JPS635911A - Amide-based resin molded item - Google Patents

Abstract

PURPOSE:To obtain an amide-based resin molded item, which has excellent rigidity and heat resistance, little strain and anisotropism of mechanical properties and excellent surface appearance and the raw material composition of which has so favorable fluidity as to facilitate the handling and molding operation by a method wherein mixing is performed so as to bring the mixing ratio of composition reinforcing material to omega-lactam, polymerization catalyst and polymerization cocatalyst within the range of specified ratios and the mixture, which is heated up to a temperature exceeding the melting point of omega-lactam, is injected or poured in a mold so as to take place polymerization reaction in the mixture. CONSTITUTION:The title amide-based resin molded item is obtained by injecting or pouring the mixture, which is produced so as to realize the mixing ratio of 5-50 parts by weight of composite reinforcing material to 100pts.wt. of the sum of omega-lactam, polymerization catalyst, polymerization cocatalyst and composite reinforcing material, at a temperature exceeding the melting point of omega-lactam in a mold so as to take place polymerization reaction therein. The obtained amide-based resin molded item has a surface appearance without the surface appearance intrinsic in amide-based resin being impaired, excellent rigidity and little strain (warpage) and anisotropism of mechanical properties. Further, although glass-based composite reinforcing material is blended in raw material composition, the handling of the raw material composition and molding operation are easy.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] The present invention relates to an amide resin molded article. More specifically, the present invention relates to a reaction injection molded product or a reaction cast molded product of an amide resin containing a glass composite reinforcing material.

[Prior art] In recent years, direct molded products, so-called reaction products, have been developed by injecting or injecting a highly reactive raw material composition consisting of two or more components into a mold, and simultaneously performing a polymerization reaction and molding in the mold. Injection molded products or reaction cast molded products are attracting attention.

Conventionally, molded products made of polyurethane have made great progress as the direct molded products mentioned above, but recently reaction molded products made of new materials such as amide resins, unsaturated polyesters, and epoxy resins have also been studied. There is. Among these, amide resins have excellent toughness, rigidity, and heat resistance, as well as good friction and abrasion properties, as well as good fluidity of the raw material composition and low heat generation during polymerization. It is particularly suitable as a material for reaction injection molding and reaction casting molding because it can be molded at low injection pressure, has good transferability on the mold surface, and can produce molded products from thin to thick walls. Attention has been paid.

In order to take advantage of the features of the amide resin and impart even higher rigidity and heat resistance, attempts have been made to incorporate glass fiber into the raw material composition as a reinforcing material.

Glass fibers blended into raw material compositions used to manufacture reaction injection molded products or reaction cast molded products are often
Milled glass fiber or cut glass fiber.

When a raw material composition containing the above-mentioned glass fibers as a reinforcing material is used, the rigidity and heat resistance of the molded article are certainly improved. However, in the - direction, the viscosity of the raw material composition increases significantly by -L, and the range of molding conditions becomes narrower.
There were problems such as warpage) and anisotropy of mechanical properties.

Furthermore, a method has been proposed in which glass flakes are blended into the raw material composition for the purpose of reducing distortion (warp) and anisotropy of mechanical properties of the molded product. In order to blend glass flakes into the raw material composition and make the rigidity of a molded article equivalent to that when glass fibers are blended, it is necessary to blend flakes with a large particle size. However, when flakes with a large particle size are blended instead of glass fibers, the rigidity of the molded product is improved, but there are problems in that the surface appearance deteriorates and distortion (warpage) increases.

Against this background, in addition to the features of amide resins, amide resin molded products have excellent rigidity, do not impair surface appearance, and have less distortion (warp) and anisotropy in mechanical properties. Its appearance was eagerly awaited.

[Problem 1 to be solved by the present invention The problems to be solved by the present invention are as follows.

(1) An amide resin molded product obtained by reaction injection molding or reaction cast molding, in which the surface appearance of the amide resin powder is not damaged, has excellent rigidity, and has no distortion.
To provide a molded product with less warpage) and anisotropy of mechanical properties.

(2) This is an amide resin molded product obtained by reaction injection molding or reaction cast molding, and even though the raw material composition contains a glass composite reinforcing material,
To provide a molded article whose raw material composition is easily handled and molded.

[Means for Solving the Problems 1] As a result of extensive studies in order to solve the above problems, the present inventors have developed a composite consisting of glass fiber and glass flakes as a reinforcing material to be added to the amide resin. If the appropriate amount of reinforcing material is used, the surface of the molded product will not be damaged, it will have excellent rigidity, and a molded product with less distortion (warp) and anisotropy of mechanical properties will be obtained, and the molding operation will be easy. This is what we have discovered and arrived at the present invention.

However, the gist of the present invention is that ω-lactam,
A polymerization catalyst, a polymerization co-catalyst, and a composite reinforcing material consisting of glass fibers and glass flakes are combined in such a manner that the ratio of the composite reinforcing material to 100 parts by weight of the total amount of the ω-lactam, the polymerization catalyst, the polymerization co-catalyst, and the composite reinforcing material is 5 to 5 parts by weight. 50 parts by weight, and this mixture is injected or injected into a mold at a temperature of -L below the melting point of ω-lactam to cause a polymerization reaction. Characteristics of amide resin molded products.

The present invention will be explained in detail below.

The amide resin molded article of the present invention is a composite reinforcing material (hereinafter simply referred to as "composite reinforcing material") comprising an ω-lactam, a polymerization catalyst, a polymerization promoter, and glass fibers and glass flakes.

) is an essential raw material.

Specific examples of ω-lactams used in the present invention include γ
-butyrolactam, δ-valerolactam, ε-caprolactam, ω-enantholactam, ω-cabryl lactam, ω-undecanolactam, 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 of reaction products with lactams include sodium salts, potassium salts, and magnesium halide salts of ω-lactams. The amount of polymerization catalyst used is o based on the total ω-lactam.
, o i to 15, or 20 mol% 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-piscarbamide, caprolactam, N,N'-diphenyl-p-phenylenebiscarbamide caprolactam, N,N'-diphenyl-p-phenylenebiscarbamide, Carbamide lactams such as pyrrolidone, acid halides such as Tele7 taloyl chloride V1 adipic acid chloride, sebacyl chloride, adipoylbiscaprolactam, adipoylbispyrrolidone, Tele7 taloylbiscaprolactam, Tele7 taloylbispirolidone, etc. polyacyllactams, or formula-1, in which A is halogen, or -h-h=U
(Here, Y is 3'-diameter γ-lyalene), a is an integer of 1, 2, or 3, b is an integer of 2 or more, and R1 is an alkyl group, an aralkyl group. , an alkyloxy group, an aryloxy group, a halogen group, or an aralkyl group, R2 is a divalent or higher group selected from a hydrocarbon group and a hydrocarbon containing an ether bond, and Z is ( 1) Lowest molecular weight 2.
(2) a polyether having the lowest molecular weight of 2.
000, or (3) a polyester segment containing a polyether segment having a minimum molecular weight i, o
oo hydrocarbons] or lactam-functional materials selected from the group consisting of: In addition, in the present invention, a crosslinking agent that undergoes a polymerization reaction with the ω-lactam, a polymerization catalyst, and a polymerization cocatalyst and enters the polymer chain;
Modifiers (soft segments) etc. can be blended. These compounds include compounds having a polyvalent hydroxyl group, mercapto group, amino group or epoxy group.

Examples of compounds having polyvalent hydroxyl groups include alkylene glycols such as diethylene gelcol, triethylene glycol, tetraethylene gelcol, tetramethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, and 1,2-propanediol. , 1°3-propanediol, 1,3-hexanediol, butylene glycol, 1,4-butanol, dicyclopentadiene glycol, heptaethylene glycol and isopropylidene bis(p-phenyleneoxypropanol-2), alkylene Polyols other than glycols such as glycerol, pentaerythritol, 1,2,6-hexanediol and 1-trimethylolpropane, polymeric polyols such as polyethylene gelcol, polypropylene glycol, polyoxypropylene diol, and triols, polytetramethylene glycol, Included are castor oil, polybutadiene glycol and a number of compounds containing substituents other than hydroxy groups such as 2,4-nochlorobutylene glycol.

Examples of compounds having a polyvalent mercapto group include hydroxyethylthioglycolate and ethylene glycol bis(
thioglycolate), pentaerythritol tetrakis-(thioglycolate), and thiodiglycol, and examples of compounds having polyvalent amino groups include hexamethylenediamine, tolylentzamine, 2,4-diethyl-1-lylenediamine, Examples include polyoxyethylenediamine, polyoxypropylenenoamine and triamine, polyoxypropylenenoamine, copolyamide with 7 amide groups at the end, and examples of compounds having polyvalent epoxy groups include resorcinol nobricidyl ether, Examples include diglycidyl ether oxide of bisphenol A, butanol diglycidyl ether, polyglycidyl ester of polycarboxylic acid, epoxidized polyolefin and glycidyl ether resins, and epoxy novolac 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 also be blended.

and glass flakes.

The glass fiber used as the above-mentioned composite reinforcing material may be one obtained by crushing or cutting long glass fibers, that is, milled glass fiber or cut glass fiber, and is not particularly limited. The composition of the glass fiber is also not particularly limited.

Milled or cut glass fibers generally have an E
〃Glass called glass is used, but it is also treated with concentrated sulfuric acid to remove acid-soluble components, such as leached brass, C glass with strong acid resistance, Alf glass, and S glass.
Known glasses such as glass, M glass, AR glass, Li, and f glass can be used.

Further, the shape and composition of the glass flakes used as the composite reinforcing material are not limited as long as they are in the shape of ordinary 7-lakes.

For glass flakes, C glass with strong acid resistance is generally used, but in addition, E glass, A glass S glass, M glass AR, f glass, which are often used for glass fiber manufacturing, are used. In order to improve the interfacial adhesion between the reinforcing material and the matrix resin, the surface of the glass reinforcing material is treated with a surface treatment agent. In the present invention, for example, a chromium-based surface treatment agent such as methacrylate-chromic chloride, vinyl-triethoxysilane, vinyltris(β-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane,
Cationic methacrylate functional silane, γ-ami7
Probyltriethoxysilane, β-(3,4-evoxinechlorhexyl)ethyltrimethoxysilane, γ-glycidoxyprobyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, phenyltrimethoxinelan, N- Silane surface treatment agents such as β-(aminoethyl)-γ-7minoprobyltrimethoxysilane, chloroprobilme)kC disilane, isopropyltriisostearoyl titanate, isopropyltridecylbenzenesulfonyl titanate, isopropyltris (dioctylpyrolyte), phosphate) titanate, tetraisopropyl bis(dioctyl phosphite)yl titanate, isopropyl tricumylphenyl natanate, isopropyl tri(N-7minoethyl-aminoethyl) titanate,
The use of glass fibers and glass flakes treated with known surface treatment agents, including other titanate surface treatment agents such as dicumyl phenyloxyacetate titanate and diisostearoyl ethylene natanate, as a composite reinforcement material . However, even when glass fibers and glass flakes without surface treatment are used as a composite reinforcing material, the effect is recognized in the present invention, so it is not essential to use a composite reinforcing material treated with a surface treatment agent.

In order to obtain the amide resin molded article according to the present invention, the above-mentioned ω
- mixing the lactam, polymerization catalyst, polymerization cocatalyst, and the composite reinforcing material, and adding this mixture (hereinafter referred to as raw material composition 1) at a temperature equal to or higher than the melting point of the ω-lactam,
It is necessary to inject or inject into a mold and cause a polymerization reaction.

In the above, it is an essential requirement that the ratio of the composite reinforcing material to 100 parts by weight of the raw material composition be in the range of 5 to 50 parts by weight.

When an acid is used, the effect of the composite reinforcing material is hardly exhibited, and the resulting molded product has insufficient rigidity.

Furthermore, if a raw material composition containing more than 50 parts by weight of composite reinforcement is used, the surface appearance of the obtained molded product will be impaired and it will become brittle, and the raw material composition used for molding will be As the viscosity increases significantly, depending on the molding method, the following disadvantages may occur, making it impossible to put it to practical use. That is, when molding is performed by injecting the raw material composition into a mold, high pressure is required, and the advantage of reaction injection molding of amide resins, which allows molding with relatively low injection pressure, is lost. . Furthermore, blockages frequently occur at the throttle part of the mixer that mixes the various raw materials to prepare the raw material composition, or in the transfer piping thereof.

In addition, when molding is performed by injecting the raw material composition into a molding die, the air bubbles caught during the preparation of the raw material composition cannot be completely removed, and these air bubbles remain in the molded product, resulting in defective molded products. give.

Next, an embodiment of manufacturing the amide resin molded article according to the present invention will be described.

The composite reinforcement material contains 10 to 50% by weight of glass fibers with a weight average fiber length in the range of 30 to 300 μm and a weight average diameter of 3-50% by weight.
90-50% by weight of glass flakes in the range of u300μm
Preferably, it consists of

Although the use of glass fibers with a weight average fiber length of more than 300 μm improves the rigidity of the resulting molded product, it is not preferable because the surface appearance deteriorates.
When glass M&fibers having a weight average fiber length of less than 30 μm are used, the surface appearance of the resulting molded product is good, but the improvement in rigidity is extremely small, which is not preferable. When glass flakes with a weight average diameter of more than 300 μm are used, although the rigidity of the resulting molded product is improved, the surface appearance deteriorates, which is undesirable. When using glass fibers, although the surface appearance of the resulting molded product is acceptable, the improvement in rigidity is small and distortions due to the orientation of glass fibers (
When using a composite reinforcing material in which the proportion of glass flakes with a uniform diameter exceeds 90% by weight, the viscosity of the raw material composition containing such a composite reinforcing material increases significantly by -L. This is not preferable because it makes the molding operation difficult and the resulting molded product has a low rigidity. - way,
When using a composite reinforcing material in which the proportion of glass fiber exceeds 50% by weight, that is, the proportion of glass flakes is less than 50% by weight, the rigidity of the resulting molded product will be sufficiently high. distortion due to fiber orientation;
Also, anisotropy in mechanical properties is observed, which is not preferable.

The glass fibers constituting the composite reinforcing material preferably have a weight average fiber length within the above range, but 3% by weight or less is less than 25 μm in fiber length, 30% by weight or less is more than 300 μm in length, and Weight average fiber length is 75-200μ
More preferably, it is in the range of 75 to 125 μm.
Particularly preferred are those within the range of . It is preferable to use lath fibers having such a fiber length distribution because it is possible to effectively improve the rigidity of the resulting molded product without impairing its surface appearance.

The diameter of the glass fibers constituting the composite reinforcement refers to the diameter (also called fineness) of the single glass fibers, and is expressed by symbols commonly used in the industry: E, F, G, HlJ, L, M, N, P, QSR.

S, T, U, i.e. 5.08μm to 25.4μm
It is desirable that the Although diameters smaller than this cannot be used, they have very low bulk specific gravity, are inconvenient to handle, and are very expensive due to poor spinning productivity. Glass fibers exceeding the above ratio are undesirable because the ratio of fiber length to fiber diameter (referred to as aspect ratio) is small, and the rigidity of the molded product is not improved much.

The glass flakes constituting the composite reinforcing material preferably have a weight average diameter within the above range, but the weight average diameter may range from 10 to 50μ.
More preferably, it is within the range of m.

When using glass flakes having such a weight average diameter range, it is preferable that the surface appearance of the resulting molded product is not impaired.

Further, it is desirable that the glass flakes constituting the composite reinforcing material have a thickness in the range of 1 to 10 μm and a 7-spectral ratio (particle size/thickness) in the range of 2 to 150. When using such glass flakes, the surface appearance of the resulting molded product is not impaired, it has excellent rigidity, and it has good properties with less distortion (warp) and anisotropy of mechanical properties. This makes it a suitable molded product.

When manufacturing the amide resin molded product according to the present invention,
After mixing the composite reinforcing material with the ω-lactam, polymerization catalyst, and polymerization cocatalyst (hereinafter collectively referred to as [starting materials]), the starting materials are injected or injected into a mold to undergo a polymerization reaction. let

The composite reinforcement can be mixed into the starting materials by any of the following methods.

(b) Method of dividing starting materials into two-component systems The starting materials are
A melt of ω-lactam containing a polymerization catalyst (hereinafter referred to as [component system (A) 1)] and a melt of ω-lactam containing a polymerization co-catalyst (hereinafter referred to as [component system (B)) 1) and prepared separately, and after blending the composite ratio reinforcement clipping into at least one of these two-component systems, these two-component systems are combined with the ratio of the composite reinforcement material to the raw material composition according to the present invention. A method of combining and mixing at a mixing ratio that falls within the range specified in .

(b) Method for dividing starting materials into ternary or more component systems - (
In addition to component system (A) and component system (B) of b), ω-
A melt consisting of only a single raw material of lactam, polymerization catalyst, and polymerization cocatalyst is separately prepared, the raw materials are divided into a three-component system, and the composite reinforcement is made into at least one component system of these three or more component systems. How to mix materials.

(c) Other methods In the method of (a) above, component system (A>, component system (B)
) A method in which the composite reinforcing material is not blended into any of the above, but when these are combined and mixed, the composite reinforcing material is directly blended into this mixed system.

Among the mixing methods (a) to c) above, the method (a) is preferred. Therefore, in the following example, the method of mixing the composite reinforcing material into the starting material will be explained using method (a).

The method for producing the amide resin molded article according to the present invention will be explained in more detail.

First, the melt of the component system (A) is prepared by adding a polymerization catalyst to the ω-lactam and adding a polymerization catalyst above the melting point of the ω-lactam (for example, ω-L).
When the lactam is ε-caprolactam, the temperature is 70℃ or less)
However, in order to prevent the polymerization reaction from proceeding in the component system (A) itself, the temperature is usually maintained at 100° C. or lower.

Similarly, the melt of component system (B) contains ω-lactam, a polymerization cocatalyst and, if necessary, a small amount of additives (for example, a crosslinking agent, a reaction product, a modifier, a plasticizing agent, and an antioxidant IIr). ,
It is prepared by adding the omega-lactam and heating it to a temperature above the melting point of the ω-lactam, and the temperature is usually maintained at 140°C or lower.

Only one of the component system (A), component system (old), or component system (A> and component system (
The entire amount of the composite reinforcing material specified in 1 of the present invention is added to both of B) in an appropriate ratio and mixed. Note that the distribution ratio is based on the component system (A) or the component system (old viscosity, ω-
It is determined each time depending on the type of lactam, etc.

Next, component M(A) in a molten state or a molten slurry state
and component system (B) are combined and mixed at a certain ratio, and the obtained raw material composition is injected or injected into a mold. For mixing the two-component system described above, an equilibrium mixing device called a mixing head, or a fluid mixing device such as a static mixer or a dynamic mixer can be used.

In this case, the mixing ratio of component system (A) and component system (B) is
It can be changed depending on the purpose and properties of the molded product to be manufactured. The mixing ratio is generally preferably in the range of 571 to 115 in terms of volume ratio (component system (A)/component system (B)).

In addition, the temperature of the mold during molding is 100 to 200°C.
, preferably maintained within the range of 120 to 160°C. When maintaining the temperature of the mold within the above range,
The polymerization reaction within the mold proceeds rapidly, and after the raw material composition is injected into the mold, the injected material hardens or solidifies within a short period of time (usually within 2 to 4 minutes), and the polymerization reaction is completed. After the polymerization reaction is completed, the molded product is removed from the mold.

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 grills, and bumpers; combination machines, word processors, etc. Housing for 0Afi devices such as;
Housing for home appliances such as televisions and audio equipment;
Other products include insulating materials for various electrical equipment, furniture parts, plastic pallets, plastic sheets, etc.
It is not limited to these examples.

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

(1) The amide resin molded product according to the present invention has excellent rigidity and heat resistance due to the compound reinforcing material, has less distortion (warp) and anisotropy of mechanical properties, and has a surface appearance. is also excellent.

(2) In manufacturing the amide resin molded product according to the present invention, the physical properties of the glass fiber and glass flakes used as the composite reinforcing material, the ratio of the two, and the blending ratio of the composite reinforcing material are selected from a specific range. As the use ends with
The raw material composition used for molding is suppressed from increasing in viscosity, has good fluidity, and is easy to handle and mold.

"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 unless it exceeds the gist thereof.

The types and properties of the glass fibers used in the following examples are listed in Table 1 below, and the types and properties of the glass flakes are listed in Table 2 below.

Note that the fiber length distribution measurement of glass fibers and the particle size distribution measurement of glass flakes were each performed by the methods described below.

Measurement of fiber length distribution of glass fibers: Place glass fibers on a slide glass, drop ethylene glycol onto it, disperse it in ethylene glycol, and then press it with a cover glass so that the two pieces of glass are almost glass. The gap was set to be the same as the fiber diameter, a photograph was taken at 125 times magnification using a polarizing microscope, and the length distribution of 1000 fibers was measured three times, and the average value was taken as the fiber length distribution. Furthermore, the weight average fiber length was calculated from the fiber length distribution thus measured.

[Measurement of particle size distribution of 7 rake particles: Standard sieves with a diameter of 200III11 were stacked in the order of 48 mesh, 100 mesh, 150 mesh, 325 mesh, and the saucer, and the sample was placed in the -L stage of the cylindrical wire mesh. The sieve containing the sample was sieved by vibrating for 15 minutes using a rotary tube type vibrating sieve machine, and the weight of the sample remaining on each cylindrical wire mesh was weighed to measure the particle size distribution. Furthermore, the weight average diameter was calculated from the particle size distribution thus measured.

-27= In addition, in the following examples, the surface appearance evaluation, bending rigidity measurement, and distortion (warp) measurement of the obtained molded products were performed as follows.

Evaluation of the surface appearance of molded products: Mainly by visual observation, using a surface roughness meter (5E-3 manufactured by Koita Research Institute)
A) was used supplementarily for evaluation. Evaluation results are ◎; Excellent, ○
It was displayed in four stages: Good, Δ: Good, and X: Not good.

Measurement of bending rigidity of molded product: Width 5 obtained by molding operation of Example or Comparative Example
10mw5 length 1,000mIa, thickness 2,5+I
A test piece was cut out from a flat plate molded product of II++, and after being left in an atmosphere at a temperature of 25° C. and a relative humidity of 50% for about one day and night, it was measured in accordance with ASTM D-790.

Measurement of warpage of a molded product: Tighten a thread in the width direction of the flat molded product (in a direction perpendicular to the operator's direction), bring this thread into contact with both edges of the molded product, and then The maximum value of the distance between and the surface of the molded product is the amount of warpage. This warpage measurement operation was performed on the center and both ends of the molded product, and the maximum value of these three points was taken as the warpage amount of the molded product.

Example 1 A component system (A) having the following composition and a component system (B) containing a composite reinforcing material were respectively prepared in two raw material tanks of a reaction injection molding machine, and both were heated to 90% while stirring.
It was kept at 0°C.

Component system (A) ε-caprolactam 8,3 kg Brominemagnesium caprolactam 2.5 kg Component system (B) ε-caprolactam 5,9 kg Polymerization promoter (B) 4.8 kg Glass fiber A 3.6 kg〃Las 7 Lake A 10.7 kg The polymerization cocatalyst (B) added to the above component system (B) is a compound represented by the following structural formula (wherein, Z represents polybutadiene with a molecular weight of 6000). be.

Next, component system (A) and component system (B) are mixed using a reaction injection molding machine in a weight-based mixing ratio - component system (A)/component system (B) - (hereinafter simply referred to as [mixing ratio]). .) 2
．． Width 510II prepared at 33/1,0 and adjusted to a temperature of 135°C while impingingly mixing in the mixing head.
II*, a mold having a length of 1,000 m and a cavity of 2.5 m in depth, was injected from a date set at one end in the longitudinal direction over medium heat, and then held for 2 minutes. Thereafter, the molded product was taken out and subjected to various physical property measurements. The results of measuring the physical properties of the obtained molded product are shown in Table 3 below, together with the type and amount of the compounded reinforcing material.

Examples 2 and 3 In the example described in Example 1, the composition of component system (B) was
Component system (A) and component M (B) were prepared in the same manner as on the same side, except for the following changes, and using the reaction injection molding machine and injection mold used on the same side. Molded articles were obtained using the same method and under the same conditions as on the same side, and the physical properties of the obtained molded articles were measured.

The results are also shown in Table 3.

Component system (B) Example 2 ε-Caprolactam 5.9 kg Polymerization promoter (13) 4.8 kg Glass fiber A 4.8 kg is lath flakes, 9.5 kg Component system (B) Example 3 ε- Caprolactam 5.9 kg Polymerization cocatalyst (B) 4.8 kg Glass fiber A 2 , 9 k.

Glass flakes a 11.6 kg Example 4 In the example described in Example 1, the compositions of the component system (A) and the component system (B) were changed as follows, but on the same side, Component system (A) and component system (B)
was prepared.

Component system (A) ε-caprolactam 10.5kFl-3
2 = Brommagnesium caprolactam 3.1k.

Component system (B) ε-caprolactam 7, 5 kg Polymerization promoter (B) 6.0 kg Glass fiber A 5, 8 kg Glass flake A 5, 8 kg
Next, the reaction injection molding machine and injection mold used in Example 1 were used, except that the mixing ratio of the component system (A) and component system (B) was changed to 1,86/1,0. A molded product is obtained by the same method and under the same conditions as on the ipsilateral side,
The physical properties of the obtained molded article were measured. The results are also shown in Table 3.

Example 5'8 In the example described in Example 4, one of the glass fibers or glass flakes to be blended in the component system (B) is of the type listed in Table #3 (S of types of composite reinforcing material) below. Component system (A) and component system (B) were prepared in the same manner as on the ipsilateral side, except that the component system (A) and the component system (B) were changed.

Next, molded products were obtained using the reaction injection molding machine and injection mold used on the same side, and in the same manner and under the same conditions as on the same side, and the physical properties of the obtained molded products were measured. . The results are also shown in Table 3.

Example 9 In the example described in Example 4, the component system (B) was prepared in the same manner as on the same side, except that resorcinol glycicyl ether was added to the component system (B) and the composition was changed as follows. A), component system (B) was prepared, and a molded product was obtained using the reaction injection molding machine and injection mold used on the same side, and by the same method and under the same conditions as on the same side. The physical properties of the molded product were measured. The results are also shown in Table 3.

Component system (B) ε-caprolactam 7.5 kg Polymerization promoter (B) 6.0 kg Resorcinol glycidyl ether 0.14 kg Glass fiber A
5,8 kg Glass flakes a 5.8 kg Comparative Examples 1 and 2 In the example described in Example 4, only glass fiber was used in Comparative Example 1 as the composite reinforcing material to be added to the component system (B), and In Comparative Example 2, component system (A) and component system (B) were prepared in the same manner as on the same side except that only the last 7 lakes were used and the composition of component system (B) was changed as follows. was prepared.

Component system (B) - Comparative example 1 ε-caprolactam 7, 5 kg Polymerization promoter (B) 6. Okg glass fiber A 11.6kg component system (
B) - Comparative Example 2 ε-caprolactam 7.5 kg Polymerization promoter (B) 6.0 kg Glass flakes a 11.6 kg Next, using the reaction injection molding machine and injection mold used in Example 4, In addition, a molded product was obtained using the same method and under the same conditions as on the same side, and the physical properties of the obtained molded product were measured. The results are also shown in Table 3.

Comparative Example 3 In the example described in Example 4, except that the composition of the component system (B) was changed as follows,
A component system (A) and a component system (B) were prepared.

Component system (B) ε-caprolactam 7,5 hF1
Polymerization promoter (B) 6.0k.

Glass fiber A O, 56 kg Glass flake a 0,056 kg Next, using the reaction injection molding machine and injection mold used in the examples, the mixing ratio of the component system (A) and component system (B) was adjusted to 1.07/ A molded article was obtained by the same method and under the same conditions as on the same side, except that it was changed to 1,0, and the physical properties of the obtained molded article were measured.

The results are also shown in Table 3.

Comparative Example 4 In the example described in Example 4, the composite reinforcing material was blended into both component system (A) and component system (B), and the compositions of both component systems were changed as follows. Component system (A) and component system (B) were prepared in the same manner as on the ipsilateral side.

Ingredient system (A) ε-caprolactam 10.5kg Bromine magnesium caprolactam 3.1kg〃Russ fiber A
6.8 kg glass flakes a6, B kg acid component (B) ε-caprolactam 7.5 k.

Polymerization co-catalyst (B) 6.0 kg is lath fiber A 10.5 kg〃Las 7V-Lia 10.5 kg Next,
Using the reaction injection molding machine and injection mold used in Example 4, the mixing ratio of the component system (A) and component system (B) was changed to 1.27/1.0, and the same as on the same side. Although molding was attempted using the same method and under the same conditions, the fluidity of the raw material composition was poor and it was not possible to obtain a molded product.

Example 10・S13 Example 4t In this example, one of the glass fibers or glass flakes added to the component system (B) is of the type listed in Table 3 below (column of type of composite reinforcing material). A component system (A) and a component system (B) were prepared in the same manner as in the same example except that the component system (A) and the component system (B) were changed.

Next, molded products were obtained using the reaction injection molding machine and injection mold used in the same example, and in the same manner and under the same conditions as in the same example, and the physical properties of the obtained molded products were measured. . The results are also shown in Table 3.

Example 14 In the example described in Example 4, except that the composition of the component system (B) was changed as follows,
A component system (A) and a component system (B) were prepared.

Component system (B) ε-caprolactam? , 5 kg Polymerization promoter (B) 6.0 kg Glass fiber A 1.15 kg Glass flakes A 1.15 kg Next, using the reaction injection molding machine and injection mold used in Example 4, the component system (A ) and component system (B) was changed to 1.17/1.0, a molded product was obtained by the same method and under the same conditions as in the same example, and the physical properties of the obtained molded product were measured. did. The results are also shown in Table 3.

Example 15 In the example described in Example 4, except that the composition of the component system (B) was changed as follows,
A component system (A) and a component system (B) were prepared.

Component system (B) ε-Caprolactam 7, 5k.

Polymerization co-catalyst (B) 6.0 kg Glass fiber A 11.5 kg〃Rath 7 Lake A 11.5 kg Next,
The same reaction injection molding machine and injection mold as used in Example 4 were used, except that the mixing ratio of the component system (A) and component system (B) was changed to 2.70/1.0. A molded article was obtained by the same method and under the same conditions, and the physical properties of the obtained molded article were measured.

The results are also shown in Table 3.

From the results in Table 3, the following is clear.

(1) A molded product that satisfies the requirements stipulated in the present invention is an amide ifS resin molded product that has excellent rigidity, does not damage the surface appearance, and has low distortion (warp) and anisotropy of mechanical properties. (
directional difference in bending stiffness) is small.

(2) Molded products that do not satisfy the requirements stipulated by the present invention, that is, molded products that contain only glass fiber as a reinforcing material (
Comparative Example 1), a molded product containing only glass flakes (Comparative Example 2), and a molded product containing a small amount of composite reinforcing material (Comparative Example 3) each have large warpage (Comparative Example 1). , the improvement in rigidity was extremely small (Comparative Example 2)
．． 3), it cannot be said to be a good molded product.

Claims (7)

[Claims] (1) A composite reinforcing material consisting of an ω-lactam, a polymerization catalyst, a polymerization co-catalyst, and a glass fiber and a glass flake is added to a composite of 100 parts by weight of the ω-lactam, a polymerization catalyst, a polymerization co-catalyst, and a composite reinforcing material. Reinforcement ratio is 5
-50 parts by weight, and this mixture is injected or injected into a mold at a temperature higher than the melting point of ω-lactam, and polymerization reaction is performed. An amide resin molded product. (2) The weight average fiber length of the composite reinforcement is 30 to 300μ
The amide resin according to claim (1), which is composed of 10 to 50% by weight of glass fibers having a weight average diameter of 3 to 300 μm and 90 to 50% by weight of glass flakes having a weight average diameter of 3 to 300 μm. Molding. (3) Glass fibers with a fiber length of less than 25 μm are 3
% by weight or less, the amount of fibers exceeding 300 μm is 30% by weight or less, and the weight average fiber length is in the range of 75 to 125 μm.
) The amide resin molded product described in item ). (4) The amide resin molded article according to claim (1), (2) or (3), wherein the glass fiber has a fiber diameter in the range of 5 to 25 μm. (5) Glass flakes have a weight average diameter of 10 to 50 μm
The amide resin molded article according to any one of claims (1) to (4), which falls within the scope of. (6) The glass flakes have a thickness in the range of 1 to 10 μm and an aspect ratio in the range of 2 to 150. The amide resin molded product described in the above item. (7) The amide resin molded article according to any one of claims (1) to (6), wherein the mixture contains a crosslinking agent and/or a reaction product modifier. .