxylic acid and the diamine contains an aromatic group. The amide-based resin molded article according to any one of items (1) to (2). 4. The dicarboxylic acids are isophthalic acid and / or terephthalic acid, and the diamines are bis- (3-methyl-4-aminocyclohexyl) methane and / or hexamethylenediamine. An amide-based resin molded article according to item (3). 5. The aromatic polyamide contained in the amide resin molded product is 1 to 50% by weight based on the amide resin molded product.
The amide-based resin molded article according to any one of claims (1) to (3), characterized in that 6. An ω-lactam melt containing a polymerization catalyst (hereinafter referred to as "component system (A)"), an ω-containing a polymerization promoter.
At least one of the molten lactams (hereinafter referred to as "component system (B)") is blended with a modified polyolefin in advance and blended with an aromatic polyamide soluble in ω-lactam in a molten state, A method for producing an amide-based resin molded article, which comprises mixing the component system (A) and the component system (B) and injecting or injecting them into a molding die to obtain a molded product.