JPH0331357A - Molding composition of thermosetting resin - Google Patents

Abstract

PURPOSE:To obtain a composition for molding electric parts, having excellent electric properties, coloring properties, surface hardness, insert moldability, comprising a melamine formaldehyde-based resin, diallyl phthalate-based resin and a fibrous reinforcing agent in a specific ratio. CONSTITUTION:(A) 10-97wt.% resin obtained by reacting melamine with formaldehyde and optionally a co-condensation component (e.g. benzoguanamine or phenol) or melamine formaldehyde-based resin comprising a blend of the resin and another resin is blended with (B) 100 pts.wt. diallyl phthalate-based resin, preferably p-diallyl phthalate-based prepolymer, (C) 10-120 pts.wt., preferably 15-80 pts.wt. fibrous reinforcing agent (e.g. preferably pulp) and optionally an inorganic filler, a colorant, melamine-based curing catalyst, etc., to give a compound suitable for molding electric parts.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention has excellent electrical properties such as arc resistance and high insulation resistance, as well as outstanding insert moldability, coloring flexibility, and high surface hardness. Regarding the thermosetting resin molding composition, which has the following characteristics, specifically, it is characterized by containing specific amounts of a melamine/formaldehyde resin, a diallylphthalate resin, and a fibrous reinforcing agent, and is particularly suitable for molding electrical parts. The present invention relates to a thermosetting resin molding composition suitable for.

[Conventional technology]

Melamine resin molding materials have long been known to have excellent electrical properties such as arc resistance and high insulation resistance, in addition to excellent surface hardness, wear resistance, and flexibility in coloring. There is. However, the melamine resin molding material is difficult to mold using K, such as injection molding, and has problems in insert moldability.

In order to improve these problems, for example, the use of phenol-modified melamine resin molding materials co-condensed with phenols has been proposed and put into practical use.

However, although the above-mentioned phenol-modified melamine resin molding materials have the advantage of enabling injection molding and improving insert resistance, the excellent electrical properties of melamine resins have deteriorated to a considerable extent. In addition, the insert resistance is still not sufficient, and
There is also the problem that the flexibility of coloring the molded product is reduced, and its use has had to be limited by itself.On the other hand, when using an alkyl f-himethylol such as methylated methylolmelamine for 100 parts by weight of diallylphthalate resin, Melamine 0.05-10 parts by weight and cellulose 10-10 parts by weight
Resin compositions comprising 200 parts by weight are also known (
JP-A-58-157846).

However, this proposal is related to a composition intended for use in tableware, and has electrical properties such as arc resistance and insulation resistance.
There is no description of insert resistance, surface hardness, etc., and the surface hardness of molded products actually obtained using the proposed composition was insufficient. As a result of research to improve the problems of the conventional technology, for example, melamine φ formaldehyde resin 80 superimposed parts and diallylphthalate resin 20
It has been discovered that a molding composition obtained by containing, for example, 40 parts by weight of pulp per 100 parts by weight of the resin component consisting of the overlapping part is an excellent molding composition that solves all of the above problems, Further research was carried out and the present invention was completed.

[Means for solving problems]

In the present invention, the following holes and (for a total of 100 parts by weight of B) are used.

Prisoner Melamine formaldehyde type tree @ 10~97 superimposed part, and.

(D Diaryl phthalate resin 90-3% by weight.

And based on a total of 100 parts by weight of the above (A) and (B).

(Q 10 to 1201 parts of fibrous reinforcing agent.

6 Hereinafter, the present invention will be described in detail, which aims to provide a thermosetting resin molding composition characterized by containing the following.

The above-mentioned melamine/formaldehyde resin (hereinafter referred to as

(A) is a melamine-formaldehyde resin obtained by reacting melamine and formaldehyde (hereinafter sometimes abbreviated as melamine resin): melamine, formaldehyde, and their co-resins. A condensable melamine cocondensation component is reacted with the resulting melamine cocondensation resin: the melamine resin and/or the melamine cocondensation resin.

Examples include melamine blend resins in which a blending resin component consisting of a melamine cocondensation resin and a thermosetting or thermoplastic resin other than the diallyl phthalate resin is blended.

Examples of the above-mentioned components for melamine cocondensation include 1.

Ureas such as urea, thiourea, and ethylene urea; Guanamines such as benzoguanamine, acetoguanamine, formguanamine/, phenylacetoguanamine, and CTU guanamine; Other amine compounds such as guanidine, dianediamide, and paratoluenesulfonamide; phenol, Cresol, xylenol, ethylphenol, butylphenol.

7 enols such as bisphenol A; xylene.

Other melamine cocondensation compounds such as saccharose; and the like can be mentioned, and these components may be used in combination.

The blending resin components include thermosetting resins such as urea resins, guanamine resins, phenol resins (novolak type, resol type), xylene resins, epoxy resins; vinyl chloride resins, vinyl acetate resins, etc. Thermoplastic resins such as resins, acrylic resins, and polyethylene terephthalate resins can be mentioned.In the above-mentioned melamine-based cocondensation resins, from the viewpoint of the surface hardness of the resulting molded product, The ratio of the components is preferably about 0.1 or less, particularly about 0.05 or less in terms of 'M'jk ratio. From the same viewpoint, the weight ratio of the resin components is preferably about 0.1 or less, particularly preferably about 0.05 or less.

The above-mentioned melamine resin or melamine-based cocondensation resin is preferably reacted with about 1 to about 3 moles of formaldehyde, and about 1.4 to about 3 moles, per mole of melamine alone or the total amount of melamine and the above-mentioned melamine cocondensation component. It is particularly preferred to react about 2.5 mol.

If the molar ratio is below the upper limit, the resulting molded product will not become brittle, and if it is above the lower limit, the curing rate of the resulting molding composition during molding will be too low. Since there is no molding and the hardness of the molded product obtained is excellent,
It is preferable that the molar ratio is within the concave range.

The above term formaldehyde is a term that includes compounds that substantially act as formaldehyde when reacting with the melamine and the melamine co-condensation component, such as paraformaldehyde. However, the formaldehyde can be partially replaced by aromatic aldehydes such as fosaldehyde; furfural; and other aldehyde compounds that can react with the melamine and the component for melamine cocondensation.

The amount of aldehyde components other than formaldehyde above is
From the viewpoint of the reactivity with melamine and the melamine cocondensation component and the curing speed of the resulting thermosetting resin molding composition, about 0.5 mol or less per 1 mol of formaldehyde,
In particular, it is preferably about 0.1 mol or less.

Among such melamine resins, the resins used in the present invention include melamine resins, melamine-phenol cocondensation resins, melamine-urea cocondensation resins, blend resins made by blending melamine resins with novolac phenol resins,
A blend resin made by blending a melamine resin with a urea resin is preferred, and a melamine resin is most preferred.

The method for producing the melamine resin powder used in the present invention includes so-called melamine crystal powder, which can be produced by a publicly used method such as the carbide method and the urea method, and, if necessary, ureas, guanamines, phenols, etc. and components for melamine cocondensation such as, for example, concentration 361i
Formaldehyde in the form of an aqueous formaldehyde solution is reacted in an aqueous medium at a pH of about 7 to 9, and then, if necessary, a blending resin component such as a urea resin or a phenol resin is added to, for example, water. For example, it may be blended in the form of a liquid or an aqueous dispersion to form an aqueous solution or an aqueous dispersion.

The water bath liquid or aqueous dispersion of the melamine resin powder described above is dried by an appropriate method such as hot air drying, vacuum drying, or spray drying to obtain a dry melamine resin. The thermosetting resin molding composition of the present invention is prepared by blending tBl (sometimes referred to as "based resin"), a fibrous reinforcing agent tel, and other additives such as an inorganic photochromic agent and a coloring agent as necessary. It can be a thing.

In addition, in the aqueous solution or aqueous dispersion of the melamine resin prisoner,
For example, fibrous reinforcing agents such as valves and other additives are added and kneaded as necessary, dried to obtain a popcorn-shaped melamine resin pre-dried product, and further Shimada resin B
The molding composition of the present invention can also be prepared by pulverizing and mixing the N1 fiber reinforcing agent and other additives, if necessary.

The amount of melamine resin used in the present invention is a total of 100 weights of the melamine resin and W-based resin [F])!
- 10 to 97% by weight relative to the If the amount used is too small, such as less than 10% by weight, the resulting molded product will have too low a hardness and will be easily damaged, which is undesirable. If the amount is too large, exceeding 97 parts by weight, the resulting molding composition will This is not preferable because it becomes difficult to mold by injection molding or the like, and insert moldability often deteriorates.

The thermosetting resin molding composition of the present invention contains a diallyl phthalate resin together with the melamine resin.

The above diallyl phthalate resin (a means 〇-m- and p-diallyl phthalate monomers usually have a number average molecular weight of 2,000 to 2,000 and is obtained by polymerizing one or more types of monomers.
0. A diallyl phthalate prepolymer that is soluble in an organic bath agent, heat-fusible, and has an allyl group in the molecule and can be post-polymerized alone, or the amount of the main component of the prepolymer and a reactive monomer and/or unsaturated A general term for mixtures with polyester.

The above-mentioned reactive monomers include diallylphthalate monomer 5-styrene containing each isomer of Oam p-, α
-Kystyrenic monomers such as chlorostyrene; methyl (
Examples include acrylic monomers 1 such as meth)acrylate, butyl(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and trimethylolpropane tri(meth)acrylate. The amount of reactive monomer is
Usually, it is preferable to use it in an amount of 30 parts or less in the diallyl phthalate resin. It is preferable that the blending amount is less than 30% by weight because undesirable phenomena such as an increase in the blocking property of the resulting molding composition and a decrease in moldability due to excessive flow are less likely to occur.

In addition, as the unsaturated polyester, polybasic unsaturated acids such as maleic acid and fumaric acid; polybasic saturated acids such as phthalic anhydride and isophthalic acid 5; diethylene glycol, propylene glycol, etc. (1'); polybasic unsaturated acids 3; Preferably used are those that are viscous liquid at room temperature and have an acid value of 5 to 100, and are solids that have a softening point of 150° C. or less. The appropriate amount is 50 parts or less in the diallylphthalate resin. If the amount is less than 50% by weight, it will not adversely affect the boiling resistance of the resulting molded product (preferably).

Among these AP-based resins, those suitable for use in the present invention are diallylphthalate polymers obtained by polymerizing one or more of the above-mentioned Oam- and p-diallyl phthalate monomers, and among these, p
-P obtained by polymerizing diallyl phthalate as the main component
- Diallyl phthalate prepolymers are particularly preferred.

Examples of the p-diallyl phthalate prepolymer include those sold under the trade name 1 Doublen'' (manufactured by Daiso ■).

The resin B of the present invention can be used as it is, as a solid or powdered resin, and may contain the melamine resin, a fibrous reinforcing agent (0) and other additives such as an inorganic filler and a coloring agent as necessary. It can be blended to form the thermosetting resin molding composition of the present invention.Furthermore, a fibrous reinforcing agent such as glass fiber and necessary K can be added to the organic solvent solution or hot melt of the DAP resin B.
[The DAP-based tree-resistant resin preformed product is prepared by adding and kneading other additives, drying or cooling, and further adding melamine-based resin (2) and, if necessary, the DAP-based resin in the fibrous rehydration invention. The amount of resin CB+ to be used is 90 to 3 parts by weight, based on a total of 100 parts by weight of the melamine resin container and the DAP resin mouth. If the amount used is too large, exceeding 90% by weight, the hardness of the resulting molded product will be too low and it will be easily damaged, which is undesirable. This is not preferable because molding by injection molding or the like becomes difficult and insert moldability often deteriorates.

The thermosetting resin molding composition of the present invention comprises a fibrous reinforcing agent (0
Contains.

Such fibrous reinforcing agents (for example, organic fibrous reinforcing agents such as bulb, cotton, rayon, polyamide, polyester, polyacrylonitrile, polyvinyl chloride, etc.)
For example, glass fI! Male, inorganic tIL such as rock wool
Mention may be made of male quality enhancers. Among these, the use of valves is preferred from the viewpoints of ease of availability, no problems in the working environment, and good appearance of the resulting molded product.

The above-mentioned pulp usually refers to a chain polymer mainly composed of α-cellulose derived from cellulose raw materials, which is used as a raw material for paper, chemical fibers, cellulose plastics, etc. Fibers made from treated cellulose raw materials are used.

Fibrous reinforcing agent (0 is the aforementioned melamine resin, DAP
The thermosetting resin molding composition of the present invention can be prepared by blending the thermosetting resin with other additives such as an inorganic filler and a coloring agent if necessary. In addition, 1 NIt fiber reinforcing agent (0 is melamine resin matrix and/or DAP)
The molding composition of the present invention is obtained by kneading with a melamine resin, a preformed product, etc., and then grinding and mixing the same with a melamine resin, a melamine resin, other additives, etc. as necessary. It can be done.

The amount of the fibrous reinforcing agent used in the present invention is 10 to 120 parts by weight, preferably 15 to 80 parts by weight, based on the total of 100 parts by weight of the melamine resin and DAP resin (B). If the amount is too low (below the lower limit), the insert moldability of the resulting molding composition tends to be insufficient, while if it is too high (below the upper limit), the heat fluidity of the molding composition will be poor. This is undesirable as it tends to cause the injection molding to become separated.

The thermosetting resin molding composition of the present invention comprises the above-mentioned
In addition to the components, it may contain an inorganic filler, a colorant, a melamine resin curing catalyst, a melamine resin no-flow improver, a lubricant, a DAP resin polymerization initiator, a DAP resin polymerization inhibitor, and the like. These additives can be blended and mixed together with the ingredients (0) to form the molding composition of the present invention. The molding composition of the present invention can also be obtained by blending with the melamine resin FB+ to form a melamine resin pre-dried product or a DAP resin preform, and then mixing these with the remaining additives by means such as crushing and mixing. can.

Examples of the above-mentioned inorganic fillers include calcium carbonate, Merck, Crane Rica, gypsum, ifi paricum, aluminum hydroxide, glass powder, and the like. and 1 fl of the DAP tree [generally 0 to 1 fl for a total of 1001 i parts of Bl
It is preferably 60 parts by weight, particularly 0 to 40 parts by weight.

Examples of the coloring agent include #R(lZ titanium, zinc oxide, zinc sulfide, red iron, navy blue, iron black, ultramarine blue, carbon black, lithopone, titanium yellow cobalt blue, Hansa yellow, benzidine yellow, lake red, aniline black, dioxazine). Inorganic or organic colorants such as violet, quinacridone red, quinacridone violet, naphthol yellow phthalocyanine green, etc. can be mentioned.
) and DAP resin (generally 0 to 10 parts by weight, particularly preferably 0 to 5 parts by weight, based on a total of 100 parts by weight of D).

Examples of the melamine resin curing catalyst include phthalic anhydride, p-toluenesulfonic acid, dimethyl oxalate, dibenzyl oxalate, dimethyl phthalate, shrimp cumylhydrin, p-toluenesulfonate IJ ethanolamine salt, p- ) Luenesulfonic acid triethylamine salt, 2-
Examples include aminoethylsullam, trimethyl phosphate, acetamide, and oxamide. The amount of the curing catalyst used is generally 0 to 1 part by weight, particularly 0.01 to 0.5 parts by weight, based on 1100 parts by weight of the melamine resin (A1).
Parts by weight are preferred.

Examples of melamine-based resin fluidity improvers include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polyethylene glycol φ polypropylene glycol block copolymer;
Polyoxyalkylene and C such as polyethylene glycol monooleate and polyethylene glycol distearate
Mono- or hashi-esters with saturated or unsaturated higher fatty acids of 8 to C9: for example, polyoxyethylene monolauryl needles, polyoxyethylene diolae k
Polyoxyalkylene c, ~C2o
Mono- or di-ethers with saturated or unsaturated higher aliphatic monoalcohols: For example, monoethers of polyoxyalkylene such as polyoxyethylene nonylphenol ether and alkylphenols of CtZ to C2o; For example, methyl oleate, ether oleate ,n
-propyl oleate 1-propyl oleate, n-7'' til stearate, n-hexyl laurate, n-octyl oleate, 2-ethylhexyl oleate, and other saturated aliphatic monoalcohols with C1 to C1° and C1 to C, Esters with saturated or unsaturated higher fatty acids (preferably oleic a1); for example, trimethylolpropane triolate, pentaerythritol triolate, etc. General 2〇 (CH,OH), +n(CH,R), -, ( However, n
is 0.1 or 2, R is water or a C8 to C8 alkyl group] (hereinafter C may be abbreviated as neopentyl polyol) and C6 to Cf1 (preferably C10 to Ctn)
saturated or unsaturated higher fatty acids (preferably esters with oleic acid; for example, C8 to C1 such as stearic acid amide, oleic acid amide, linoleic acid amide, etc.)
Amides of saturated or unsaturated higher fatty acids: e.g.
C1~ such as dioctyl phthalate, dibutyl phthalate, etc.
Examples include heptatalic diesters of saturated alcohols such as Cat; other fluidity improvers such as caprolactam and glycerin. Among these, from the viewpoint of excellent appearance of the molded product obtained, polyalkylene glycols, mono- or di-esters of polyoxyalkylene and C8 to C2 saturated or unsaturated higher fatty acids,
It is preferable to use esters of 01 to CIG saturated aliphatic monoalcohols and C1 to C1 saturated or unsaturated higher fatty acids, and esters of neopentyl polyols and C6 to Cfi saturated or unsaturated higher fatty acids. Particularly preferred is the use of esters of C8 to Cfl saturated or unsaturated higher fatty acids. The amount of these fluidity improvers used is generally 0 to 2 parts by weight, based on 100 parts by weight of the melamine resin.
In particular, it is preferable to use oFle-114 to 1 part by weight. Examples of the lubricant include zinc stearate, zinc myristate, aluminum stearate, and calcium stearate. The amount of the lubricant to be used is generally 0 to 5 parts by weight, particularly 0.1 to 2 parts by weight, per 100 parts by weight of the melamine resin and DAP resin.

Examples of the island W-based resin polymerization initiator include dicumyl peroxide, t-butyl perbenzoate, and benzoyl peroxide. The amount of the polymerization initiator used is usually 1 to 100 parts by weight of the D-type resin.
As the DAP resin polymerization inhibitor, for example, hydroquinone can be exemplified, and the amount used is generally about O-0.1 part by weight per oz part of the DAPA phase resin. It is.

As a method for producing the thermosetting resin molding composition of the present invention, for example, Depending on the situation, the above-mentioned additives such as powdered or liquid q inorganic fillers, colorants, melamine resin curing catalysts, melamine resin thermal fluidity improvers, lubricants, DAB resin polymerization initiators, DAP resin polymerization inhibitors, etc. Additives other than component 0 are added and mixed with stirring, and if necessary, the resulting powdery mixture is heated and kneaded to form a preformed composition, which is then re-pulverized to form a powdery or granular molding composition. Method for obtaining; ■ Add and knead other additives such as a fibrous reinforcing agent such as gelatin and, if necessary, an inorganic filler to the aqueous solution or aqueous dispersion of the melamine resin, and dry. Popcorn-shaped melamine resin pre-dried product is added with DAP resin and, if necessary, further fibrous reinforcing agent and the above-mentioned prisoner (O
Method of adding additives other than the ingredients and pulverizing and mixing; ■D above
D obtained by adding and mixing a fibrous reinforcing agent such as glass fiber and other additives as necessary to an organic bath agent solution or hot melt of AP resin, drying or cooling, and preforming.
A method of adding and pulverizing a melamine resin and, if necessary, a further fibrous reinforcing agent and additives other than the O component to the AP resin preform: ■ A method of appropriately combining these methods. Examples of the powdery melamine resin used in the above production method (1) include those obtained by spray drying an aqueous solution or dispersion of the melamine resin, or methods such as hot air drying and vacuum drying. Examples include those obtained by pulverizing the solid dry melamine resin obtained by, for example, an impact pulverizer, a hammer mill, a ball mill, a vibration mill, a tower mill, or the like.

In the above manufacturing method, the means for stirring and mixing the powdery components (2) to (0) and the powdered or liquid components other than the components (2) to (0), which are added as necessary, include, for example,
Examples include a V-type mixer, a super mixer, a Nauta mixer, a tumbler, an omnimixer, a Henschel mixer, a Lodeige mixer, a ribbon blender, and a planetary mixer. Further, examples of means for heating, kneading, and preforming the resulting powdery mixture include an extruder, a heated roll machine, and the like. Furthermore, examples of the means for re-pulverizing the obtained preform include an impact crusher, a hammer mill, an atomizer-pin mill, a roll mill, and a pulverizer.

A kneader-co-kneader or the like can be used as a cross-contacting means when forming a popcorn-shaped melamine resin pre-dried product in the production method (2), and examples of drying means include hot air drying, band dryer drying, fluidized drying, etc. be able to.

In addition, as a means for pulverizing and mixing the pre-dried material, the DAP resin, and additives added as necessary, a ball mill, a vibration mill, etc. can be exemplified.

The organic eczema agent used in the manufacturing method (①) is as follows:
For example, acetone, methyl ethyl ketone, etc. can be used, and the crosstalk means can be exemplified by a kneader-co-kneader. In the case of thermal melting, examples of kneading means include heating roll mills, pressure kneaders, etc., and preforming means include:
Examples include hot rolls. In addition, the obtained preform,
As a means for pulverizing and mixing the melamine resin and optionally added additives, the same means as in the above manufacturing method (2) can be used.

The thermosetting resin molding composition according to the present invention can be used for compression molding,
It can be molded by conventionally known methods such as transfer molding and injection molding. Furthermore, it exhibits excellent insert moldability, and the resulting molded product exhibits excellent arc resistance and insulation resistance, making it particularly suitable for molding electrical parts.

〔Example〕

Examples will be given below along with comparative examples. [Several aspects of the present invention will be explained in more detail.
Test methods and plans for type 1, molded product hardness, heat crack resistance, insert resistance, arc resistance, and insulation resistance are as follows.

(1) Disc flow test Using the same root type test mold shown in Section 5.3.2 of JIS K-6911, sample 52 was placed approximately in the center of the mold with the mold temperature kept at 160 ± 3°C. Inner diameter approximately 50m, height approximately 10■
Place the sample in a conical shape using a metal cylinder.
Compression molding is carried out within 15 seconds under a load of 2000hf and a pressurization time of 2 minutes.

Measure the long and short axes of the shiny part of the molded disc using a dimension measuring device to 1-1, calculate the average value, and calculate the elongation (w) of the sample.
shall be.

(2) Disc #-type test Using the same equipment as in (1) above, the test was conducted under the same conditions as in (1) except that the pressurization time was changed, and the resulting disc was removed from the mold by hand. Find the minimum pressurizing time (seconds) that allows the mold to be released by just pressing lightly.

It is preferable that the disk flow in the above item (1) is 96 m or more and the disk am is 30 to 120 seconds because the molding composition exhibits excellent injection moldability.

(3) Molded product surface hardness After preheating approximately 18 g of the sample to 115°C using a high-frequency preheater, test at 55w x 65m and thickness 3±0.2mm under conditions of mold temperature 175°C/175°C, molding time 2 minutes. Create pieces. This is a pencil for the scratch value test that has been tested on the day.
Mitsubishi Uni: Using Mitsubishi Pencil ■], JIS K-5400
Perform the pencil hardness test according to Sections 6 and 14.

(4) Molded product heat resistance Using a test piece prepared in the same manner as in (3) above,
The heat resistance value is determined by changing the temperature of the constant temperature bath in accordance with JIS K-6911 Section 5.23 "Appearance after heating" test, and the highest temperature within the range where no significant change in appearance occurs.

(5) Molded product insert resistance Brass knurling (38 mφ, 7 mm thick disc) is set in the middle 6 part of the transfer mold cavity, mold temperature is 170°C, molding time is 60 seconds. The knurling is inserted into the center and integrally molded, and the outer diameter is 5.
A test is conducted in a house where cracks occur, with one cycle of cooling at 0 mφ for 5 minutes, and the average value of the number of cycles at which cracks occur is taken as the value of insert resistance.

(6) Molded product arc resistance Using a test piece prepared in the same manner as in (3) above,
The test was conducted in accordance with JIS K-6911 Section 5.15 "Arc resistance" test, and the average value of arc resistance time (seconds) was taken as the value of arc resistance.

(7) Molded product insulation resistance Using a transfer mold having the shape shown in Section 5.12 “Insulation resistance” of JIS K-6911, molded product insulation resistance at 170°C.
Place the sample in a pot adjusted to 170°C and pressurize it.
A test piece is molded by injecting the sample into a cavity adjusted to 100% and holding the pressure for 60 seconds. Using this test piece, measurement is carried out using a measuring device (TR-42) manufactured by Takeda Riken Kogyo 1 in accordance with the test method of JIS K-691105, Section 12.

Example 1 Pulverized product (1
(passed through 2 meshes) 640f, phthalic anhydride 1.5
9,1.3-bis-(t-butylperoxy-isoprobyl)-benzene [Parkadock 14: Compound Nouri ■
]1591 Zinc stearate 40f and titanium oxide 75
2 was pulverized and mixed in a ball mill for 4 hours, and then 1050 g of powdered pulp and 50 f of calcined lehr were added and further pulverized and mixed for 4 hours. Transfer this mixture to a twin-screw extruder
Heat, knead and extrude at 0 to 130°C, cool and crush to 24
A granular molding composition having a mesh passing rate of 96% by weight was obtained.

According to the above test method, the properties of the molding composition obtained and the physical properties of various bottom-shaped articles of the composition were measured. The results of these tests are shown in Table 1.

Examples 2 to 3 and Comparative Examples 1 to 2 A molding composition was obtained in the same manner as in Example 1 except that the proportions of the powdered melamine resin and p-diallyl phthalate prepolymer were changed, and the following was the same as in Example 1. Various tests were conducted. Table 1 shows the composition of the molding composition and the results of multiple tests.

Examples 4 to 5 In Example 1, molding compositions were obtained by changing the amount of powder pulp used and the amount of inorganic filler used accordingly, and the following 4ji tests were conducted in the same manner as in Example 1. went. The composition of the molding composition and various test results are shown in Table 1. Comparative Example 3 Using the molding composition of the present invention
2. Various tests were conducted in the same manner as in Example 1 using Nippon Carbide Kogyo ■. The test results are shown in Table 1.

Procedural amendment written on August Z, 1999 rf! Fumiaki Yoshida, Commissioner of the F Correction Office Display of the case 1999 Patent Application No. 165220 Name of the invention Relationship to the case of person who amends a thermosetting resin molding composition Patent applicant address 100 Marunouchi, Chiyoda-ku, Tokyo Contents of the amendment to the column ``Detailed explanation of the invention in 1.Detailed explanation of the invention'' in the Specification No. 3-1 On page 27, line 8 of the specification, there is a line break after ``The value shall be...'' and ``In addition, the insert If the test piece cannot be molded or if the test piece has cracks before the test, the number of cycles is indicated as 0.

” he added.

(2) In the first to last lines of page 29 of the same page, there is a statement that "Examples 2 to 3 and Comparative Examples 1 to 2 In Example 1...K was shown." Examples 2 to 6 and Comparative Examples 1 to 2 In Example 1, the proportions of the powdered melamine resin and p-diallyl phthalate prepolymer were changed, and accordingly phthalic anhydride and "Parkadoc 14" (trade name)
A molding composition was obtained in the same manner except that the amount used was changed,
Various tests were conducted in the same manner as in Example 1.

The composition of the molding composition and various test results are shown in Table 1.

Examples 7 to 10 and Comparative Examples 3 to 4 In Example 1, the total usage amount of powdered melamine resin and bulk p-diallyl phthalate prepolymer pulverized product was 3.
500f, the blending ratio of both resins was changed, the amount of powder pulp used was changed to 150Of, and a molding composition was obtained in the same manner except that the amounts of phthalic anhydride and "Parkadoc 14" were changed accordingly, Thereafter, various tests were carried out under the same pressure as in Example 1. The composition of the molding composition and various test results are shown in Table 1.

Examples 11 to 12 and Comparative Example 5 Molding was carried out in the same manner as in Example 1, except that the amount of powder bulb used was changed or was not used, and the amount of inorganic filler used was changed accordingly. obtain a composition;
Various tests were conducted in the same manner as in Example 1. The composition of the molding composition and various test results are shown in Table 1. Comparative Example 6 Instead of using the molding composition of the present invention, a melamine/phenolic resin molding material for electrical parts [Nicaret MP: Nippon Carbide Kogyo Co., Ltd. (2)], various tests were conducted in the same manner as in Example 1. The test results are shown in Table 1.''

(3) Table 1 on page 30 of the same page is corrected as shown in the attached table.

that's all.

Claims (1)

[Claims] (1) Based on 100% by weight of the following (A) and (B) in total, (A) melamine/formaldehyde resin 10 to 9
7% by weight, and (B) 90 to 3% by weight of diallyl phthalate resin, and 10 to 120 parts by weight of (C) fibrous reinforcing agent, based on a total of 100 parts by weight of the above (A) and (B). 1. A thermosetting resin molding composition comprising: .