JPH08337708A - Epoxy resin composition - Google Patents

Abstract

PURPOSE: To obtain an epoxy resin composition comprising an epoxy resin, an organic metal compound, and an organic Si compound containing) (an Si-H group-having repeating unit, and giving a cured product excellent in dimensional stability, physical characteristics and electric characteristics by the irradiation of light. CONSTITUTION: This epoxy resin composition capable of giving a cured product excellent in dimensional stability and good in physical characteristics, mechanical characteristics, electric characteristics, etc., in a short time by the irradiation of light comprises (A) an epoxy resin (e.g. a bisphenol A epoxy resin), a (B) an organic metal compound (e.g. tris-ethylacetoacetateacetate aluminum), (C) an organic Si compound having a repeating unit of the formula [R is H, a 1-24C (substituted)alkyl, a 6-24C (substituted)aryl, an aromatic heterogeneous ring group, a 7-24C (substituted)aralkyl] (e.g. polysilane), and further, a photosensitizer (e.g. benzophenone).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an epoxy resin composition which can be polymerized by irradiation with light.

[0002]

2. Description of the Related Art Epoxy resin compositions have been used as electric, electronic devices, aviation, vehicles, etc. until now, as paints, adhesives, encapsulants, etc., which have excellent heat resistance, chemical resistance, and electrical characteristics.
It is widely used in a wide range of fields such as civil engineering and construction. Recently, attention has been paid to a technique of polymerizing an epoxy resin composition by irradiating it with light from the viewpoint of energy saving and workability, and the technique is mainly classified into the following two types.

First, the epoxy resin itself is modified with a vinyl group-containing compound such as acrylic acid having photopolymerizability, and the epoxy resin is photopolymerized via the introduced vinyl group. However, the epoxy resin modified with the vinyl group-containing compound has a problem that the adhesion and heat resistance are extremely lower than those of the unmodified epoxy resin.

On the other hand, the second one is one in which an epoxy resin is cured by using a photolytic catalyst. As a catalyst that can be used at this time, for example, a complex represented by the following formula can be mentioned {Macromolecules, Volume 10,
1307, 1977 [Macromolecules, Vol. 10, 1307 (197
7)]; Journal of Radiation Curing Volume 5, page 2, 1978 [Journal of Radiation Curing
ing, Vol. 5, 2 (1978)]; Journal of Polymer Science, Polymer Chemistry Edition, Volume 17, p. 2877, 1979 [Journal of Polymer Sci
ence, Polymer Chemistry Edition, Vol. 17, 2877 (197
9)]; ibid., Vol. 17, page 1047, 1979 [ibid., Vol. 17,
1047 (1979)]; Journal of Polymer Science Polymer Letters Edition, Volume 17, 759.
Page, 1979 [Journal of Polymer Science, Polymer Le
tters Editoin, Vol. 17, 759 (1979)]; JP-A-55-
65219; U.S. Pat. No. 4,690,054; British Patent No. 1516511; British Patent No. 1.
No. 518141, etc.}.

[0005]

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Therefore, although the cured product of the epoxy resin composition obtained by using the above-mentioned catalyst has good physical properties such as heat resistance and mechanical properties, the catalyst which is a strong acid is ionic. Due to remaining as impurities,
The electrical properties of the cured product tend to deteriorate, and the corrosion resistance is insufficient and deterioration progresses over time.
It was not satisfactory in terms of workability and handling.

On the other hand, an organometallic compound and an α-ketosilyl compound are blended as a catalyst which does not remain as an ionic impurity in a cured product and can cure an epoxy resin in a short time. An epoxy resin-based composition comprising the above is also proposed in JP-A-57-125212. However, until now, when an epoxy resin was cured using such a catalyst, there was a problem that volume shrinkage generally accompanies polymerization of the epoxy resin, and shrinkage occurs in a molded product of the cured product.

[0008]

As described above, in the epoxy resin composition containing the conventional catalyst, a cured product having excellent dimensional accuracy is obtained due to the volume shrinkage when the epoxy resin is cured. The problem of being difficult to obtain could not be avoided.

The present invention has been made to solve such a problem, and is to obtain a cured product having excellent dimensional accuracy and good physical properties, mechanical properties, electrical properties and the like in a short time. The object is to provide an epoxy resin composition capable of

[0010]

The epoxy resin composition of the present invention comprises: (a) an epoxy resin (b) an organometallic compound (c) an organic compound having a repeating unit represented by the following general formula (1): It contains a silicon compound. That is, the epoxy resin composition of the present invention is characterized in that polysilane having a hydrogen atom directly bonded to a silicon atom in a side chain is used as a catalyst for curing an epoxy resin together with an organometallic compound.

[0011]

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In the present invention, the epoxy resin as the first component can be used without particular limitation as long as it has at least one, preferably 2 to 5 epoxy groups in the molecule. Examples of the epoxy group of

[0013]

[Chemical 4] Etc. Further, the epoxy resin may have an unsaturated double bond in the molecule represented by an acrylic modified epoxy resin, and such an epoxy resin includes, for example, a group having an unsaturated double bond shown below. Those introduced into the molecule can be used.

[0014]

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In the present invention, in these epoxy groups and groups having an unsaturated double bond, the hydrogen atom bonded to the carbon atom is a halogen atom such as a chlorine atom, a bromine atom or a fluorine atom, or a carbon number of 1 to 12. It may be substituted with an alkyl group, a phenyl group or the like. Examples of the alkyl group here include a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, n-butyl group, isobutyl group, sec
Examples include -butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group and dodecyl group. Further, two or more kinds of groups having an epoxy group and an unsaturated double bond may be introduced in combination in the molecule.

The above-mentioned acrylic modified epoxy resin can be arbitrarily synthesized by a molecular design according to the purpose, and a monofunctional or polyfunctional epoxy compound and an unsaturated carboxylic acid are mixed with a catalyst such as choline chloride. The reaction may be carried out in an organic solvent in the presence of. The unsaturated carboxylic acid at this time, for example, acrylic acid, methacrylic acid, cinnamic acid,
Maleic acid and derivatives thereof may be used.

On the other hand, examples of monofunctional epoxy compounds that can be used here include ethylene oxide,
Examples thereof include propylene oxide, butylene oxide, styrene oxide, phenyl glycidyl ether, butyl glycidyl ether and the like. The polyfunctional epoxy compound is not particularly limited as long as it is generally known as an epoxy resin, and is a bisphenol A type epoxy resin; a bisphenol F type epoxy resin; a phenol novolac type epoxy resin; an alicyclic epoxy resin; Heterocyclic epoxy resins containing triglycidyl isocyanurate, hydantoin epoxy, etc .; hydrogenated bisphenol A type epoxy resins; propylene glycol-diglycidyl ether,
Aliphatic epoxy resin such as pentaerythritol-polyglycidyl ether; glycidyl ester type epoxy resin obtained by reaction of aromatic, aliphatic or alicyclic carboxylic acid with epichlorohydrin; spiro ring-containing epoxy resin; o-allyl- Glycidyl ether type epoxy resin which is a reaction product of a phenol novolac compound and epichlorohydrin; glycidyl ether type epoxy resin which is a reaction product of a diallyl bisphenol compound having an allyl group at the o-position of each hydroxyl group of bisphenol A and epichlorohydrin Etc. are illustrated. In addition, these monofunctional or polyfunctional epoxy compounds can be used individually or in mixture of 2 or more types.

Further, examples of the acrylic modified epoxy resin as described above will be specifically shown below. However, all the epoxy resins here are acrylic groups in the formula: —COOCH =
Instead methacrylic group CH _2: -COOC (CH ₃₎
It may be the one in which = CH ₂ is introduced.

[0019]

[Chemical 6]

[0020]

[Chemical 7]

[0021]

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In the present invention, particularly by using the acrylic modified epoxy resin, it is possible to increase the number of cross-linking points when the acrylic modified epoxy resin is cured, and it is possible to further increase the mechanical strength of the obtained cured product. However, since the acrylic modified epoxy resin has lower adhesiveness, heat resistance, etc. of itself than the unmodified epoxy resin, the compounding amount of the acrylic modified epoxy resin in all the epoxy resins should be set to 5 to 95% by weight. preferable. In the present invention, examples of the second component, an organometallic compound, include various metal complexes, metal oxides, metal-containing halides, complex salts and the like. Among them, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, aluminum, zirconium, and the like, an alkoxy group, a phenoxy group, an acyloxy group, a β-diketonato group, an o-carbonylphenolate. Those having a group bonded thereto are preferable.

Here, the alkoxy group has 1 to 1 carbon atoms.
10, such as methoxy group, ethoxy group, n-propoxy group, n-butoxy group, sec-butoxy group, tert-
Butoxy group, n-pentyloxy group, n-hexyloxy group, n-hebutyloxy group and the like can be mentioned. As the phenoxy group, a phenoxy group, an o-methylphenoxy group,
o-methoxyphenoxy group, p-nitrophenoxy group,
2,6-dimethylphenoxy group and the like, and as the acyloxy group, acetato, propionato, isopropionato, butyrate, stearate, ethylacetoacetato, propylacetoacetato, butylacetoacetato,
Examples of the ligand include diethyl malolato and dibivaloylmethanato. Examples of the β-diketonato group include acetylacetonato, trifluoroacetylacetonate, hexafluoroacetylacetonate, and the like.

[0024]

[Chemical 9] And the like. Examples of the o-carbonylphenolate group include salicylaldehyde.

Further, in the present invention, it is preferable to use an organoaluminum compound as the organometallic compound because it is possible to cure the epoxy resin in a particularly short time. Specifically, for example, trismethoxyaluminum, trisethoxyaluminum, trisisopropoxyaluminum, trisphenoxyaluminum, trisparamethylphenoxyaluminum, isopropoxydiethoxyaluminum, trisbutoxyaluminum, trisacetoxyaluminum, trisstearatoaluminum, trisbutyrate. Latoaluminum, trispropionato aluminum, trisisopropionato aluminum, trisacetylacetonato aluminum, tristrifluoroacetylacetonato aluminum, trishexafluoroacetylacetonato aluminum,
Aluminum trisethylacetoacetato, aluminum trissalicylaldehyde, trisdiethylmalolatoaluminum, aluminum trispropylacetoacetato, aluminum trisbutylacetoacetato, aluminum trisdivivaloylmethanato, aluminum diacetylacetonatodivivaloylmethanato,

[0026]

[Chemical 10] Etc. can be used.

In the organometallic compound used in the present invention, it is not necessary that all the bonds of the metal atom are bonded to the ligand, and for example, aluminum has one or two alkoxy groups, phenoxy groups, Acyloxy group, β-
It may be bonded to a diketonato group, an o-carbonylphenolate group or the like. The above-mentioned organometallic compounds may be used alone or in combination of two or more.

In the epoxy resin composition of the present invention,
The amount of the organometallic compound is 0.0 with respect to the epoxy resin.
It is preferably set to 01 to 10% by weight, more preferably 0.1 to 5% by weight. This is because if the content of the organometallic compound is less than 0.001% by weight, the polymerization efficiency when curing the epoxy resin tends to be insufficient, and conversely if it exceeds 10% by weight, the cured product adheres well. This is because there is a possibility that the property and the like may be deteriorated and the cost may be increased.

Further, the organosilicon compound which is the third component of the present invention is not particularly limited as long as it is a polysilane having a hydrogen atom directly bonded to a silicon atom in its side chain.
It may be a homopolymer or a copolymer having the repeating unit represented by the general formula (1), or a copolymer with another repeating unit. In the present invention, such polysilane can be irradiated with light or heated to
After the bond between the silicon atom and the hydrogen atom is broken, it is oxidized by taking in oxygen and moisture in the atmosphere, etc., and forms a silanol hydroxyl group. At the same time, the main chain Si-Si
Similarly, the bond can be cleaved and then oxidized to form a silanol group.

Therefore, in the epoxy resin composition of the present invention, the silanol hydroxyl group thus produced exhibits a high catalytic activity with respect to the epoxy resin and can cure the epoxy resin in a very short time and with sufficient polymerization efficiency. it can. Moreover, as described above, the volume of the polysilane expands due to the incorporation of oxygen and the like when the polysilane is oxidized, so that the volume contraction due to the polymerization of the epoxy resin is offset. As a result, it becomes possible to effectively suppress the occurrence of shrinkage in the molded product of the cured product, and the polysilane here becomes an ionic impurity that causes the deterioration of the electrical properties and the like, and becomes It does not remain.

Further, in the present invention, polysilane in which R in the general formula (1) is a substituted or unsubstituted aryl group having 6 to 24 carbon atoms or an aromatic heterocyclic group is particularly preferably used. This is because when R in the general formula (1) is, for example, a hydrogen atom or an alkyl group, the silanol hydroxyl groups generated during curing of the epoxy resin react with each other and the catalytic activity is easily deactivated. On the other hand, when the aromatic ring is directly bonded to the silicon atom, the silanol hydroxyl group is stabilized, and as a result, the epoxy resin can be cured with extremely sufficient polymerization efficiency. Here, specific examples of polysilane that can be preferably used in the present invention will be shown.

[0032]

[Chemical 11]

Such polysilanes can be obtained by the reductive coupling reaction of RSiHCl _{2 in} the presence of a sodium catalyst and RSi in the presence of a titanium or zirconium catalyst.
It can be synthesized by dehydrogenation reaction of H ₃ , electrolytic polymerization and the like.
Further, here, a copolymer is synthesized by copolymerizing with R'R "SiCl ₂ (where R'and R" represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group) by, for example, a reductive coupling reaction. You can also Further, from the viewpoint of controlling the degree of polymerization, RSiHACl (where A represents a terminal group) and the like may be copolymerized in an appropriate amount.

However, when polysilane is synthesized by the reductive coupling reaction, the sodium catalyst remains as an ionic impurity in the polysilane, resulting in deterioration of electrical properties and the like in the cured product of the epoxy resin composition. There is a risk. On the other hand, the polysilane synthesized through the dehydrogenation reaction using a zirconium catalyst does not contain ionic impurities at all, and the silanol-containing hydroxyl group bonded to the silicon atom at the polymer end is not formed. It can be used particularly preferably in the invention.

The degree of polymerization of the polysilane used in the present invention is preferably about 5 to 10,000, more preferably about 10 to 6,000. The reason for this is that when the degree of polymerization of polysilane is lower, when curing the epoxy resin composition of the present invention by light irradiation, polysilane tends to absorb less light and the polymerization efficiency tends to decrease, while the degree of polymerization of polysilane is higher. If it is too much, the compatibility with the epoxy resin and the organometallic compound becomes small and the preparation of the epoxy resin composition of the present invention becomes complicated.

In the epoxy resin composition of the present invention,
The compounding amount of the polysilane as described above is preferably set to 0.1 to 20% by weight, and more preferably 1 to 10% by weight based on the epoxy resin. This is because if the amount of polysilane blended is less than 0.1% by weight, the polymerization efficiency at the time of curing the epoxy resin tends to be insufficient, and conversely 20% by weight.
This is because when the amount exceeds the above range, the amount of polysilane photooxide remaining in the cured product of the epoxy resin composition increases and the cost also increases.

Further, in the epoxy resin composition of the present invention,
In particular, in consideration of curing the epoxy resin by light irradiation, it is preferable to appropriately add a photosensitizer.
The photosensitizer here may be selected according to the type of epoxy resin and the light source used for curing it,
For example, aromatic hydrocarbon and its derivative, benzophenone and its derivative, o-benzoylbenzoic acid ester and its derivative, acetophenone and its derivative, benzoin, benzoin ether and its derivative, xanthone and its derivative, thioxanthone and its derivative, disulfide compound, Examples thereof include quinone compounds, halogenated hydrocarbon group-containing compounds and amines.

Specifically, as aromatic hydrocarbons and their derivatives, for example, benzene, benzene-d ₆ , toluene,
p-xylene, fluorobenzene, chlorobenzene, bromobenzene, iodobenzene, naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, 1-fluoronaphthalene, 1-chloronaphthalene, 2-chloronaphthalene, 1-bromonaphthalene, 2-bromo Naphthalene, 1
-Iodonaphthalene, 2-iodonaphthalene, 1 naphthol, 2-naphthol, biphenyl, fluorene, p
-Terphenyl, acenaphthene, p-quaterphenyl, triphenylene, phenanthrene, azulene, fluoranthene, chrysene, pyrene, 1,2-benzpyrene, anthracene, 1,2-benzanthracene, 9,
Examples thereof include 10-dichloroanthracene, 9,10-dibromoanthracene, 9,10-diphenylanthracene, perylene, tetracene and pentacene.

As benzophenone and its derivatives,
Examples thereof include benzophenone, 2,4-dimethylbenzophenone, 2,4-dichlorobenzophenone and 4,4'-bis (dimethylamino) benzophenone.

Examples of the o-benzoylbenzoic acid ester and its derivative include, for example, o-benzoylbenzoic acid methyl ester, o-benzoylbenzoic acid ethyl ester, o.
-Benzoylbenzoic acid phenyl ester,

[0041]

[Chemical 12] Etc.

As acetophenone and its derivatives,
For example, acetophenone, 4-methylacetophenone, 3
-Methyl acetophenone, 3-methoxy acetophenone, etc. are mentioned.

Examples of benzoin, benzoin ether and its derivatives include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin triphenylsilyl ether,

[0044]

[Chemical 13] Etc.

Examples of xanthone and its derivatives include xanthone, 2,4-dimethylxanthone and 2,4.
-Dichloroxanthone and the like. Examples of thioxanthone and its derivatives include thioxanthone, 2,
4-dimethylthioxanthone, 2,4-dichlorothioxanthone and the like can be mentioned. Examples of the disulfide compound include

[0046]

Embedded image Etc.

Examples of the quinone compound include benzoquinone, naphthoquinone, anthraquinone, 5,12-naphthacenedione and 2,7-pyrendione. Examples of the halogenated hydrocarbon group-containing compound include carbon tetrachloride, hexachloroethane, carbon tetrabromide,

[0048]

[Chemical 15]

[0049]

Embedded image Etc. Examples of amines include diphenylamine, carbazole, triphenylamine,

[0050]

[Chemical 17] Etc.

Other photosensitizers other than these are propiophenone, anthrone, benzaldehyde, butyrophenone, 2-naphthylphenyl ketone, 2-naphthaldehyde, 2-acetonaphthone, 1-naphthylphenyl ketone, 1-acetonaphthone, 1 -Naphthoaldehyde, fluorenone, 1-phenyl-1,2-propanedione, benznitrile, acetone, biacetyl, acridine orange, acridine, rhodamine B, eosin,
Fluorescein,

[0052]

Embedded image Etc.

In the present invention, the above-mentioned photosensitizers may be used alone or in combination of two or more, and the compounding amount thereof is 0.001 to 10 relative to the epoxy resin.
It is preferable to set the content by weight, more preferably 0.01 to 5% by weight. That is, if the blending amount of the photosensitizer is less than 0.001% by weight, the improvement in sensitivity when curing the epoxy resin by light irradiation is small, and conversely if it exceeds 10% by weight,
The residual amount of the photosensitizer in the cured product of the epoxy resin composition increases.

The epoxy resin composition of the present invention can be prepared as a solvent-free liquid form or solid form at room temperature by appropriately selecting the type of epoxy resin and the compounding ratio of each component. . Further, it is also possible to dissolve each component in an organic solvent to prepare the epoxy resin composition of the present invention. As the organic solvent here, for example, toluene, an aromatic solvent such as xylene, cyclohexane, etc. Aliphatic solvents, ketone solvents such as acetone and methyl ethyl ketone, ester solvents such as cellosolve, and the like can be used. Further, the epoxy resin composition of the present invention,
In addition to the components described above, components such as an acid anhydride, a phenol derivative, a colorant such as a pigment, and an inorganic filler may be blended as necessary.

In the epoxy resin composition of the present invention,
In curing the epoxy resin, light irradiation, heating or a combination thereof, and further methods such as light irradiation and after-cure may be appropriately adopted, but light irradiation alone or a combination of light irradiation and heating or after-cure. It is preferred to cure the epoxy resin by. The wavelength of the light to be applied at this time varies depending on the composition of the epoxy resin-based composition, but is usually preferably about 180 to 700 nm, and the irradiation of ultraviolet rays is particularly effective.

The light irradiation time is appropriately set depending on the composition of the epoxy resin composition and the light source used, but is usually 1 second to 180 minutes, preferably several seconds to 10 minutes. On the other hand, when the epoxy resin is cured by a combination of light irradiation and heating, the heating temperature may be set in the range of 20 to 200 ° C, and further 60 to 150 ° C in consideration of the composition of the epoxy resin composition. preferable. Furthermore, when after-curing is performed after light irradiation, depending on the composition of the epoxy resin-based composition, the temperature is 50 to 200 ° C., preferably 100 to 180 ° C., for 10 minutes to 10 hours, preferably about 20 minutes to 5 hours. Just heat.

The light source used herein is not particularly limited as long as it is a commonly used light source, and examples thereof include a low pressure mercury lamp, a high pressure mercury lamp, a carbon arc lamp, a metal halogen lamp, a xenon-mercury lamp, and a xenon. Lamp, hydrogen discharge tube, tungsten lamp, halogen lamp, sodium discharge tube, neon discharge tube, argon discharge tube, He-Ne laser, Ar ion laser,
Examples thereof include N ₂ laser, Cd ion laser, He-Cd laser, dye laser and the like. In the present invention, these may be used alone or in combination.

As described above, the epoxy resin composition of the present invention can be prepared in liquid or solid form at room temperature,
It can be widely used for casting, impregnation, molding, etc. Therefore, it can be preferably used for various applications such as paints, adhesives, sealing materials, electric insulating materials, inks, surface coating materials, and plate-making materials.

[0059]

Examples of the present invention will be described below. Example 1 First, as an epoxy resin, Celoxide 2021 (trade name, manufactured by Daicel; alicyclic, epoxy equivalent 145), Epicoat 828 (trade name, manufactured by Shell Chemical Co .; bisphenol A type, epoxy equivalent 190 to 210) and epicoat 1001 (trade name, manufactured by Shell Chemical Co .; bisphenol A type, epoxy equivalent 450 to 525, molecular weight 900);
Trisethylacetoacetatoaluminum (TEAACA), trispropylacetoacetatoaluminum (TPAAA), trisacetylacetonatoaluminum (TAANA) and trissalicylaldehidatoaluminum (TSAA) as organometallic compounds; polysilane (PS-) as organosilicon compound 1) to (PS-5) and triphenylbutyloxysilane; benzophenone and thioxanthone as photosensitizers were mixed according to the formulations shown in Table 1 to prepare epoxy resin compositions of Examples or Comparative Examples. Furthermore, instead of the organometallic compound and the organosilicon compound, an epoxy resin-based composition of Comparative Example using triphenylsulfonium hexafluoroarsinate as a catalyst was also prepared. However, the compounding amounts of the respective components in the table all indicate parts by weight, and the same applies to the following. The chemical formulas of polysilanes (PS-1) to (PS-5) used here are shown below.

[0060]

[Chemical 19]

Next, these epoxy resin-based compositions were
It was applied on a tin plate treated with No. 400 sandpaper to form a coating film. Subsequently, three 80 W / cm air-cooled mercury lamps were introduced into the photo-curing box arranged at a height of 10 cm from the conveyor surface, and the conveyor speed was 10 m / m.
As a result, the curing of the epoxy resin proceeded. At this time,
Light irradiation in the box was repeated until all curing was completed by finger touch, and the number of repetitions was counted.

After curing, the pencil hardness and adhesion of the cured product were measured, and the number of days until gelation was examined when the epoxy resin composition was left in the dark at 25 ° C. before curing the epoxy resin. . However, regarding the adhesion of the cured product here, a peeling test using an adhesive tape was performed after putting a scoring scratch on the cured product of the coating film, and the scoring scale remaining on the tin plate in 100 scoring scales was evaluated. It was evaluated by the number. Furthermore, the specific gravity of the epoxy resin composition before curing and the specific gravity of the cured product were determined and compared with each other to calculate the volume shrinkage rate of the epoxy resin during curing. The results are also shown in Table 1. As shown in Table 1, sample No. 1 which is an example of the present invention. It can be seen that with the epoxy resin compositions 1 to 7, a cured product having a small volume shrinkage and good physical properties, mechanical properties, etc. can be obtained by light irradiation for a short time.

[0063]

[Table 1]

Example 2 Sample No. 1 of Example 1 1. Epoxy resin composition 100
Titanium oxide, calcium carbonate, zinc stearate, phthalocyanine green, phthalocyanine blue, and carbon black are used as pigments, respectively, based on parts by weight.
Sample No. Epoxy resin compositions 1 to 6 were prepared. Also, the sample N of Example 1
o. To 100 parts by weight of 10 epoxy resin composition,
10 parts by weight of carbon black was blended to prepare Sample No. 7
An epoxy resin composition of Comparative Example was prepared.

Then, for these epoxy resin compositions, a cured product of a coating film was obtained on a tin plate in the same manner as in Example 1, and then the dryness to touch, pencil hardness, adhesion and volume shrinkage were measured. Was done. The results are also shown in Table 2. As shown in Table 2, the sample No. Good results were obtained for all of the epoxy resin compositions of Examples 1 to 6.

[0066]

[Table 2]

Example 3 First, as an epoxy resin, Celoxide 2021 and Chissonox 234 (trade name, manufactured by Chisso Corporation, alicyclic epoxy resin, epoxy equivalent of about 140), TEAACA as an organometallic compound, and polysilane as an organosilicon compound. (PS-1), (PS-3) to (PS-5), phthalocyanine green as a pigment, an inorganic filler having a purity of 99% or more, a thickness of 4 μm, and a particle size of 20 to 24 mesh,
Glass flakes having an apparent specific gravity of 0.29 g / ml were blended according to the formulations shown in Table 3 to prepare epoxy resin compositions of Examples or Comparative Examples. Furthermore, instead of the organometallic compound and the organosilicon compound, an epoxy resin-based composition of Comparative Example using triphenylsulfonium hexafluoroarsinate as a catalyst was also prepared.

Next, these epoxy resin-based compositions were uniformly mixed, and then rust was removed beforehand with sandpaper and degreasing cleaning was performed to 120 mm × 40 mm × 1.6 m.
A 0.5 mm thick coating was applied on a m-sized mild steel substrate. Subsequently, the resin was introduced into an ultraviolet irradiation device equipped with a metal halide lamp of 80 W / cm for 3 minutes to cure the epoxy resin.

Thereafter, each sample was treated with a 5% caustic soda solution,
By immersing in a 15% hydrochloric acid solution or tap water and observing the presence or absence of rust and the coating state, an alkali resistance test,
An acid resistance test and a water resistance test were conducted respectively. Separately from this, in exactly the same manner as in Example 1, the volumetric shrinkage rate of the epoxy resin during curing was calculated. The results are also shown in Table 3. As shown in Table 3, sample No. 1 which is an example of the present invention. It is apparent that in Nos. 1 to 4, a cured product having a small volume shrinkage and excellent corrosion resistance was obtained.

[0070]

[Table 3]

Example 4 First, as the epoxy resin, Celoxide 2021 and Epicoat 828, TEAACA as the organometallic compound,
Polysilane (PS-1), (P
S-4), (PS-5), and benzophenone as a photosensitizer were blended according to the formulations shown in Table 4 to obtain a sample N.
o. Epoxy resin compositions 1 to 4 were prepared. on the other hand,
6 pieces of plain weave glass cloth that had been cut to a size of 0.12 mm x 10 cm x 20 cm in advance were stacked, and the whole of them was 1 mm wide
The glass cloth was impregnated with each of the epoxy resin compositions uniformly sandwiched between two glass plates with the silicone rubber of (1) interposed therebetween as spacers at 60 to 80 ° C. under a pressure of 3 mmHg.

Then, this glass cloth was placed in a 1 kW high pressure mercury lamp H1000PQ (manufactured by Tokyo Shibaura Electric Co., Ltd.) for 2 times.
It was introduced into the main photocuring box and irradiated with ultraviolet rays for 3 minutes while rotating at a speed of 5 times / min. continue,
The epoxy resin was cured by heating at 150 ° C. for 30 minutes to prepare a resin plate having a thickness of 1 mm.

Thereafter, the dielectric loss tangent value tan δ and the volume resistivity at 180 ° C. were measured for each sample. Separately from this, the number of days until gelation when the epoxy resin composition was left in the dark at 20 ° C. was examined prior to the curing of the epoxy resin, and the curing of the epoxy resin was performed in the same manner as in Example 1. The volumetric shrinkage rate was calculated. The results are also shown in Table 4. As is clear from Table 4, it was possible to obtain a cured product having a small volume shrinkage and good electric characteristics in any of the epoxy resin compositions.

[0074]

[Table 4]

Example 5 First, a 10% solution of polyvinyl alcohol having a polymerization degree of about 500 dissolved in water was prepared, and 40 g of this solution and TH-106 (trade name, heat-sensitive color former manufactured by Hodogaya Chemical Co., Ltd .: 2- (2-chlorophenylamino)
-6-diethylaminofluorane) 4 g and diameter 3 mm
90 g of the glass beads of 3 were kneaded in a stainless steel container for 3 hours to prepare a first composition. Then, 40 g of the same 10% polyvinyl alcohol solution was added to 7 g of bisphenol A, 10 g of distilled water, and glass beads 9 having a diameter of 3 mm.
0g, or dimethyl terephthalate 7g, distilled water 10
and 90 g of glass beads having a diameter of 3 mm were kneaded in the same manner to prepare second and third compositions, respectively.

Next, these first to third compositions were mixed in a weight ratio of 3: 10: 3, and the mixture was applied to high quality paper of 50 g / m and dried at room temperature to obtain a thermal paper. Was produced. However, the coating amount was about 5 g / m ^{3 as} dry solid. Further, the sample No. The epoxy resin composition of No. 1 is applied to a thickness of 5 μm, and the epoxy resin is cured by irradiating ultraviolet rays with a distance of 25 cm from the light source in the ultraviolet irradiator equipped with an 80 W / cm metal halide lamp to cure the epoxy resin and top coat. Was applied.

Subsequently, after performing a color development test on the thermal paper as described above with a rhoaceta-type thermotester,
When dibutyl phthalate, dilauryl phthalate, dioctyl phthalate and tricresyl phosphoric acid were applied on the surface and left at room temperature for 1 week or longer, no particular discoloration was observed. On the other hand, when the same treatment was applied to the thermal paper without the top coat, in each case, 3
Fading was observed within the day.

Example 6 Sample No. 1 of Example 1 After injecting the epoxy resin composition of No. 6 into a transparent container and burying the light emitting element to a predetermined position in the transparent container, the distance from two 2 kW high pressure mercury lamps serving as a light source is set to 10 cm, and 1 min. The epoxy resin was cured by irradiation with light once. Table 5 shows the results of examining the characteristics of the resin-sealed light emitting device manufactured in this manner. As shown in Table 5, in the resin-sealed light emitting device here, sufficient results were obtained for all properties, and the physical properties, mechanical properties, and physical properties of the cured product of the epoxy resin composition were It can be seen that the electrical characteristics and the like are good.

[0079]

[Table 5]

Example 7 First, 3-carboxy-N-phenylmaleimide 22
280 g, CY175 (trade name, Ciba Geigy alicyclic epoxy resin: epoxy equivalent 133 to 154), 55 g of toluene and 1.5 g of choline chloride are charged into a reaction vessel and reacted at the reflux temperature of toluene, and the reaction is completed. After extraction, the solvent was distilled off to synthesize an epoxy resin. The acid value of the epoxy resin synthesized here is 1 mg (KOH) /
g.

Next, with respect to 100 parts by weight of this epoxy resin, 1.0 part by weight of TEAACA as an organometallic compound,
4 parts by weight of polysilane (PS-1) as an organosilicon compound and 1.0 part by weight of benzophenone as a photosensitizer were blended and uniformly mixed to prepare an epoxy resin composition. Then, one of the conductors A to E shown below is dipped in the epoxy resin composition, and then the light source is irradiated with light for 5 minutes with the distance from the light source of 5 kW metal halide lamp (Toshiba: 80 W / cm) being 10 cm. , 150 ° C
The epoxy resin was cured by heating for 1 hour.

A: A helical coil produced from an amide-imide-treated electric wire (Showa Denki AIW wire, diameter 1 mm) B: Ester-imide treated electric wire (Showa Denki EIW wire,
Helical coil made from diameter 1 mm C: Untreated bare wire (Showa Denki KIW wire, diameter 0.9 m)
Helical coil made from m) D: 0.75 kW motor rotor (Showa Densen AIW line) E: 2 cm wide aluminum silane wrapped with epoxysilane-treated glass cloth 4 times with half wrap (100 × 50 × 50)
0 mm) Sample No. The resin dripping rate was obtained for each of the wire-wound electrical devices 1 to 5. Moreover, the sample No. in which the conductor is a helical coil. 1-3, JIS
Bending strength was also measured according to the -C2103-29-3 (1977) test method. On the other hand, for comparison with these examples, sample N except that the organosilicon compound compounded in the epoxy resin composition is polysilane (PS-5).
o. Sample No. 1 which is exactly the same as No. 1 Sample No. 6 except that BF ₃ piperidine was blended in place of the organometallic compound and the organosilicon compound as a catalyst in the wire-wound electric device of 6 and the epoxy resin composition. Sample N exactly the same as 1
o. The wire-wound electric device of No. 7 was manufactured, and the resin dripping rate and bending strength were similarly examined. The results are shown in Table 6. As shown in Table 6, the sample No. In Examples 1 to 5, good results were obtained in all cases.

[0083]

[Table 6]

Further, trisethylacetoacetatotitanium (TEAATi) or trisethylacetoacetatochrome (TEAACr) was added as the organometallic compound in the epoxy resin composition instead of TEAACA, and the heating time after light irradiation was changed. Sample N except 3 hours
o. A wire-wound electric device was produced in exactly the same manner as 1 and the bending strength was measured. Also in this case, the bending strength is 5.
The values were 8, 5.1, which were all good values.

Example 8 To 100 parts by weight of either (EP-1) or (EP-2) as an epoxy resin, 0.4 parts by weight of TAANA as an organometallic compound and polysilane (PS- as an organosilicon compound) 1), (PS-4) or (P
S-5) 2 parts by weight was added, and the sample No.
Epoxy resin compositions 1 to 4 were prepared. The chemical formulas of the epoxy resins (EP-1) and (EP-2) used here are shown below.

[0086]

Embedded image

Next, these epoxy resin-based compositions are applied onto a tin plate to form a coating film, which is then used as a light source.
Distance to 0W / cm metal halide lamp is 6.5c
Light was irradiated as m and the curing time until the epoxy resin was cured was measured. Separately from this, in exactly the same manner as in Example 1, the volumetric shrinkage rate of the epoxy resin during curing was calculated. The results are also shown in Table 7. As shown in Table 7, Sample No. which is an example of the present invention. It was confirmed that with each of the epoxy resin compositions 1 to 3, a cured product could be obtained by light irradiation for a short time, and the volume shrinkage due to the curing of the epoxy resin at this time was extremely small.

[0088]

[Table 7]

[0089]

As described in detail above, in the epoxy resin composition of the present invention, a cured product having a small volume shrinkage, excellent dimensional accuracy, and good physical properties, mechanical properties, electrical properties and the like can be obtained. It can be obtained in a short time, and its industrial value is enormous.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Shuji Hayase 1 Komukai Toshiba-cho, Sachi-ku, Kawasaki-shi, Kanagawa Incorporated Toshiba Research and Development Center

Claims (2)

[Claims] 1. An epoxy resin composition comprising (a) an epoxy resin, (b) an organometallic compound, and (c) an organosilicon compound having a repeating unit represented by the following general formula (1). Embedded image 2. R in the general formula (1) has 6 to 24 carbon atoms.
2. The epoxy resin composition according to claim 1, which is one of the substituted or unsubstituted aryl group and the aromatic heterocyclic group.