JPS6147730A - Photo-setting composition - Google Patents

Abstract

PURPOSE:To provide a photo-setting composition having high photo-curability and excellent water resistance and boiling water resistance, by compounding an epoxy compound and a fluorine-containing compound each having photo-reactive unsaturated double bond, with an organometallic compound and an organic silicon compound. CONSTITUTION:The objective composition can be prepared by compounding (A) 100pts.(wt.) of a compound having one or more epoxy group and photo-reactive unsaturated double bond, e.g. a compound obtained by the reaction of an epoxy resin with (meth)acrylic acid with (B) 1-50pts., preferably 1-15pts. of a compound having one or more fluorine atom and photo-reactive unsaturated double bond, preferably a fluorine-containing (meth)acrylate, (C) an organometallic compound, preferably trismethoxy aluminum and (D) an organic silicon compound generating silanol group by photo-irradiation, preferably a compound having peroxysilyl group or O-nitribenzyloxy group. The amounts of the components C and D are 0.1-5wt% and 1-10wt% based on the sum of the components A and B.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a novel photocurable composition, and more particularly,
The present invention relates to photocurable compositions that are effective for use in various fields such as paints, inks, adhesives for optical parts, and surface coating materials.

[Technical background of the invention 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 significantly lower adhesion and heat resistance than the epoxy resin itself.

Another method is to cure the epoxy resin itself using a photodecomposition type catalyst. The catalyst used at this time has the following formula; YO Ar-X-Ar (wherein, Ar represents a phenyl group, etc.;
, PF6, AgF2, SbF6, etc.

) can be mentioned.

However, although the cured resin products obtained using these catalysts have good mechanical properties and heat resistance, the catalyst components are strong and become ionic impurities, so the cured resin products obtained using these catalysts cannot be heated for a long time. This causes the properties of the cured product to deteriorate and also causes corrosion. In addition, there are serious problems in terms of handling and workability, and there is also the problem that adhesive strength is completely lost when rapidly curing.

[Object of the invention] The present invention aims to provide a photocurable composition that has good photocurability, and the obtained cured product has excellent optical, physical, and mechanical properties, and in particular, has significantly improved water resistance. purpose.

[Summary of the invention]

The photocurable composition of the present invention comprises a compound having at least one epoxy group and at least one photoreactive unsaturated double bond; at least one fluorine atom and at least one photoreactive unsaturated double bond; It is characterized by consisting of a compound having a reactive unsaturated double bond; an organometallic compound; and an organosilicon compound that generates a silanol group when irradiated with light.

The present invention will be explained in more detail below.

In the present invention, a compound having at least one epoxy group and at least one photoreactive unsaturated double bond is used as the epoxy resin component, which is the first essential component.

Examples of the epoxy group in this compound include: On the other hand, examples of the photoreactive element and saturated double bond that simultaneously exist in this compound include OHH HOOH.

In the above structural formula, the hydrogen atoms bonded to the carbon atoms 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 depending on the purpose, but on the other hand, it can be made by adding acrylic acid, methacrylic acid, cinnamic acid, maremono-shun, etc. to commonly used epoxy resin. It can also be easily synthesized by formula. The epoxy resin used in this latter method includes, for example, bisphenol A epoxy resin;
Bisphenol F type epoxy resin; Phenol novolac type epoxy resin; Alicyclic epoxy resin; Heterocyclic-containing epoxy resin such as triglycidyl isocyanate and hydantoin epoxy; Hydrogenated bisphenol A type epoxy resin; Propylene glycol-diglycidyl ether and pentaerythritol- Aliphatic epoxy resins such as polyglycidyl ether; epoxy resins obtained by the reaction of aromatic, aliphatic or alicyclic carboxylic acids with epichlorohydrin; spiro ring-containing epoxy resins; 0-allylphenol novolac compounds and epichlorohydrin Glycidyl ether type epoxy resin which is a reaction product; Glycidyl ether type epoxy resin which is a reaction product of a diallylbisphenol compound having an allyl group at the ortho position of each hydroxyl group of bisphenol A and epichlorohydrin, etc.; One or more selected from the group can be used arbitrarily.

Specific examples of the epoxy compounds used in the present invention include the following.

(Integer greater than or equal to n-0 Integer greater than or equal to 1m-1) (n=Integer greater than or equal to 2) OH, -0H-OH.

I \d OH, -0H-OH.

1 σ 0HOHO-C-α (H2 In the present invention, a compound having at least one fluorine atom and at least one photoreactive unsaturated double bond is used as the second essential resin component □ Due to the presence of fluorine atoms in the compound, the water resistance of the cured product obtained from the composition of the present invention is dramatically improved.

The number of fluorine atoms present in the compound-molecule is not particularly limited, but it is preferably 3 or more, and more preferably more. Further, examples of the photoreactive unsaturated double bond include the same groups as those described for the epoxy oil component.

In the present invention, any material may be used as long as it has a fluorine atom and a photoreactive unsaturated double bond, but fluorine-containing (meth)acrylic ester is preferably used. Specific examples include the following compounds.

Trifluoroethyl acrylate, trifluoroethyl methacrylate, trifluoro-n-propyl acrylate, trifluoro-n-7'ovir methacrylate, trifluoro-n-butyl acrylate, trifluoro-n-butyl methacrylate, trifluoroisopropyl acrylate, Trifluoroinpropyl methacrylate.

OH,=0HOOOOH,OHF', ,OR,
= 0HOOOQH, (CF,)30HF,,0H2=
CHooooll, 0H2 (CF2), OF, .

OFH= 0HOOOOH20H20H3, 0I12
= 0FOOOOH*0HzcHs, OHM = 0
HOOOOIJOF20H35OH2= 0HOOOO
F! OHs pentafluorostyrene (0,F,OH=
0H2)% Be/Tafluorocinnamic acid (0,F,OH=
0HOO,H).

Pentafluoroallylbenzene (06FSC!H,0H
=OH ri, 4-7 Ay oros f shi7 (4-FO
@l140H=OHM), 3-fluorostyrene (
3-FO,)1. OH= OH,), 2-fluorostyrene (2-FO, I (40H= OH,).

4-fluorocinnamic acid (4FO, H40H= 0HOO
, H).

3-fluorocinnamic acid (a-FO, H40H= 0HO
O engineering H), 2-fluorocinnamic acid (2FO, H, OH=
0HOO,H), 4-trifluoromethylstyrene (
4-F, OO, H40H==OH,), 3-) Lifluoromethylstyrene (3-F300@H40H= OH2
), 2-trifluoromethylstyrene (2-OF, O,
H,OH=OH,)% α,-Trifluoromethylstyrene (0sHiO(OFs)=OH*) These compounds can be used alone or in combination of two or more f'i. The compounding amount of the compound is 1:1 of the epoxy resin component.
00 parts by weight, usually 1 to 50 parts by weight, preferably 1
It is within the range of ltl to 15 parts by weight.

The third component of the composition of the invention is an organometallic compound. Organometallic compounds include titanium, vanadium, chromium,
Metal atoms such as manganese, iron, cobalt, nickel, copper, zinc, aluminum, zirconium, etc., alkoxy groups, phenoxy groups, acyloxy groups, β-diketonato groups,
A complex to which an 0-carbonylphenolad group or the like is bonded is preferable.

Among the metal atoms mentioned above, aluminum is preferred because its organometallic compound is useful for increasing the photocuring rate. As such organoaluminum compounds,
Specifically, trismethoxyaluminum, trisethoxyaluminum, trisisopropoxyaluminum,
trisphenoxyaluminum, trisparamethylphenoxyaluminum, inpropoxyjethoxyaluminum, trisbutoxyaluminum, trisacetoxy7aluminum, trisstearadoaluminum, trisbutyradoaluminium, trispropionatoaluminum, trisisopropionatoaluminum, trisacetylacetonadoaluminum, These include tristrifluoroacetylacetonadoaluminum, trishexafluoroacetylacetonadoaluminum, trisethylacetoacetoacetoaluminum, trissalicylaldehydatoaluminum, trisdiethylmaloradoaluminum, and the like.

These organometallic compounds can be used alone or in an appropriate combination of two or more. The blending amount is 0.0 in weight ratio to the total amount of the first essential component and the second essential component.
It ranges from 0.01 to 10%, preferably from 0.1 to 5%.

If this amount 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 fourth essential component of the present invention is an organosilicon compound that generates silanol groups upon irradiation with light. As such a silicon compound, a silicon compound having any one of a peroxysilyl group, an O-nitrobenzyloxy group, and an α-ketosilyl group is preferable.

Among these silicon compounds, those having a peroxysilyl group have the following formula:
represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group having 1 to 5 carbon atoms, an unsubstituted or substituted aryl group or an aralkyl group;
Pn represents an integer satisfying the following conditions: O≦J, m, n≦3%, 1≦l+m, and n≦3.

Specific examples of such silicon compounds include 1, for example -1
Examples include compounds represented by the following formula:

A silicon compound having a 0-nitrobenzyloxy group is
The following formula: (In the formula, R, R and R may be the same or different, and each represents a hydrogen atom, a halogen atom, a vinyl group,
represents an allyl group, an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an unsubstituted or substituted aryl group, an aryloxy group, or a siloxy group; R is a hydrogen atom, and R is a hydrogen atom; 10 unsubstituted or substituted alkyl groups, phenyl groups, substituted)enyl groups;
R, R, R, and R may be the same or different, and each represents a hydrogen atom, a nitro group, a cyano group, a hydroxy group, a mercapto group, a halogen atom, an acetyl group, an allyl group, and a carbon number of 1 to 5 alkyl group, an alkoxy group having 1 to 5 carbon atoms, an unsubstituted or substituted aryl group, or an aryloxy group; p.

q, r are 0≦p*q*r≦3, 1≦p + q + r
Represents an integer that satisfies the condition ≦3. ).

In addition, as a silicon compound, the above-mentioned O-nitrobenzyloxysilyl group is the terminal group, the main chain is and R5 has the same meaning as above; , represents an oxygen atom, an alkylene group, an aryldiyl group, etc. ) may be a compound consisting of a group represented by the following.

Specific examples of silicon compounds having an unsubstituted or substituted O-nitrobenzyloxy group directly bonded to a silicon atom used in the present invention include, for example, trimethyl(0-nitrobenzyloxy)silane dimethylphenyl(0-nitrobenzyloxy) 7) Silane diphenylmethyl (0-nitrobenzyloxy) silane triphenyl (0-nitrobenzyloxy) 7) silane vinylmethylphenyl (0-nitrobenzyloxy) silane t-butylmethylphenyl (
0-Nitrobenzyloxy)silane Triethyl(0-nitrobenzyloxy)silane)! J(2-chloroethyl)-〇-nitrobe/zyloxysila/t! J(p-)Lifluoromethylphenyl)-0-nitrobenzyloxysilanetrimethyl[α-(0-nitrophenyl)-〇-nitrobenzyloxy]silanedimethylphenyl[α-(0-nitrophenyl)-〇-
nitrobenzyloxy]silanemethylphenyldi[α-(0-nitrophenyl)-〇-
nitrobenzyloxy]silanetriphenyl(α-ethyl-〇-nitrobenzyloxy)7lanetrimethyl(3-methyl-2-nitrobenzyloxy)silanedimethylphenyl(3t4#5-)'J
methoxy-2-nitrobenzyloxy)silanetriphenyl(4,5,6-drimethoxy-2-nitrobenzyloxy)silane diphenylmethyl(5,methyl-4-methoxy-2-nitrobenzyloxy)silanetriphenyl( 4,5-dimethyl-2-nitrobenzyloxy)silanevinylmethylphenyl(4,5-dichloro-2-nitrobenzyloxy)silanetriphenyl(2,6-dinitrobenzyloxy)silanediphenylmethyl(2,4- dinitrobenzyloxy)silanetriphenyl(3-methoxy-2-nitrobenzyloxy)silanevinylmethylphenyl(3,4-dimethoxy-2-nitrobenzyloxy)silanedimethyldi(0-nitrobenzyloxy7)silanemethylphenyldi (0-nitrobenzyloxy)7ranvinylphenyldi(0-nitrobenzyloxy)silane t-y
“Tylphenyldi(0-nitrobenzyloxy)silanedi(6-nitrobenzyloxy)silane2-chloroethylphenyldi(0-nitrobenzyloxy)silanediphenyldi(0-nitrobenzyloxy)silanediphenyldi(3-methoxy) -2-nitrobenzyloxy)
Silane diphenyldi(3,4-dimethoxy-2-nitrobenzyloxy)silane diphenyldi(2,6-dinitrobenzyloxy)silane diphenyldi(2,4-dinitrobenzyloxy)silanemethyltri(o-nitrobenzyloxy) Silanephenyltri(o-nitrobenzyloxy)silanerubis(0-nitrobenzyloxydimethylsilyl)benzene 1.1,3.3-tetraphenyl-1,3-di(0-
Reaction of 1,3,3,5,5-hexaphenyl-1,5-di(o-nitrobenzyloxy)siloxane and 5taz-containing silicone resin with 0-nitrobenzyl alcohol Examples include silicon compounds that generate z5.

The silicon compound having an α-keto or silyl group has the following formula: (wherein R, R, R, and RFi may be the same or different, and each is a hydrogen atom.

Represents a vinyl group, allyl group, unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, unsubstituted or substituted alkoxy group having 1 to 10 carbon atoms, unsubstituted or substituted aryl group, or aryloxy group: t, u, v is 0≦t, u, v≦
3, represents an integer that satisfies the condition of 1≦t+u+v≦3)
It is indicated by.

Specific examples of such silicon compounds include, for example, OH, OH3 H3 Examples include compounds represented by:

These organosilicon compounds can be used alone or in an appropriate combination of two or more. The blending amount is 0.1 to 2% of the total amount of the first essential component and the second essential component.
0% by weight, preferably in the range 1-10% by weight. If the amount of Fi is less than 0.1% by weight, 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 desirable as it may cause

The composition of the present invention may further contain a photosensitizer, if necessary. The sensitizer to be used may be any sensitizer as long as it can photosensitize each of the above-mentioned components, and may be appropriately selected depending on the composition of the composition, the rice species used as the light source, etc.

Examples of such photosensitizers include aromatic hydrocarbons, benzophenone and its derivatives, o-benzoylbenzoate ester, acetophenone and its derivatives, benzoin and benzoin ether and its derivatives, xanthone and its derivatives, thioxanthone and its derivatives. derivative,
Examples include disulfide compounds, quinone compounds, halogenated hydrocarbons, and amines.

Specific examples of aromatic hydrocarbons include benzene, benzene-d+, ) toluene, p-xylene, fluorobenzene, chlorobenzene, and bromobenzene.

iodobenzene, 7talene, 1-methylnaphthalene,
2-methylnaphthalene, 1-fluoronaphthalene, 1-
Chloronaphthalene% 2-chloronaphthalene, 1-bromonaphthalene, 2-bromonaphthalene, 1-iodonaphthalene, 2-iodonaphthalene, 1-naphthol% 2
- Naphthol, biphenyl, fluorene, p-terphenyl, acenaphthene, p-quaterphenyl, triphenylene.

Phenanthrene, azulene, fluoranthene, chrysene, pyrene, 1,2-benzubire/, anthracene, 1,
Examples include 2-benzanthracene, 9.10-dichloroanthracene, 9,1o-dibromoanthracene, 9.10-diphenylanthrace/, perylene, tetracene, and pentacene.

Examples of benzophenone and derivatives thereof include benzophenone, 2,4-dimethylbenzophenone, 2,4
Examples thereof include -dichlorobenzophenone and 4°4'-his(dimethylamino)benzophenone.

As the o-benzoylbenzoate ester, for example, 0
-Benzoylbenzoic acid methyl ester, 0-benzoylbenzoic acid H ethyl ester, 0-benzoylbenzoic acid phenyl ester.

etc.

Examples of acetophenone and its derivatives include acetophenone% 4-methylacetophenone/7.3-methylacetophenone and 3-methoxyacetophenone.

Examples of benzoin, benzoin ether, and derivatives thereof include benzoin, benzoin methyl ether, and benzoin ethyl ether.

Benzoin isoglobyl ether, benzoin-n-butyl ether, benzoin triphenylsilyl ether, and these photosensitizers can be used alone or in an appropriate combination of two or more. The ratio is o, ooi to 10 for the total amount of the first essential component and the second essential component.
It is preferably 0.01% by weight, more preferably 0.01% by weight.
~5% by weight.

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 photocured at room temperature, photocured by heating,
Depending on the purpose and use, it can be cured and put into practical use by a method such as after-curing performed after photo-curing.

The wavelength of light irradiated to a composition during photocuring varies depending on the vertebrate of the composition, but is usually 180~
700 nm. In particular, ultraviolet irradiation is effective. The light irradiation time varies depending on the composition of the composition, the type of catalyst, the type I 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 one that is used for normal photocuring, such as a low-pressure mercury lamp, high-pressure mercury lamp, carbon arc lamp, metal halogen lamp, xenon-mercury lamp, or xenon lamp. , hydrogen discharge tube, tungsten lamp, halogen lamp, sodium discharge tube,
Neon discharge tube, argon discharge tube, helium-neon laser, argon ion laser, nitrogen, '/slaser, cadmium ion laser, helium-cadmium laser, dye laser, and one or two types of radiation such as various electron beams and X-rays More than seeds can be given.

After-cure is applied as needed after photo-curing.

Although the mode differs depending on the composition of the composition, the type of catalyst, etc.1, the temperature is usually 50 to 200°C, preferably 100 to 200°C.
At 180°C, usually 10 minutes to 10 hours, preferably 20
Do this for 5 minutes to 5 hours.

〔Effect of the invention〕

The composition of the present invention has good photocurability, and when used, it can be cured by light irradiation for a short period of time. Moreover, the obtained cured product has excellent water resistance and boiling water resistance, and has sufficient hardness. However, since the curing catalyst used is not ionic, it does not cause corrosion phenomena. In addition, it has good adhesion to substrates such as aluminum. From the above, the composition of the present invention can be used as a valuable material in various fields such as paints, inks, adhesives for optical parts, and surface coating materials.

[Embodiments of the invention]

Examples 1 to 6 and Comparative Examples 1 to 2 ERL-4206 (trade name) was placed in a four-day flask equipped with a thermometer, a reflux device, an N2 gas inlet, and a stirrer.

Manufactured by UCC, vinyl cyclohexane geboxide, epoxy equivalent: 70) 210. lit, acrylic acid 117,
lit,) Ruen 400. lit, hydroquinone 0.
01. lit, and 1.56 g of choline chloride as a catalyst.
were added, the temperature was gradually raised while stirring, and the reaction was carried out at the reflux temperature of toluene. Progress of the reaction The amount of acrylic acid consumed was monitored by oxidation measurement using a standard NaOH solution at θ and IN, and the reaction was terminated when oxidation reached almost zero. After the reaction was completed, the reaction solution was mixed with ion-exchanged water (No. 11) and washed three times. The toluene layer was separated using a separating funnel, and the toluene was distilled off under reduced pressure. The viscosity of the synthesized compound is z5 voids (25°C), and it is an acrylic acid epoxy resin with an epoxy equivalent of 94 represented by the following structural formula (
Hereinafter abbreviated as HEA) was obtained. - On the other hand, Viscoat 17F (OH,=OHOOOOOH
tOHt(OFz)yOFs: manufactured by Osaka Organic Chemical Co., Ltd.).

Viscoat 4 F (OH, = 0HOOOOH, C!
HF mushrooms (manufactured by Osaka Organic Chemical Co., Ltd.) were used. As the organoaluminum compound, trisethylacetoacetatoaluminum (TEAAA/)% trissalicylaldehydatoaluminum (T8AAl) was used, and as the organosilicon compound, triphenylsilyl-t-buf/
l/peroxide ('rpstpo) and benzophenone, 2-hydroxy-2 as sensitizers.
-Methylacetophenone (trade name, Darocu 7-117
3: manufactured by Merck & Co.) was used. These compounds were blended into the composition shown in Table 1 (expressed in parts by weight).

The following compositions of the present invention were prepared.

Table 1 These compositions were coated on an aluminum plate (0.3 m thick) by a conventional method. Next, these were introduced into a photocuring box equipped with an 80 W/cm air-cooled mercury lamp installed at a height of 10 nm from the conveyor surface, and UV light was irradiated for 1 to 60 seconds. After curing, the coating film was cured. water resistance.

Boiling water resistance, hardness in hot water (80°C), and basic properties as a coating film (adhesion, pencil hardness, bending) were measured.

The results are shown in Table 2 below.

By using the above skeleton material of the present invention, the photocurable composition of the present invention showed excellent results in terms of water resistance, boiling water resistance, adhesiveness, and hardness.

Examples 7 to 10, Comparative Examples 3 to 4 Celoxide 8 to HEA glue 9 used in Examples 1 to 6
-2021 (manufactured by Daicel) and Viscoat 8F (6H,=OHOOOOHI(O
Fz)+0HFz: manufactured by Osaka Organic Chemical Co., Ltd.) and Viscoat 3 F (OR3=OHOOOOOHzOFs: manufactured by Osaka Organic Chemical Co., Ltd.) were prepared in the same manner as in Examples 1 to 6. Table 3) and its water absorption rate (Table 4) was measured.

Table 3 Table 4 As mentioned above, it is a photocurable resin with low water absorption and excellent water resistance and moisture resistance.

Claims (3)

[Claims] (1) Compounds having at least one epoxy group and at least one photoreactive unsaturated double bond; at least one fluorine atom and at least one photoreactive unsaturated double bond A photocurable composition comprising: a compound having; an organometallic compound; and an organosilicon compound that produces a silanol group upon irradiation with light. (2) The photocurable composition according to claim 1, wherein the organometallic compound is an organoaluminum compound. (3) The organosilicon compound has a beroxysilyl group, an o-
The photocurable composition according to claim 1, which is a compound having a nitrobenzyloxy group or an α-ketosilyl group.