JPS61211332A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:The titled composition useful as an electrical insulating filler for semidry capacitors, comprising an epoxy resin, a specified resin and an aromatic hydrocarbon having a (non)fused aromatic ring. CONSTITUTION:To 100pts.wt. hydrocarbon fraction consisting mainly unsaturated hydrocarbon, b.p. 80-280 deg.C, formed as a byproduct in the thermal cracking of petroleum, 7-45pts.wt. phenol and 0.05-5wt% Friedel-Crafts catalyst are added, and the obtained mixture is reacted at -10-+80 deg.C for 10min-15hr to obtain a resin (B) of a softening point of 50-120 deg.C and a number-average MW of 500-1,500. 100pts.wt. epoxy resin (A) of a MW of 300-3,000 and an epoxy equivalent of 300-3,500 is mixed with 5-900pts.wt. component B, 4-200 pts.wt. aromatic hydrocarbon (C) having three (non)fused aromatic rings and an average MW of 230-350 (e.g., dibenzyltoluene) and 5-100pts.wt. curing agent (D) (e.g., diethylenetriamine).

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to an epoxy resin composition. More specifically, the present invention relates to a filler composition for electrical insulation, and particularly to an epoxy resin composition suitable as a filler for use in so-called semi-dry capacitors.

(Prior art and its problems) Epoxy resins have been widely used for electrical insulation. However, since epoxy resins are expensive, inexpensive additives are added to reduce the price. For example, JP-A-53-125461 proposes an epoxy resin composition in which a petroleum resin according to a specific manufacturing method is added.

However, the epoxy resin composition proposed in the above publication is not necessarily satisfactory as a filler for electrical insulation. In particular, there are points to be improved in the composition for filling metallized plastic film capacitors.

(Means for Solving the Problems) The present invention provides an aromatic hydrocarbon having three roughly condensed or non-condensed aromatic rings to an epoxy resin and a petroleum resin produced by the specific production method described in the above-mentioned publication. By adding it, the performance of the composition as an electrically insulating filler is improved.

That is, the present invention comprises: (a) 100 parts by weight of an epoxy resin; (b) 100 parts by weight of a hydrocarbon fraction containing as a main component unsaturated hydrocarbons having a boiling point range of 80 to 280°C and produced as a by-product from thermal decomposition of petroleum. (c) 5 to 900 parts by weight of a resin obtained by adding 7 to 45 parts by weight of a phenol to the mixture and polymerizing with a Friedel Krach catalyst, and (c) an average molecular weight of 230 having three fused or non-fused aromatic rings. ~350
The present invention relates to an epoxy resin composition comprising 4 to 200 parts by weight of an aromatic hydrocarbon.

The present invention will be further explained below.

The main raw material of the resin used in the composition of the present invention is a by-product of 80 to 80% by-product when producing olefins such as ethylene and propylene by thermal decomposition of naphtha, kerosene, diesel oil fraction, or butane, etc., by thermal decomposition such as steam cranking. The cracked oil fraction has a boiling point range of 280° C., each distillate fraction divided by distillation within the boiling point range, or a mixture of these distillate fractions as appropriate. In such a fraction having a boiling point of 80 DEG to 280 DEG C., aromatic olefins having 8 to 10 carbon atoms such as styrene and alkylstyrenes, indenes and alkylindenes are present in large amounts, for example, 35 to 65% by weight. boiling point 8
A cracked oil fraction at a temperature below 0° C. is not preferred because the resin obtained therefrom has poor compatibility with epoxy resins.

However, within the range in which the effects of the present invention are achieved, a small amount, such as 20% by weight or less, of a cracked oil fraction with a boiling point of less than 80 °C, for example, a boiling point range of 20 to 80 °C, is used, and the carbonization used in the present invention is used. It can also be used as a hydrogen fraction and polymerized.

Next, the phenols to be added to the above hydrocarbon fraction are phenol, cresol, xylenol, tert-
It is a single or a mixture of two or more alkyl-substituted phenols such as butylphenol and nonylphenol.

Add 7 to 7 parts of phenols to 100 parts by weight of the above hydrocarbon fraction.
45 heavy mother parts are mixed and polymerized using a Friedel-Crauch type catalyst. If the amount of phenols is less than 7 parts by weight, the resulting resin will have poor compatibility with the epoxy resin, and the performance of the capacitor will also deteriorate. On the other hand, if the amount exceeds 45 parts by weight, it is not preferable because not only will a resin with an extremely poor hue be obtained, but it will also be uneconomical.

Polymerization is carried out by adding 0.05 to 5% by weight of a Friedel-Kraf type catalyst such as boron trifluoride, aluminum chloride, boron trifluoride phenol complex, or boron trifluoride dialkyl ether complex to the raw material, and -10 It is carried out for 10 minutes to 15 hours at a temperature range of ~+80°C. After polymerization, the catalyst is decomposed and removed using an alkaline solution such as caustic soda or zyda carbonate, washed with water if necessary, and unreacted oil and low-molecular polymers are separated by evaporation or distillation. A yellow resin is obtained. The resulting resin has a softening point (J'l
2531-60) and a number average molecular weight of 500 to 1,500.

The resin used in the present invention obtained as described above is: ■R
The spectrum shows that it contains a large amount of phenolic hydroxyl groups, making it clearly different from conventional petroleum resins.

The epoxy resin referred to in the present invention is not particularly limited, and is a conventionally known epoxy resin, and those having a molecular weight of 300 to 3,000 and an epoxy equivalent of 150 to 3,500 are usefully used.

A typical example of this epoxy resin is one obtained as a reaction product of a compound having active hydrogen and epichlorohydrin. Compounds having active hydrogen include compounds having two or more phenolic OH in the molecule, such as bisphenol A1 novolak resin and derivatives thereof, and may also include compounds having carboxyl groups, amino groups, etc. . In particular, in the present invention, an epoxy resin obtained by the reaction of bisphenol A and epichlorohydrin can be advantageously used.

In the present invention, the mixing ratio of the resin and the epoxy resin is 5 to 900 parts by weight of the resin per 100 parts by weight of the epoxy resin.
Parts by weight. If the amount of the resin exceeds 900 parts by weight, the epoxy resin will not be sufficiently cured and the original characteristics of the epoxy resin will be lost, which is undesirable, and if it is less than 5 parts by weight, the effect of adding the resin will not be produced.

Further, the aromatic hydrocarbon which is the component (c) of the epoxy resin composition of the present invention is compatible with the epoxy resin having an average molecular weight of 230 to 350. Preferably, it is liquid or viscous semi-solid at room temperature, but it may be solid at room temperature as long as it is compatible with the epoxy resin. For example, typical aromatic hydrocarbons include triarylalkanes, diara/
1<kyl aromatic hydrocarbon, aromatic hydrocarbon such as triaryl, aralkyldiaryl, arylnaphthalene, aralkylnaphthalene. These can be used alone or as a mixture of two or more. Average molecular weight is 350
If it exceeds 100%, the compatibility with the epoxy resin decreases, so it is not preferable.

Here, dialkyl aromatic hydrocarbon, triaryl,
Aralkyl diaryl and the like are more specifically represented by the following general formula (I).

Here, R+ and R2 are methane, ethane, propane,
It is a divalent hydrocarbon group derived from an aliphatic hydrocarbon having 1 to 4 carbon atoms such as butane, and j and k are O or 1
It is. Further, R3 to R5 are alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, and j, ra and n are integers of O to 3.

Specific compounds of formula (I>) include, as examples of dialkyl aromatic hydrocarbons, dibenzyltoluene, dibenzylxylene, dibenzyl-ethylbenzene, dibenzylcumene, benzyl-methylbenzylbenzene, benzyl-ethylbenzylbenzene, and benzyl. -dimethylbenzylbenzene, benzyl-propylbenzylbenzene, 1-tolyl-1-benzylphenyl-ethane, 1-xylyl-1-benzylphenyl-
Ethane, 1-ethylphenyl-1-benzylphenyl-
Ethane, 1-cumenyl-1-benzylphenyl-ethane, 1-phenyl-1-methylbenzylphenyl-ethane, 1-phenyl-1-dimethylbenzylphenyl-ethane, 1-phenyl-1-ethylbenzylphenyl-ethane, 1 -Phenyl-1-propylbenzylphenyl-ethane, 1-phenyl-1-benzyltolyl-ethane, 1-phenyl-1-benzylxylyl-ethane, 1-phenyl-
Examples include 1-benzylethylphenyl-ethane, 1-phenyl-1-penzylcumenyl-ethane, and the like.

Furthermore, di(α-methylbenzyl)benzene, α-methylbenzyl-(methyl-α-methylbenzyl)
Benzene, α-methylbenzyl-(dimethyl-α-methylbenzyl)benzene, α-methylbenzyl-(ethyl-α-methylbenzyl)
Benzene, α-methylbenzyl-(propyl-α-methylbenzyl)benzene, di(α-methylbenzyl)toluene, di(α-methylbenzyl)xylene, di(α-methylbenzyl)-ethylbenzene, di(α-
methylbenzyl)-cumene, etc.

Examples of triaryl and aralkyldiaryl are 4
-inpropyl-I-terphenyl, 3-butyl-m-
Examples include terphenyl and 2-phenylethyl-biphenyl.

Arylnaphthalenes and aralkylnaphthalenes include those represented by the following formula (II).

Here, R+ is a divalent group derived from an aliphatic hydrocarbon having 1 to 4 carbon atoms such as methane, ethane, propane, butane, etc., and J is 0 or 1.

Further, R2 and R3 are alkyl or cycloalkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, and m or n is an integer of 0 to 3.

Specifically, the compounds include 1-(ethylphenyl)-naphthalene, 1-benzyl-
2-methyl-naphthalene, 1-benzyl-4-methyl-
Naphthalene, 1-methyl-3-(o-tolyl)-naphthalene, 1-methyl-3-(p-tolyl)-naphthalene,
1-Methyl-4-(phenylethyl)-naphthalene, 2.7-dimethyl-(p-tolyl)-naphthalene, 2-
(1-(o-tolyl)-ethyl)-naphthalene, etc.

Examples of the three-ring aromatic hydrocarbons other than those of formula (I) or (II) include triarylalkane consisting of a hydrogenated product of a styrene trimer such as styrene, vinyltoluene, and α-methylstyrene.

The above aromatic hydrocarbon is added in an amount of 4 to 200 parts by weight per 100 parts of the epoxy resin. If the aromatic hydrocarbon is added in an amount less than 4 parts by weight, the effects of the present invention cannot be achieved, and if the aromatic hydrocarbon is added in an amount exceeding 200 parts by weight, the curing of the epoxy resin becomes insufficient, so both are not preferred.

Furthermore, the epoxy resin composition of the present invention is made by mixing a known curing agent for curing epoxy resin in an amount of 5 to 100 parts by weight, preferably 30 to 50 parts by weight, per 100 parts by weight of epoxy resin. Known curing agents include aliphatic amines such as diethylenetriamine, triethylenetetramine, adducts of epoxy resins and aliphatic amines, aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, diaminophenyl sulfone, and methylnadic anhydride. In addition to acid anhydrides such as , hexahydroanhydride, urea resins, melamine resins, phenolic resins, and polyisocyanates.

Further, in order to improve the thixotropic properties of the epoxy resin composition, inorganic fillers such as mica, silica, calcium carbonate, and talc can be mixed in any proportion. Other known flame retardants for epoxy resins, such as tetrabromobisphenol A1 decabrom diphenyl ether, halogenated flame retardants such as chlorinated paraffin, ammonium phosphate, tricresyl phosphate, triethyl phosphate, tris(β-chloroethyl ) Phosphorus-based flame retardants such as phosphates, acidic phosphate esters, nitrogen-containing phosphorus compounds, red phosphorus, tin oxide, ammonium trioxide, zirconium hydroxide, barium metaborate,
Inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide can also be used. Additionally, reactive diluents such as monoepoxides such as styrene oxide, olefin oxide, polyepoxides such as divinylbenzene dioxide, and non-reactive diluents such as dioctyl phthalate may also reduce the viscosity of the epoxy resin composition and reduce the viscosity of the epoxy resin composition. Used to improve sex and for other reasons.

Although the epoxy resin composition of the present invention can be used for paints and other purposes, it is preferably useful as a filler for electrical insulation.

Here, a preferred form of use as an electrically insulating filler will be explained below, in which the periphery of a capacitor element, at least a portion of which is made of a gilded plastic film, is filled with an epoxy resin composition as a filler. , a cured metallized film (MF) capacitor.

That is, a metallized film capacitor can be obtained by filling the above-mentioned epoxy resin composition into a case housing a capacitor element and heating and curing the composition. The case may be an exterior case for a capacitor, or a case may be a mold or a container.

Here, the capacitor element is an element formed by winding a plastic film metallized on one or both sides with a metal such as aluminum or zinc. As the plastic film, a polyolefin film such as polypropylene or a polyester film such as polyethylene terephthalate is used. When winding, insulating paper or plastic film can be layered together with the metallized film. The end face of the wound element is usually treated with metallicon and lead wires are attached.

The case for housing the capacitor element as an exterior and the case as a container or mold may have any shape, and the material thereof is not particularly limited.

A capacitor element is housed in a case, filled with an epoxy resin composition, and then heated to harden the epoxy resin. When the case is used as a container or mold, the case is removed after curing. When heating, care is taken not to adversely affect the plastic film inside the element, but usually the heating temperature is 7.
A heating time of 0 to 100°C and a heating time of 1 to 5 hours is sufficient.

(Effects of the Invention) By mixing a 3-ring aromatic hydrocarbon, an epoxy resin with excellent electrical properties can be obtained. The compositions of the present invention are particularly useful as fillers for electrical insulation, especially metallized plastic film capacitors.

(Example) The present invention will be specifically described below based on resin preparation examples, examples, and comparative examples. Note that all formulation values in Tables 1 and 2 are parts by weight.

Phenol 18 is added to 100 parts by weight of a hydrocarbon fraction with a boiling point range of 140 to 210°C and containing 51% by weight of unsaturation among cracked oil fractions obtained from steam cranking of milk LLLL di naphtha.
Add 0 parts by weight of boron trifluoride ethyl ether complex
, 7 layers were added and polymerized at 60° C. for 3 hours. After polymerization, the catalyst was decomposed with an aqueous solution of caustic soda, washed with water, and unreacted oil was removed by distillation under reduced pressure to obtain a resin (I>) with a softening point of 95° C. The resin yield was 58% by weight.

Resin Preparation Example 2 A resin with a softening point of 83°C (I [
) was obtained. The resin yield was 62% by weight.

Resin Preparation Example 3 The hydrocarbon fraction used in Resin Preparation Example 1 was fractionated by precision distillation into a fraction having a boiling point of 176 to 190°C. The unsaturated component in this fraction was 58% by weight, and the indene content was 37% by weight. 25 parts by weight of nonylphenol was added to 100 parts by weight of this fraction, 0.7% by weight of boron iofluoride phenol complex catalyst was added, and the mixture was polymerized at 40°C for 3 hours, followed by the same treatment as in Resin Preparation Example 1. Resin (I[[)
I got it. Resin yield is 58% by weight, softening point is 97°C
Met.

Examples 1 and 2 and Comparative Examples 1 and 2 Aluminum was vapor-deposited on one side of a biaxially stretched polypropylene film with a thickness of 15 μm according to a conventional method to obtain a metallized plastic film with a width of 40 mm with a 3M margin. A capacitor element made by winding this was housed in a case to create a model capacitor. Next, epoxy resins, resin (1) obtained in Resin Preparation Example 1, and epoxy resin compositions containing 3-ring aromatic hydrocarbons (Examples 1 to 2) having the compositions shown in Table 1 were added, respectively. A capacitor with a capacitance of 5 μF was obtained.

Subsequently, the epoxy resin was cured by heating at 90° C. for 3 hours. After curing, the performance of the capacitor was investigated by applying a constant voltage to the capacitor and measuring the change in capacitance over time. The results are shown in Figure 1.

For comparison, MF capacitor filled with epoxy resin only (Comparative Example 1), epoxy resin and resin preparation example 1
The MF capacitor filled with the epoxy resin composition (Comparative Example 2) containing the resin (I>) obtained in (1) was also tested for capacitor performance.

Table 1 *1: Bisphenol A type epoxy resin (product name: Pelnox M E-350, manufactured by Nippon Pelnox Co., Ltd.)
, *2: Aromatic hydrocarbon oil whose main component is di(arylethyl)aryl with an average molecular weight of 320 (trade name: 8-koku Hysol 5AS-Ll-1, manufactured by Nippon Petrochemical Co., Ltd.), *3:
Fine powder silica, *4: Decabrom diphenyl ether, *5: Trade name;
Percure HV-130, manufactured by Bellnox Japan.

From the results in Figure 1, it can be seen that the MF capacitors filled with the epoxy resin compositions of Examples 1 and 2 have a higher capacity over time than the MF capacitors filled with the epoxy resins or epoxy resin compositions of Comparative Examples 1 and 2. It can be seen that this is an excellent capacitor with little change.

Examples 3-8 Epoxy resin, resin preparation examples 1-3 having the composition shown in Table 2
Using the epoxy resin compositions containing the resins (I>, (I), (DI) and 3-ring aromatic hydrocarbons obtained in Example 1), a model capacitor was filled in the same manner as in Example 1 and cured. After that, the rate of change in capacitance over time was determined.As a result, all of the capacitors were almost the same as the capacitor of Example 1, and the performance was satisfactory.

Table 2

[Brief explanation of the drawing]

FIG. 1 is a graph showing the relationship between capacitance changes and time of the capacitors of Examples 1 and 2 and Comparative Examples 1 and 2.

Claims (1)

[Claims] 1. (a) 100 parts by weight of an epoxy resin; (b) a hydrocarbon distillate containing as a main component an unsaturated hydrocarbon with a boiling point range of 80 to 280°C, which is a by-product of thermal decomposition of petroleum. 5 to 900 parts by weight of a resin obtained by adding 7 to 45 parts by weight of a phenol to 100 parts by weight and polymerizing with a Friedel-Crafts catalyst, and (c) an average having 3 fused or non-fused aromatic rings. An epoxy resin composition comprising 4 to 200 parts by weight of an aromatic hydrocarbon having a molecular weight of 230 to 350. 2. The epoxy resin composition according to claim 1, wherein the epoxy resin composition further contains 5 to 100 parts by weight of a curing agent per 100 parts by weight of epoxy resin.