JPS6245644A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To provide a thermosetting resin compsn. which has excellent storage stability, gives cured articles having excellent heat resistance, electrical characteristics, etc. and is suitable for use as an electrical material, by blending an org. Al compd. and an organosilicon compd. with an epoxy resin having a specified structure. CONSTITUTION:An org. Al compd. (e.g. trisacetylacetonatoaluminum) and an organosilicon compd. (e.g. a compd. of formula V) contg. a hydroxyl or hydrolyzable group directly attached to a silicon atom are blended with an epoxy resin of formula I (wherein R1 is a residue of an org. compd. contg. 1-100 active hydrogen atoms; n1, n2,... nl are each 0-100 and the sum thereof is 1-100; lis 1-100; A is a group of formula II: X is a group of formula III or IV,, etc.; R2 is H, alkyl, etc.; at least one group of formula III must exist in formula I).

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Background) The present invention relates to an epoxy resin composition that exhibits good storage stability at room temperature, has excellent curability, and becomes a cured product with excellent heat resistance and electrical properties.

(Prior Art) When curing an epoxy resin, for example, (A) a curing agent such as a polyamine, acid anhydride or phenol, or (B) a curing catalyst such as a BFs complex or a tertiary amine compound is added to the epoxy resin. Usually, it is added to and blended with. However, in case (A), when a polyamine is used, there is the disadvantage that the composition cannot be stored for a long period of time due to its strong reactivity with the epoxy resin, and when an acid anhydride is used, it requires high temperatures for curing. The disadvantage is that it requires long-term heating.

On the other hand, in case (B), when the B F 3 complex is squared, it can be cured at a relatively low temperature, but there is a drawback that the electrical and mechanical properties of the cured resin at high temperatures are poor. Further, when a tertiary amine is used, a high temperature is required for the curing reaction, and there are also operational problems such as skin irritation.

Furthermore, when curing epoxy resins, attempts have been made to add and blend metal chelate compounds as latent curing catalysts. However, in this case, not only does the curing reaction require a high temperature of 200°C or higher, but also the metal chelate compound is added in a relatively large amount of about 5%, and has good properties due to the poor solubility fraction. There is also the disadvantage that it is difficult to form a hardened resin layer.

From this point of view, it is possible to use an organic aluminum compound and an organosilicon compound having a hydroxyl group or a hydrolyzable group directly bonded to a silicon atom as an epoxy curing catalyst.
JP-A-56-2319.56-462557-5352
2.57-133122 etc.

However, epoxy resins that can be cured with these catalysts include 3,4-epoxyisochlorohexylmedyl-3',
4'-Evoxin chlorohegysancarboxylate (manufactured by Daicel Chemical Industries, Ltd., Celoxide 2021, UC
The so-called E RL-4221 manufactured by Company C is typified by
Alicyclic epoxy resins are preferred. Conventional epi-bis type epoxy resins and novolac epoxy resins produced from epichlorohydrin and bisphenol A or novolac phenol have the drawback of slow curing speed.

Furthermore, since the conventional alicyclic epoxy resins are liquid resins with low viscosity, the range of application of the resulting photocurable resin compositions is narrow, and they are mainly used as liquid coating agents.

On the other hand, epoxy resin can be used for printed circuit boards, IC encapsulation, LED encapsulation, resistors, capacitor encapsulation, etc. by utilizing its properties.
It is widely used in the electrical field, paint field, adhesive field, and ink field such as solder resist ink. Further improvements in heat resistance and electrical properties are desired in these various fields.

(Problems to be solved by the invention) As a result of intensive study in view of the above situation, the inventors of the present invention have solved the following problems:
By using a new epoxy resin with a cyclohexane skeleton proposed in Japanese Patent Application No. 59-014859, an organoaluminum compound and an organosilicon compound, a cured product with excellent heat resistance and electrical properties can be obtained, and a suitable organoaluminium. The present inventors have discovered that an epoxy resin composition that is stable at room temperature and also has so-called latent properties can be obtained by using a compound and an organosilicon compound.

(Structure of the Invention) That is, the present invention provides: ``(a) an epoxy resin represented by formula (I), (b) an organic aluminum compound, and (c) an organosilicon compound having a hydroxyl group or a hydrolyzable group directly bonded to a silicon atom. However, R is an organic compound residue containing active hydrogen.

nl, n2... nfi is an integer of 0 or 1-100, and the sum thereof is 1-100.

E represents an integer from 1 to 100.

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

One or more are contained in the resin represented by. ”.

In the epoxy resin of formula (I) of the present invention, R3 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.

For example, methanol, ethanol, pro? Aliphatic alcohols such as alcohol, butanol, pentanol, hexanol, octatool, aromatic alcohols such as benzyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol,
1.3 butanediol, 1.4 butanediol, betanediol, 1.6 hexanediol, neopentyl glycol, oxypivalic acid neopentyl glycol ester, nclohexane dimethanol, glycerin, diglycerin, polyglycerin, trimethylolpropane, Examples include polyhydric alcohols such as trimethylolethane, pentaerythritol, and dipentaerythritol.

Examples of phenols include phenol, cresol, catechol, pyrogallol, hydroquinone, hydroquinone monomethyl ether, bisphenol A, bisphenol F, 4,4'-dihydroxybenzophenone, bisphenol S1 phenolic resin, Talesol novolak resin, and the like.

Carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, fatty acids from animal and vegetable oils, fumaric acid, maleic acid, adipic acid, dodecanoic acid, trimellitic acid, pyromellitic acid,
Examples include 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, hequinylamine, cyclohexylamine, octylamine, dodecylamine, 4,4'-diaminone phenylmethane, isophorone diamine, toluenediamine, hexamethylene diamine, xylene diamine. , ethylenetriamine, triethylenetetramine, ethanolamine, etc.

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, such as ethylene glycol dimercaptopropionic acid ester, trimethylolbroban trimercabutobro Examples include bionic acid ester, pentaerythritol benthamercabutopropionic acid ester, and the like.

In addition, other active hydrogen-containing compounds include polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, cellulose, cellulose acetate, cellulose acetate butylate, hydroxyethyl cellulose, acrylic polyol resin, styrene allyl alcohol copolymer resin, styrene. - Maleic acid copolymer resins, alkyd resins, polyester polyol resins, polyester carboxylic acid resins, polycaprolactone polyol resins, polypropylene polyols, polyetramethylene glycols, and the like.

In addition, compounds containing active hydrogen have unsaturated 2 atoms in their skeleton.
It may have a double bond, and specific examples include allyl alcohol, acrylic acid, methacrylic acid, 3-cyclohexenemethanol, and tetrahydrophthalic acid. The unsaturated double bonds of these compounds may also have an epoxidized structure.

n I+ n t...ni in general formula (1) is O
Alternatively, it is an integer from 1 to 100, and the sum thereof is t-too, but if it is 100 or more, it becomes a resin with a high melting point and is difficult to handle, and cannot be used in practice.

2 is an integer from 1 to 100.

Among the substituents X of A in formula (1) The less the better.

That is, in the present invention, it is particularly preferable that the substituent X has the above-mentioned structure, since this increases the crosslinking density when cured.

Specifically, the epoxy resin represented by formula (1) of the present invention is a polyether resin obtained by ring-opening polymerization of 4-vinylcyclohexene-1-oxide using an organic compound having active hydrogen as an initiator, i.e. , can be produced by epoxidizing a polycyclohexene oxide polymer having one vinyl group side chain with an oxidizing agent such as a peracid.

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

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

Examples of catalysts include amines such as methylamine, ethylamine, propylamine, and piperazine, organic basic acids such as birinones and imidazoles, a-organic acids such as formic acid, acetic acid, and propionic acid, inorganic acids such as sulfuric acid and hydrochloric acid, and sodium. Alcolades of alkali metals such as mezilate, KOH, N
Alkali such as aOH, BF3, Z n C, f: 2
, Afficfa, SnC 兇. Lewis acids such as or their complexes, triethylaluminum, diethyl 1
Examples include hammer metal compounds such as zinc.

These catalysts can be used in an amount of 0.01 to 10%, preferably 0.1 to 5%, based on the reactants. The reaction temperature is -70 to 200°C, preferably -30°C to 100°C.
It is ℃.

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

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

Now, in order to epoxidize the thus synthesized borine chlorohexene oxide polymer having a vinyl group side chain to produce the epoxy resin of (1) of the present invention, either peracids or hydroperoxides are used. be able to.

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 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 hydroperoxides, the catalytic effect can also be obtained by using a mixture of tungstic acid and caustic soda with hydrogen peroxide, or an organic acid with hydrogen peroxide, or molybdenum hexacarbonyl with tanyabutyl 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 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 substituent mainly has the structure shown below, and is generated from the evoquine group produced and the acetic acid produced as a by-product.

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

In the present invention, the epoxy resin obtained as described above may be used in combination with ordinary alicyclic epoxy resins, Ebis type epoxy resins, nopolac epoxy resins, etc.

Both the organic aluminum compound and the organic silicon compound used in the method of the present invention function as a curing catalyst.

It represents an aralkyl group such as a paramethylbenzyl group, an alkenyl group such as a vinyl group, an allyl group, a propenyl group, a butenyl group, and an acyl group such as an acetyl group, a benzoyl group, a trifluoroacetyl group. In particular, at least one of the structural units contains at least one silanol hydroxyl group.

Among the above organosiloxanes, those having a degree of polymerization of 50 or less and a silanol hydroxyl equivalent of 1000 or less, more preferably 50 to 500 are suitable for the method of the present invention.

Specific examples of such organosiloxanes include l,
3-dihydroxy-1,8-dimethyl-1,3-diphenyldisiloxane, 1,5-dihydroxy-1,3,5
-Trimethyl-1,3,5-1-rephenyltrisiloxane, 1,7-cyhydroxy-1.3.5.7-titramethyl-1.3.5.7-tetraphenyltetrasiloxane, 1,3-dihydroxytetra Phenyldisiloxane, 1,5-dihydroxyhexaphenyltrisiloxane, 1,7-dihydroxyoctaphenyltetranoxane, 5-dihydroxy-8,3-dimethyl-1,
1,5,5-tetraphenyltrisiloxane, 1,3-
dihydroxytetra(dimethylphenyl)disiloxane, l,5-dihydroquinohexaethyltrisiloxane,
1.7-Sihydroquine octapropyltetrasiloxane, ■.

3.5-trihydroxy-8-ethyl-1,1,5゜5
-tetramethyltrisiloxane, 1,5-dihydroxy-1,l, 5,5-tetraphenyl-3,8-p
-Tolyltrisiloxane, φ crab\si/ CH,OHOH CH3-Si -0-Si -0-3t-CH30HO
CH3CHs-S! CH3H etc., and 5H6018 (Toray Silicone Co., Ltd.)
This also applies to silicone resins available under trade names such as methylphenylpolysiloxane, manufactured by Co., Ltd., hydroxyl equivalent: 400, Publication No. 1600).

Furthermore, an organosilicon compound having a hydrolyzable group is a silanol hydroxyl group (=Si-OH) obtained by directly bonding the silanol hydroxyl group listed above to a silicon atom and hydrolyzing it at a certain temperature or higher in the presence of water. It is substituted with a residue (hydrolyzable group) that produces .

Examples of such hydrolyzable groups include alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy groups, phenoxy groups, vinyloxy groups and their substituted substances, methylcarbonyloxy groups, ethylcarbonyloxy groups, and propylcarbonyl groups. Oxy group, carboxy group such as butylcarbonyloxy group, ethylidene aminooxy group,
Examples include alkylidene aminooxy groups such as propylidene aminooxy group, butylidene aminooxy group, and pentylidene amino okine group.

The amount of these 2N curing catalysts to be used varies depending on the type of epoxy compound used, so it cannot be stated unconditionally, but in general, each is 0.001 parts by weight per 100 parts by weight of the epoxy compound.
~IO parts by weight, preferably within the range of 0.01 to 5 parts by weight.

At this time, it is preferable to mix and use the organosilicon compound so that the amount of silanol hydroxyl group or hydrolyzable group is 1 equivalent or more, more preferably 1 to 5 equivalents, per 1 mole of the organic aluminum compound.

In the method of the present invention, in addition to the above-mentioned curing catalyst, a commonly used acid anhydride curing agent may be blended as needed. Examples of such acid anhydride curing agents include phthalic anhydride, maleic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhimic anhydride, pyromellitic anhydride, ben-
Examples include cyphenonetetracarboxylic acid, chlorendic anhydride, methyltetrahydrophthalic anhydride, and dodecenylsuccinic anhydride.

Since both the organic aluminum compound and the organosilicon compound of the present invention begin to show activity at about 80°C, the curing temperature may be 30 to 200°C, preferably 80 to 180°C.
It is ℃. Note that this curing reaction does not need to be carried out in a closed system unlike conventional organometallic compound catalysts, and it is sufficient to carry out it in air.

In the present invention, fillers such as phosphoric acid, pigments, dyes, etc. may be added as necessary.

(Effects of the present invention) The epoxy resin composition of the present invention is not only suitable for casting, impregnation, molding, etc. as a so-called solvent-free type by selecting the type of epoxy resin and the composition ratio, but also suitable for use with dioxane, tetrahydrofuran, etc. Easily dissolved in low boiling point solvents. Therefore, it can be easily impregnated into glass cloth, paper, etc., so it can also be used for forming laminates. It can also be used in powder coatings, norder resist inks, etc. However, sulfurized resin maintains and exhibits excellent heat resistance, mechanical properties, and electrical insulating properties.

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

Synthesis Example-1 Allyl alcohol 58g (1 mol), 4-vinylcyclohexene-1-oxide 868g (7 mol) and B
F, 4.7 g of etherate were mixed at 60°C, and gas chromatography analysis revealed that 4-vinylcyclohexene-1-
The reaction was continued until the conversion of oxide reached 98% or more. 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 spectrum of the product, the absorption by the epoxy group at 8 10.850 cm""' that was observed in the raw material has disappeared, and the absorption by the epoxy group at 1080.1150 cm"-'
The presence of absorption due to ether bonds in the product, gas chromatography analysis showed that although there was only a trace amount of allyl alcohol in the product, the infrared absorption spectrum showed that it was 3450 cm.
It was confirmed that this compound has the structure shown by the following formula since there is an absorption of 0■I group in '.

40.2 g of this compound was dissolved in ethyl acetate and charged into a reactor, to which 395 g of peracetic acid was added dropwise as an ethyl acetate solution over 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 6 hours.

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

The ethyl acetate layer was condensed 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 1260 cm' in the infrared absorption spectrum. Furthermore, absorption due to residual vinyl groups can be seen at 1640 cm-', and at 3450 cm-'
Since absorption is observed by an OH group at ' and a -C〇- group at 1730 cm', this compound has a structure of general formula (I) (R, nigericidyl group or allyl group, n-average 7, acetic acid added to the epoxy group). It was confirmed that the compound contained a small number of groups.

Synthesis Example 2゜By the same operation as in Example-1, trimethylolpropane 1
34g, 4-vinylfuclohexene-1-oxide 1
86.3 g was reacted to obtain a viscous liquid product.

In the infrared absorption spectrum of the product, the absorption by the epoxy group at 810.850 cm'-' that was observed in the raw material has disappeared, i o so o.

The presence of absorption due to an ether bond at 1150 cm' and NMR analysis confirmed that this compound has a structure represented by the following formula.

Furthermore, 573 g of this compound was reacted with 387 g of peracetic acid in the same manner as in Synthesis Example 1 to obtain a viscous transparent liquid.

This compound had an oquinane oxygen content a of 9.03%, and characteristic absorption due to epoxy groups was observed at 1260 cm' in the infrared absorption spectrum. Furthermore, absorption due to residual vinyl groups is observed at 1640 cm', and 34.50 cm-
OHM at 1730cm and -6o-* absorption at 1730cm 5,
It was confirmed that the epoxy group contained a group in which acetic acid was added to an epoxy group.

Examples 1-6, Comparative Examples-1-2 Epoxy resins obtained in Synthesis Examples-■ and 2, 3.4-
Eboxyisochlorohexylmethyl-3'.

4'Evoquinoclohexanecarboxylate (Daicel Chemical Co., Ltd. Celloxide 202+) Epicote 828
(Bisphenol A type Evokin resin manufactured by Shell Chemical Co., Ltd.)
Contains trisacetylacetonadoaluminum (TAAA) and trisedylacetoacetatoaluminum (TEAACA) as organic anotominium compounds, and diphenylshedkin silane (DPDES) and triphenylsilanol (TPSO) as organosilicon compounds in the proportions shown in Table 1. 2mm by curing at 120℃ for 3 hours
A plate with a thickness of The results are shown in Table-1.

Claims (1)

[Claims] It is characterized by consisting of (a) an epoxy resin represented by formula (I), (b) an organic aluminum compound, and (c) an organosilicon compound having a hydroxyl group or a hydrolyzable group directly bonded to a silicon atom. Thermosetting resin composition ▲Mathematical formula,
There are chemical formulas, tables, etc. ▼ (I) However, R_1 is an organic compound residue with 1 active hydrogens. 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,
It is expressed by the following formula. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ group, carboalkyl group, or carboaryl group), but there are mathematical formulas, chemical formulas, tables, etc., and at least one or more ▼ is contained in the resin represented by formula (I).