JPS6381123A - Organometallic composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition, consisting of an organometallic compound, OH group-containing compound and hydrolyzable group-containing silicon compound, usable in a solventless system since the composition is liquid at room temperature and suitable as a curing catalyst assistant for epoxy resins. CONSTITUTION:A composition consisting of (A) an organometallic compound, preferably organoaluminum compound having liquid properties at room temperature, e.g. tris(butylacetoacetato)aluminum, (B) a silicon compound having OH groups, preferably a compound, expressed by the formula (R1 and R2 are H, alkyl, aromatic group, unsaturated group or haloalkyl) and having one or more OH groups in the same molecule and (C) a silicon compound having a hydrolyzable groups, preferably a silicon compound capable of forming one or more OH groups by hydrolysis, e.g. trimethylmethoxysilane, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to an organometallic composition preferred as an epoxy resin curing catalyst aid.

(Prior art) As methods for curing epoxy resins by heat curing, curing with aromatic amines or curing with acid anhydrides has been known. A curing catalyst having silanol groups is added to cure the epoxy resin.

However, organoaluminum chelate compounds that are solid at room temperature, such as tris(acetylacetonato)aluminum, tris(ethylacedoacetate)aluminum, and tris(naliteraldehyde)aluminum, have been used until now, and these are added to epoxy resins as caloric compounds. However, it was often used after being melted by heating.

(The pinnacle of what the invention is trying to solve) The present invention has been made in view of the above-mentioned drawbacks of the prior art, and is capable of easily curing epoxy resin.
The purpose is to provide 6 sets of parabolas.

[111th aspect of the invention] (Means and effects for solving the problem in question 1) In the present invention, the organometallic compound is in a liquid state, particularly at room temperature. Tris(butylacetoacetate)aluminum is used.

This tris(acetoacetate)aluminum is used as a curing catalyst for epoxy resin, and the silicon compound having a milanol group is used as a curing catalyst, whether in liquid or solid form. It maintains a moderate condition. In other words, it is not only a catalyst that is added to the epoxy resin and cured in the nine-dimensional state, but also a soluble additive for the epoxy resin, etc.? Alone without wealth! The present invention provides a curing catalyst comprising an organic aluminum chelate compound, a silicon compound containing silanol tV, and a metal organic acid salt. Therefore, when curing the epoxy resin, it has the advantage that it can be conveniently added just before heating and curing.

The present invention will be explained in more detail below. In the present invention, the organometallic compound (a) is an organoaluminum chelate compound, and the organoaluminum chelate compound is preferably an aluminum chelate compound in which various organic groups are coordinated to the aluminum atom. Examples of such ligands include alkyl groups having 1 to 5 carbon atoms, haloalkyl groups having 1 to 5 carbon atoms, methoxy groups, ethoxy groups, butyl groups, and isopropoxy groups.

Alkoxyl having 1 to 5 carbon atoms ia such as Kusunoki: Acyloxy group such as acetoxy group, propionyloxy group, isopropionyloxy group, butyryloxy group, stearocloxy group, benzoyloxy group etc. 4 groups: Phenoxy group,
Tolyloxy group, p-methylphenoxy group, p-methor diphenoxy 4% aryloxy group: and acetylacetone, trifluoroacetylacetone, pentafluoroacetylacetone, ethylacetone acetate, salicylaldehyde, diethylmalonate, β-diketone. .

Specifically, for example, tris(acetylacetonato)aluminum, tris(ethylacetoacetate)aluminum, tris(propylacetoacetate)aluminum, tris(pteracetoacetate)aluminum, tris(pentaacetoacetate)aluminum ) aluminum, tris(heptaacetoacetate)aluminum, tris(diethylmalonato)aluminum, tris(salicylaldehydeto)aluminum, tris(fluoroacetylacetonato)aluminum, tris(propylacedoacetaldehyde)aluminum, etc. Can be mentioned.

These ρ organoaluminum chelate compounds can be used alone or in an appropriate combination of two or more. But that combination gk+'! ) Lith(butylacetoacetate)aluminum is used as an aluminum chelate compound in an amount of 40 tes or more, preferably 80 tes, and as an epoxy resin curing catalyst composition, an organometallic composition is used as an organometallic composition.
~60% by weight, preferably 20-50%! Used in the range of quantities.

Next, the silicon compound in which the OH group in (b) is M has the general formula (R1 is a hydrogen atom, an alkyl group, or an aromatic group.

unsaturated group, herooalkyl group) Specifically, it is expressed as .

and their copolymers, etc. However, these must contain one or more sivcg-bonded OH groups in the same molecule. A part of each substituent may have a partial alkoxy group or a silicone branch.

These silicone compounds do not need to have a single molecular weight, and any type of silicone compound, ranging from a low molecular weight to a single polymer, can be used. These silicon compounds having OH groups can be used as a single component or in an appropriate combination of two or more. Heavy weight, preferably 40-701! Used in a range of quantities.

If the silicon compound having a hydrolyzable group (c) is a compound directly bonded to a silicon atom that can be hydrolyzed to a certain degree or more in the presence of water to produce a silanol hydroxyl group, 'l!
! P1/l: No limit. Examples of such organosilicon compounds include organosilane compounds and organosilokinane compounds described below.

The organosilane compound having a hydrolyzable group used in the present invention has a defective general formula (I) (λ di.

[In the formula, R+ is a hydrolyzable group and has 1 to 5 carbon atoms
alkoxyl group; phenoxy group, tolyloxy group,
p-methoxyphenoxy group, p-nitrophenoxy group,
Aryloxy groups such as p-chlorophenoxy Jij; aralkyloxy groups such as benzyloxy group and phenethyloxy group; acyloxy groups such as acetoxy group, propionyloxy group, butyryloxy group, benzoyloxy group, phenylacetoxy group, formyloxy group; or the following formula (wherein 1% I and R″ may be the same or different,
Represents an alkyl group having 1 to 5 carbon atoms. ), xt, xt, and Xl may be the same or different, and carbon X has 1 to 12 atoms.

Alkyl groups; phenyl group, tolyl group, p-methodiphenyl group, p-nitrophenyl M, p-chlorophenyl group; benzyl group, phenethyl, etc., p-
Methoxybenzyl≦, aralxy groups such as p-methylbenzyl group; alkenyl groups such as vinyl group, allyl group, propenyl group, butenyl group; or acetyl group, benzoyl group,
represents an acyl group such as a trifluoroacedel group, p,
q and r are integers of O to 3. However, p+q+r≦3
It is. ). Examples of these organosilanes include trimethylmethoxysilane.

Triethylmethoxysilane, triprobylmethoxine 2
, tributyl ethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, tri(p-methoxyphenyl)methoxysilane, tri(p-1-)xyJphenyl)ethoxysilane, tri(p-nitrophenyl)methoxysilane, Triacetylmethoxysilane, triacetylethoxysilane, diphenylmethylmethoxysilane, diphenylmethylmethoxysilane, 1-diphenylpropylethoxysilane, 2-butynyldiphenylmethoxysilane, di(2-pentenyl)phenylethoxysilane, phenyldipropylmethoxysilane , phenyldivinylgloboxysilane, phenylvinylmethylmethoxysilane, triisobutylacetoxysilane, triphenylacetoxysilane, diphenylmethylacetquinsilane, diphenyldimethoxysilane, diphenyljethoxysilane, diphenyldipropoxysilane, di(p
-chlorophenyl)jetoxysilane, p-methylbenzyltrimethoxysilane, trifluoroacetyltrimethoxysilane, (wherein φ represents a phenyl group. The same applies hereinafter), and the like.

Furthermore, the organosiloxane compound having a hydrolyzable group used in the invention has a molecular chain consisting of a bifunctional unit represented by the following formula (III) and/or a trifunctional unit represented by the following formula [■]. In some cases, it may contain a tetrafunctional unit represented by It is capped by nine monofunctional units as shown.

Yl (wherein, Yl, Yatsu, Yl, Y4. Y” and Y@
may be the same or different; hydrolyzable group: alkyl group having 1 to 5 carbon atoms; phenyl group, tolyl group.

p-methoxyphenyl group, p-chlorophenyl group.

Aryl groups such as p-nitrophenyl group, p-cyanophenyl group; aralkyl groups such as benzyl group, phenethyl group, p-methoxybenzyl group; alkenyl groups such as vinyl group, allyl group, propenyl group, butenyl group; or acetyl group 2 represents an acyloxy group such as a benzoyl group, a trifluoroacetyl group, etc. ) At least one of the above structural units is
It contains one or more hydrolyzable properties. Among these organosiloxane compounds, it is particularly preferable to use those having a degree of polymerization of 50 or less and an equivalent weight of a hydrolyzable group of 1000 or less, and more preferably one having an equivalent weight of a hydrolyzable group of 50 to 500. It is something.

As such an organosiloxane compound, for example, 1
．． 3-dimethoxy-1,3-dimethyl-1,3-diphenyl disiloxane, 1,5-jethoxy-1,3,
5-) Limeter-1,3,5-triphenyltrisiloxane, 1,7-simethoxy1,3,5,7-titramethyl-1,3,5°7-titraphenyltetrasiloxane, 1t3-dimethoxy-tetraphenyldi Siloxane, 1°5-dimethoxy-3,3-dimethyl-1,115
, 5-tetraphenyltrisiloxane, 1,3゜5-trimethoxybentaphenyltrisiloxane% 1.5
-dimethoxy-hexa(p-methoxyphenyl)trisiloxane, φ 抛φ からF margin OCR.

φ-8i-CH1 fermentation HsC-8i-φ and 0CH.

etc.

In the present invention, V! Hydrolyzable group to be river? The M isosilicon compound having the above-mentioned organosilane and organosiloxane compounds is one or more selected from the group consisting of organosilane and organosiloxane compounds. ) can be used in a range of 30 to 80 times, preferably 40 to 70 times, as an organosilicon compound.

As for the metal organic acid salt other than the organoaluminum chelate compound in (g), a metal organometallic soap is used.

Naphthenic acid, stearic acid, octylic acid, etc. are generally used as organic acids in organometallic soaps.

Among these organic acids, octylate is selected and used. Heavy metal octolates have oil-soluble properties and are accepted as drying agents for printing inks or paints.

Regarding the present invention, among the many metal salts of octylic acid, tin octylate and zinc octylate are particularly important. Select.

The above is an OH group produced by hydrolysis of an organic aluminum chelate compound, which is the main component of the organic gold lacquer of the present invention, and an OH group during curing of the epoxy resin. It acts as an epoxy resin curing catalyst aid that accelerates the catalytic curing of silicon compounds. For Formulation 1, the metal content is 0.01 to 3 times as 8% by weight octylate.

Preferably 0.1-1! Used within the scope of telephone staff.

The present composition has the advantage that it can be used without a solvent.

However, it can also be used as a solvent-based paint.

(Example) Tris(butylacetoacetato)aluminum, a liquid organoaluminum chelate compound which is the main component of the present invention, was synthesized in a reaction vessel using tris(ethylacetoacetato)aluminum [(Yoken 7 Aire Chemical Co., Ltd.)] fi) is white in appearance, crystalline, and has a melting point of about 75℃.
Keep it at 0℃~105℃ and heat it for 1 hour while stirring.
0th heating temperature 2 io.

℃ to 105℃, the volatile components were removed in 2 hours under reduced pressure of 1 to 3 mmHj, and the reaction was completed.The appearance of the obtained tris(buteracetoacetate)'aluminum was yellow liquid. The viscosity is 3584 (Cp8/2 s
℃) to this ″f4 value was 0.45 yen.The viscometer used was E-Viscometer 2 manufactured by Tokyo Keiki Co., Ltd.

The following nine compounds used in the present invention are diphenyldimethoxysilane (manufactured by Toshiba Silicone), a pale yellow transparent liquid with a viscosity of 5 (CpS/25°C), and diphenyldimethoxysilane (manufactured by Toshiba Silicone).
Toshiba silicone! ! Appearance Pale yellow transparent liquid, viscosity 6
(Cps 725°C), Triphenylmethoxy 7 run (Toshiba Silicone II) Appearance, white crystals, melting point 40-60°C
, Triphenylethoxysilane (manufactured by Toshiba Silicone) Appearance: white crystals, melting point: 50-70°C, Diphenylsilanediol (manufactured by Toshiba Silicone): Appearance: white crystals, melting point: 130~
150°C, Triphenylsilanol (manufactured by Toshiba Silicone) Appearance: White crystals Melting point: 140-160°C, 8Llj Octyl L Nocturnal Zinc (manufactured by Nihon Kagaku Sangyo) Appearance: Pale yellow solid or paste.

Composition of Table 1 Example (1) to (2) The composition of Table 1 was stirred in a chamber for 61 hours to obtain a pale yellow liquid composition 3 ( The viscosity of 1) is 25 (c
ps/25℃), my friend. Also, the viscosity of Example (2) was 29
(cps/25°C).

5 PHR of the obtained organometallic composition of the present invention was added to an epoxy resin, Nipico-) 82B (Yuka shell fi),
Cured for 12 hours at a heating temperature of 150°C using a single-sided Teflon Koh Lang mold with a spacer of lrrm thickness,
A test piece with a size of 1 tXlXloommX100 was obtained. The electrical properties of this test piece include a volume resistivity of 4 x 10" Ω Cat and a dielectric constant of 2.8 (50
Hz), and the dielectric top layer was 2.31.

Examples (3) to (6) The composition shown in Table 1 was heated to 80°C to uniformly dissolve it to obtain a liquid product, and the viscosity of Example fO (3) was 493 (cps/
(30℃), the viscosity of (4) is 516 (cps/30℃)
, (5) has a viscosity of 1587 (cps/30°C), (6)
The viscosity is 2010 (cps/30°C).

These organometallic compositions are the same as in Examples (1) to (2),
3 to 7 PHR was added to Epikote 828 and cured by heating, and the properties of the compound were the same as in Examples (1) and (2).

〔Effect of the invention〕

According to the present invention, since the epoxy resin is liquid at room temperature, the epoxy resin can be used without a solvent, making it easy to handle.

Agent Patent Attorney Noriyuki Chika Same bamboo flower Kikuyu

Claims (5)

[Claims] (1) An organometallic composition that is liquid at room temperature and is used as a curing catalyst for an epoxy resin, which is composed of an organometallic composition, a silicon compound having an OH group, and a silicon compound having a hydrolyzable group. (2) Claim 1 in which the organometallic compound is an organoaluminum chelate compound having liquid properties at room temperature.
The organometallic composition described in . (3) A silicon compound having an OH group has 1 OH group in the same molecule.
The organometallic composition according to claim 1, which is a silicon compound having one or more OH groups. (4) Silicon compound having a hydrolyzable group The organometallic composition according to claim 1, which is a silicon compound that generates one or more OH groups upon hydrolysis. (5) The organometallic composition according to claim 1, wherein the organometallic compound is a metal organic acid salt other than an organoaluminum chelate compound.