JPS60170620A - Novel epoxy resin composition - Google Patents

Abstract

PURPOSE:The titled alicyclic composition, obtained by incorporating a specific epoxy resin with a curing agent, capable of giving an optional state ranging from a liquid - solid states, and having improved water, heat and weather resistance. CONSTITUTION:A novel epoxy resin composition obtained by incorporating an epoxy resin of formula I {R1 is organic compound residue having l active hydrogen atoms; n1-nl are 0 or integers 1-100; and the sum thereof is 1-100; l is an integer 1-100; A is oxycyclohexane skeleton of formula II having a substituent group [X is formula III, IV or V (R2 is H, alkyl, alkylcarbonyl or arylcarbonyl) and contains at least one group of formula III in the resin of formula I ]}with a curing agent, e.g. diethylenetriamine, and if necessary a filler, e.g. silica sand, and a flame retardant, e.g. tetrabromobisphenol A, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel epoxy resin composition having excellent thermal properties, water spray properties, and weather resistance.

The most widely used epoxy resin in industry today is the shrimp-bis type epoxy resin produced by the reaction of bisphenol A and epichlorohydrin.This resin can be produced in a wide range of products from liquids to solids. Moreover, the epoxy group has a low reactivity and can be cured by polyamine at room temperature.

However, although the cured product has excellent water resistance and is strong, it has drawbacks such as poor weather resistance, poor electrical properties such as tracking resistance, and low heat distortion temperature.

In particular, recently, epoxy resins made by reacting phenol or novolak resin with epichlorohydrin have been used as sealing resins for VLSIs, etc., but the number of chlorine in the resin is...
, p, which causes problems such as worsening the drowsiness characteristics of electronic components.

Alicyclic epoxy resins are epoxy resins that do not contain chlorine and have excellent electrical properties and heat resistance.These resins are manufactured by the epoxidation reaction of compounds having a 5- or 6-membered cycloalkenyl skeleton. There is. The epoxy groups of these resins are so-called internal epoxy groups, and are usually cured by heating with acid anhydrides, but cannot be cured at room temperature with polyamines because of their low reactivity. Therefore, the range of use of alicyclic epoxy resins is extremely narrow.

As alicyclic epoxy resins, those having structures (II) and (III) are industrially produced and used.

(II) is used as a heat-resistant epoxy diluent because of its extremely low viscosity, but it is highly toxic and causes problems such as severe irritation of the skin of workers.

(l [I) has low impurities and ω and has a low hue, and its cured product has a high heat deformation temperature, but has a problem of poor water resistance due to ester bonds.0 Furthermore, both (■) and (■) Since it is a liquid epoxy resin with a commercial strength of 1, it is not possible to apply a solid epoxy resin molding system such as transfer molding.

In view of these problems, the present inventors have conducted intensive research to develop a new epoxy resin. Although it is an alicyclic type, it can be formed into any shape from liquid to solid, has water resistance,
An epoxy resin composition having excellent heat resistance and excellent reactivity has been discovered, and the present invention has been completed.

That is, the present invention provides a novel epoxy resin characterized by blending an epoxy resin represented by the following general formula with a curing agent and, if necessary, a filler, a flame retardant, and its Sendai'4'ffi additive. 0 regarding the composition, where Th R+ is the residue of a specific compound having active hydrogen 0111 Hnl...
...nl is an integer of O or 100, and the sum is 1 to 10
It is 0.

represents an integer from 1 to 100.

A is an oxycyclo-all-xane skeleton having a substituent X, and is represented by the following formula.

Next, the present invention will be explained in detail.

In the novel epoxy resin represented by formula (I) of the present invention, R1 is an organic residue having active hydrogen, and examples of the organic substance having active hydrogen, which is a precursor thereof, include alcohols, phenols, carboxylic acids, Examples include amines and thiols.

The alcohol may be 11 alcohols or polyhydric alcohols.

For example, methanol, ethanol, propatool, butanol, pentanol, hexanol, aliphatic alcohols such as octatool, aromatic alcohols such as penzyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, ropylene glycol, 1
．． 3-butanediol, 1,4-butanediol, betanediol, 1,6-hexanediol, neopentyl glycol, oxypivalic acid neopentyl glycol ester, cyclohexane dimetatool, glycerin, diglycerin, polyglycerin, trimethylolpropane, tri- Examples include polyhydric alcohols such as methylolethane, pentaerythritol, and dipentaerythritol.

Phenols include phenol, cresol, catechol, pyrogallol, noitroquinone, hydroquinone monomethyl ether, bisphenol A1 bisphenol F% 4.4'-dihydroxybenzophenone, bisphenol S1 phenolic resin, cresol novolac resin, etc.0 Carboxylic acids include Formic acid, acetic acid, propionic acid, butyric acid, fatty acids from animal and vegetable oils, fumaric acid,
Examples include maleic acid, adipic acid, dodecanedioic acid, trimellitic acid, pyromellitic acid, polyacrylic acid, phthalic acid, isophthalic acid, and terephthalic acid. Also included are compounds having both a hydroxyl group and a carboxylic acid, such as lactic acid, citric acid, and oxycaproic acid.

Examples of amines include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, dodecylamine, 4,4'-diaminodiphenylmethane, inphorondiamine, toluene diamine, hexamethylene diamine, xylene diamine. 1 diethylenetriamine,
Examples include triethylenetetramine and ethanolamine.

Examples of thiols include mercapto compounds such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, and phenyl mercaptan; mercaptopropionic acid or polyhydric alcohol esters of mercaptopropionic acid;
Examples include ethylene glycol dimethyl captopropionate, trimethylolpropane trimercaptopropionate, and pentaerythritol benthamercaptopropionate.

In addition, examples of compounds having active hydrogen include polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, f starch, cellulose, cellulose acetate, cellulose acetate butyrate, hydroxyethyl cellulose,
Examples include acrylic polyol resin, styrene allyl alcohol copolymer resin, styrene-maleic acid copolymer resin, alkyd resin, polyester polyol resin, polyester carboxylic acid resin, polycaprolactone polyol resin, polypropylene polyol, polyetramethylene glycol, and the like.

In addition, the compound having active hydrogen may have an unsaturated double bond in its skeleton, and specific examples include monoallylic alcohol, acrylic acid, methacrylic acid, 3-cyclohexene, tanol, and tetradrophthal. There are acids etc. The unsaturated double bonds of these compounds may also have an epoxidized structure.

n1lnl...nj in general formula (I) is 0
Or, it is 1 to 100, but if it is 100 or more, it becomes a resin with a high melting point, which is difficult to handle and cannot be used in practice.

l is an integer from 1 to 100.

Among the substituents X of A in formula (I), HORi Yes.

That is, in the present invention, the 1 ha substituent X is (
Specifically, the new epoxy resin of formula I) is a polyether resin obtained by ring-opening polymerization of 4-vinylcyclohexene-1-oxide using an organic compound having active hydrogen as an initiator, that is, It can be produced by epoxidizing a polycyclohexene oxide polymer having a vinyl side chain with an oxidizing agent such as a peracid.

4-Vinylcyclohexene-1-oxide is obtained by partially epoxidizing vinylcyclohexene obtained by a dimerization reaction of butadiene with peracetic acid.

It is preferable to use a catalyst when polymerizing 4-vinylcyclohexene-1-oxide in the presence of active hydrogen.

Catalysts include amines such as methylamine, ethylamine, propylamine, and piperazine; organic basic acids such as pyridines and imidazoles; organic acids such as formic acid, acetic acid, and propionic acid; inorganic acids such as sulfuric acid and hydrochloric acid; and sodium methylate. Alcolades of alkali metals such as KOH%N
a Alkali such as OH, BF3. ZWC12+A#C
A! Examples include organometallic compounds such as s+5rLC14 (Dk isfi or its complexes, triethylaluminum, diethylzinc, etc.).

These catalysts contain o, o i ~ 1o%, based on the reactants.
It can be used preferably in a range of 0.1 to 5%. The reaction temperature is -70 to 2°C, preferably -30°C.
°C to 100 °C.

The reaction can also be carried out using a solvent. A solvent containing active hydrogen cannot be used.

Namely, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, Hensen, toluene,
Aromatic solvents such as xylene, ethers, aliphatic hydrocarbons, esters, etc. can be used.

Now, in order to epoxidize the thus synthesized polycyclohexene oxide polymer having a vinyl group side chain and produce the novel epoxy resin of the formula (I) of the present invention, either peracids or hydroperoxides can be used. can be used.

As peracids, performic acid, peracetic acid, perbenzoic acid, trifluoroperacetic acid, etc. can be used.

Among these, peracetic acid is a particularly preferred epoxidizing agent because it is industrially available at low cost and has high stability.

As the hydroperoxides, hydrogen peroxide, tert-butyl hydroperoxide, cumene peroxide, etc. can be used.

A catalyst can be used during epoxidation if necessary. For example, in the case of oxidation, an alkali such as soda carbonate or an acid such as sulfuric acid may be used as a catalyst. In the case of hydroperoxides, the catalytic effect can be obtained by using a mixture of tungstic acid and caustic soda with hydrogen peroxide, an organic acid with hydrogen peroxide, or molybdenum hexacarbonyl with tert-butyl hydroperoxide. .

The epoxidation reaction is carried out by adjusting the presence or absence of a solvent and the reaction temperature depending on the equipment and physical properties of the raw materials.

Depending on the conditions of the epoxidation reaction, the substituents in the raw materials undergo side reactions with the epoxidizing agent and the like at the same time as the olefin bond is epoxidized, resulting in modified substituents that are included in the target compound. The ratio of the three substituents in the target compound is determined by the type of epoxidizing agent, the molar ratio of the epoxidizing agent to the olefin bond, and the reaction conditions.

For example, when the epoxidizing agent is used too much, the modified t-ho group mainly has the structure shown below, and is produced from the raw epoxy and by-produced vinegar.

10 The target compound can be taken out from the reaction crude solution by ordinary chemical industrial means such as concentration.

Furthermore, the epoxy resin used in the present invention can be mixed with other epoxy resins without impairing the properties of the composition. Here, other epoxy epoxies are those that are generally used (l'J may be used, but examples include Ebibis type epoxy, bisphenol F epoxy, novolac epoxy, fatty Hw epoxy, styrene oxide, butyl glycidyl An epoxy diluent such as ether is added.

The curing agent used in the present invention can be a curing agent used in known epoxies (0.; , amine complexes of boron trifluoride, etc.

Here, the amines include the following.

Aliphatic polyamines such as diethylenetriamine, triethylenetetramine, menzendiamine, metaxylylenediamine, bis(4-amino-3-methylcyclohexyl)methane, adducts of the aliphatic polyamines with known epoxy compounds, and reactions with acrylonitrile. substances, reactants with ketones.

metaphenylenediamine, diaminodiphenylmethane,
Aromatic polyamines such as diaminodiphenylsulfone and diaminodiphenylsulfide, and adducts of the aromatic polyamines and known epoxy compounds.

Secondary and tertiary amines and salts thereof such as tris(dimethylaminomethyl)phenol, piperidine, imidazole and derivatives thereof.

Polyamide resins include reactants of fatty acids, such as fatty acids, dimer acids, trimer acids, and aliphatic polyamines.

Acid anhydrides include the following:

Phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl anhydride Acid anhydrides such as nadic acid, succinic anhydride, dodecenylsuccinic anhydride, succinic anhydride, and mixtures of the above acid anhydrides.

Nophorac resins include low molecular weight resinous products made by the condensation of phenol or mixtures of phenol and cresol, dihydroxybenzene, and formaldehyde.

Amine complexes of boron trifluoride include monoethylamine, piperidine, aniline, butylamine, dibutylamine, cyclohexylamine, dicyclohexylamine,
Includes complexes of low molecular weight amine compounds such as tributylamine and triethanolamine and boron trifluoride.

Examples of other curing agents include diazonium salts, iodonium salts, bromonium salts, sulfinium salts, and other salts of super strong acids such as boron tetrafluoride, phosphorus hexafluoride, and arsenic hexafluoride. Also, among these curing agents, aliphatic polyamines,
Aromatic polyamines, polyamide resins, and polymercaptan resins can be used as a mixture in any proportion, and can be used alone or in combination with a curing accelerator for the purpose of adjusting the curing rate. Here, the aforementioned secondary and tertiary amines can be used as the curing accelerator.

The acid anhydride can be used as it is, but a curing catalyst and a curing accelerator can also be used together for the purpose of adjusting the curing rate and improving the physical properties of the cured product.

Here, the curing catalysts include the secondary and tertiary amines, and the tin octylate curing accelerators include water, ethanol, alcohols such as propatool, isoproptool, cyclohexanol, and ethylene glycol, acetic acid, and propionic acid. , carboxylic acids such as succinic acid and hexahydrophthalic acid, and amines having active hydrogen such as ethylenediamine and diethylenetriamine.

The novolac resin can be used alone or in combination with a curing catalyst for the purpose of adjusting the curing rate. Here, the curing catalysts are the aforementioned secondary and tertiary amines.

Dicyandiamide can be used alone or in combination with a curing catalyst for the purpose of adjusting the curing rate. Here, the curing catalysts are the aforementioned secondary and tertiary amines.

The amine complex of boron trifluoride can be used alone or in combination with a curing rate regulator for the purpose of adjusting the curing rate.

Here, any curing rate regulator may be used as long as it can be used in conventional epoxy resins, but specifically, for example, Carbo/CI! amines, acetylacetone complexes of metals, organometallic compounds of metals such as titanium and tin, glycols, organoboron compounds, and the like.

The filler used in the present invention may be anything as long as it can be used as a filler for resin, but specific examples include silica sand, silica, alumina, diatomaceous earth, calcium carbonate, asbestos, crow, and magnesium carbonate. , kaolin, metal powder, etc. The shape is fibrous,
Various types such as flake-like ones are used.

Any flame retardant may be used as long as it can be used as a flame retardant for resins, but specific examples include halides such as tetrabromobisphenol A1 and hexabromobenzene, tris (dibromopropyl) phosphate, and trischloroethyl phosphate. phosphorus compounds, antimony trioxide, etc.

Various other additives can be used in combination depending on the purpose, such as denaturing agents such as Aerosil and Olben, conductivity imparting agents such as carbon black, mold release agents, lubricants, dyes,
- Pigments; Knobbling agents, flexibility imparting agents, plasticizers, etc., and can also be used after being diluted with a solvent.

By molding and hardening the resin composition obtained in this way, it has excellent mechanical properties such as tensile strength and hardness, electrical properties such as tracking resistance and arc resistance, and heat distortion temperature, and is hardened with little corrosion. Encapsulants for semiconductors, insulation panels for motors and transformers, fiber-reinforced plastics, and cast products.

It can be used for molded products, etc.

The present invention will be further explained in detail with reference to Examples below.

Synthesis Example 1 Allyl alcohol 1189 (2 mol), 4-vinylcyclohexene-1-oxide 49614 mol) and BF
3 Nieteller) 3.19 were mixed at 60°C, and gas chromatography analysis revealed that 4-vinylcyclohexene-1
- The reaction was carried out until the conversion of oxide reached 98% or more.

Ethyl acetate was added to the resulting reaction crude liquid, washed with water, and then the ethyl acetate layer was concentrated to obtain a viscous liquid.

In the infrared absorption spectrum of the product, the absorption due to the epoxy group at 810,850 cm-' observed in the raw material has disappeared, the absorption due to the ether bond exists at 1080.11501-1, and gas chromatography analysis shows that Allyl alcohol in the product is in trace amounts, but OHA is present at 8450 nt in the infrared absorption spectrum.
It was confirmed that this compound had the structure shown by the following formula from the absorption of 'G.

434 g of this compound was dissolved in ethyl acetate and charged into a reactor, and peracetic acid (psssg) was added dropwise as an ethyl acetate solution over a period of 2 hours.
It was kept at ℃. After completing the preparation of the C nucleus, the M8 was grown in a tube at 40°C for 6 hours.

Inoki ether was added to the reaction crude solution, washed with alkaline water containing 416I sodium carbonate, strained, and thoroughly washed with distilled water.

Ethyl acetate was condensed to obtain a viscous transparent liquid.

This compound had an oxirane oxygen content of 97%, and a characteristic absorption due to the epoxy group was observed at 12 tl Om' in the infrared absorption spectrum. Roughly, absorption due to residual vinyl groups is observed in 1640cTff, 84500゛1((OH73 in 1m-1, -C in 1730CIIL-',
Since absorption by the 〇- group is observed, this compound has the structure of general formula (I) (Rt nigericidyl group or allyl group, n=
2 on average, including some groups in which a'r w is added to the epoxy group].

Synthesis Example 2 By the same procedure as Example 1, allyl alcohol 58 & (
1 mol), 868.9 (7 mol) of 4-vinylcyclohexene-1-oxide, and 47I of BF3 etherate were reacted to obtain a viscous, shield-like product.

In the infrared absorption spectrum of the product, the absorption due to the epoxy group at 810.8 δocm-' observed in the raw material has disappeared, 1080.1150c! Gas chromatography analysis shows that there is absorption due to ether bonds at rL ~ 1.Although there is a trace amount of allyl alcohol in the product, the infrared absorption spectrum shows that it is 8450rx-'K.
This compound is due to the absorption of OH group! It was confirmed that 1so is the 41q structure shown by formula 1. Then, this compound + 92g and 111i were added in the same manner as in Synthesis Example 1.
395 g of acetic acid was reacted to obtain a viscous transparent liquid.

This compound had an oxirane oxygen content of 9.27%, and a characteristic absorption due to the epoxy group was observed at 126 OctfL-' in the infrared-like absorption spectrum. Furthermore, absorption due to residual vinyl groups is observed on the 1640C side-1.

Since absorption by OH group is seen at 34501-' and absorption by 01 -C〇- group at 1780 tX-', this compound has the general formula CI
) of I@ structure (R1 nigericidyl group or allyl group, n = average 7, a group with a part of acetate added to an epoxy group).

Synthesis Example & Using the same procedure as Synthesis Example 1, methanol 64.9 (2,000 l), 4-vinylcyclohexene-1-oxide 744
．． ! 7 (6 mol) BP's Nieteller) 41. ! il is reacted, and a viscous liquid product is produced.

In the infrared absorption spectrum of the product, the absorption by the epoxy group at 8 10.850 cm-' observed in the raw material has disappeared, and the absorption due to the ether bond exists at 1080.1150 cm. Allyl alcohol in the product is in trace amounts, but in the infrared +v11 absorption spectrum it is 3450 bv-
From the absorption of Of(group at r), it was confirmed that this compound #IJ has the structure shown by the following formula.

Furthermore, in the same manner as in Synthesis Example 1, 573 g of this compound and
* 887 g of reaction was carried out to obtain a viscous transparent liquid.

This compound has an oxirane allotrope content of 1L08%,
In the infrared absorption spectrum, characteristic absorption due to epoxy groups was observed at 1260c71L. Furthermore, 1640cm-
Absorption due to residual vinyl groups is observed in ', 8460
cm has an OH group, and the 1730cIrL-1 compound has the general formula (I
) (R1: methyl group, n=3 on average, including a group in which a portion of acetic acid is added to an epoxy group).

Reference Example The total amount of chlorine in the epoxy resin synthesized in Synthesis Example 1.2.3 was measured.

The measurement was performed by weighing approximately 2 g of the sample and decomposing and burning it in an oxygen cylinder, and the results shown in Table 1 were obtained. Considering that ordinary epoxy resins using epichlorohydrin as a starting material usually contain about several hundred ppm of total chlorine, it can be seen that the total chlorine content of the resin of the present invention is extremely small.

Table 1 Total amount of chlorine in epoxy resin Example 1 A curing agent was added to the product of Synthesis Example 1.2.3, gel time was measured, and a cross-section of the epoxy resin was conducted.

Novolak-type phenolic A fat (PSF-
43001! +, Song Chemical Industry (H) was used, and 2-undecylimidazole (Curezol C,
IZ Shikoku Kasei Kogyo θ-1) was used. Father, comparison 4++
・(A typical alicyclic epoxy)] 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate
021, Daicel Kajin Kogyo 9, Kari), all the formulations were carried out according to the following formulation, and after being melt-mixed at 120° C. for about 1 minute, the mixture was discarded and a mixture was obtained. The obtained compound was JIS-C
The gel time at 120° C. was measured using 2104-7 (hot plate method), and the results shown in Table 2 were obtained. It was found that Honshunmei's resin has poorer curing properties than conventional alicyclic epoxy resins.

Compounding recipe Epoxy resin 1・θ equivalent psp-4soo 1.1 Curazol C,,Z (for the compound) 0.7 electric wire φ Table 2 Gel time of compound Example 2゜Synthesis example 1.2.8 The physical properties of the cured product were measured using this compound.

Using the same curing agent and curing catalyst as in Example 1, the following formulation was mixed in the same manner as in Example 1 to obtain a mixture. The resulting mixture was pulverized and press molded to obtain a test piece.

Molding is done under pressure of 90-100 kgf/c4
The temperature was raised from ℃ to 170℃ in about 30 minutes, and then heated to 170℃ under pressure.
After being left at 0°C for 10 minutes, the obtained cured product was cured for 2 hours in an oven set at 180°C.The obtained cured product was cut into test pieces, and the physical properties were measured according to JIS-0911. I looked at the results of 3.

Compounding recipe Epoxy resin 1.0 units PSF-4300 (1g unit - Haren Cure Sol CIIZ (for the compound) 0.7 tonne
Example A: The product of Synthesis Example 2 was oxidized by using 4-methylbexahydrophthalate as a curing agent (Rikazid MH-700, Shin Nippon Rika C).Also, comparative resin 8,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Celoxide 2021. Daicel Chemical Industries (4)), which is a typical alicyclic epoxy 1-fat, was used, and was blended according to the following formulation. After melt-mixing at 80℃ for about 5 minutes, degassing under reduced pressure and curing by casting to obtain a cured product.Rika was pre-cured at 160℃ for 1 hour in an oven, and then heated to 180℃ for 2 hours. Time hardening was performed.

The obtained cured product was cut into test pieces, and JIS
-Measurements were made on the heat-deformed matrices using -6911, and Table 4
The results were 11:

Compounding recipe 1.0 equivalents of epoxy resin (M) i-700α 8 equivalents 4-Methylhexahydrophthalic anhydride (Rikazid MH-, 700. Shin Nippon Chemical ■) as a curing agent to the products of Synthesis Examples 1 and 2 ) and benzyldimethylamine as a curing catalyst. In addition, using 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexa/carboxilade (Shichiloxide 2021, Daicel Chemical Industries ■), which is a typical alicyclic epoxy resin, as a comparative resin, the following formulation was used. After blending according to the recipe and melt-mixing at 80° C. for about 5 minutes, the mixture was defoamed under reduced pressure and cured by casting to obtain a cured product. For curing, pre-curing was performed at 100° C. for 1 hour in an open environment, and post-curing was further performed at 160° C. for 2 hours.

The obtained cured product was cut into test pieces, and JIS
The heat distortion temperature was measured using -6911 in Table 5.
I got the result.

Combination prescription Epoxy resin 10 equivalents Ml (-7000, g equivalent benzyldimethylamine (for 1□IC1*I) 0.5 car freight procedure amendment (voluntary) March 13, 1985 1, Display of the case 1982 Patent Application No. 27693 3, Relationship with the person making the amendment Patent applicant Postal code 590 Address 1, Teppo-cho, Sakai City, Osaka Prefecture Name (290) Daicel Chemical Industries, Ltd. Full specification Civilization Specification 1, Title of the Invention New Epoxy Resin Composition 2, Claims A novel epoxy resin represented by general formula (I), a curing agent, and optionally fillers, flame retardants, and other additives. A novel epoxy resin composition characterized by containing an agent.

However, R1 is l! organic compound residue with active hydrogen.

nl, R2...nJ are 0 or an integer from 1 to 100, and the sum thereof is from 1 to 100.

represents an integer from 1 to 100.

A is an oxycyclohexane skeleton having a substituent,
It is expressed by the following formula.

(R2qH, alkyl group, alkylcarbonyl group, V Contains one or more in the resin.

3. Detailed Description of the Invention The present invention relates to a novel epoxy resin composition having excellent heat resistance, water resistance, and weather resistance.

The epoxy resin that is currently widely used in industry is the bis-type epoxy resin, which is produced by the reaction of bisphenol A and ebichlorohinophosphorus. This resin can be used in a wide range of products ranging from liquids to solids, and has the advantage that the epoxy group has high reactivity and can be cured with polyamines at room temperature.

However, although the cured product has excellent water resistance and is strong, it has drawbacks such as poor weather resistance, poor electrical properties such as tracking resistance, and low heat distortion temperature. In particular, recently, epoxy resins made by reacting phenol or novolac resin with echylchlorohydrin have been used as sealing resins for VLSIs, etc., but the resin contains several tens of thousands of percent chlorine, which is harmful to electronic components. Problems such as deterioration of electrical characteristics occur.

Alicyclic epoxy resins are examples of epoxy resins that do not contain chlorine and have excellent electrical properties and heat resistance.

These are manufactured by epoxidation reaction of compounds having a 5-membered or 6-membered cycloalkenyl skeleton. The epoxy groups of these resins are so-called internal epoxy groups,
Heat curing with acid anhydrides is usually performed, but curing at room temperature with polyamines is not possible due to low reactivity. Therefore, the range of use of alicyclic epoxy resins is extremely narrow.

As the alicyclic epoxy resin, those having the structure (It), 1) are industrially produced and used.

(Ill is used as a heat-resistant epoxy diluent because of its extremely low viscosity, but it is highly toxic and causes problems such as severe irritation of the skin of workers.

(II) has few impurities and a low hue, and its cured product has a high heat deformation temperature and has a problem of poor water resistance due to the ester bond.

Furthermore, since both (1) and (1) are low-viscosity liquid epoxy resins, solid epoxy resin molding systems such as transfer molding cannot be applied.

In view of these problems, the present inventors have conducted intensive research to develop a new epoxy resin, and as a result, they have developed an alicyclic resin,
Any amount from liquid to solid.

An epoxy resin composition has been found which has excellent water resistance, heat resistance, and excellent reactivity, and has led to the present invention.

That is, the present invention relates to a novel epoxy resin composition comprising an epoxy resin represented by the following general formula, a curing agent, and, if necessary, fillers, flame retardants, and other additives. .

However, R1 is an organic compound residue having active hydrogen.

n1+n2...nl is O or an integer from 1 to 100, and the sum thereof is from 1 to 100.

l represents an integer from 1 to 100.

A is an oxycyclohexane skeleton having a substituent X, and is represented by the following formula.

＼ CH=CH2 (R2 is any one of H1 alkyl group, alkylcarbonyl group, and aryl-W rubonyl group) contains one or more in the resin.

Next, the present invention will be explained in detail.

In the novel epoxy resin represented by formula (1) of the present invention, R1 is an organic residue having active hydrogen, and examples of the organic substance having active hydrogen, which is a precursor thereof, include alcohols, phenols, carboxylic acids, Examples include amines and thiols.

The alcohol may be a monohydric alcohol or a polyhydric alcohol.

Aliphatic alcohols such as methanol, ethanol, pro/senol, citanol, pentanol, hexanol, octatool, aromatic alcohols such as benzyl alcohol, ethylene dalycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol,
1.3 phthanediol, 1.4 butanediol, tantanediol, 1,6 hexanediol, neoanthyl IJ cole, oxypivalic acid neoanthyl IJ cole ester, cyclohexane dimetatool, IJ serine, diglycerin, Examples include polyhydric alcohols such as polyglycerin, trimethylolpropane, trimethylolethane, zuntaerythritol, and dipentaerythritol.

Phenols include phenol, cresol, catechol, pyrogallol, hydroquinone, hydroquinone monomethyl ether, bisphenol A, bisphenol F, 4,4'-dihyto90xybenzophenone,
Hisphenol S, phenol novolak resin, cresol novolank resin, etc. are available.

Carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, fatty acids from animal and vegetable oils, fumaric acid, maleic acid, adipic acid, P-decanedioic acid, trimenoic acid, pyromellitic acid, polyacrylic acid, phthaloic acid, and isophthalic acid. acids, terephthalic acid, etc. Also included are compounds having both a hydroxyl group and a carboxylic acid, such as lactic acid, citric acid, and oxycaproic acid.

Examples of amines include methylamine, ethylamine, propylamine, methylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, dodecylamine, 4,4'-diaminodiphenylmethane, isophorone diamine, toluene diamine, hexamethylene diamine, xylene diamine. , diethylenetriamine, triethylenetetramine, ethanolamine, etc.

Examples of thiols include mercapto compounds such as methyl mercaptan, ethyl mercaptan, flobyl mercaptan, and phenyl mercaptan, mercaptopropionic acid or polyhydric alcohol esters of mercaptopropionic acid, such as ethylene dalicol dimethylcabutoprobionic acid ester, and trimethylolpropane trichloride. Examples of mercabutoprobionic acid ester and taerythritol include tamercaptopropionic acid ester.

Furthermore, other compounds having active hydrogen include polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, cellulose, cellulose acetate, cellulose acetate sotylate, hydroxyethyl cellulose,
Examples include acrylic polyol resin, styrene allyl alcohol copolymer resin, styrene-maleic acid copolymer resin, Alkitsubi resin, polyester polyol resin, polyester carboxylic acid resin, polycaprolactone polyol resin, polypropylene polyol, polyetramethylene glycol, and the like.

Further, the compound having active hydrogen may have an unsaturated double bond in its skeleton, and specific examples include allyl alcohol, acrylic acid, methacrylic acid, 3-cyclohexenemethanol, tetrahydro-90 phthalic acid, etc. There is.

The unsaturated double bonds of these compounds may also have an epoxidized structure.

In general formula (1), n□, R2...nl are 0
or 1 to 100, the sum of which is 1 to 100,
If it is 106 or higher, it should be treated as a resin with a high melting point.
In reality, it is not something that can be used.

l is an integer from 1 to 100.

Of the substituents X of A in formula (I), the more ゝ℃H-CH2 there is, the more preferable it is.

That is, in the present invention, the substituent X is (I
Specifically, the new epoxy resin represented by formula 1 is a polyether resin obtained by ring-opening polymerization of 4-vinylcyclohexene-1-oxide using an organic compound having active hydrogen as an initiator, that is, a polyether resin obtained by ring-opening polymerization of 4-vinylcyclohexene-1-oxide, that is, It can be produced by epoxidizing a polycyclohexene oxide polymer having a chain with an oxidizing agent such as peracid.
Ru.

It is obtained by partially epoxidizing vinylcyclohexene obtained by a dimerization reaction of 4-vinylcyclohexene-1-oxidohaphtadiene with peracetic acid.

When polymerizing 4-vinylcyclohexene-1-oxytra in the presence of active hydrogen, it is preferable to use a catalyst.

Examples of catalysts include amines such as methylamine, ethylamine, propylamine, and piperazine; organic bases such as pyridines and imidazoles; organic acids such as formic acid, acetic acid, and propionic acid; inorganic acids such as sulfuric acid and hydrochloric acid; and sodium methylate. Alcolades of alkali metals, KOH, NaO
Alkali such as H, BF3, ZtLCA! 2 +
Examples include Lewis acids such as AA'C'13 + E3n014 or complexes thereof, and organometallic compounds such as triethylaluminum and diethylzinc.

These catalysts can be used in an amount of 0.01 to 10 parts, preferably 0.1 to 5 parts, based on the reactants. The reaction temperature is -70 to 200°C, preferably -30°C to 10°C.
It is 0°C.

The reaction can also be carried out using a solvent. A solvent containing active hydrogen cannot be used.

In other words, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, benzene, toluene,
Aromatic solvents such as xylene, ethers, aliphatic hydrocarbons, esters, etc. can be used.

Now, in order to produce the novel epoxidizing agent of the formula (I) of the present invention by epoxidizing the thus synthesized sulpolycyclohexene oxide polymer having vinyl group side chains, peracids, You can use either of the following.

As peracids, performic acid, peracetic acid, perbenzoic acid, trifluoroperacetic acid, etc. can be used.

Among these, peracetic acid is a particularly preferred epoxidizing agent because it is industrially available at low cost and has high stability.

As the hydroperoxides, hydrogen peroxide, tajarizotylhydride 90 peroxide 9, cumenooxide, etc. can be used.

A catalyst can be used during epoxidation if necessary. For example, in the case of a peracid, an alkali such as soda carbonate or an acid such as sulfuric acid may be used as a catalyst. In the case of hydroperoxide 9, a mixture of tungstic acid and caustic soda may be mixed with hydrogen peroxide, or an organic acid may be mixed with hydrogen peroxide.
Alternatively, molybdenum hexacarbonyl can be used with tert-butylhydronog-oxide to achieve catalytic effect.

The epoxidation reaction is carried out by adjusting the presence or absence of a solvent and the reaction temperature depending on the equipment and physical properties of the raw materials.

Depending on the conditions of the epoxidation reaction, substituents in the raw materials undergo a side reaction with the epoxidizing agent and the like at the same time as the olefin bond is epoxidized, resulting in modified substituents that are included in the target compound. The ratio of the three substituents in the target compound is determined by the type of epoxidizing agent, the molar ratio of the epoxidizing agent to the olefin bond, and the reaction conditions.

For example, when the epoxidizing agent is peracetic acid, the modified substituents mainly have the structure shown below, and are generated from the 6D-generated epoxy group and the by-product acetic acid.

The target compound can be extracted from the reaction crude solution by ordinary chemical industrial means such as concentration.

Further, the epoxy resin used in the present invention can be mixed with other epoxy resins as long as the properties of the composition are not impaired. Here, other epoxy resins may be any commonly used epoxy resins, such as epibis type epoxy, bisphenol F epoxy, novolac epoxy, alicyclic epoxy, and epoxy diluents such as styrene oxide and butyl glycidyl ether. is included.

As the curing agent used in the present invention, curing agents used for known epoxy resins can be used, including amines, polyamide resins, acid anhydrides, polymercaptan resins, novolac resins, dicyandiamide, and amine complexes of boron trifluoride. etc. are included.

Here, the amines include the following.

Aliphatic polyamines such as diethylenetriamine, triethylenetetramine, menzendiamine, metaxylylenediamine, bis(4-amino-3-methylcyclohexyl)methane, adducts of the aliphatic polyamines with known epoxy compounds, and reactions with acrylonitrile. substances, reactants with ketones.

Metaphenylene diamine, diaminodiphetrimethane,
Aromatic polyamines such as diaminodiphenylsulfone and diaminodiphenylsulfide, and adducts of the aromatic polyamines and known epoxy compounds.

tris (dimethylamine methyl) phenol, p ej
Secondary and tertiary amines and salts thereof, such as J gin, imidazole and derivatives thereof. and mixtures of the aforementioned amines.

The $1J amide resin includes a reaction product of a fatty acid such as a fatty acid, a dimer acid, a trimer acid, and an aliphatic polyamine.

Acid anhydrides include the following:

Phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, insiphenotetracarboxylic dianhydride, tetrahydroheptalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride , methylnadic anhydride, succinic anhydride, dodecenylsuccinic anhydride, succinic anhydride, and mixtures of the aforementioned acid anhydrides.

Novolak resins include low molecular weight resinous products made by the condensation of phenol or a mixture of phenol and cresol, dihydroxyine, and formaldehyde.

Amine complexes of boron trifluoride include monoethylamine, piperidine, aniline, butylamine, dibutylamine, cyclohexylamine, dicyclohexylamine,
Includes complexes of low molecular weight amine compounds such as tributylamine and triethanolamine and boron trifluoride.

Other curing agents include diazonium salts of super strong acids such as phosphorus tetrafluoride, phosphorus hexafluoride, arsenic hexafluoride, and iodine.
There are salts such as udonium salt, bromonium salt, and sulfinium salt. Furthermore, among these curing agents, aliphatic polyamines, aromatic polyamines, polyamide resins, and polymercaptan resins can be used in combination in any ratio, and may be used alone or in combination with a curing accelerator for the purpose of adjusting the curing speed. You can also. Here, the aforementioned secondary and tertiary amines can be used as the curing accelerator.

The acid anhydride can be used as it is, but a curing catalyst and a curing accelerator can also be used together for the purpose of adjusting the curing rate and improving the physical properties of the cured product.

Here, the curing catalysts are the aforementioned secondary and tertiary amines and tin octylate. As curing accelerators, alcohols such as water, ethanol, propatool, inpropatol, cyclohexanol, and ethylene glycol, carboxylic acids such as acetic acid, propionic acid, succinic acid, and hexahyto-90 phthalic acid, and ethylene diamine, diethylene triamine, etc. These are amines with active hydrogen.

The novolak resin can be used alone or in combination with a curing catalyst for the purpose of adjusting the curing rate. Here, the curing catalysts are the aforementioned secondary and tertiary amines.

Dicyandiamide 9 can be used alone or in combination with a curing catalyst for the purpose of adjusting the curing rate. Here, the curing catalysts are the aforementioned secondary and tertiary amines.

The amine complex of boron trifluoride can be used alone or in combination with a curing rate regulator for the purpose of adjusting the curing rate.

Here, any curing rate regulator may be used as long as it can be used in conventional epoxy resins, but specific examples include carboxylic acids, amines, metal acetylacetone complexes, titanium, tin, etc. Includes organometallic compounds of metals, glycols, organoboron compounds, etc.

The filler used in the present invention may be anything as long as it can be used as a filler for resin, but specific examples include silica sand, silica, alumina, diatomaceous earth, calcium carbonate, asbestos, glass, and magnesium carbonate. , kaolin, metal powder, etc. The shape is fibrous,
Various types such as flake-like ones are used.

Any flame retardant may be used as long as it can be used as a flame retardant for resins, but specific examples include halides such as tetrabromobisphenol A1 and hexabromobenzene, tris(dibromopropyl) phosphate, and triscrotetraethyl phosphate. There are phosphorus compounds such as antimony trioxide.

Various other additives can be used in combination depending on the purpose, such as Aerosil, Olben's vibration imparting agent, conductivity imparting agent such as carbon black, mold release agent, lubricant, dye,
Coupling agents, sinterability agents, plasticizers, etc. are included, and they can also be diluted with bath additives.

The resin composition obtained in this way is molded and cured.
It has excellent mechanical properties such as hardness, tensile strength, and hardness, electrical properties such as tracking resistance and arc resistance, and good heat deformation temperature. It is also possible to obtain a cured product with low corrosive properties, and is suitable for sealing for electronic parts. It can be used for agents, encapsulant motors for light-emitting diodes, insulation panels for transformers, fiber-reinforced plastics, adhesives, powder coatings, electrolytic coatings, printed circuit boards, cast products, molded products, etc.

The present invention will be further explained in detail with reference to Examples below.

Synthesis Example 1 116 g (2 mol) of allyl alcohol, 496.9 (4 mol) of 4-vinylcyclohexene-1-oxide and B
F3 Nieteller) 3.1 g were mixed at 60°C, and gas chromatography analysis revealed that 4-vinylcyclohexene-
The reaction was continued until the conversion of 1-oxide reached 981 or higher. Ethyl diacetate was added to the resulting reaction crude liquid, washed with water, and then the ethyl acetate layer was concentrated to obtain a viscous liquid.

In the infrared absorption spectrum of the product, the absorption due to the epoxy group at 810.850 crrL observed in the raw material has disappeared, the absorption due to the ether bond exists at 1080.1150 cIrL, and gas chromatography analysis shows that the allyl in the product has disappeared. Alcohol is in trace amount, but infrared absorption is 3450 crrc
It was confirmed that this compound has the structure shown by the following formula from the absorption of OH group at "-".

This compound 434 I! was dissolved in ethyl acetate and charged into a reactor, to which 388 g of peracetic acid was added dropwise as an ethyl acetate solution over 2 hours. During this time, the reaction temperature was 40
It was kept at ℃. After adding peracetic acid, heat at 40°C for another 6 hours.
Time aged.

Ethyl acetate was added to the reaction crude solution, and the mixture was washed with alkaline water containing 416β sodium carbonate, and then thoroughly washed with distilled water.

The ethyl acetate layer was concentrated to obtain a viscous clear liquid.

This compound had an oxirane oxygen content of 9.971, and a characteristic absorption due to the epoxy group was observed at 1260 cm-' in the infrared absorption spectrum. Furthermore, absorption due to residual vinyl groups is observed at 1640cIrL, and 3450cm
This compound has the structure (
It was confirmed that R1 was a nigericidyl ether group or an allyloxy group, n = 2 on average, and some groups containing acetic acid added to an epoxy group).

Synthesis Example 2゜ 58g (1 mol) of allyl alcohol and 868g of 4-vinylcyclohexene-1-oxide were prepared in the same manner as in Synthesis Example 1.
g (7 mol) and 4.7 g of BF3 etherate were reacted to obtain a viscous liquid product.

The infrared absorption spectrum of the product was determined by gas chromatography analysis, which showed that the absorption due to the epoxy group at 810.850 crrb-'', which was observed in the raw material, had disappeared, and that there was absorption due to an ether bond at 1080.1150 cm. Although the allyl alcohol in the product was in a trace amount, it was confirmed that this compound had the structure shown by the following formula from the absorption of OH group at 3450 cm by infrared absorption spectroscopy.

Further, this compound 49.211 was reacted with peracetic acid 39511 in the same manner as in Example 1 to obtain a viscous transparent liquid.

This compound had an oxirane oxygen content of 9.271, and a characteristic absorption due to the epoxy group was observed at 1260 cm 2 in the infrared absorption spectrum. Furthermore, absorption due to residual vinyl groups is observed at 16'4011, and 3450 cm-
Absorption by an OH group at ' and a 1-C〇- group at 1730 cm indicates that this compound has a structure of general formula (It) (R1 nigericidyl ether group or allyloxy group, n = 7 on average, acetic acid in the epoxy group). (contains some added groups).

Synthesis Example 3゜In the same manner as in Synthesis Example 1, 64 g of methanol, 4-vinylcyclohexene-1-oxy)'744#BF3/Nieterer)4. IJ was reacted to obtain a viscous liquid product.

In the infrared absorption spectrum of the product, the absorption due to the epoxy group at 810.850 cyti-" observed in the raw material disappeared, and the absorption due to the ether bond was present at 1080.1150 cm. Gas chromatography analysis revealed that the product Although the methanol in the product remains still, the infrared absorption is 3450 crtt-"
It was confirmed that this compound had the structure shown by the following formula since there was an absorption of OH group in .

Furthermore, in the same manner as in Synthesis Example 1, 573 g of this compound and 3 peracetic acid were added.
A viscous transparent liquid was obtained by reacting 87 g.

The Kono compound had an oxirane oxygen content of 9.031, and characteristic absorption due to epoxy groups was observed at 1260 cWL in the infrared absorption spectrum. Furthermore, since absorption at 1640 cm is observed, this compound has the structure of general formula (I) (
R□: methoxy group, n=3 on average, including some groups in which acetic acid was added to epoxy groups).

Reference Example The total amount of chlorine in the epoxy resin synthesized in Synthesis Example 1.2.3 was measured.

The measurement was performed by weighing approximately 2 g of the sample and decomposing and burning it in an oxygen cylinder, and the results shown in Table 1 were obtained. Considering that ordinary epoxy resins using epichlorohydrin as a starting material contain approximately several hundred chlorine in total, it can be seen that the total chlorine in the resin of the present invention is extremely small.

Synthesis Example 4゜Methanol 32p (1 mol), 4-vinylcyclohexene-1-oxide 868p (7 mol/I/) and BF
Nieteller) 9.2p were mixed at 60° C. and reacted until the conversion of 4-vinylcyclohexene-1-oxide reached 98% or more as determined by gas chromatography analysis.

Ethyl acetate was added to the obtained reaction crude liquid and washed with water, and then the ethyl acetate layer was concentrated to obtain a viscous liquid.

In the infrared absorption spectral of the product, the absorption by the epoxy group of 810,850 an-" observed in the raw material has disappeared, 1080.1150 cML-"
Gas chromatography analysis revealed that the allyl alcohol in the product had an absorption of 3450 cm in the infrared absorption spectrum even though it was left still.
It was confirmed that this compound has the structure shown by the following formula since there is an absorption of OH group at -'.

434 g of this compound was dissolved in ethyl acetate and charged into a reactor.
dripped over time. During this time, the reaction temperature was maintained at 40°C. After the addition of peracetic acid, the mixture was further aged at 40°C for 6 hours.

Ethyl acetate was added to the reaction crude solution, and the mixture was washed with alkaline water containing 416 g of sodium carbonate, and then thoroughly washed with distilled water.

The ethyl acetate layer was concentrated to obtain a solid resin at room temperature. This compound had an oxirane oxygen content of 9.971, and a characteristic absorption due to the epoxy group was observed at 1260 crn-' in the infrared absorption spectrum. Furthermore, 1640cIIL-”
This compound has the structure of general formula (I) (R
It was confirmed that the group was a nigericidyl group or an allyl group, n = 2 on average, and included a number of groups in which acetic acid was added to an epoxy group).

Example 1゜A curing agent was added to the product of Synthesis Example 1.2.3, gel time was measured, and the curability of the epoxy resin was investigated. Novolac type phenolic resin (PSF-43) was used as a curing agent.
00 Gunei Chemical Industry Co., Ltd., and 2-
Undecylimidazole (Curezol C□□Z, Shikoku Kasei Kogyo Co., Ltd.) was used. In addition, using 3,4-epoxycyclohexylmethyl-1,4'-epoxycyclohexane carpoxylate (Celoxide 2021. Daicel Chemical Industries, Ltd.), which is a typical alicyclic epoxy resin, as a comparative resin, the following Compound according to the combination prescription,
After melt mixing at 120° C. for about 1 minute, the mixture was cooled to obtain a blend. The obtained leta compound was tested according to JIS-a2104-7 (
The gel time at 120° C. was measured using a hot plate method (hot plate method), and the results shown in Table 2 were obtained. It can be seen that the resin of the present invention has higher curability than conventional alicyclic epoxy resins.

Blending recipe Epoxy resin 1.0 equivalent PSF-43001, 1 equivalent Table 2 Gel time example of blend 2゜The physical properties of the cured product were measured using the compound of Synthesis Example 1.2.3. .

Using the same curing agent and curing catalyst as in Example 1, the following formulation was mixed in the same manner as in Example 1 to obtain a mixture. The resulting mixture was pulverized and press molded to obtain a test piece. Molding is 9f/crIL to 90-100
The temperature was raised from 60° C. to 170° C. under pressure in step 2 in about 30 minutes, and after being left at 170° C. for 10 minutes under pressure, it was post-cured for 2 hours in an auxin set at 180° C. The obtained cured product was made into a test piece by cutting and rated according to JIS-691.
The physical properties were measured using No. 1, and the results shown in Table 3 were obtained.

Formulation Epoxy resin 1.0 equivalent PSF-43000, g equivalent Curazol C1□Z (relative to the formulation) 0.7 weight layer Example 3゜4-MethylbexahyP as a curing agent in the product of Synthesis Example 2
Curing was performed using phthalic anhydride (Rikasira rMH-700, Shin Nippon Rika Co., Ltd.). In addition, 3,4-epoxycyclohexylmethyl-3:4/-epoxycyclohexanecarboxylate (Celoxide 2021, Daicel Chemical Industries, Ltd.), which is a typical alicyclic epoxy resin, was used as a comparison resin, and the following formulation was used. The mixture was blended according to the recipe, melted at 80° C. for about 5 minutes, defoamed under reduced pressure, and cured by casting to obtain a cured product. For curing, pre-curing was carried out at 160°C for 1 hour in an open environment, and post-curing was further carried out at 180°C for 2 hours.

The obtained cured product was cut into test pieces, and JIS
The heat distortion temperature was measured using -6911 in Table 4.
I got the result.

Compounding recipe Epoxy resin 1.0 equivalent MH-700 0.8 equivalent Table 4. Example of heat distortion temperature of cured product Curing was performed using dimethylamine. In addition, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Celoxide 92021, Daicel Chemical Industries, Ltd.), which is a typical alicyclic epoxy resin, was used as a comparison resin, and the following formulation was used. Blend with 80
After melting at ℃ for about 5 minutes, degassing was carried out under reduced pressure, and hardening was performed by casting to obtain a cured product. Curing is 10 in the open
Pre-curing was performed at 0°C for 1 hour, and post-curing was further performed at 160°C for 2 hours.

The obtained cured product was cut into test pieces, and JIS
The heat distortion temperature was measured using -6911.
The results shown in Table 5 were obtained.

Blending recipe Epoxy resin 1.0 equivalent MH-700 0. g equivalent batter 5. Example of heat distortion temperature of cured product 5゜The product of Synthesis Example 4 was prepared using 4-methylhexahydrophthalic anhydride (Rikazid MH-700゜Shin Nippon Chemical Co., Ltd.) as a curing agent and benzyldimethylamine as a curing catalyst. Curing was performed. In addition, as comparative resins, 3,4-epoxycyclohexylmethyl-37,<I-epoxycyclohexanecarboxylate (Celoxide 2021. Daicel Chemical Industries, Ltd.), which is a typical alicyclic epoxy resin, and a general-purpose epoxy resin Bisphenol A diglycidyl ether (Ebicor) 828. Using Yuka Shell Epoxy Co., Ltd., the mixture was formulated according to the following formulation, mixed at 80° C. for about 5 minutes, defoamed under reduced pressure, and cured by casting to obtain a cured product. For curing, pre-curing was performed at 100° C. for 1 hour in an open environment, and post-curing was further performed at 160° C. for 2 hours.

The obtained cured product was cut into test pieces, and JIS
-K-6911 was used to measure the physical properties, and the results shown in Table 6 were obtained. As is clear from the table, the resin of the present invention has good heat resistance and excellent electrical properties.

Compounding recipe Epoxy resin 1 equivalent MH-700 1 equivalent Example 6゜The product of Synthesis Example 4 was used as a curing agent with 4-methylhexahyto90 phthalic anhydride (Rikazid MH-700゜Shin Nippon Rika Co., Ltd.) Curing was performed. In addition, Celoxide 2021 and Epicote 828 were used as comparative resins in the same manner as in Example 5, and they were mixed according to the following formulation and heated at 80°C.
After mixing for about 5 minutes, the mixture was defoamed under reduced pressure and cured by casting to obtain a cured product. Cured at 130'C in the open
: Precuring was performed for 1 hour. Celoxai) '2021 and Epicote 828 were still in liquid form at this stage, so
Heating was continued for an additional 2 hours (3 hours in total) at 130°C, but no gelation was observed, so when heating was further performed at 140°C for 1 hour, gelation was observed in Celoxide 2021. After pre-curing under the above conditions, post-curing was carried out at 180° C. for 2 hours, but no cured product could be obtained with Epikote 828.

The obtained cured product was cut into test pieces, and JIS
Physical properties were measured using -6911.

The obtained cured product was cut into test pieces, and JIS
The physical properties were measured using -6911, and the results shown in Table 7 were obtained. As is clear from the table, the resin of the present invention has good heat resistance and excellent electrical properties.

Compounding recipe Epoxy resin 1 equivalent MI (-700 Table 7 Written amendment for the characteristics of the cured product (voluntary) March 1, 1985 Manabu Shiga, Commissioner of the Patent Office1, Indication of the case Patent Application No. 27693 of 1980 2. Name of the invention New epoxy resin composition 3. Relationship with the case of the person making the amendment Patent applicant Postal code 590 Address 1 Teppocho, Sakai City, Osaka Name (290) Daicel Chemical Industries, Ltd. Specification “Detailed Description of the Invention” Column 5, Contents of Amendment (1) Procedural Amendment Written on March 13, 1985
The following "Synthesis Example-5" and "Example-7" are added to page 36 of the attached specification.

Synthesis Example-5 Trimethylolpropane 134.9 (1 mol), vinylcyclohexene monoepoxide 1863 g (15 mol)
were reacted in the same manner as in Example 1 to obtain a product.

Analysis of the obtained product by elemental analysis, IR, and NMR revealed that it had a structure represented by the formula OV).

n, , n, , n, Kyiken 5 In IR analysis, 810, 850 and 1 as in Example-1.
The absorption of the epoxy group at 850α-1 disappears, and the absorption at 1080α-1 disappears.
cm' ether bond absorption was newly generated. Furthermore, Binny 1 absorption of 910σ-' and 1640σ-1 remains.

In NMR, peaks similar to those in Example 1 were confirmed. The elemental analysis values are shown below.

Theoretical value 75.82 9.73 From the above results, the structure of formula (5) was confirmed.

Example 7 Physical properties of the cured product were measured using the compound of Synthesis Example 5 and cresol novolak epoxy (Toto Kasei, YDCN-702).

Using the same curing agent and curing catalyst as in Example 1, the following formulation was mixed in the same manner as in Example 1 to obtain a mixture. The resulting mixture was pulverized and press molded to obtain a test piece. For molding, the temperature was raised from 60℃ to 170℃ in about 30 minutes under pressure of 9f/ffl to 90-100, then left at 170℃ under pressure for 10 minutes, and then cured after 2 hours in an open set at 180℃. I did it. The obtained cured product was cut into a test piece, and its physical properties were measured according to JIS-6911, and the results shown in Table 8 were obtained.

Compounding recipe Epoxy resin 1.0 equivalent P 8 F -43001, Q equivalent cu r'/-"C++ Z (for the formulation) 0.
7 Weight table 8 Physical properties of cured product

Claims (1)

[Claims] A new epoxy resin represented by the general formula (I) and a filler, a flame retardant, and its Sendai type additives are blended according to the convenience rule. Epoxy resin composition. However, %R1 is a residue of a mantle compound having 4 active hydrogens. n4 I11+ °"'nl l'j O or 100'M number 1 of 41] is 1 to 100. l is the strain number of 1 to 100. A Irl +J, oxy with J wing' It has a cyclohexane skeleton and is coated with the following formula: υ One or more particles are present in the coated resin.