JPS6310658A - Wear-resistant molding material - Google Patents

Abstract

PURPOSE:To provide the title molding material which gives molded products having excellent resistance to heat and wear, mechanical strengths and adhesion to metal, containing a cyanic ester resin compsn. and a milled carbon fiber having a specified length. CONSTITUTION:100pts.wt. cyanic ester resin compsn. (A) such as a cyanate resin, a cyanic ester/maleimide(/epoxy) resin, a cyanic ester/epoxy resin, etc. is blended with 20-100pts.wt. milled carbon fiber (B) which is a short carbon fiber having a length of not longer than 2mm, pref. 1.0-0.03mm prepd. from rayon, acrylic pitch, lignin, Poval, etc. as a starting material, 0.01-5wt% (based on the amount of the component A) curing catalyst (C) and optionally, not more then 100pts.wt. filler aid (D) selected from the group consisting of graphite, wallastonite and mica. If desired, a flame retarder, a parting agent, a dye, etc. are added thereto to obtain the desired molding material. The molding material is molded by heating it under pressure so as to be fluidized and bonded to the surface of metal.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention is characterized in that a molding material is flow-adhered to the metal surface by a molding method such as compression molding, transfer molding, or injection molding, so that the metal and resin are firmly bonded. A cyanate ester resin molding material for producing adhesive and integrated molded products.It has excellent heat resistance, abrasion resistance, and mechanical strength, and has strong adhesion to metal surfaces. The coefficient of thermal expansion in this direction is significantly reduced.

[Conventional methods and their problems]

Thermosetting resin molding materials made by mixing graphite, carbon fiber, etc. with thermosetting resins such as epoxy resins and cyanate ester resins are well known.

In addition, methods for producing molded products in which molding materials such as thermoplastic resins or thermosetting resins are molded and simultaneously integrated with metal by injection molding or other methods are known.

By the way, a wear-resistant thermosetting resin molding material made by mixing graphite, carbon fiber, etc. with a thermosetting resin does not necessarily have a small coefficient of thermal expansion; for example, in the case of metal material, it is about 12 x 10-''. Because of the large difference in coefficient of thermal expansion, if the operating temperature range is wide, for example from room temperature to 100°C or higher, or if the bonding area is large, the stress and strain generated at the bonding interface will be of a size that cannot be ignored. There are disadvantages such as peeling of the adhesive surface, cracking of the integrated resin, and distortion of the molded product.

A way to overcome this drawback is to make the molding material have the same coefficient of thermal expansion and behave in the same way as the metal, which is theoretically possible if a large amount of graphite, carbon fiber, etc. is blended into the thermosetting resin. However, a practical molding material has not yet been developed due to poor mechanical strength, moldability, etc.

Therefore, in practice, it is recommended to provide a buffer surface (adhesive layer = stress absorbing surface) using a flexible material at the adhesive interface to buffer stress and maintain adhesive strength, or to add flexibility to the molding material itself. A method such as an endowment is adopted. However, molding materials that are made with a buffer surface (adhesive layer) or flexibility that is intended to relieve stress inevitably contain a considerable amount of soft material, resulting in inferior physical properties such as heat resistance. Furthermore, it is impossible to integrate as a thin layer such as abrasion-resistant and sliding coatings, and while maintaining excellent formability, heat resistance, abrasion resistance, mechanical strength, and compatibility with metals are impossible. Adhesive strength, and
It has been difficult to create a molding material with excellent durability at the adhesive interface with metal.

[Means for solving problems]

The present inventors have developed a molding material that has excellent moldability, heat resistance, abrasion resistance, mechanical strength, adhesive strength with metal, and excellent durability of the adhesive interface with metal. As a result of extensive research, we discovered a molding material made by blending a specific carbon milled fiber with a cyanate ester resin composition, and completed the present invention.

That is, the present invention provides a molding material that is molded by heating and pressurizing so as to fluidly adhere to a metal surface, comprising (a) 100 parts by weight of a cyanate ester resin composition, (b) a length of 2H.
A wear-resistant molding material containing 20 to 100 parts by weight of the following carbon fiber milled fibers and fC) curing catalyst as essential components, and in a preferred embodiment,
This is a wear-resistant molding material in which graphite, wollastonite, or mica are each independently used as a filling aid in an amount of 100 parts by weight or less based on the cyanate ester resin composition (a).

The present invention will be explained below.

The cyanate ester-based resin composition (a) of the present invention is a composition comprising a polyfunctional cyanate ester of the following general formula (1), its prepolymer, etc. as essential components, No. 45-11712,
44-1222, German Patent No. 1190184, etc.), cyanate ester-maleimide resin, cyanate ester-maleimide-epoxy resin (Japanese Patent Publication No. 54-304
No. 40, etc., Special Publication No. 52-31279, USP-411
0364, etc.), cyanate ester-epoxy resin (Japanese Patent Publication No. 46-41112), and the like.

Here, suitable polyfunctional cyanate esters are expressed by the following general formula (1)% formula% (1) (m in the formula is an integer of 2 or more and usually 5 or less, and R is an aromatic organic ester) group, in which the cyanato group is bonded to the aromatic ring of the organic group. To give a concrete example, 1゜3-
or 1.4-dicyanatobenzene, 1.3.5-tricyanatobenzene, 1.3-. 1.4-. 1.6-. 1.
8-. 2.6- or 2゜7-dicyanatonaphthalene, 1
．． 3.6-tricyanatonaphthalene, 4.4'-dicyanatobiphenyl, bis(4-cyanatophenyl)methane, 2.2-bis(4-cyanatophenyl)propane,
2.2-bis(3,5-dichloro-4-cyanatophenyl)propane, 2.2-bis(3*5-Schif"mo4-cyanatophenyl)propane, bis(4-cyanatophenyl) ether , bis(4-cyanatophenyl) thioether, bis(4-cyanatophenyl) sulfone, tris(4-cyanatophenyl) phosphite, tris(4-cyanatophenyl) phosphate, and polycarbonate oligomers containing terminal OH groups. Cyanic acid esters obtained by reaction with cyanogen halides (US
P-4026913), cyanic acid esters obtained by the reaction of novolacs with cyanogen halides (USP-4
022755, USP-3448079).

In addition to these, Tokuko Shou 41-1928, Sho 43-18
468, 44-4791, 45-11712, 46-41112, 47-26853, JP-A-1987-
63149, USP-3553244, 3755402
, 3740348, 3595900, 3694410 and 4116946 may also be used.

In addition, a prepolymer obtained by polymerizing the above-mentioned polyfunctional cyanate ester in the presence or absence of a mineral acid, a Lewis acid, a salt such as sodium carbonate or lithium chloride, a phosphate ester such as tributylphosphine, etc. used as. These prepolymers generally have a sym-triazine ring in the molecule, which is formed by trimerization of the cyanide group in the cyanate ester.

Furthermore, the polyfunctional cyanate esters described above can also be used in the form of prepolymers with amines. Examples of amines that can be suitably used include meta- or para-phenylenediamine;
meta- or para-xylylenediamine, 1,4- or 1
．． 3-Cyclohexanediamine, hexahydroxylylenediamine, 4,4'-diaminobiphenyl, bis(4
-aminophenyl)methane, bis(4-aminophenyl)ether, bis(4-aminophenyl)sulfone, bis(4-amino-3-methylphenyl)methane, bis(
4-amino-3,5-dimethylphenyl)methane, bis(4-aminophenyl)cyclohexane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-
Amino-3-methylphenyl)propane, 2,2-bis(4-amino-3-chlorophenyl)propane, bis(
4-amino-3-chlorophenyl)methane, 2,2-bis(4-amino-3,5-dibromophenyl)propane, bis(4-aminophenyl)phenylmethane, 3.4
-diaminophenyl-4-aminophenylmethane, 1.
1-his(4-aminophenyl)-1-phenylethane and the like.

The above-mentioned polyfunctional cyanate esters, prepolymers thereof, and prepolymers with amines can be used alone or in the form of mixtures, and the number average molecular weight of the individual and mixtures is preferably 1.700 or less, especially 500 to 1,500. A range of is preferred.

Cyanate ester-maleimide resin (Special Publication No. 54-30
440, etc.), cyanate ester-maleimide-epoxy resins (Japanese Patent Publication No. 52-31279, etc.), and cyanate ester-epoxy resins (Japanese Patent Publication No. 46-41112, etc.). Maleimide, which is a compositional component, is a compound represented by the following general formula (2) and its prepolymer.

(In the formula, R3 is an aromatic or alicyclic organic group having a valence of 2 or more and usually 5 or less; X, , X2 are hydrogen, halogen, or an alkyl group, and n is usually an integer of 2 to 5 ) The maleimide represented by the above formula is produced by a method known per se in which maleic anhydride is reacted with a polyamine containing 2 to 5 amino groups to prepare maleamic acid, and then the maleamic acid is cyclized by dehydration. can be manufactured. It is preferable that the polyamines used are aromatic polyamines in terms of the heat resistance of the final resin, but if flexibility and flexibility of the resin are desired, alicyclic amines may be used alone or in combination. Good too. Further, it is desirable that the polyamines be primary amines from the viewpoint of reactivity, but secondary amines can also be used. Suitable amines include those exemplified as those used as prepolymers with cyanate esters, and melamines having an s-triazine ring;
These are polyamines made by reacting aniline with formalin and linking benzene rings with methylene bonds. In the present invention, the maleimide component usually accounts for 60% of the resin component in the composition.
It is best to use the following amounts.

In addition, the epoxy resin can be any resin that has been conventionally used as a molding material, and specifically, bisphenol A type epoxy resin, phenol nopofuku type epoxy resin, and Talesol. These include novolac type epoxy resin, halogenated bisphenol A type epoxy resin, halogenated phenol novolac type epoxy resin, and known polyfunctional epoxy resins having three or more functions, which are used alone or as a mixture of two or more types. . In the present invention, it is preferable to use the resin in an amount of usually 50% or less of the resin component in the composition.

The cyanate ester resin composition (al) of the present invention preferably includes the above components, but in addition to these, for the purpose of improving the adhesiveness, curability, flexibility, etc. of the composition, Thermosetting resins such as diallyl phthalate resins, unsaturated polyester resins, phenolic resins, acrylic resins, and urethane resins; mixtures of thermoplastic resins such as thermoplastic polyurethane resins, polyolefins, and saturated polyester resins can also be used.

Carbon fiber milled fiber (b
) is carbon fiber made from rayon, acrylic, pitch, lignin, poval, etc., and has a length of 2m.
It is a short fiber of m1 or less, preferably 1.0 to 0.03 mm. Carbon fiber milled fiber (bl is 20 to 100 parts by weight per 100 parts by weight of the cyanate ester resin composition)
Use within parts by weight. If the amount used is less than 20 parts by weight, it will be difficult to set the coefficient of thermal expansion, etc. to the set value, and 1
If it exceeds 0.00 parts by weight, fluidity will be poor, which is not preferable.

In the present invention, in order to further reduce the coefficient of thermal expansion of the molding material while maintaining fluidity, it is preferable to blend a specific inorganic filler as an auxiliary material, and graphite, wollastonite or mica is combined with cyanate ester. Resin composition 10
They are each used in combination in an amount of 100 parts by weight or less, preferably 20 to 80 parts by weight, relative to 0 parts by weight.

Graphite here refers to natural and synthetic graphite,
It is preferable that the components passing through a 105 sieve are 75 or more. Wollastonite is a crushed product of naturally occurring wollastonite, preferably has a particle size distribution of 5 to 50, has a large aspect ratio, and is effective in improving mechanical strength. Furthermore, mica is a crushed product of natural or synthetic mica, and a particle size distribution of 5 to 50 is preferable, and since it is oriented in the flow direction of the molding material during molding, it is possible to reduce thermal expansion in the direction of the flow surface. It is.

The curing catalyst tel of the present invention may be any known curing catalyst for cyanate ester resin compositions, including organic metal salts (including metal chelate compounds), turnip metal salts, Organic peroxides are suitable, and in particular, organic metal salts alone and combination systems of organic metal salts and organic peroxides are mentioned.

Examples of organic metal salts include zinc naphthenate, lead stearate, lead naphthenate, zinc octylate, tin oleate, tin octylate, diptyltin malate, manganese naphthenate,
Cobalt teftenoate, iron acetylacetone, manganese acetylacetone, etc., and organic peroxides include benzoyl peroxide, lauroyl peroxide, caprylic peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-
Examples include jeperphthalate and the like. The amount of these curing catalysts used is sufficient within the range of catalyst amount in a general sense, for example, 0.01 to 5% by weight based on the total resin composition.
used in amounts of

Further, if necessary, a t1c fuel, a mold release agent, a dye, and other additives can be mixed.

The above ingredients can be mixed using a roll or Banbury mixer.
, Henschel mixer, Kneader 1 extruder, and other known kneading machines.

The kneading temperature and time are appropriately selected depending on the molecular weight of the resin component in the composition, the composition component ratio, the kneading equipment used, etc., but in general, the kneading temperature and time are in the range of 1 minute to 30 minutes at 60 to 140°C. suitable.

The abrasion-resistant molding material of the present invention obtained by the above method is melted and molded to flow adhere to a metal surface to form an integrated product firmly adhered to the metal.

The molding method is not particularly limited as long as part or all of the molten resin flows along the surface of the metal to be integrated, and examples thereof include compression molding, transfer molding, injection molding, and the like. Part or all of the molten resin is made to flow along the metal surface to integrate part or most of the milled carbon fiber, which is the component (b) in the molding material of the present invention. By oriented parallel to the surface of the metal, the coefficient of thermal expansion in the direction parallel to the surface is reduced and the strength is increased, and the flow distance is preferably 511 or more.

The molding conditions are preferably a temperature of 170 to 200°C and a pressure of 500 to 1500 kg/cra in the case of injection molding.
30-180 seconds, pressure 50 for transfer molding
~150 kg/cj, molded for 1 to 3 minutes, and optionally post-cured at a temperature of 170 to 300°C for 1 to 24 hours.

(Examples) The present invention will be explained below with reference to Examples.It should be noted that parts in Examples, etc. are based on weight unless otherwise specified.

Example-1 2,2-bis(4-cyanatophenyl)propane was heated and stirred at a temperature of 140°C for 12 hours, and the number average molecular weight was 1,00.
0 prepolymer was obtained.

500 parts of this prepolymer, carbon fiber (pitch-based milled fiber, average length 0.7fl, manufactured by Kureha Chemical Industry),
Product name i M-1077) 400 parts, 2 parts of dicumyl peroxide and 2 parts of zinc octylate were mixed into 2 parts of 8 inch diameter.
The mixture was kneaded using this roll at 120°C for 5 minutes to obtain a molding material.

This molding material was heated to 23 inches (at 170°C, EMM
I 1-66 method).

This molding material was heated to 180°C and 100 kg/pressure.
Transfer molding was carried out under the conditions of c++1.3 minutes, 1
Table 1 shows the properties of a molded article of 00 tmφ x 3 (thickness) which was cured at 180° C. for 3 hours.

In addition, ioo1mφXIQmm (thickness) held in the mold
This molding material was applied to both sides of the steel plate at 180℃ and 100K.
After transfer molding was carried out under the conditions of g/cd for 3 minutes to fluidly bond both sides to a thickness of 0.5N, the molded product was taken out and post-cured at 180° C. for 3 hours. Table 1 shows the results of a heat cycle test on this molded product.

Example-2 2,2-bis(4-cyanatophenyl)propane and bis(4-maleimidophenyl)methane (6:4 weight ratio) were heated and stirred at 140°C for 6 hours to produce cyanide with a melting point of 80°C. An acid ester-maleimide prepolymer was obtained.

500 parts of this prepolymer, carbon fiber (pinch milled fiber, average length LOlm, manufactured by Toshi ■, product name,
MLD-1000) 200 parts, powdered graphite (manufactured by Nippon Graphite Industries ■, product name: AP) 400 parts, dicumyl peroxide 2 parts and iron acetylacetonate 2 parts, and lubricant (manufactured by Hoechst Japan ■, product name: Hoechst Wax E) 15
part in a 2-inch twin-screw extruder at a composition temperature of 100 to 1
The temperature was set at 20° C., and kneading was carried out at a rate of 30 kg/Hr.

Table 1 shows the results of using this molding material in the same manner as in Example 1, except that the atto-curing was carried out at 200° C. for 10 hours.

Example-3 320 parts of the cyanate ester-maleimide prepolymer obtained in Actual Mfli Example-2, Talesol novolac type epoxy resin (manufactured by Ciba Geigy, trade name: Araldite EC)
N 1273 > 80 parts, carbon fiber (product name: H-10
77) 160 parts, powdered graphite (Nippon Graphite Industries type,
Product name: AP) 400 copies, Wolastonite (Product name: N
YAD 325, manufactured by Interpace Co) 20
0 parts, mica powder (product name, A-21.0, manufactured by Kikuyama Romica Kogyo Co., Ltd.) 80 parts, dicumyl peroxide 1.6 parts, iron acetylacetonate 1.6 parts, and lubricant (manufactured by Hoechst Java ■, product name; A molding material was obtained in the same manner as in Example 2 using 12 parts of Hoechstwax OP), and test pieces were prepared and tested in the same manner.

The results are shown in Table 1.

Comparative example-1 Cresol novolak type A epoxy resin (ECN127
3) 400 parts of phenol novolac resin (manufactured by Hitachi Chemical (Il), product name i HP607N), 600 parts of powdered graphite (AP), 4 parts of 2-ethyl-4-methylimidazole, and lubricant (manufactured by Hoechst Java AL, product name) Example: Using 12 parts of Hoechstwax E)
A molding material was obtained in the same manner as in 2, and a test piece was prepared in the same manner.
Tested.

The results are shown in Table 1.

Comparative Example-2 In Example-3, carbon fiber (product name: M-1077)
The same procedure was carried out except that 160 parts was not used. The results are shown in Table 1.

Note that the description in Table 1 is as follows.

*1: Heat deformation temperature load 18.6 kg/crA book 3
: Using S-45C as the mating material, V.35.
Measured at 8m/min.

Book 4: Temperature 170°C, E test 11-66 method.

[Operation and effects of the invention]

The molded product made of the molding material of the present invention as described above has extremely excellent heat resistance (HDT >), abrasion resistance (limit pv value), and durability against thermal shock during actual use (heat cycle resistance). Therefore, it is suitable for use in wear-resistant applications that could not be used in the past, opening up new applications and products.

Claims (1)

[Scope of Claims] 1 A molding material that is molded by heating and pressurizing so as to fluidly adhere to a metal surface, which comprises: (a) 100 parts by weight of a cyanate ester resin composition; (b) a length of 2 mm or less; A wear-resistant molding material containing 20 to 100 parts by weight of carbon fiber milled fibers and (c) a curing catalyst as essential components. 2. The wear-resistant molding material according to claim 1, which contains graphite in an amount of 100 parts by weight or less as a filling aid. 3. The wear-resistant molding material according to claim 1 or 2, in which wollastonite is used in an amount of 100 parts by weight or less as a filling aid. 4. The wear-resistant molding material according to claim 1, 2, or 3, which uses mica as a filling aid in an amount of 100 parts by weight or less.