JPH06206166A - Heat-resistant resin-bonded grinding wheel - Google Patents

Abstract

PURPOSE:To improve the shaping workability and mechanical strength in heating by dispersing the grinding grains of diamond or cubic crystal boron nitride in a specific rate into the mixture of the modified polyaminomaleimide resin, silicon. carbide powder, and copper or silver powder. CONSTITUTION:A grinding wheel is made from the material which is formed by dispersing the grinding grains of diamond or cubic crystalline boron nitride in a rate of 10-40vol% of the whole volume, into the mixture of the modified polyaminomaleimide resin consisting of the aromatic hydrocarbon modified maleimide resin and polyamine, silicon carbide powder and copper or silver powder. As the aromatic hydrocarbon modified maleimide resin, is used the composition obtained by joining (a) the unsaturated bis-imide compound which is obtained from the aromatic group diamine, or polyamine conmpound, and the dicarboxylic acid, etc., having the ethylene type carbon-carbon double bond and (b) the aromatic hydrocabon formaldehyde reaction substance which is formed by reacting the aromatic hydrocarbon and formaldehyde reaction substance under the presence of the acid catalyst.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant resin-bonded grinding wheel which exhibits excellent grinding performance such as high accuracy and high efficiency under high load.

[0002]

2. Description of the Related Art Conventionally, a phenol resin has been widely used as a binder in a general grinding wheel using a synthetic resin as a binder. On the other hand, in grinding wheels used under heavy grinding conditions, high heat resistance is required for the binder, and aromatic polyimide resin, polyamino bismaleimide resin,
Highly heat-resistant resins such as bismaleimide triazine resins have come to be used. Although a high performance grinding wheel can be obtained by using these high heat resistant resins, the aromatic polyimide resin itself is expensive, requires high temperature and high pressure for the molding process, and does not require power during grinding. It had the drawback of being expensive. In addition, in polyamino bismaleimide resin and bismaleimide triazine resin,
Although it has excellent moldability, it has a drawback that it is still insufficient in terms of mechanical strength when heated.

[0003]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention In the present invention, as a result of earnest research to improve the mechanical strength under heat without impairing the excellent molding processability of polyaminobismaleimide resin, the aromatic amine in the maleimide resin was found. Aromatic hydrocarbon-modified maleimide resin having a hydrocarbon group introduced and a modified polyaminomaleimide resin obtained by reacting a diamine or a polyamine compound are used as a binder to achieve both excellent moldability and mechanical strength during heating. As a result, it has been found that a heat-resistant resin-bonded grinding wheel having an unprecedented excellent grinding performance can be manufactured. Further, based on this knowledge, various researches have been advanced to complete the present invention.

[0004]

The present invention uses a mixture of a modified polyaminomaleimide resin composed of an aromatic hydrocarbon-modified maleimide resin and a polyamine, a silicon carbide powder and a copper or silver powder as a matrix, and the total amount dispersed in the matrix. The present invention relates to a resin-bonded grinding wheel made of diamond or cubic boron nitride abrasive grains occupying 10 to 40% by volume.

The aromatic hydrocarbon-modified maleimide resin used in the present invention is an unsaturated bisimide derived from an aromatic diamine or polyamine compound and a dicarboxylic acid having an ethylene type carbon-carbon double bond or a reactive derivative thereof. An aromatic hydrocarbon-modified maleimide resin obtained by combining a compound (a) with an aromatic hydrocarbon formaldehyde reaction product (b) obtained by reacting an aromatic hydrocarbon with formaldehyde in the presence of an acid catalyst. It is preferable. The modification amount of the aromatic hydrocarbon is preferably 0.02 to 0.3 in terms of a molar ratio of the aromatic hydrocarbon nucleus as a modifier to the unsaturated imide-substituted aromatic nucleus, and 0.02.
Below, the effect of imparting toughness is small, and above 0.3, moldability and heat resistance deteriorate. The ratio of the diamine or polyamine compound to the aromatic hydrocarbon-modified maleimide resin compound is preferably 50% by weight or less, more preferably 10% by weight or more and 40% by weight or less. When the proportion of the diamine or polyamine compound with respect to the aromatic hydrocarbon-modified maleimide resin compound is 50% by weight or more, the melting point is largely lowered, and the moldability and heat resistance are lowered. On the other hand, if it is 10% by weight or less, the adhesiveness to the abrasive may be insufficient, and sufficient mechanical strength may not be obtained.

To produce such aromatic hydrocarbon-modified polyimide resin, aromatic diamine and aromatic hydrocarbon formaldehyde resin, dimethylolated aromatic hydrocarbon, dimethoxymethylated aromatic hydrocarbon, dihalogenomethylated aroma are used. In the presence of an acid catalyst, a group hydrocarbon is nucleophilically reacted to form an aromatic hydrocarbon-modified polyamine, and then a dicarboxylic acid anhydride having an ethylene-type carbon-carbon double bond is further reacted by a conventional method to produce an aromatic hydrocarbon. It is a modified maleimide compound. Further, the desired polyaminomaleimide resin can be obtained by reacting a diamine or a polyamine compound under melting.

As the aromatic hydrocarbon for obtaining the aromatic hydrocarbon formaldehyde reaction product, which is a modifier for the aromatic hydrocarbon-modified maleimide resin compound, which is the above-mentioned intermediate raw material, benzene, toluene, xylene, ethylbenzene, diethylbenzene are used. , Lower alkylbenzenes such as mesitylene, chlorobenzene, dichlorobenzene, bromobenzene, dibromobenzene, chlorotoluene, chloroxylene, bromoxylene, dibromoxylene, and other halogenated benzenes or halogenated lower alkylbenzenes.

The aromatic diamine or polyamine used here includes metaphenylenediamine, paraphenylenediamine, 2,2-bis (4-aminophenyl) propane, 4.4'-diaminodiphenylmethane, 1,
3,5-triaminobenzene, bis (4-aminophenyl) diphenylsilane, bis (4-aminophenyl) methylphosphine oxide, bis (3-aminophenyl) methylphosphine oxide, bis (4-aminophenyl) phenyl Phosphine oxide, bis (4
-Aminophenyl) phenylamine, metaxylylenediamine, paraxylylenediamine, 1,1-bis (p-
Aminophenyl) phthalane, 6,6′-diamino-2.
2'-dipyridyl, 4,4'-diaminobenzophenone, 4,4'-diaminoazobenzene, bis (4-aminophenyl) phenylmethane, 1,1-bis (4-aminophenyl) cyclohexane, 1,1-bis ( 4-amino-3-methylphenyl) cyclohexane, 2,5-bis (m-aminophenyl) -1,3,4-oxadiazole, 2,5-bis (p-aminophenyl) -1,3,3.
4-oxadiazole, 2,5-bis (m-aminophenyl) thiazolo (4,5-α) thiazole, 5,5′-
Di (m-aminophenyl) -2,2'-bis (1,3,3
4-oxadiazolyl) diphenyl sulfide, 4,
4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 2,6-diaminopyridine, tris (4-aminophenyl) phosphine oxide, bis (4-aminophenyl) ) N-methylamine, 1,5-diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxybenzidine, 2,5-diamino-1,3,4-oxadi Azole, 2,4-bis (β-amino-tert-butyl) toluene, bis (p
-Β-amino-tert-butylphenyl) ether,
Bis (p-β-methyl-α-aminophenyl) benzene, bis-p- (1,1-dimethyl-5-aminopentyl) benzene, 1-isopropyl-2,4-m-phenyldiamine, 4,4 ′ -Bis (p-aminophenyl)-
2,2′-dithiazole, m-bis (4-p-aminophenyl-2-thiazolyl) benzene, 2,2′-bis (m-aminophenyl) -5,5′-dibenzimidazole, 4,4 ′ -Dibenzanilide, 4,4'-diaminophenylbenzoate, N, N'-bis (4-aminobenzyl) -p-phenylenediamine, 3,5-bis (m-aminophenyl) -4-phenyl-1 , 2,4-
Triazole etc. are mentioned. Further, the aromatic amine compound of the present invention also includes triazine ring compounds such as melamine, cyclohexanecarboguanamine, acetoguanamine and benzoguanamine. In addition, these may be used alone or as a mixture of two or more kinds.

As the diamine and polyamine compounds,
In addition to the aromatic diamine or polyamine, an aliphatic, cycloaliphatic, or heterodiamine or polyamine compound can be used, and a silicone compound such as diaminodimethylsiloxane can also be used. The aromatic hydrocarbon formaldehyde reaction product used here is a reaction product of an aromatic hydrocarbon and formaldehyde in the presence of an acid catalyst, which is then neutralized and washed, and diallylmethanes and other Those produced by removing the low boiling fraction are preferred,
It is preferable that the oxygen content is 8% or more and that a non-reactive binuclear component such as diallylmethane is not included as much as possible.

As the acid catalyst, organic acids such as oxalic acid, paratoluenesulfonic acid, xylenesulfonic acid and phenolsulfonic acid, and inorganic acids such as hydrochloric acid and sulfuric acid can be used. As the unsaturated dicarboxylic acid anhydride, for example, maleic anhydride, citraconic anhydride, itaconic anhydride, pyrocinconic anhydride, α, β-unsaturated dicarboxylic acid anhydride such as dichloromaleic anhydride or their anhydrides Examples thereof include Diels-Alder reaction products of one with an acyclic, alicyclic or heterocyclic diene, such as cyclopentadiene. Further, as a curing accelerator, for example, radical polymerization initiators such as azo compounds and organic peroxides, tertiary amines, quaternary ammonium salts, phosphonium compounds, imidazoles, boron trifluoride compounds, amine salts and other ions May be added. If necessary, organic or inorganic additives and fillers other than these may be added.

The modified polyaminomaleimide resin powder, silicon carbide (SiC) fine powder and copper or silver powder obtained as above, and diamond or cubic boron nitride nitride occupying 10 to 40% by volume of the total volume. The heat-resistant resin-bonded grinding wheel of the present invention can be obtained by dispersing and mixing the particles, and shaping and processing. The silicon carbide and copper or silver powder used as the filler is preferably a fine powder having a particle size of 1 to 50 μm, more preferably a fine powder having a particle size of 10 to 30 μm. The blending amount of this silicon carbide with respect to the modified polyaminomaleimide resin is preferably 10 to 80% by weight based on the total amount of the resin, silicon carbide and copper or silver powder. Also,
Diamond or cubic boron nitride used as abrasive grains has a total volume of 10 to 4 including the abrasive grains of the grinding wheel.
It is preferably 0% by volume, more preferably 12.5 to 25% by volume.

[0012]

EXAMPLES The present invention will be described in detail below with reference to examples. All "parts" and "%" described herein indicate "parts by weight" and "% by weight". <Production Example> 4,4′-diaminodiphenylmethane 3000
Part, 300 parts of Mitsubishi Gas Chemical's xylene formaldehyde resin Nikanol G (oxygen content 15%) was placed in a flask equipped with a stirrer, a reflux condenser and a thermometer, and the internal temperature was set to 11
The mixture was heated to 0 ° C., and when 4,4′-diaminodiphenylmethane was completely dissolved, 40 parts of paratoluenesulfonic acid was added, and the mixture was further reacted under reflux with heating for 2 hours. Further, the reaction is carried out for 2 hours under atmospheric pressure dehydration, 1000 parts of methyl cellosolve is added while cooling, and the aromatic polyamine solution 42 is added.
50 parts were obtained. The viscosity of this product at 25 ° C is 0.2.
At Pa · S, the non-volatile content was 135% after 1 hour at 135 ° C.

Separately, 1925 parts of acetone was placed in a reactor similar to the above, 600 parts of maleic anhydride was added and completely dissolved, and then 825 parts of the aromatic polyamine solution obtained above were maintained while maintaining the temperature at 40 ° C. or lower. Drop over 90 minutes,
After the dropping was completed, the temperature was maintained at the same temperature for 1 hour. Then, 165 parts of triethylamine and 19.5 parts of nickel acetate tetrahydrate were added, and 800 parts of acetic anhydride was further added, and the mixture was reacted at a reflux temperature for 2 hours. After the reaction is completed, the solvent is immediately distilled off under vacuum,
1500 parts of hot water at 70 ° C. was added and mixed with stirring for 10 minutes. Then, the mixture was allowed to stand and the supernatant aqueous layer was removed. Furthermore, while stirring at the same temperature, add 1500 parts of 90 ° C. warm water,
After stirring and mixing at 90 ° C. for 10 minutes, the mixture was left standing and the supernatant aqueous layer was removed. Then, after repeating this operation twice, 500 parts of methanol was added, and after stirring at 70 ° C. for 10 minutes,
The supernatant is removed and the internal temperature is adjusted to 1 while dehydrating and desolvating under reduced pressure.
Raised to 20 ° C. At this point, 390 parts (corresponding to 28.6%) of 4,4′-diaminodiphenylmethane was added, and the mixture was stirred and reacted at the same temperature for 20 minutes to give a solid resin 1370.
I got a part. This solid resin was pulverized to obtain a fine powdery modified polyaminomaleimide resin having an average particle diameter of 25 μm. The melting point of this product was 74 ° C.

Example 17.5 parts of the modified polyaminomaleimide resin obtained in the production example, 5 parts of finely powdered silicon carbide passing through 800 mesh, 17.5 parts of finely powdered copper having an average particle size of 25 μm, Further, 60 parts of nickel-clad artificial diamond is dry-mixed and filled in a mold equipped with a predetermined aluminum core or a solidified product of aluminum powder resin, and the temperature is set to 200 ° C. and the pressure is set to 1000 kg / cm ² for 30 minutes. The ring-shaped grindstone layer portion was hot-pressed to form a ring-shaped grindstone layer portion bonded to the core, and was further baked in an atmosphere of 250 ° C. for 5 hours to obtain a resin-bonded grinding wheel A.

Comparative Example A resin-bonded grinding wheel B was prepared in the same manner as in Example except that the modified polyaminomaleimide resin obtained in Production Example was replaced with a commercially available polyaminobismaleimide resin.
Got

The resin-bonded grinding wheels A and B thus obtained and a commercially available resin-bonded grinding wheel were compared under the following conditions. Shape of grindstone 1A1, 200D × 6T × 3X × 5
0.8H Work Material Carbide P30 Grinder OKAMOTO WORKS CNC-52B, 7.5K
W Grinding conditions Peripheral speed: 1500 m / min., Table speed: 10 m / min., Cross feed: 2 mm / pass, Depth of cut: 0.025 mm Grinding liquid Klecut NET-909 1:50 aqueous solution The results obtained are shown in Table 1. Show.

[0017]

[Table 1]

[0018]

EFFECTS OF THE INVENTION The heat-resistant resin-bonded grinding wheel using the modified polyaminomaleimide resin of the present invention shows that the grinding ratio is extremely high and the grinding resistance is low. It is clear that it provides a highly efficient grinding wheel.

Claims (2)

[Claims] 1. A mixture of a modified polyaminomaleimide resin composed of an aromatic hydrocarbon-modified maleimide resin and a polyamine, a silicon carbide powder and a copper or silver powder is used as a matrix, and 10 to 40% by volume of the total volume dispersed therein is used. A resin-bonded grinding wheel consisting of diamond or cubic boron nitride abrasive grains. 2. An unsaturated bisimide compound (wherein the aromatic hydrocarbon-modified maleimide resin used is derived from an aromatic diamine or polyamine compound and a dicarboxylic acid having an ethylene-type carbon-carbon double bond or a reactive derivative thereof ( An aromatic hydrocarbon-modified maleimide resin obtained by combining a) with an aromatic hydrocarbon formaldehyde reactant (b) obtained by reacting an aromatic hydrocarbon with formaldehyde in the presence of an acid catalyst. The resin-bonded grinding wheel according to claim 1, which is characterized in that.