JPS61197626A - Photocurable composition - Google Patents

Abstract

PURPOSE:A composition excellent in photocurability, coating quality, etc., obtained by mixing a compound containing an epoxy group and a photocurable unsaturated double bond with an organometallic compound, a silicon compound which generates silanol groups upon irradiation with light and a surfactant. CONSTITUTION:The purpose photocurable composition is obtained by mixing a compound (A) having at least one epoxy group and at least one photocurable unsaturated double bond in one molecule (e.g., acrylated epoxy resin) with an organometallic compound (B), e.g., trismethoxyaluminum, a silicon compound (C) which generates silanol groups upon irradiation with light (e.g., formula I or formula II), a surfactant (D) (e.g., formula III or tetramethyldisiloxane) and, optionally, a sensitizer and necessary additives such as a metal naphthenate. This composition is excellent in the homogeneity, smoothness, etc., of a film and can be suitably used for paints, inks, sealants, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a photocurable composition, and more specifically, it has good photocurability, fluidity, smoothness, and 1'! ! The present invention relates to a photocurable composition with excellent coating properties such as film uniformity.

[Technical Background of Ill from U.S. and Its Problems] In recent years, there has been interest in the process of curing resin by irradiating it with light from the viewpoints of energy saving and workability. Among these, the process of photo-curing epoxy resins has a wide range of applications and is important.

By the way, there are currently two types of processes for photocuring epoxy resins.

One method is to modify an epoxy resin with a photopolymerizable vinyl group-containing compound such as acrylic, and photopolymerize only through this vinyl group. However, this method has a problem in that the epoxy resin completely modified with vinyl groups such as acrylic groups has considerably lower adhesive properties and heat resistance than the epoxy resin itself.

Another method is to cure the epoxy resin itself using a catalyst in a photodegradable layer. The catalyst used at this time has the following formula: % formula % (wherein, Ar represents a phenyl group, etc.; X represents an iodine atom, a sulfur atom, a diazo group, etc.; Y is BF
4. PF6. A! Representing IPB, 5bFB, etc.
) can be mentioned.

However, although the cured resin products obtained using these catalysts have good mechanical properties and heat resistance, the catalyst component is a strong acid and becomes ionic impurities, so it is difficult to heat or over time. This causes deterioration of the properties of the cured product and causes corrosion phenomena. Furthermore, there are major problems in terms of handling and workability, and there is also the drawback that there is no adhesive force when rapidly curing.

[Object of the invention] The object of the present invention is to eliminate the above-mentioned drawbacks, and to provide a photocurable composition that has good photocurability and excellent coating properties such as flowability, smoothness, and uniformity of the coating film. Our goal is to provide the following.

[Summary of the invention] The photocurable composition of the present invention.

(a) Compounds each having at least one epoxy group and one photocurable unsaturated double bond in the same molecule (b) Organometallic compounds (c) Silicon compounds that generate silanol groups when irradiated with light (d) Surface active It is characterized by consisting of an agent.

The compound (a) used in the composition of the present invention may be any compound having at least one epoxy group and at least one photocurable unsaturated double bond in the same molecule.

Examples of the epoxy group in this compound include those shown in 1 below. On the other hand, examples of photocurable unsaturated double bonds that are simultaneously present in this compound include the following.

In the above structural formula, the hydrogen atom bonded to the carbon atom may be substituted with a halogen atom such as chlorine or fluorine, an alkyl group having 1 to 6 carbon atoms, a phenyl group, or the like.

This compound can be arbitrarily synthesized and constructed by molecular design according to the purpose, but it can be easily synthesized by reacting commonly used epoxy resin with acrylic acid, methacrylic acid, cinnamic acid, maleic acid, etc. You can also.

Epoxy resins used in this method include, for example, bisphenol A type epoxy resins; bisphenol F type epoxy resins; phenol novolac type epoxy resins; alicyclic epoxy resins; nitrogen-containing epoxy resins such as triglycidyl isocyanate and hydantoin epoxy; Aliphatic epoxy resins such as bisphenol A-type epoxy resins, propylene glycol diglycidyl ether, and pentaerythritol polyglycidyl ether; epoxy resins obtained by the reaction of aromatic, aliphatic, or alicyclic carboxylic acids with epichlorohydrin; Spiro ring-containing epoxy resin; glycidyl ether type epoxy resin which is a reaction product of an 0-allylphenol novolak compound and epichlorohydrin; reaction product of a diallylbisphenol compound having an allyl group at the ortho position of each hydroxyl group of bisphenol A and epichlorohydrin Examples include glycidyl ether type epoxy resins, and at least one type selected from the group consisting of these resins is used.

The organometallic compound used in the composition of the present invention may be any compound that promotes photocuring.
Examples include various metal complexes, metal oxides, metal-containing halides, complex salts, and the like. Among these, titanium,
An alkoxy group, phenoxy group, acyloxy group, β-diketonato group, 0-carbonylphenolate group, etc. is bonded to a metal atom such as vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, aluminum, or zirconium. Of the above-mentioned metal atoms, aluminum is particularly preferred because its organometallic compounds are useful for increasing the photocuring rate. Ethoxyaluminum, trisethoxyaluminum paramethylphenoxyaluminum, isopropoxyjethoxyaluminum, trisbutoxyaluminum, trisacetoxyaluminum, trisstearadoaluminum, trisbutyradaluminum, trispropionatoaluminum, trisisopropionatoaluminum, trisacetylacetonadoaluminum , tristrifluoroacetylacetonatoaluminum, trisfluoroacetylacetonatoaluminum, trisethylacetoacetoacetoaluminum, trissalicylaldehydatoaluminum, trisdiethylmaloradoaluminum, and the like.

These organometallic compounds can be used alone or in an appropriate combination. The blending amount is (
0.00 by weight for the content of component a) and component (b)
It ranges from 1 to 10%, preferably from 0.1 to 5%. This blending amount is O. If it is less than 0.001%, sufficient curing properties cannot be obtained, and if it exceeds 10%, it will result in increased costs and decreased adhesion.

The silicon compound (c) used in the composition of the present invention may be any compound that produces a silanol group when irradiated with light, such as an organosilicon compound, an inorganic silicon compound, a silicon-containing polymer (silicone ), silicone oil, etc. Among these, silicon compounds having any one of a peroxysilane group, an o-nitrobenzyloxy group, and an α-ketosilyl group are preferred.

Among these silicon compounds, those having peroxysilanno S have the following formula; (r?')n-Si4 0-0
-R2)4, (wherein R and R2 may be the same or different, and each is a hydrogen atom, a halogen atom,
It represents an alkyl group or an aryl group having 1 to 5 carbon atoms, and n is an integer of θ to 3. ).

In the above formula, the alkyl group having 1 to 5 carbon atoms is 1, for example, methyl group, ethyl group, isopropyl group, n-propyl group, n-butyl group, t-butyl group, 1so-butyl group, n-pentyl group. , methoxy group, ethoxy group, and chloromethyl group; examples of aryl groups include phenyl group, naphthyl group, anthranyl group, and benzyl group; and alkyl groups and aryl groups having 1 to 5 carbon atoms include / It may have a substituent such as a \rogen atom, a nitro group, a cyano group, or a methoxy group.

A specific example of such a silicon compound is the following formula: %formula% Examples include compounds such as.

The amount of these silicon compounds added is usually in the range of 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the total of components (a) and (b).

If the blending amount is 0.1% by weight without swirling, sufficient curing properties cannot be obtained, and although it is possible to use more than 20% by weight, there are problems with high cost and decomposition products of the catalyst component. This is not preferable because it may occur.

The surfactant (d) used in the composition of the present invention may be any surfactant as long as it improves the leveling properties and coating properties of the coating film. For example, C9F19COOH1C7H15COOH
, C3F11(OOH, C5F7COOH, C2F5c
:0OH1CF3COOH etc. perfluoro acid; H(
cF2)3GOOK, H(cF2)3COONa, H
(cF2)10(OOK, H(cF2)10(0ON
a, H(cF2)12(OOK, H(cF2)12C
1) ONa, CBF17S03N((:2H5)((H
2) 20H1CBF17SO3N (c2H5) SO4N
a, H(cF2)BPO(OH)2, CF3(cF2
)6((82)5(0ONa, CF3(cF2)6CH
CH(cH2)3COONa, C7F 15CONHC
3H6N((H3)2C2H4COOH1C7)+15
(Fluorine-containing compounds such as ONHC3H6N(cH3)31; organic interfaces such as nonionic surfactants such as uric acid ester, stearic acid ester, oleic acid ester, lauryl alcohol, oleyl alcohol, alkylphenol, octylphenol, myristic acid ester, etc.) Activator; tetramethyldisiloxane, polydimethylsiloxane, polymethylhydrosiloxane, polymethylhydro-dimethylsiloxane, polyethylhydrosiloxane,
Polydimethyl-polydiphenylsiloxane vinyl, polydimethyl-polymethylvinylsiloxane, polydimethylsiloxane methyldivinyl, polydimethylvinylsiloxane, polymethylphenethylsiloxane vinyl, bis(
vinyldimethylsilyl)benzene, vinylmethylsiloxane, polydiphenylsiloxane, polydimethyl-diphenylsiloxane, bis(hydroxydimethylsilyl)
Benzene, polytetramethyl-p-silylphenylenesiloxane, polydimethylsiloxane carbinol, polydimethylsiloxane hydroxypropylene, boridimethyl-hydroxyalkylene oxide methyl siloxane, bis(aminopropyldimethyl)siloxane, bis(aminopropyldimethylsilyl) ) benzene, 1,3-bis(
chloromethyl)tetramethyldisiloxane, 1,3-his(chloropropyl)tetramethyldisiloxane, polydimethyl-chloropropylmethylsiloxane, tetramethyldichlorodisiloxane, 1,5-dichlorohexamethyltrisiloxane, polydimethyl- Methacryloxypropylmethylsiloxane, polymercaptopropylmethylsiloxane, polymethyl-3,3,3-trifluoropropylsiloxane, polymethyl-1,1,2,2-tetrahydroperfluorooctylsiloxane, polymethylethylsiloxane, polymethyloctylsiloxane , polymethyloctadecylsiloxane, tetraphenyldimethyldisiloxane, tetraphenyltetramethyltrisiloxane, pentaphenyltrimethyltrisiloxane, polyphenylsilsesquioxane, poly-poron-diphenylsiloxane, (N-1-rimethoxysilylbropyl) -〇-Polyethylene oxide urethane, triethoxysilylpoly(l,2-butadiene), tetra-n-butoxysilane, tetra-syw-butoxysilane, tetrakis(2-ethylbutoxy)silane, tetrakis(2-
ethylhexoxy)silane, hexakis(2-ethylbutoxy)disiloxane, methyltris(Tree S!■-
Examples include silane compounds such as (butoxysiloxanyl) silane.

Among these, fluorine-containing compounds are particularly preferred because they have good leveling properties, and silicone compounds are particularly preferred because they have good coating properties.

The usage amount of this (d) component is (a) component, (b)
Usually 0.05 to 5 for the content of component and component (c)
It is preferably 0.1 to 1.0% by weight. If the amount used is less than 1% of Q, 05mff, problems will arise in so-called coating properties such as leveling properties and coating, and if it exceeds 5% by weight, it will have a negative effect on curability and surface tackiness.

Compound (e) can be used in the composition of the present invention. Any material may be used as long as it contributes to improving the coating properties. Specific examples of this compound (e) include cobalt naphthenate, iron naphthenate, manganese naphthenate, nickel naphthenate, copper naphthenate,
Lead naphthenate, cadmium naphthenate, molybdenum naphthenate, terbium naphthenate, tantalum naphthenate,
Naphthenic acid metal salts such as tin naphthenate, chromium naphthenate, gallium naphthenate, tin naphthenate, germanium naphthenate; toluene, xylene, methyl ethyl ketone, ethyl acetate, petroleum benzene, methanol, ethanol, n-hexane, cyclohexane, acetone, etc. At least one kind selected from the group consisting of these organic solvents is used.

Regarding the usage amount of component (e), the naphthenic acid metal salt is usually 0.01 to 5.0% by weight, preferably 0.01 to 5.0% by weight in a 20% solvent solution based on the total of components (a) to (d). 0.
05 to 1.0% by weight. If the amount used is less than 0.01% by weight, the coating properties will not be improved, and if it exceeds 5.0% by weight, the coating properties will be significantly reduced. Moreover, the organic solvent is usually the total amount of components (a) to (d).

It is 2.0% by weight or less, preferably 0.5 to 1% by weight. If the amount used exceeds 2.0% by weight, the curability is particularly reduced.

In addition, examples of solvents when using naphthenic acid metal salts include xylene, toluene, methyl ethyl ketone,
Examples include methyl isobutyl ketone.

A photosensitizer may be added to the composition of the present invention, if necessary. The sensitizer may be any substance as long as it can photosensitize each of the above-mentioned components, such as aromatics, hydrocarbons, benzophenone and its derivatives, lobenzoyl benzoate, acetophenone and its derivatives. Examples include derivatives, benzoin, benzoin ether and its derivatives, xanthone and its derivatives, thioxanthone and its derivatives, disulfide compounds, quinone compounds, halogenated hydrocarbons, and amines.

Examples of acetophenone and its derivatives include acetophenone, 4-methylacetophenone, 3-methylacetophenone, and 3-methoxyacetophenone. Examples of benzoin, benzoin ether and derivatives thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin-
Examples include n-butyl ether, benzointriphenylsilyl ether, and the like. These photosensitizers can be used alone or in an appropriate combination of two or more.

The blending amount thereof is preferably o, oot to 10% by weight, more preferably 0.01 to 3% by weight, based on the contents of the first essential component and the second essential component.

The composition of the present invention may further include a conventional coloring agent, if necessary.
Inorganic fillers or other various additives may also be blended.

The photocurable composition of the present invention can be cured and put into practical use by methods such as room temperature curing, heating photocuring, and after-curing after photocuring, depending on the purpose and use.

During photocuring, the wavelength of the light irradiated to the composition varies depending on the type of composition, but is usually 180~
It is 700mn. In particular, ultraviolet irradiation is effective.

The light irradiation time varies depending on the composition of the composition, the type of catalyst, the type of light source, etc., but is usually from several seconds to 180 minutes, preferably from 1 second to 10 minutes.

The heating temperature in the case of heating photocuring is usually 20 to 200°C,
Preferably it is 60-150°C. The light source at this time may be any light source used for normal photocuring, but examples include low-pressure mercury lamps, high-pressure mercury lamps, carbon arc lamps, metal halogen lamps, xenon-mercury lamps, and xenon/mercury lamps. lamps, hydrogen discharge tubes, tungsten lamps, halogen lamps, sodium discharge tubes,
Neon discharge tube, argon discharge tube, helium-neon laser, argon ion laser, nitrogen gas laser, cadmium ion laser, helium-cadmium laser, dye laser, and one or more types of radiation such as various electron beams and X-rays Things can be mentioned.

The temperature of after-cure by heating, which is applied as necessary after photocuring, varies depending on the composition of the composition, the type of catalyst, etc., but is usually 50 to 200°C, preferably 100 to 180°C, and usually 10°C. Minutes to 10 hours, preferably 20 minutes to 5 hours.

EXAMPLES Below, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

[Embodiment of the invention] ERL-4208 (trade name; manufactured by 100 Company, vinyl cyclohexane diepoxide, epoxy resin) was placed in a four-way flask equipped with a thermometer, a reflux device, a nitrogen gas inlet, and a stirrer. n
70) 280 g (2.0 mol), 72 g (1.0 mol) of acrylic acid (manufactured by Wako Tsumugi Co., Ltd.), 1 portion of toluene,
1 g of p-methoxyphenol O, O and 1.20 g of tetrabutylammonium chloride as a catalyst were added.

The mixture was stirred and heated gradually, and the reaction was carried out at the reflux temperature of toluene.

The progress of the reaction was determined when the amount of acrylic acid consumed was 0. The reaction was monitored by measuring the acid value using a standard KOH alcohol solution of IN, and the reaction was terminated when the acid value became almost zero. After the reaction was completed, the reaction solution was mixed with 1 ml of ion exchange water, washed three times, the toluene layer was separated using a separating funnel, and the toluene was distilled off under reduced pressure. An acrylated epoxy resin (hereinafter abbreviated as VfEA) with a viscosity of the synthesized compound having a viscosity of 25 voids (at 25° C.) and an epoxy equivalent of 480 was obtained. In addition to the obtained V) IEA, FC-430 and Modaflow (manufactured by Sumitomo 3M, fluorine-based surfactant) were used as leveling agents, and Darocure (D)-117 was used as a photosensitizer.
3 (acetophenone sensitizer, manufactured by Merck & Co., Ltd.) and penzophenone (manufactured by Kanto Kagaku Co., Ltd.), and aluminum as a photoinitiator/trialkyl aluminum (AL; abbreviated as L-TR) as a silanol catalyst. and triphenylsilyl-1-butyl peroxide (abbreviated as 3φP1), and an epoxy compound (abbreviated as 3φP1) as an additive.
E-+02S; Cresol novolak epoxy resin, 1
one or more compounds of the present invention using
A composition of the present invention was prepared by blending the composition (expressed in parts by weight) shown in Table 1 below as an F-suko material. In addition, as a comparative example, bisphenol A type epoxy acrylate B-540 (manufactured by Osaka Organic Chemical Co., Ltd.), diluent trimethylolpropane triacrylate (↑MPT
A composition containing A) as a base resin was prepared.

Each of these compositions was applied by a conventional method onto a tin plate having an undercoat layer made of a thermosetting resin. These were then introduced into a photocuring box equipped with an 80 W/cm air-cooled mercury lamp placed at a height of 8 cm from the conveyor surface, and irradiated for 1 to 5 seconds. After irradiation, the surface condition was visually observed. The leveling property was also determined using a gloss meter, and the results are shown in Table 2 below.

Table 2 From the above results, it was shown that the leveling agents FC-430, Modaflow, etc. exhibited excellent leveling properties.

The composition of the present invention was prepared in the same manner as in Examples 1 to 8, except that the following additives (shown in Table 3) were further added to the main composition used in Examples 1 to 8. Obtained.

Table 3 The above compositions were photocured in the same manner as in Examples 1 to 8, and the results shown in Table 4 were obtained. In addition, the dryness is determined by the touch of the finger after exposure to light.
Indicated by slightly sticky (T), dry (υ), and very dry (TF).

Table 4 From the above, it was found that a coating film with excellent homogeneity could be obtained in a short time by using various additives.

[Effects of the Invention] As detailed above, the photocurable composition of the present invention has good photocurability, flowability, and smoothness.

It has excellent coating properties such as uniformity of the coating film, and is expected to be used for applications such as paints, inks, optical component adhesives, and electronic component sealants, and its industrial value is extremely large. be.

Claims (1)

[Claims] 1. (a) A compound having at least one epoxy group and at least one photocurable unsaturated double bond in the same molecule (b) An organometallic compound (c) A compound having a silanol group by light irradiation A photocurable composition comprising the resulting silicon compound (d) and a surfactant. 2. The composition according to claim 1, wherein the organometallic compound is an aluminum compound. 3. The silicon compound contains at least one selected from the group consisting of peroxysilane group and o-nitrobenzyloxy group.
A composition according to claim 1, which is a compound containing a species group. 4. The composition according to claim 1, wherein the surfactant is a fluorine-based compound. 5. The composition according to claim 1, wherein the surfactant is a silicon-based compound. 6. The composition according to claim 1, wherein the surfactant is a long-chain fatty acid alkyl ester. 7. The composition according to claim 1, further comprising a sensitizer. 8. The composition according to claim 1, further comprising at least one compound selected from the group consisting of naphthenic acid metal salts and organic solvents.