JPS621723A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:An epoxy composition, consisting of an epoxy resin, formimidate compound, organosilicon compound and organic complex compound, having excellent storage stability and improved quick-curing properties as a two-pack type composition and useful as adhesives, coating materials, etc. CONSTITUTION:An epoxy resin composition consisting of (A) 100pts.wt. com pound having >=1 epoxy groups, (B) 0.01-60pts.wt. compound having >=1 formimidate groups, e.g. methyl N-phenylformimidate or diphenyl N- hexylformimidate, (C) 0.0001-20pts.wt., preferably 0.01-10pts.wt. organosilicon compound having silanol group or producing silanol group, (D) 0.001-10pts.wt., preferably 0.01-5pts.wt. organic complex compound, preferably an organoaluminum complex, and preferably further containing 5-90pts.wt. phenolic derivative and consisting of a two-pack system prepared by separating the components (C) and (D) as another solution system.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to an epoxy resin composition, and more particularly, the present invention relates to an epoxy resin composition that has extremely good storage stability as a two-component type, and whose mixture has excellent rapid curing at low temperatures. The present invention relates to an epoxy resin composition having properties.

[Technical background of the invention and its problems]

Epoxy resin compositions are widely used in applications such as paints, adhesives, electrical insulation materials, casting materials, molding materials, and laminates. In order to achieve this, it is desired to develop an epoxy resin composition that simultaneously has storage stability and fast curing properties in a well-balanced manner.

Conventionally, epoxy resin compositions include compositions consisting of an epoxy resin and boron trifluoride (BF3) or socyanthamide.This composition is a liquid type in which each component is mixed in advance. It is heated and cured according to the conditions. In addition, other epoxy resin compositions include
The composition consists of an epoxy resin and a relatively highly active curing agent containing so-called active hydrogen, such as an amine compound, a carboxylic acid compound, and a phenol compound.This composition is a two-part type in which each component is mixed at the time of use. The material is cured at room temperature or by heating, if necessary.

These compositions generally must contain a curing accelerator such as a tertiary amine compound or an imidazole compound in order to speed up the curing reaction rate.

However, in these compositions, once a curing accelerator is blended into the composition system, a curing accelerating effect acts and the curing speed is desirable, but on the other hand, gluing progresses and storage stability is lost. On the other hand, if no curing accelerator is blended, storage stability will be maintained well, but on the other hand, the curing rate will inevitably decrease. As described above, it has been extremely difficult to simultaneously provide an epoxy resin composition with storage stability and fast curing properties in a well-balanced manner.

[Purpose of the invention]

The purpose of the present invention is to solve the above-mentioned problems, and to provide an epoxy resin composition which has extremely good storage stability as a two-component type and whose mixture has excellent fast curing properties at low temperatures. .

[Summary of the invention]

The present inventors have achieved the above-mentioned objective.As a result of intensive research, the following components (a) and (b) have almost no polymerization activity when used alone as a curing accelerator. It has been discovered that, like component (c), high activity can be achieved by combining component (d), which has low activity when used alone, and has completed the present invention.

That is, the epoxy resin composition of the present invention has (a)
Compounds with at least one epoxy group
100 parts by weight (b)° Compound having at least one formimidate group 0. '01 to 60 parts by weight (C) 0.0001 to 20 parts by weight of an organosilicon compound having or producing a silanol group (d) 0.001 to 10 parts by weight of an organic complex compound .

The compound (a) used in the present invention may be any compound having at least one epoxy group, such as bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol A type epoxy resin, etc. Epoxy resin, bisphenol F type epoxy resin,
Phenol-rank type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, complex-containing epoxy resin such as triglycitur isocyanate and hydantoin epoxy, hydrogenated bisphenol A type epoxy resin, propylene greeny luthoglycis aliphatic epoxy resins such as polyether and pentaerythritol-polyglycidyl ether, epoxy resins obtained by the reaction of aromatic, aliphatic or alicyclic carbanoic acid with epichlorohydrin, °spiroyl-containing epoxy resins,
Orun-aryruphenolno? Glycidyl ether type epoxy resin is a reaction product of a rank compound and epichlorohydrin, and glycidyl ether type epoxy is a reaction product of a soaryl pisphenol compound having an allyl group at the ortho position of each hydroxyl group of bisphenol A and epichlorohydrin. Examples include resins, derivatives such as ethylene oxide, globylene oxide, styrene oxide, cyclohexene oxide, and phenyl glycidyl ether, and these compounds may be used alone or as a mixture of two or more.

The compound (b) used in the present invention may be any compound as long as it has at least one formimidate group; for example, it has the general formula: H X + N=C-0R)n ( In the formula, X is an aliphatic group having 1 to 10 carbon atoms, and 3 to 10 carbon atoms.
8 alicyclic group, a substituted or unsubstituted aromatic group, or a methylene group, an oxy group, a keto group, a sulfonyl group, a car-nylimino group, or a divalent heterocycle such as oxazole, triazole, triazino, etc. 6 carbon number 2-20
represents a hydrocarbon group, R represents an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted phenyl group, and n is an integer of 1 to 4. ) are listed.

Aliphatic groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, inpropyl, butyl, isobutyl, pentyl, neopentyl, hexyl, nonyl, decyl, chloromethyl,
Bromomethyl, hydroxypropyl, etc. are substituted or Unsubstituted aromatic groups include phenyl, non-logonated phenyl,
Tolyl, xylyl, naphthyl, quinolyl, anthranyl, pyridyl, nitrophenyl & t-means 2 to 3 carbon atoms bonded via methylene group, oxy group, keto group, etc.
20 hydrocarbon groups include methylenetsuphenylene, oxypropylene, sophenylene/ether, sulfonylsophenylene, 2-oxapropylene, 2-oxypropylene,
It means methylenecyclohexyl, sulfonyldicyclodecyl, etc., and the alkyl group having 1 to 6 carbon atoms is methyl,
It means ethyl, propyl, isopropyl, pentyl, hexyl, methyl, etc., and substituted phenyl groups include hydroxyphenyl, tolyl, xylyl, halogenated phenyl, methoxyphenyl, pentulfenyl, norcagutophenyl, phenoxyphenyl. , two types of lophenyl etc.

Specific examples of this (b) for 11 m include methyl N-phenylformimidate, sophenyl N-hexylformimidate, ethyl N-pentylformimidate,
Methyl N-methylformimidate, methyl N-butylformimidate, ethyl N-cyclohexylformimidate, soethyl N.

N'(methylene-cyP-phenylene) bisformimidate f-1-1N, N'-xylylene bisformimidate, methyl NP-(hydroxypentyl)phenyleneformimidate, soethylene N, N'(sulfonyl-cy) Examples include P-phenylene-bisformimidate, sozolopyr N, N-p, p'-penzophenonylene)formimidate, and at least one selected from the group consisting of these is used. Among these, the component (b), a compound having a formimidate group, can be easily obtained by applying a commonly used method [R.O.H. Lopertz & B. Soei. Gutt (R, H, Roberts & P, J, Vogt,
), Soei Am Chem Tsuk (J, Am, Che
M, Soc, ), 78, 4778 (1956) etc.]. That is, in the general formula: X + NH2)nC, X and n have the same meanings as above. ) and a compound represented by the general formula: HC (OR) Easily synthesized.

If the blending ratio of component (b) is less than 0.01 part by weight, no sufficient effect will be obtained, and if it exceeds 60 parts by weight, the compatibility with the resin will decrease.

The Cl component used in the present invention may be any organosilicon compound having a silanol group or producing a silanol group.

Among these, examples of those having a silanol group include organosilanes and organosiloxanes described below.

That is, the following general formula [I]: (In the formula, R, R', and R# may be the same or different from each other, and each represents an alkyl group, a phenyl group,
represents an aralkyl group, a vinyl group, an allyl group, or 7'-
P + q + r are each positive integers from 0 to 3,
p+q+r is less than 4. ) or the following general formula [n]: (wherein, R5+ R2+
R3+ R4°r R5r Re * Rt may be the same or different and each represents an alkyl group, a phenyl group, a vinyl group, an aralkyl group, an allyl group or a hydrolyzable group, and a, t, x, y is a positive integer of O~2, s+ and x+y are each less than 3, u is a positive integer of WiiO~2, a, b are O
Alternatively, it represents a positive integer of 1 or more. ) is an organosiloxane represented by

Further, examples of those having a hydrolyzable group include organosilanes and organosiloxanes described below.

That is, the following general formula [l]: (wherein, R, R', R#, and R"' may be the same or different, and each represents an alkyl group, a phenyl group, an aralkyl group, and a vinyl group. , allyl groups, p+
Q+r are positive integers from θ to 3, respectively, and p+q+r
is less than 4. ): (In the formula, R1+ R2* Ra + R4
+ Rs + Re + R7 + Rs・Re.

Rlo may be the same or different, such as an alkyl group, a phenyl group, a vinyl group, an aralkyl group,
Allyl group or hydrolyzable group, at least one of them
is a hydrolyzable group. ' + t + x + y is
s+ is a positive integer of 0 to 2, and x and y are each less than 3, u and w are positive integers of O to 2, and a and b are positive integers of 0 or 1 or more. ) is an organosilane represented by

Specific examples of these organosilanes and organosiloxanes include those described in Japanese Patent Publication No. 57-5403, etc., and at least one selected from the group consisting of these is used. If the blending ratio of component (c) is less than 0.0001 part by weight, the curing accelerating effect will be small, and if it exceeds 20 M& parts, the resin properties may deteriorate.

Preferably it is 0.01-1 ONt part.

Examples of the organic complex compound (d) used in the present invention include aluminum (AJ), titanium (Ti), chromium (Cr), zorconium (Zr), copper (Cu), and iron (
Examples include complexes formed with metals such as Fe), manganese (Mn), nickel (Nl), panasium (V), and copal (Co), and at least one selected from the group consisting of these. Seeds are used. Among these organic complex compounds, organic aluminum complex compounds are preferred. Specific examples of this organic aluminum complex compound include alkoxyl groups having 1 to 10 carbon atoms such as methoxy group, ethoxy group, and impropoxy group; acetoxy group, stearoyl group, butyryloxy group, propionyloxy group, and isopropionyloxy group. Acyloxy groups such as; those having aryloxy groups such as phenoxy group and p-methylphenoxy group, and acetylacetone,
Examples include complexes having trifluoroacetylacetone, pentafluoroacetylacetone, ethylacetoacetate, salicylaldehyde, diethylmalonate, etc. as a ligand.

If the blending ratio of component (d) is less than 0.001 parts by weight, the curing accelerating effect will be small, and if it exceeds 10 parts by weight, the resin properties may deteriorate. Preferably 0.01-5
It is a heavy groin area.

The epoxy resin composition of the present invention can be further blended with a phenol derivative to impart high moisture resistance and mechanical strength. The phenol derivative may be anything having a phenolic hydroxyl group, such as phenol, resorcinol, cresol, halogenated phenol, picric acid, hydroquinone, birocatenyl, pyrogallol, aminephenol, etc. '-Sohydroxysophenylpronogun, 4.
4'-dihydroxophenylprono7ane, 4,4'-
Dihydroxysophenylmethane, 3,3'-dihydroxydiphenylpropane, 4,4'-sohydroxydiphenyl ether, 2,4'-sohydroxydiphenyl sulfone, 4,4'-dihydroxy-2,2'-nomethylduff enyl ether, 4,4'-dihydroxysophenylethane, 4,4'-dihydroxysophenyl ether;, leketone, 2-allylphenol, 2-a! J
/L/ Sole; Compounds obtained by reacting these above-mentioned phenol compounds with aldehydes such as formaldehyde and acetaldehyde are mentioned, and at least one kind selected from the group consisting of these is used.

The blending ratio of this phenol derivative is (a) component 100
It is usually 5 to 90 parts by weight, preferably 10 parts by weight.
~50 parts by weight. If the blending ratio is less than 5 parts by weight, sufficient strength may not be obtained, and if it exceeds 90 parts by weight, moisture resistance may be reduced.

The epoxy resin composition of the present invention may further contain an inorganic filler, if necessary. Specific examples of inorganic fillers include fused silica powder, crystalline silica powder, magnesia powder, aluminum powder, silica powder, glass fiber, talc, carbonate powder, barium sulfate powder, etc. Melted with 7 Lika powder, crystalline silica powder is most preferred. The composition of these inorganic fillers depends on the application and the above resin components (epoxy resin fraction and phenolic resin as hardener).
Although it varies depending on the type of inorganic filler, for example, when used in transfer molding, 11 (fat component 10
The amount may be about 150 to 400 parts per 0 parts by weight. In addition, if necessary, release agents such as natural waxes, base waxes, metal salts of straight chain fatty acids, acid amides, esters or paraffins, bromotoluene, hexabromobenzene, antimony trioxide, etc. Flame retardants, colorants such as Carzen Black, silane coupling agents, etc. may be added and blended as appropriate.

The method for producing the epoxy resin composition of the present invention will be explained. The composition of the present invention can be easily produced by, for example, finely pulverizing each of the above-mentioned components and then mixing them with a special mixer. This composition may be as described above as long as it is used at the same time as manufactured, but when used appropriately for various purposes, it may be used, for example, in (a) and (b) as described above.
) and (C), A solution consisting of each component (a), (b) and (
A two-liquid yarn called liquid B is made up of each component of d), and is mixed and used as required. In any case, the components of the two-liquid system may be combined in any combination as long as the components (c) and (d) are prevented from being components of the same solution system. .

In the following 1. The present invention will be explained in more detail with reference to Examples and Comparative Examples.

[Embodiments of the invention]

1 mole of N,N'-methylene-&-P-phinylene-sformimidate (DABM) soaminodiphenylmethane (CDAM) and 2.1 moles of trimethyl orthoformate in the presence of a catalytic amount of acetic acid. , obtained by reaction in methanol (about 80°C).

It was obtained by reacting xylylensoamine l-ryl and 2.1 mol of trimethyl orthoformate in the same manner as in the case of DABM.

Muimidate (AFCFIM) 931.2 P of aniline, 235.3 Y of phenol and 10.4 P of formic acid were charged into a 51 three-necked tube equipped with a stirrer, a thermometer, and a reflux condenser, and heated to 60-75°C. After making it uniform, 202.71 of the forma 11 aqueous solution of Section 37 was added.
．． It was gradually dropped over a period of 5 to 3 hours.

Next, the whole was heated to 90-100°C and reacted for 1 hour, and then the pressure was reduced (final conditions = 155-165°C, 720-1
Water and unreacted components were distilled off. Using 1 mol of the obtained aminophenol compound (AFC) and 1.1 mol of trimethyl orthoformate, it was reacted in the same manner as in the case of DABM.

Epicoat 828 (product name, manufactured by Shell Co., Ltd., epoxy equivalent: 185) 98 y! /C) Lisacetylacetonatoaluminum Uno 2F was added and the whole was heated to 85°C to obtain a uniform liquid A. On the other hand, Epicote 828 9
Add triphenyl 7 ranol 3 to 'l; f, 80
A homogeneous liquid was obtained by heating and dissolving at °C.

These A liquid and B liquid were each left at room temperature for 3 months, but no viscosity change (increase) was observed.

Next, the above-mentioned solutions A and B, and L) ABIVI, XB11″IM and AF obtained by the above synthesis.
Using CFIM and bisphenol A as the phenol gm form, the epoxy resin composition of the present invention was obtained by blending as shown in Table 1.

The resulting composition was applied onto a hot plate kept at a constant temperature, and the time required for gluing was measured. The results are collectively shown in Table @1.

Comparative Examples 1 to 3 Comparative compositions were obtained by blending the components in the composition ratios shown in Table @1. The obtained compositions were evaluated in the same manner as in Examples 1 to 6. The results are collectively shown in 1F.

Examples 7 to 12 Example 1 except that trisacetylacetonatotitanium, trisacetylacetonatochromium, and trisacetylacetonatoturconium were used in place of trisacetylacetonatoaluminum in Examples 1 to 3, respectively.
-A-1 (Ti) solution, A-2 (Cr) in the same manner as in 3.
A-3 (Zr) solution and A-3 (Zr) solution were prepared and 6 shown in Table 2 was prepared.
Various composition systems were prepared.

Using these systems, evaluation tests similar to those in Examples 1 to 6 were conducted, and the time to cure was measured. The results are summarized in Table 2.

Application Examples 1 to 3 and Comparative Examples 1 to 3 (a) Components include cresol nogelac type epoxy resin (epoxy weight: 220) (A) and bisphenol A type epoxy resin (epoxy weight: 450) (2)
), (b) component D A B M (c), (c)
Triphenylmethoxysilane ([), (d) as a component
■ Trisacetoacetatoaluminum as a component, and phenol as a phenol rust conductor. Ralek resin (
Molecular weight = 700) [F], 2-methylimidazole as a curing accelerator (0, Fluid 9 Rough-in City as a moisture resistance modifier).

A composition for application examples was prepared using quartz glass powder (I) and crystalline silica powder (carnauba wax, carbon black, and a coupling agent (epoxy silane type) as inorganic fillers in the composition shown in Table 3). (Application Examples 1 to 3) and compositions for comparative examples (Comparative Examples 1 to 3) were prepared.

Using the obtained composition, an integrated circuit was sealed under molding conditions of 170° C. for 3 minutes. The resin-sealed semiconductor device thus obtained was subjected to a moisture resistance test in high-temperature, high-pressure steam (PCT: 120° C.). For each Example and each Comparative Example, 100 samples were tested, and the number of defective samples after a certain period of time was determined, and the results are shown in Table 3. Incidentally, a case in which the aluminum wiring was broken due to corrosion was determined to be defective.

WJa Table [Effects of the Invention] As detailed above, the epoxy resin composition of the present invention is as follows:
It has extremely good storage stability as a two-component paint, and the mixture has excellent fast curing properties at low temperatures, making it useful for a variety of applications including adhesives and paints. , and its industrial value line is extremely large.

Furthermore, by appropriately selecting the type and composition of the epoxy resin, it can be applied as a so-called solvent-free type for casting, impregnation, molding, etc.

Furthermore, since it is easily soluble in low-boiling point solvents such as sooxane and tetrahydrofuran, it can be easily impregnated and applied to glass cloth, paper, etc., and can also be applied to laminate board molding.

Furthermore, the obtained cured product not only maintains and exhibits excellent mechanical properties and electrical properties, but also has good thermal stability.

Claims (1)

[Claims] 1. (a) 100 parts by weight of a compound having at least one epoxy group (b) 0.01 to 60 parts by weight of a compound having at least one formimidate group (c) silanol group An epoxy resin composition comprising: 0.0001 to 20 parts by weight of an organosilicon compound having or producing a silanol group; and (d) 0.001 to 10 parts by weight of an organic complex compound. 2. The composition according to claim 1, further comprising a phenol derivative. 3. The composition according to claim 1 or 2, wherein the organometallic compound is an organoaluminium complex.