JP2002265762A - Benzocyclobutene resin composition, resin-bonded metallic molded part - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition comprising a resin imparting excellent insulating characteristics even when added in a small amount, which gives a resin-bonded metallic molded part improved in electrical/magnetic characteristics. SOLUTION: The benzocyclobutene resin composition comprises (a) a benzocyclobutene resin, (b) an epoxy resin having an epoxy equivalent of at least 800 g/eq and/or a phenolic resin having a hydroxyl group equivalent of at least 500 g/eq and (c) powder of a metal or of a metallic compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a benzocyclobutene resin composition having excellent electric and magnetic properties and a resin-bonded metal molded part using the same.

[0002]

2. Description of the Related Art Toroidal cores and choke coils for noise filters, deflection yokes for electron beams, magnetic cores of transformers and high-frequency components, and parts of electric and electronic components such as magnetic heads are made of magnetic metal powder using resin as a binder. There is a resin-bonded metal molding type obtained by compacting. recent years,
Under the demand for miniaturization and thinning of various parts, improvement of electric and magnetic properties is required for the above-mentioned resin-bonded metal molded type parts. However, the electrical and magnetic properties largely depend on the binder resin used, and there is still insufficient research into binder resins that can provide excellent electrical and magnetic properties in response to demands for miniaturization and thinning, and satisfactory components can be obtained. Not.

[0003]

As a method for improving the electric and magnetic properties of a resin-bonded metal molded part, 1) improving the insulation between metal powders, 2) increasing the content of the metal powder, and the like. Is known. However, there is a contradictory situation that if the insulating property is regarded as important, the metal component must be reduced, and if the metal component is increased, the insulating property cannot be maintained. An object of the present invention is to provide a resin composition using a resin that gives good insulating properties with a small amount of addition, and that can improve the electric and magnetic properties of a resin-bonded metal molded part. To provide things.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, completed the present invention. That is, the present invention relates to (1) a benzocyclobutene resin (a), an epoxy resin having an epoxy equivalent of 800 g / eq or more and / or a phenol resin (b) having a hydroxyl equivalent of 500 g / eq or more, and a powder of metal or metal compound (c). )
A benzocyclobutene resin composition containing (2) a benzocyclobutene resin (a) having the formula (1)

[0005]

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(Where X is the following formulas (X1) to (X12)

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(R in the formulas (X1) to (X12) represents a hydrogen atom, a methyl group, an ethyl group, a t-butyl group or a phenyl group, and may be different from each other.) Is a seed. The benzocyclobutene resin composition according to the above (1), wherein (3) X is the formula (X1), the benzocyclobutene resin composition according to the above (2),
(4) The resin according to any one of (1) to (3) above, wherein the epoxy resin having an epoxy equivalent of 800 g / eq or more and / or the phenol resin (b) having a hydroxyl equivalent of 500 g / eq or more is a resin having a bisphenol skeleton. The benzocyclobutene resin composition according to any one of (1) to (4), wherein (5) the metal or metal compound powder (c) is a powder containing a metal or metal compound exhibiting magnetism. (6) The benzocyclobutene resin composition according to (5), wherein the powder containing a metal or metal compound exhibiting magnetism is a powder containing at least an iron component; The present invention relates to a resin-bonded metal molded part using the benzocyclobutene resin composition according to any one of (1) to (6).

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The benzocyclobutene resin (a) used in the present invention will be described. The benzocyclobutene resin used in the present invention is not particularly limited as long as two benzocyclobutene groups are bonded directly or via an organic group having two bonding sites. Here, the organic group having two binding sites may or may not have a bond in its structure that undergoes a polymerization reaction by heating or other means.

Such a benzocyclobutene resin can be obtained by a known method. For example, a benzocyclobutene resin in which X of the formula (1) is the formula (X1) is obtained by converting 2-bromobenzocyclobutene and divinyltetramethylsiloxane in acetonitrile in the presence of a palladium catalyst.
It is obtained by performing the reaction at 00 ° C. or higher.

The benzocyclobutene resin (a) used in the present invention is preferably a compound represented by the above formula (1)
And these can be used alone or as a mixture of two or more. Among them, X in the formula (1) is (X1), (X2), (X3),
Those having a structure of (X9), (X11) or (X12) are preferable, and (X1), (X9), (X11) or (X
The structure of (12) is more preferable, and the structure of (X1) is particularly preferable. Formula (X12) indicates that the benzocyclobutene group is directly bonded.

Further, in order to impart more excellent insulating properties, it is more preferable to use a B-staged benzocyclobutene resin obtained by increasing the molecular weight of these resins. The B-staged benzocyclobutene resin is used in a solvent capable of dissolving the benzocyclobutene resin (a) in a range of 150 to
It can be obtained by heating at 190 ° C. while refluxing. The degree of the increase in the molecular weight is adjusted by adjusting the reflux time for a solution of the benzocyclobutene resin / solvent of about 30 to 50% by weight so that the benzocyclobutene resin having the increased molecular weight is dissolved in the solvent. preferable. The solvent is not particularly limited as long as it can dissolve the benzocyclobutene resin, but examples thereof include methyl ethyl ketone, mesitylene, dimethylformamide and the like, and in consideration of the drying step, a low boiling solvent such as methyl ethyl ketone and mesitylene is preferable. . The benzocyclobutene resin having a high molecular weight may be used by mixing with a benzocyclobutene resin having no high molecular weight.

The epoxy equivalent used in the present invention is 800 g
/ Eq or more epoxy resin and / or hydroxyl equivalent is 50
The phenol resin (b) of 0 g / eq or more (hereinafter, these are collectively referred to simply as resin (b)) will be described. As the resin (b), the epoxy resin having an epoxy equivalent of 800 g / eq or more, preferably 1200 g / eq or more, more preferably 1500 g / eq or more for the purpose of improving the insulation properties of the resin-bonded metal molded part of the present invention. Is used, and the hydroxyl equivalent is 500 g / eq or more,
Preferably, a phenol resin of 1000 g / eq or more is used. The epoxy resin that can be used in the present invention is not particularly limited as long as it satisfies the epoxy equivalent range, for example, an epoxy resin obtained by glycidyl etherification of a phenolic compound, an alicyclic resin having an aliphatic skeleton such as cyclohexane. Examples include an epoxy resin, a heterocyclic epoxy resin having a heterocyclic ring such as an isocyanuric ring and a hydantoin ring. These epoxy resins can be used alone or in combination of two or more. Examples of the phenolic compound in the epoxy resin obtained by converting the phenolic compound to a glycidyl ether group include bisphenol A, bisphenol F, bisphenol S, 4,
4′-biphenylphenol, 2,2′-methylene-bis (4-methyl-6-tert-butylphenol),
2,2'-methylene-bis (4-ethyl-6-tert
-Butylphenol), 4,4'-butylene-bis-
(3-methyl-6-tert-butylphenol),
1,1,3-tris (2-methyl-4-hydroxy-5
-Tert-butylphenol), phenols having a skeleton of diisopropylidene, pyrogallol, diisopropylidene, phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene, and polyphenol compounds such as phenolized polybutadiene. And various novolak resins. In the above, as the various novolak resins, phenol,
Novolak resins made from various phenols such as cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, naphthols, phenol novolak resins containing a xylylene skeleton, phenol novolak resins containing a dicyclopentadiene skeleton And various novolak resins such as a phenol novolak resin having a fluorene skeleton.

The phenolic resin is not particularly limited as long as it is a resin having a phenolic hydroxyl group in the molecule and satisfies the above range of hydroxyl equivalents.
The hydroxyl equivalent among the phenolic compounds and the like is 500 g
/ Eq or more. In the resin (b), the epoxy resin and the phenol resin can be used in a mixture at an arbitrary ratio.

The resin (b) is particularly preferably a resin having a bisphenol skeleton.
Examples thereof include F, S, and epoxidized products thereof. There is no particular limitation as long as the compound has a bisphenol skeleton. Further, a halogen atom, a methyl group, an ethyl group, a propyl group, or a t-butyl group is added to the bisphenol skeleton. And the like.

The resin (b) is usually 5 to 40% by weight in the resin component (benzocyclobutene resin (a) + resin (b)),
Preferably, it is used in the range of 5 to 30% by weight, more preferably 5 to 20% by weight. If it is less than 5% by weight, good insulation properties cannot be obtained, and if it exceeds 40% by weight, the heat resistance of the molded metal part becomes insufficient.

In the present invention, other resins than the benzocyclobutene resin (a) and the resin (b) can be used as long as the electric and magnetic properties are not impaired. Examples of other resins include, for example, phenolic resins, urethane resins, epoxy resins, silicone resins, polyester resins, urea resins, phenoxy resins, isocyanate resins, acrylic resins, thermosetting polyimide resins, and other thermoplastic resins. However, the present invention is not limited to these.

As the metal or metal compound powder (c), those containing a metal or metal compound having magnetism for use as a magnetic component after compacting are preferable, but other than these, for example, aluminum powder, copper powder, Ni powder, A
Nonmagnetic materials such as l-ni powder and various alloys may be contained. Specific examples of the magnetic metal or metal compound that can be used include atomized iron powder, reduced iron powder, permalloy (Ni-Fe alloy), silicon steel and silicon iron (Fe-S
i), those containing an iron component such as sendust (Fe-Si-Al alloy) and alpalm (Fe-Al alloy). Besides, alnico alloy powder, rare earth metal powder,
Examples include powders of metals or metal compounds having various magnetisms such as metal oxide powders.

The mixing ratio of the metal or metal compound powder (c) is usually from 70.0 to 99.8% by weight, preferably from 90.0 to 9% by weight in the benzocyclobutene resin composition of the present invention.
It is good to adjust to 9.5% by weight, more preferably 95.0 to 99.0% by weight. The average particle size of the metal or metal compound powder (c) to be used is not particularly limited, and it is necessary to select an optimum particle size according to molding conditions, electric and magnetic properties, etc., but generally 2 mm or less. , Preferably 1 mm or less, more preferably 500 μm
The following should be used:

To the benzocyclobutene resin composition of the present invention, a coloring agent, a coupling agent such as a silane coupling agent, a leveling agent, a lubricant and the like can be added according to the purpose. There is no particular limitation on the coloring agent. , Lead sulfate, zinc oxide, chrome yellow, zinc yellow, chrome vermilion, red iron oxide, cobalt purple, navy blue, ultramarine blue, carbon black, chrome green, chromium oxide, cobalt green and the like.

The silane coupling agent is not particularly limited, but specific examples include 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-chloropropyl. Methyldimethoxysilane, 3-
3-glycidoxypropyltrimethoxysilane, 3-glycidyl having at least one functional group or structure selected from the group consisting of chloropropyltrimethoxysilane and an epoxy group, an amino group, a ketimine structure and an imidazole structure in the molecule Xypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,
4-epoxycyclohexyl) ethyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, N- (1,3 dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, imidazole type silane cup As the ring material, for example, a reaction product of 2-methylimidazole and 3-glycidoxypropyltrimethoxysilane, 2-ethyl-4-methylimidazole and 3
A reaction product of 2-glycidoxypropyltrimethoxysilane with 2-ethyl-4-methylimidazole and 3-methacryloxypropyltrimethoxysilane. Among these silane coupling agents, those having at least one functional group or structure selected from the group consisting of an epoxy group, an amino group, a ketimine structure and an imidazole structure in the molecule are preferable.

In the present invention, a silane coupling agent and another coupling agent can be used in combination as long as the insulating properties are not adversely affected. As other coupling agents,
Examples include a zirconium-based coupling agent, an aluminum-based coupling agent, and a titanate-based coupling agent. Specific examples of the coupling agent that can be used include isopropyl (N-ethylaminoethylamino) titanate, isopropyl triisostearoyl titanate, titanium di (dioctyl pyrophosphate) oxyacetate, tetraisopropyl di (dioctyl phosphite) titanate, neo Alkoxy tri (p-
Titanium-based coupling agents such as N- (β-aminoethyl) aminophenyl) titanate, Zr-acetylacetonate, Zr-methacrylate, Zr-propionate;
Neoalkoxy zirconate, neoalkoxytris neodecanoyl zirconate, neoalkoxytris (dodecanoyl) benzenesulfonyl zirconate, neoalkoxytris (ethylenediaminoethyl) zirconate, neoalkoxytris (m-aminophenyl) zirconate, ammonium zirconium Examples include zirconium such as carbonate, Al-acetylacetonate, Al-methacrylate, and Al-propionate, or an aluminum-based coupling agent.

The amount of the coupling agent containing such a silane coupling agent cannot be specified unconditionally because it is necessary to appropriately change and select an optimum amount. 0% by weight, preferably 0.05 to 1.0
%, More preferably 0.1 to 0.5% by weight. When a silane coupling agent is used in combination with another coupling agent, the silane coupling agent usually accounts for 30% by weight or more, preferably 50% by weight or more, more preferably 80% by weight or more of all the coupling agents. Use in proportion.

Examples of the leveling agent include acrylates such as ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate having a molecular weight of 4000.
~ 12000 oligomers, epoxidized soy fatty acids,
Epoxidized aviethyl alcohol, hydrogenated castor oil, and the like. Examples of the lubricant include hydrocarbon lubricants such as paraffin wax, micro wax, and polyethylene wax, higher fatty acid lubricants such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid, stearylamide, palmitylamide, Higher fatty acid amide lubricants such as oleylamide, methylenebisstearamide, ethylenebisstearamide, hydrogenated castor oil, butyl stearate, ethylene glycol monostearate, pentaerythritol (mono-, di-, tri-, or tetra-) ) Higher fatty acid ester lubricants such as stearate, cetyl alcohol, stearyl alcohol,
Alcohol-based lubricants such as polyethylene glycol and polyglycerol, and metals such as magnesium, calcium, cadmium, barium, zinc, and lead such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, ricinoleic acid, and naphthenic acid Examples include natural waxes such as salt metal soaps, carnauba wax, candelilla wax, beeswax and montan wax.

In order to obtain a resin-bonded metal molded part using the benzocyclobutene resin composition of the present invention, the above-mentioned components are mixed at a predetermined ratio by an arbitrary method and a resin-coated metal or metal compound is prepared. A powder (the benzocyclobutene resin composition of the present invention; it may be pulverized if necessary to make the particle size uniform) is obtained, and then compacting and heat curing are performed. As a mixing method at this time, the above-mentioned resins (premixed with a kneader or the like are also possible) are dissolved in an appropriate solvent in advance, and the solution is uniformly mixed with a metal or metal compound powder. A method of removing powder to obtain a powder, or a method in which raw materials (including metal powder) are dry-mixed using a Henschel mixer or the like, and then kneaded by heating and melting in a kneader, extruder, batch kneader, reaction vessel, or the like. There is a method in which a melt heating and melt mixing treatment is performed by a machine, then the mixture is cooled and solidified, and after pulverization, a powder having a desired particle size is collected to obtain a powder. The method of mixing the resin and the powder of the metal or metal compound is not limited to these, and it is necessary to perform the method under appropriate methods and conditions so as not to impair the electric and magnetic properties. In the above, the solvent is not particularly limited as long as each component can be dissolved, and examples thereof include organic solvents such as methyl ethyl ketone, mesitylene, and dimethylformamide.

[0025]

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the following examples, "parts" means parts by weight.

Example 1 B-staged benzocyclobutene resin (A) 70 wherein X in the formula (1) is (X1) and R is all methyl groups
Parts, bisphenol A having an epoxy equivalent of 1900 g / eq
7 parts of the epoxy resin (B) was added to methyl ethyl ketone 308.
The mixture was uniformly dissolved in the solution to prepare a resin solution having a concentration of 20% by weight. Using this resin liquid, the resin component in the total solid content was 1.
After mixing with the reduced iron powder so as to have a proportion occupying 0% by weight and uniform mixing, the solvent was naturally dried to obtain a powdery benzocyclobutene resin composition of the present invention. 40 g of the obtained benzocyclobutene resin composition was put into a molding die, and compacted with a press pressure of 200 kg / cm ² to obtain a tablet having a diameter of 4 cm and a thickness of 5 mm. Next, this was heated and cured at 200 ° C. for 1 hour to obtain a molded product for measuring insulation resistance, and the resistance value was measured with a digital multimeter manufactured by Advantest Corporation. The results are shown in the column of physical properties of the molded product in Table 1.

Examples 2 and 3 A molded article for measuring insulation resistance of the present invention was obtained in the same manner as in Example 1 except that the components shown in the column of the composition of the composition in Table 1 were used. The insulation resistance of the obtained molded product was measured in the same manner as in Example 1, and the results are shown in Table 1. In addition, the numerical value in the column of the composition of the compound in Table 1 represents "part". Comparative Example 1 The reduced iron powder used in the example was compression-molded as it was in the same manner as in Example 1, but the insulation resistance was measured in the same manner.

Table 1 Example 1 Example 2 Example 3 Composition of the formulation Benzocyclobutene resin (A) 70 56 70 Bisphenol A epoxy resin (B1) 714-Bisphenol A phenolic resin (B2) -7 MEK 308 308 308 Physical properties of molded product Electric resistance value / Ω 0.383 0.421 0.322

The raw materials shown in Table 1 are as follows. Benzocyclobutene resin (A): X in the formula (1) is X
1, R is a benzocyclobutene resin represented by a methyl group, and a B-staged benzocyclobutene resin having a weight average molecular weight of 27,000 in terms of polystyrene by gel permeation chromatography, bisphenol A epoxy resin (B1 ): Solid bisphenol A epoxy resin having an epoxy equivalent of 1900 g / eq Bisphenol A phenol resin (B2): Solid bisphenol A phenol resin having a hydroxyl equivalent of 700 g / eq MEK: Methyl ethyl ketone

[0030]

The benzocyclobutene resin composition of the present invention can provide a resin-bonded metal molded part having excellent insulation properties. The resin-bonded metal molded part of the present invention is used for a toroidal core for preventing noise, a choke coil, a deflection yoke for an electron beam, a magnetic core of a transformer or a high-frequency part, a magnetic head, and a motor used for home appliances or automobiles. It is extremely useful as a bonded magnet or the like.

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Claims (7)

[Claims] 1. A benzocyclobutene resin (a), an epoxy resin having an epoxy equivalent of 800 g / eq or more and / or a phenol resin having a hydroxyl equivalent of 500 g / eq or more (b), and a metal or metal compound powder (c). Benzocyclobutene resin composition. 2. A benzocyclobutene resin (a) having the formula (1): (Wherein X is the following formulas (X1) to (X12): (R in the formulas (X1) to (X12) represents a hydrogen atom, a methyl group, an ethyl group, a t-butyl group or a phenyl group, and may be different from each other.)
Is a seed. The benzocyclobutene resin composition according to claim 1, wherein 3. The benzocyclobutene resin composition according to claim 2, wherein X is the formula (X1). 4. The resin according to claim 1, wherein the epoxy resin having an epoxy equivalent of 800 g / eq or more and / or the phenol resin (b) having a hydroxyl equivalent of 500 g / eq or more is a resin having a bisphenol skeleton. Benzocyclobutene resin composition. 5. The metal or metal compound powder (c) is a powder containing a metal or metal compound exhibiting magnetism.
5. The benzocyclobutene resin composition according to any one of items 4 to 4. 6. A powder containing a metal or a metal compound exhibiting magnetism is a powder containing at least an iron component.
3. The benzocyclobutene resin composition according to item 1. 7. A resin-bonded metal molded component using the benzocyclobutene resin composition according to any one of claims 1 to 6.