JPH0410471B2 - - Google Patents

Description

[Detailed description of the invention]

<<Industrial Application Field>> The present invention relates to a novel fat-reduced epoxy resin that has excellent heat resistance, weather resistance, and water resistance. <<Prior Art>> The epoxy resin currently most widely used in industry is the so-called EPIS type epoxy resin, which is produced by the reaction of bisphenol A and epichlorohydrin. This resin can be used in a wide range of products, from liquids to solids, and has the advantage that the epoxy group has high reactivity and can be cured at room temperature with polyamines. 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 epichlorohydrin have been used as sealing resins for VLSIs, but the resin contains several hundred ppm of chlorine, which deteriorates the electrical characteristics of electrical parts. Problems such as this are occurring. Alicyclic epoxy resins are examples of epoxy resins that do not contain chlorine and have excellent electrical properties and heat resistance. These are produced 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, and are usually cured by heating with acid anhydrides, but cannot be cured at room temperature with polyamines due to their low reactivity. Therefore, the scope of use of alicyclic epoxy resins is extremely narrow. As alicyclic epoxy resins, those having the structures () and () are industrially produced and used. (Problems to be Solved by the Invention) () is used as a heat-resistant epoxy diluent because of its extremely low viscosity, but it has the problem of being highly toxic and causing severe irritation to the skin of workers. () has few impurities, a low hue, and a cured product having a high heat deformation temperature, but the problem is poor water resistance due to ester bonds. Furthermore, since both () and () are low-viscosity epoxy resins, solid epoxy resin molding systems such as transfer molding cannot be applied. In view of this problem, the present inventors have conducted intensive research to develop a new epoxy resin, and as a result, they have found that it is an alicyclic resin, has any properties from liquid to solid, and has excellent water resistance and heat resistance. Furthermore, they discovered an epoxy resin with excellent reactivity and completed the present invention. ≪Means for solving the problem≫ That is, the present invention has the following general formula () [However, R ¹ is a residue of an organic compound having l active hydrogen groups, and the organic compound contains at least one hydroxyl group as an active hydrogen group, or a compound containing at least one hydroxyl group as an active hydrogen group. 1 selected from unsaturated alcohols containing at the same time an unsaturated double bond-containing group
Consisting of a species or a mixture of two species, n ₁ , n ₂ ,...nl
are 0 or an integer from 1 to 30, and their sum is from 1 to
100, l is an integer from 1 to 10 and represents the number of active hydrogen groups of R, A is an oxycyclohexane skeleton having a substituent X, and is represented by the following formula, X is

[Formula] −CH=CH ₂ R ² is H, an alkyl group, an alkylcarbonyl group,
Any one of the arylcarbonyl groups, is contained in the compound represented by the formula ()] A novel epoxy resin represented by: It is. The present invention will be explained in detail below. The compound having active hydrogen described in the present invention is a compound containing at least one hydroxyl group as an active hydrogen group, or a compound containing at least one hydroxyl group as an active hydrogen group, and simultaneously containing an unsaturated double bond-containing group. It refers to the unsaturated alcohol it contains. However, some of the hydrogen atoms in the residues of the above compounds may be substituted with fluorine or alkyl groups. Therefore, 1, which is the number of active hydrogen groups in the initiator compound used in the present invention, represents the number of hydrogen groups. In the general formula (), _n1 ...nl are each 0 or an integer of 1 to 30. The sum is between 1 and 100, but if it is over 100, the resin will have a high melting point and will be difficult to handle, making it practically unusable. l is an integer from 1 to 10. Among the substituents X of A in formula (),

Contains at least one [formula] is required, but

[Formula] The larger the number, the better. especially The smaller the number, the better. That is, in the present invention, the substituent X is is the main one. In the novel epoxy resin represented by formula () in the present invention, R ¹ is a compound containing at least one hydroxyl group as an active hydrogen group, or a compound containing at least one hydroxyl group as an active hydrogen group, and unsaturated. It is an unsaturated alcohol that also contains a double bond-containing group, and representative compounds include the following. For example, methanol, ethanol, propanol, butanol, pentanol, hexanol,
Aliphatic alcohols such as octanol, aromatic alcohols such as benzyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1.3 butanediol, 1.4 butanediol, pentanediol, 1.6 hexanediol, Neopentyl glycol, oxypivalic acid neopentyl glycol ester, cycloexane dimethanol, glycerin, diglycerin, polyglycerin, trimethylolpropane, trimethylolethane, pentaerythritol, dipentaerythritol, hydrogenated bisphenol A, hydrogenated bis Examples include polyhydric alcohols such as phenol F and hydrogenated bisphenol S. In addition, alcohol compounds with active hydrogen are
It may have an unsaturated double bond in its skeleton, and specific examples include allyl alcohol. These compounds may be used in combination of two or more. In the present invention, the novel epoxy resin represented by the formula () is manufactured using a polyether resin obtained by ring-opening polymerization of 4-vinylcycloxene-1-oxide using the above compound as an initiator, that is, It can be produced by epoxidizing the vinyl group side chain of a polycyclohexene oxide polymer having a vinyl group side chain with an oxidizing agent such as a peracid. 4-vinylcycloxene-1-oxide can be obtained by a dimerization reaction of butadiene, and can be obtained by partially epoxidizing 4-vinylcyclohexene with peracetic acid or the like. It is preferable to use a catalyst when polymerizing 4-vinylcycloxene-1-oxide in the presence of active hydrogen. Examples of catalysts include amino acids 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. Alcoholates of alkali metals, alkalis such as KOH.NaOH, Lewis acids such as BF ₃ , ZnCl ₂ , AlCl ₃ , SnCl ₄ or their complexes, organometallic compounds such as triethylaluminum, diethylzinc, etc. I can do it. These catalysts are 0.01-10% based on the starting material,
It can be used preferably in a range of 0.1 to 5%. The reaction temperature is -70 to 200℃, preferably -30℃ to
It is 100℃. The reaction can also be carried out using a solvent. A solvent containing active hydrogen cannot be used. That is, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, aromatic solvents such as benzene, toluene, and xylene, as well as ethers, aliphatic hydrocarbons, esters, and the like can be used. Now, the polycyclohexene oxide polymer having a vinyl side chain synthesized in this way is epoxidized with an epoxidizing agent to produce a novel epoxy resin of the formula () according to the present invention. As the epoxidizing agent, peracids and hydroperoxides can be used. Peracids include performic acid, peracetic acid, perbenzoic acid,
Trifluoroperacetic acid and the like 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, tertiary butyl hydroperoxide, cumene peroxide, 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 nitric acid may be used as a catalyst. In the case of hydroperoxides, the catalytic effect can also 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 tertiary butyl hydroperoxide. . The epoxidation reaction is carried out by adjusting the use of a melt filter and the reaction temperature depending on the equipment and physical properties of the raw materials. Depending on the conditions of the epoxidation reaction, the olefin bond can be epoxidized and the substituents in the raw material can be and the substituents that are generated. As a result of reaction with the epoxidizing agent, modified substituents are generated and included in the target compound. , substituents and modified substituents in the target compound, substituent The ratio of the three modified substituents is determined by the type of epoxidizing agent, the molar ratio of the olefin bond of the epoxidizing agent, and the reaction conditions. When the epoxidizing agent is peracetic acid, the modified substituent has the structure shown below, and is generated from the generated epoxy group and by-produced acetic acid. The target compound can be removed from the reaction crude solution by conventional chemical engineering means such as concentration. The new epoxy compound obtained in this way can be used as an excellent LSI encapsulation material due to its low chlorine impurity when crosslinked with phenol novolac resin or other curing agent. can. Furthermore, as an alternative to conventional uses of epoxide, such as impregnating coils, it has the advantage that performance can be adjusted by freely adjusting the degree of polymerization. Furthermore, it can be applied to a wide range of applications such as LED and semiconductor encapsulants, paints, etc. [Effects of the Invention] The present invention will be further explained with reference to Examples below. Example 1 Allyl alcohol 115g (2 moles), 4-vinylcyclohexene-1-oxide 496g (4 moles)
and 3.1 g of BF ₃ etherate 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 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, gas chromatography analysis revealed that the absorption due to epoxy groups at 810 and 850 cm ^-1 observed in the raw material disappeared, and that absorption due to ether bonds existed at 1080 and 1150 cm ^-1 . , in the product,
Although allyl alcohol was present in trace amounts, the infrared absorption spectrum showed absorption of OH group at 3450 cm ^-1 , which confirmed that this compound had the structure shown by the following formula. (n is 2 on average) 434 g of this compound was dissolved in ethyl acetate and charged into a reactor, to which 388 g of peracetic acid was added as an ethyl acetate solution for 2 hours. 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 4 hours. Add ethyl acetate to the reaction crude solution and add sodium carbonate.
It was washed with alkaline water containing 416 g, and thoroughly washed with distilled water. The ethyl acetate layer was concentrated to obtain a viscous liquid. This compound has an oxirane oxygen content of 9.97%
In the infrared absorption spectrum, characteristic absorption due to epoxy groups was observed at 1260 cm ^-1 . Furthermore, absorption due to residual vinyl groups is observed at 1640 cm ^-1 , -OH group at 3400 cm ^-1 , and -OH group at 1730 cm -1.
-To ¹

[Formula] Based on the observed absorption by the group, this compound has the structure of the general formula () (R ¹ : glycidyl ether group or allyloxy group, n=2 on average, contains some groups in which acetic acid is added to the epoxy group) It was confirmed. Example 2 In the same manner as in Example 1, allyl alcohol 25
g (1 mol), 4-vinylcyclohexene-1-
868 g (7 moles) of oxide and 4.7 g of BF ₃ etherate were reacted to obtain a viscous liquid product. In the infrared absorption spectrum of the product, gas chromatography analysis revealed that the absorption due to epoxy groups at 810 and 850 cm ^-1 observed in the raw material disappeared, and that absorption due to ether bonds existed at 1080 and 1150 cm ^-1 . , in the product,
Although allyl alcohol was present in trace amounts, the infrared absorption spectrum showed absorption of OH group at 2450 cm ^-1 , which confirmed that this compound had the structure shown by the following formula. (n is 7 on average) Furthermore, in the same manner as in Example 1, 492 g of this compound was reacted with 395 g of peracetic acid to obtain a viscous transparent liquid. This compound has an oxirane oxygen content of 9.27%
In the infrared absorption spectrum, characteristic absorption due to epoxy groups was observed at 1260 ^-1 . Furthermore, absorption due to residual vinyl groups is observed at 1640 cm ^-1 , -OH group at 3400 cm ^-1 , and -OH group at 1730 cm -1.
-To ¹

[Formula] Based on the observed absorption by the group, this compound has the structure of the general formula () (R ¹ : glycidyl ether group or allyloxy group, n=7 on average, contains some groups in which acetic acid is added to the epoxy group) It was confirmed. Example 3 In the same manner as in Example 1, 64 g of methanol (2
744 g (6 mol) of 4-vinylcyclohexene-1-oxide and 4.1 BF ₃ etherate
g was reacted to obtain a viscous liquid product. In the infrared absorption spectrum of the product, the absorption by epoxy groups at 810 and 850 cm ^-1 observed in the raw material disappeared, and the presence of absorption due to ether bonds at 1080 and 1150 cm ^-1 , and gas chromatography analysis revealed that Although the methanol in the product is a trace amount, it is 3450 cm ^-1 in the infrared absorption spectrum.
It was confirmed that this compound has the structure shown by the following formula because there is an absorption of OH group in . (n is 3 on average) Furthermore, in the same manner as in Example 1, 573 g of this compound was reacted with 387 g of peracetic acid to obtain a viscous transparent liquid. This compound has an oxirane oxygen content of 9.03%
In the infrared absorption spectrum, characteristic absorption due to epoxy groups was observed at 1260 cm ^-1 . Furthermore, absorption due to residual vinyl groups is seen at 1640 cm ^-1 , -OH group at 3400 cm ^-1 , and absorption by residual vinyl groups at 1730 cm ^-1.

[Formula] This compound has the structure of general formula (I) (R ¹ : methoxy group,
It was confirmed that n=3 on average, including some groups in which acetic acid was added to epoxy groups). Example 4 134g (1 mol) of trimethylolpropane was added to 4
-vinylcyclohexene-1-oxide 1863g
(15 mol) was reacted in the same manner as in Example 1 to obtain a product. In the same way as in Example 1, the infrared absorption spectrum of the obtained product showed that it was found in the raw material at 810 and 850 cm ^-1
The absorption by epoxy group at 1850cm ^-1 has disappeared, and the absorption by ether bond newly exists at 1080cm ^-1 .
Since there is absorption by the vinyl group at cm ^-1 , the following [However, n1 + n2 + n3 = average 5, A is an oxycyclohexane skeleton having the following vinyl groups

It was confirmed that the structure is represented by [Formula]]. In addition, peaks similar to those in Example 1 were confirmed in NMR analysis. The elemental analysis values are shown below. C H Analytical value 76.05 9.65 Theoretical value 75.82 9.73 From the above results, the above formula was confirmed. Furthermore, in the same manner as in Example 1, 573 g of this compound was reacted with 387 g of peracetic acid to obtain a viscous transparent liquid. This compound had an oxiranic acid content of 9.03%, and a characteristic absorption due to the epoxy group was observed at 1260 cm ^-1 in the infrared absorption spectrum. Furthermore, absorption due to residual vinyl groups is observed at 1640 cm ^-1 , -OH group at 3400 cm ^-1 , and -OH group at 1730 cm -1.
-To ¹

[Formula] This compound has the structure of general formula (I) (R ₁ : trimethylolpropane residue, l = 3, n1, n2, n3 = average 5, acetic acid is present in the epoxy group because absorption is observed due to the - group). (including some added groups)
It was confirmed that Reference Example The total amount of chlorine in the epoxy resins synthesized in Examples 1, 2, and 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 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] Application Example 1 A curing agent was added to the products of Examples 1, 2, and 3, and the gel time was measured to study the curability of the epoxy resin. Using novolak type phenolic resin [PSF-4300, manufactured by Gunei Chemical Industry Co., Ltd.] as a curing agent,
2-undecylimidazole [Kyuazole C ₁₁ Z, manufactured by Shikoku Kasei Kogyo Co., Ltd.] was used as a curing catalyst. In addition, as a comparison resin, 3,4-epoxycyclohexylmethyl-3'.4'-epoxycyclohexanecarboxylate [Celoxide 2021,] manufactured by Daicel Chemical Industries, Ltd., which is a typical alicyclic epoxy resin, was used. The compositions were blended according to the following formulation, melt-mixed at 120°C for 1 minute, and then cooled to obtain a blend. The gel time of the obtained formulation at 120°C was measured according to JIS-C2104-7 (hot plate method), and the results are shown in Table 2.
I got the result.

[Table] Compounding recipe: Epoxy resin 1.0 equivalent PSF-4300 1.1 equivalent Kyuazol C ₁₁ Z 0.7% by weight (based on the compound) It can be seen that the resin of the present invention has higher curability than conventional alicyclic epoxy resins. . Application Example 2 The physical properties of the cured product obtained by adding a curing agent to the products of Examples 1, 2, and 3 were measured. The same curing agent and catalyst as in Application Example 1 were used, and the following The blended formulation was mixed in the same manner as in Application Example 1 to obtain a blended product. The resulting mixture was pulverized and press-molded to obtain a test piece. Molding is done under pressure of 90-100Kgf/ ^cm2 from 60℃.
The temperature was raised to 170℃ in about 30 minutes, and then heated to 170℃ under pressure.
After being left for 10 minutes, it was post-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-K-6911.
The results shown in Table 3 were obtained.

[Table] Compounding formula: Epoxy resin 1.0 equivalent PSF-4300 0.9 equivalent Kyuazol C ₁₁ Z (based on the compound) 0.7% by weight

Claims (1)

[Claims] 1. The following general formula () [However, R ¹ is a residue of an organic compound having l active hydrogen groups, and the organic compound contains at least one hydroxyl group as an active hydrogen group, or a compound containing at least one hydroxyl group as an active hydrogen group. 1 selected from unsaturated alcohols containing at the same time an unsaturated double bond-containing group
Consisting of species or a mixture of two or more species, n ₁ , n ₂ ,...
nl is 0 or an integer from 1 to 30, and the sum is 1 to 30.
100, l is an integer from 1 to 10 and represents the number of active hydrogen groups of R, A is an oxycyclohexane skeleton having a substituent X, and is represented by the following formula, X is [formula] -CH=CH ₂ R ² is H, an alkyl group, an alkylcarbonyl group,
Any one of the arylcarbonyl groups, is contained in the compound represented by the formula ()] A novel epoxy resin represented by: