JPH11322818A - Photo-setting composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in photo-setting characteristics by irradiation of visible radiations and having a great photo- setting depth by including an ethylenically unsaturated compound, a bisacylphosphine oxide compound and an organic phosphine compound. SOLUTION: This composition is obtained by including (A) an ethylenically unsaturated compound, (B) a bisacylphosphine oxide compound represented by the formula (R1 is a 1-18C alkyl, phenyl or the like; R2 and R3 are each a 1-18C alkyl, O, S or the like) [e.g. bis(2,4,6-trimethylbenzoyl)methylphosphine oxide] and (C) an organic phosphine compound (e.g. phenylphosphine). In the composition, the amounts of the contained components based on 100 pts.wt. of the component A are preferably 0.1-10 pts.wt. of the component B and 0.01-10 pts.wt. of the component C. Furthermore, (D) a photopolymerization initiator (e.g. 2-hydroxy-2-methyl-1-phenylpropan-1-one) is preferably contained in an amount of 0.01-10 pts.wt. based on 100 pts.wt. of the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention can be used in various fields as an adhesive, a coating agent, a sealing agent, a resist agent, a molding material, and the like, and is a photocurable composition sensitive to visible light with high sensitivity. About things.

[0002]

2. Description of the Related Art It is widely known that an ethylenically unsaturated compound is activated by irradiation with an active energy ray in the presence of a photopolymerization initiator and is easily polymerized. For example, JP-A-2-196866 discloses a photopolymerizable composition containing a compound having a radically polymerizable unsaturated double bond in a molecule and an acylphosphine oxide compound as a photopolymerization initiator. Is disclosed that imparts conductivity by blending the compound. However, such a conventional photopolymerizable composition exhibits excellent curability when irradiated with ultraviolet light, but generally has low sensitivity to visible light and cannot achieve a practical polymerization rate.

In recent years, attempts have been made to polymerize the above-mentioned photopolymerizable composition by irradiating it with visible light from the viewpoints of safety, miniaturization of an irradiation device, and high-speed polymerization. I have. That is, a photocurable composition that can be polymerized by irradiation with visible light has many advantages as listed below, and is therefore strongly demanded to be put to practical use.

(1) Use of a dangerous ultraviolet light irradiation device can be avoided. Since a large amount of ultraviolet light and ozone generated from the ultraviolet light irradiation device is harmful to the human body, it is necessary to take measures to completely block ultraviolet light and ozone. Workers must be protected by safety glasses and gloves. Therefore, the ultraviolet light irradiating device cannot be easily installed anywhere, and it is necessary to provide a light-shielding device, an exhaust device, and the like with sufficient measures for installation. On the other hand, when a photocurable composition having high sensitivity to visible light and a high polymerization rate is used, a visible light irradiation device whose light amount is about the same as that of a normal room light can be used. The visible light irradiation device does not generate ultraviolet light or ozone and has no danger.
Therefore, there is an advantage that it can be installed anywhere without choosing an installation place.

(2) The size of the irradiation device can be reduced, and the irradiation device can be built in a small device. As described above, in the visible light irradiation device, for example, it is only necessary to use one general small fluorescent lamp for indoor lighting as a light source, and it is advantageous for miniaturization in that ancillary facilities are not required. Thereby, it can be built in various small devices. Therefore, it can be used for devices for various uses in which the conventional ultraviolet light irradiation device could not be incorporated, thereby increasing the added value of a small device.

(3) Polymerization by a visible laser beam is possible. Polymerization using a visible laser beam having a large output is possible, which is an effective means for forming a precise image. In addition to the method of irradiating the entire surface with a visible laser beam through a mask, it is also possible to irradiate while scanning a visible laser beam, and a planar or three-dimensional image can be formed by these methods.

(4) Deep polymerization becomes possible. Since ultraviolet light is easily absorbed, when a photocurable composition is formed into a thick film, there is a problem that the deep portion is hardly polymerized. Even when polymerization is possible, long-time ultraviolet light irradiation is required.
On the other hand, since visible light easily reaches the deep part of the photocurable composition, a molded product can be relatively easily obtained even with a thick film.

(5) Polymerization can be performed in a transparent mold. Since ultraviolet light is easily absorbed by the transparent mold, it is difficult to polymerize the photocurable composition in the transparent mold by irradiation with ultraviolet light. On the other hand, according to visible light, polymerization in a transparent mold becomes possible, and in addition to relatively easy polymerization in a deep part as described above, a molded article having a complicated shape is obtained. You can also.

(6) It can be applied to a photocurable composition containing a pigment and a dye. When a pigment or dye is blended with the photocurable composition, the pigment or dye absorbs ultraviolet light, so it is difficult to polymerize with ultraviolet light, but visible light is easily transmitted to the inside because the wavelength is long, Even in this case, polymerization is easy.

(7) The polymerization can be carried out by directly irradiating the human body with light. Since ultraviolet light is harmful to the human body, applications for directly irradiating the human body should be avoided, but visible light can avoid this danger. For this reason,
It is suitable for applications in which the photocurable composition is polymerized on the human body by directly or indirectly irradiating light to the human body for treatment or other purposes. For example, in the field of dentistry, it can be applied to bonding of dental resin in the oral cavity.

[0011]

As described above, the photocurable composition which can use visible light as a light source is useful in many respects and can be expected to be applied to various uses. However, many conventional photocurable compositions cannot be polymerized by irradiation with visible light, and even when polymerizable, they have problems such as extremely low sensitivity and low polymerization rate. Conventionally, camphorquinone is well known as a visible light polymerization initiator (see, for example, JP-A-2-252775, International Application Publication WO 94/14913). However, when a photocurable composition containing an ethylenically unsaturated compound together with camphorquinone as a photopolymerization initiator is used, a long polymerization time is required due to a slow polymerization rate, and a long time is required for curing. However, there is a problem that the light curing depth is insufficient and the light curing depth is shallow. Further, there is a disadvantage that the obtained cured product is inferior in light resistance.

The present invention has been made in view of the problems of the conventional visible light curable composition as described above, and an object thereof is to provide a photocurable composition which is excellent in photocuring properties by irradiation with visible light and has a relatively low light amount. An object of the present invention is to provide a photocurable composition in which the curing progresses sufficiently, the gel time until curing is short, and the photocuring depth is large.

[0013]

In order to achieve the above object, according to the present invention, (A) an ethylenically unsaturated compound,
(B) A photocurable composition characterized by containing a bisacylphosphine oxide compound represented by the following general formula (1) and (C) an organic phosphine compound.

Embedded image According to a preferred embodiment of the photocurable composition of the present invention, in addition to the components (A) to (C), a photopolymerization initiator (D) other than the bisacylphosphine oxide compound (B)
According to another preferred embodiment, in addition to the components (A) to (C), or in addition to the components (A) to (D),
In addition to the components, it further contains at least one compound (E) selected from the group consisting of tertiary amines, secondary amines, and amides.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The photocurable composition of the present invention comprises an ethylenically unsaturated compound (A) and a bisacylphosphine oxide compound (B) represented by the general formula (1) and an organic phosphine compound (C). Is also combined. Bisacylphosphine oxide compound (B)
Is a visible light curable photopolymerization initiator from which a cured product having good light resistance is obtained unlike the camphorquinone,
With this alone, the photopolymerization rate of the ethylenically unsaturated compound (A) is low, the gel time is long, the curing is insufficient, and a sufficient photocuring depth cannot be obtained. On the other hand, the organic phosphine compound (C) does not act as a photopolymerization initiator. However, according to the study of the present inventors, the coexistence of the bisacylphosphine oxide compound (B) and the organic phosphine compound (C) significantly increases the visible light curability and the curing speed. As a result, they have found that the gel time is extremely short and the photocuring depth is large. Although the reason is not always clear, the sensitization is caused by the electronic interaction between the bisacylphosphine oxide compound (B) and the organic phosphine compound (C), and the absorbance of visible light is increased. It is presumed that even if the amount is small, the bisacylphosphine oxide compound is decomposed to generate a sufficient amount of active radicals. The above effects were surprisingly unexpected from the effects obtained when the bisacylphosphine oxide compound (B) or the organic phosphine compound (C) was used alone.

In general, when a radical polymerization initiator is used, the radicals easily trap oxygen in the air and cause oxygen inhibition (polymerization disorder due to oxygen), and the surface curability is often insufficient. On the other hand, when a bisacylphosphine oxide compound is used as a visible light-curable photopolymerization initiator, a photochemical reaction occurs quickly, so that a photocurable composition having excellent surface curability can be obtained. Acylphosphine oxide compounds similar to the above compounds are also known as photopolymerization initiators, but bisacylphosphine oxide compounds are advantageous in that a photochemical reaction occurs more quickly than acylphosphine oxide compounds.

In a preferred embodiment of the photocurable composition of the present invention, in addition to the components (A) to (C), a photopolymerization initiator other than the bisacylphosphine oxide compound (B) (D) Preferably, a phenyl ketone or titanocene-based photopolymerization initiator is used in combination. By using the bisacylphosphine oxide compound (B) and the other photopolymerization initiator (D) in such a manner, the gel time is extremely shortened and the photocuring depth is markedly reduced, as will be apparent from the examples described later. The effect of increasing is obtained. Further, the ethylenically unsaturated compound easily polymerizes even with a relatively small amount of visible light irradiation.

Further, in another preferred embodiment of the photocurable composition of the present invention, in addition to the components (A) to (C),
Alternatively, in addition to the components (A) to (D), at least one selected from the group consisting of tertiary amines, secondary amines, and amides
It is characterized by containing a kind of compound (E). The organic phosphine compound (C) is easily oxidized, which may affect the reactivity of the curable composition. Therefore, the amine compound is allowed to coexist to prevent oxidation of the organic phosphine compound, and as a result, the storage stability of the photocurable composition is improved. Even if an amine compound is added,
Upon irradiation with visible light, the bisacylphosphine oxide compound (B) and the organic phosphine compound (C) as described above are used.
Alternatively, the effect of using another photopolymerization initiator (D) in combination is not inhibited. Further, since the amine compound (E) also acts as a photopolymerization accelerator, an effect that the gel time can be considerably improved can be obtained.

Hereinafter, each component of the photocurable composition of the present invention will be described in detail. First, the ethylenically unsaturated compound (A), which is a photopolymerizable component, is not particularly limited as long as it is a compound in which the ethylenically unsaturated double bond undergoes radical polymerization upon irradiation with active energy rays. Compounds, unsaturated polyester compounds, unsaturated urethane compounds, styrene compounds, butadiene compounds, and the like. Among such ethylenically unsaturated compounds, (meth) acrylate-based compounds are particularly preferable, and the (meth) acrylate-based compound may be any of monofunctional, polyfunctional and monomeric or oligomer (prepolymer), Further, it may have a functional group other than an acryloyl group (methacryloyl group). Specifically, monomers such as substituted or unsubstituted aliphatic acrylates, alicyclic acrylates, aromatic acrylates and ethylene oxide-modified acrylates thereof, epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, polyol acrylate, Alkyd acrylate, melamine acrylate,
Examples include oligomers such as silicone acrylate and polybutadiene acrylate, and methacrylates corresponding thereto.

Specific examples of the ethylenically unsaturated compound (A) include butoxymethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth)
Acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycerol (meth) acrylate, 4- (meth) acryloxytricyclo [5.2.1.0 ^2.6 ] decane, isobornyl (meth) acrylate, isodecyl (Meth) acrylate, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, tetrahydrofur Monofunctional (meth) acrylates such as furyl (meth) acrylate, 4- (meth) acryloxyalkyl acid phosphate, and γ- (meth) acryloxyalkyl trialkoxysilane; acrylo Monofunctional monomers such as ilmorpholine, N-vinylpyrrolidone, N, N-dimethylacrylamide, N-vinylcarbazole, styrene, vinyl acetate, acrylonitrile, trialkoxyvinylsilane; bisphenol-A-di (meth) acrylate;
Alkylene oxide-modified bisphenol-A-di (meth) acrylate, 1,4-butanediol di (meth)
Acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonandiol-di (meth) acrylate, ethylene glycol di (meth) acrylate,
Triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate , Bis [4- (meth) acryloxymethyl] tricyclo [5.2.1.0
^2.6 ] decane, bis [4- (meth) acryloxy-2-
[Hydroxypropyloxyphenyl] propane, isophorone diisocyanate-modified urethane di (meth) acrylate, hexamethylene diisocyanate-modified urethane di (meth) acrylate, trimethylhexamethylene diisocyanate-modified urethane (meth) acrylate, trimethylhexamethylene diisocyanate-modified urethane (meth) acrylate, aliphatic Polyfunctional (meth) acrylates such as epoxy-modified (meth) acrylate and oligosiloxanyl di (meth) acrylate; and polyfunctional monomers such as triallyl isocyanurate, vinyl (meth) acrylate, and allyl (meth) acrylate. These ethylenically unsaturated compounds can be used alone or in combination of two or more. In addition, by using a monomer having an alkoxysilane in the molecule such as trialkoxyvinylsilane and γ- (meth) acryloxyalkyl trialkoxysilane together, glass,
Adhesion with inorganic materials such as ceramics and metals can be further enhanced.

In the photocurable composition of the present invention, as the number of ethylenically unsaturated double bonds in the ethylenically unsaturated compound (A) increases, the polymerization rate upon irradiation with visible light increases. In addition, the photopolymerization rate is also affected by the type and molecular skeleton of the functional group in the ethylenically unsaturated compound, and for example, when having an acryloyl group, polymerization is performed at a higher polymerization rate than when having a methacryloyl group. I do. Therefore, in the photocurable composition of the present invention, the polymerization rate during photopolymerization can also be adjusted by appropriately selecting the ethylenically unsaturated compound to be blended.

In the photocurable composition of the present invention, the above-mentioned general formula (1) used as a visible light curable photopolymerization initiator.
The bisacylphosphine oxide compound (B) represented by the formula (1) generates radicals upon irradiation with visible light to induce radical polymerization of the ethylenically unsaturated compound (A). Specific examples of such bisacylphosphine oxide compounds include bis (2,4,6-trimethylbenzoyl) methylphosphine oxide and bis (2,4,6-
Trimethylbenzoyl) ethylphosphine oxide, bis (2,4,6-trimethylbenzoyl) isopropylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -n-propylphosphine oxide, bis (2,4,6-trimethylbenzoyl) ) -N-butylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -t-butylphosphine oxide, bis (2,
4,6-trimethylbenzoyl)-(2-methyl-prop-1-yl) -butylphosphine oxide, bis (2,4,6-trimethylbenzoyl)-(1-methyl-prop-1-yl) -butylphosphine Oxide, bis (2,4,6-trimethylbenzoyl) cyclohexylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -n-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -n-hexyl Phosphine oxide, bis (2,4,6-trimethylbenzoyl)-(2-ethyl-hex-1-yl) phosphine oxide, bis (2,4,6-trimethylbenzoyl) -n-octylphosphine oxide, bis (2 ,
4,6-trimethylbenzoyl) (2,4,6-trimethyl-pent-1-yl) phosphine oxide, bis (2,4,6-trimethylbenzoyl) -n-decylphosphine oxide, bis (2,4 6-trimethylbenzoyl) phenylphosphine oxide, bis (2,4,
6-trimethylbenzoyl)-(4-methylphenyl)
Phosphine oxide, bis (2,6-dimethylbenzoyl) methylphosphine oxide, bis (2,6-dimethylbenzoyl) ethylphosphine oxide, bis (2
6-dimethylbenzoyl) -i-propylphosphine oxide, bis (2,6-dimethylbenzoyl) -n-propylphosphine oxide, bis (2,6-dimethylbenzoyl)-(2,4,4-trimethyl-pent-1 −
Yl) phosphine oxide, bis (2,6-dimethylbenzoyl)-(2-methyl-prop-1-yl) phosphine oxide, bis (2,6-dimethylbenzoyl)-
n-butylphosphine oxide, bis (2,6-dimethylbenzoyl) -t-butylphosphine oxide, bis (2,6-dimethylbenzoyl)-(1-methyl-prop-1-yl) phosphine oxide, bis (2 6-dimethylbenzoyl) cyclohexylphosphine oxide, bis (2,6-dimethylbenzoyl) -n-pentylphosphine oxide, bis (2,6-dimethylbenzoyl) -n-hexylphosphine oxide, bis (2
6-dimethylbenzoyl)-(2-ethyl-hex-1
-Yl) phosphine oxide, bis (2,6-dimethylbenzoyl) -n-octylphosphine oxide, bis (2,6-dimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethylbenzoyl)-(2
5-dimethylphenyl) phosphine oxide, bis (2,6-dimethylbenzoyl) -n-octylphosphine oxide, bis (2,4,6-triethylbenzoyl) -methylphosphine oxide, bis (2,4,6-
Triethylbenzoyl) -ethylphosphine oxide,
Bis (2,4,6-triethylbenzoyl) -i-propylphosphine oxide, bis (2,4,6-triethylbenzoyl) -n-propylphosphine oxide, bis (2,4,6-triethylbenzoyl) -n- Butylphosphine oxide, bis (2,4,6-triethylbenzoyl) -t-butylphosphine oxide, bis (2,4,6-triethylbenzoyl)-(2-methyl-prop-1-yl) phosphine oxide, bis ( 2,
4,6-triethylbenzoyl)-(1-methyl-prop-1-yl) phosphine oxide, bis (2,4,6
-Triethylbenzoyl) cyclohexylphosphine oxide, bis (2,4,6-triethylbenzoyl)-
n-pentylphosphine oxide, bis (2,4,6-
Triethylbenzoyl) -n-hexylphosphine oxide, bis (2,4,6-triethylbenzoyl)-
(2-ethyl-hex-1-yl) phosphine oxide, bis (2,4,6-triethylbenzoyl) -n-
Octylphosphine oxide, bis (2,4,6-triethylbenzoyl)-(2,4,4-trimethyl-pent-1-yl) phosphine oxide, bis (2,4,6
-Triethylbenzoyl) -n-dodecylphosphine oxide, bis (2,4,6-triethylbenzoyl)-
n-phenylphosphine oxide, bis (2,6-diethylbenzoyl)-(2,4,4-trimethyl-pent-1-yl) phosphine oxide, bis (2,6-diethylbenzoyl)-(2-methyl-prop -1-yl)
Phosphine oxide, bis (2,6-diethylbenzoyl) -n-butylphosphine oxide, bis (2,6-
Diethylbenzoyl) -t-butylphosphine oxide, bis (2,6-diethylbenzoyl)-(1-methyl-prop-1-yl) phosphine oxide, bis (2,6-diethylbenzoyl) cyclohexylphosphine oxide, bis (2 , 6-Diethylbenzoyl)-
n-pentylphosphine oxide, bis (2,6-diethylbenzoyl) -n-hexylphosphine oxide,
Bis (2,6-diethylbenzoyl)-(2-ethyl-
Hex-1-yl) phosphine oxide, bis (2,6
-Diethylbenzoyl) -n-octylphosphine oxide, bis (2,6-diethylbenzoyl) phenylphosphine oxide, bis (2,4,6-triisopropylbenzoyl) -n-butylphosphine oxide, bis (2,4,6 -Triisopropylbenzoyl) -t-butylphosphine oxide, bis (2,4,6-triisopropylbenzoyl)-(2-methyl-prop-1-yl) phosphine oxide, bis (2,4,6-triisopropylbenzoyl) )-(1-Methyl-prop-1-yl) phosphine oxide, bis (2,4,6-triisopropylbenzoyl) cyclohexylphosphine oxide, bis (2,4,6-triisopropylbenzoyl)
-N-pentylphosphine oxide, bis (2,4,6
-Triisopropylbenzoyl) -n-hexylphosphine oxide, bis (2,4,6-triisopropylbenzoyl)-(2-ethyl-hex-1-yl) phosphine oxide, bis (2,4,6-triisopropylbenzoyl) ) -N-octylphosphine oxide, bis (2,4,6-triisopropylbenzoyl)-(2
4,4-trimethyl-pent-1-yl) phosphine oxide, bis (2,4,6-triisopropylbenzoyl) -n-decylphosphine oxide, bis (2,4
6-triisopropylbenzoyl) phenylphosphine oxide, bis (2,4,6-tri-n-propylbenzoyl)-(2-methyl-prop-1-yl) phosphine oxide, bis (2,4,6-tri- n-propylbenzoyl) -n-butylphosphine oxide, bis (2,4,6-tri- (1-methyl-prop-1-yl) benzoyl) -n-octylphosphine oxide,
Bis (2,4,6-tri- (1-methyl-prop-1-
Yl) benzoyl) -n-butylphosphine oxide,
Bis (2,4,6-tri- (2-methyl-prop-1-
Yl) benzoyl)-(2,4,4-trimethyl-pent-1-yl) phosphine oxide, bis (2,4,6
-Tri- (2-methyl-prop-1-yl) benzoyl)-(2-methyl-prop-1-yl) phosphine oxide, bis (2,4,6-tri-t-butyl-benzoyl) -n- Butylphosphine oxide, bis (2,6
-Dimethyl-4-n-butylbenzoyl)-(2-methyl-prop-1-yl) phosphine oxide, bis (2,6-dimethyl-4-n-butylbenzoyl) -phenylphosphine oxide, bis (2,4 , 6-trimethylbenzoyl)-(2,5-dimethylphenyl) phosphine oxide, bis (2,6-dimethyl-4-n-butylbenzoyl)-(2,5-dimethylphenyl) honsphine oxide and the like. it can. These bisacylphosphine oxide compounds can be used alone or in combination of two or more.

The compounding amount of the bisacylphosphine oxide compound (B) depends on the amount of the ethylenically unsaturated compound (A).
It is usually selected in the range of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight. If the amount of the bisacylphosphine oxide compound is less than the above range, a sufficient photopolymerization rate cannot be obtained, and if the amount is more than the above range, the degree of polymerization of the ethylenically unsaturated compound becomes insufficient, In addition, it is not preferable because it may remain after polymerization and deteriorate the properties of the cured product.

In the present invention, the organic phosphine compound (C) compounded in combination with the bisacylphosphine oxide compound (B) is a primary phosphine, a secondary phosphine or a tertiary phosphine represented by the following general formula (2). is there. Specifically, the first phosphine includes phenyl phosphine, octyl phosphine, hexadecyl phosphine, and the like, and the second phosphine includes diphenyl phosphine, dioctyl phosphine, di (2-chlorophenyl) phosphine, di (methoxy phenyl). Phosphine, di (pentachlorophenyl) phosphine, butylphenylphosphine, bis (phenylphosphino)
Examples of tertiary phosphines include triphenylphosphine, tri (p-methoxyphenyl) phosphine, tri (p-tolyl) phosphine, tri (m-tolyl) phosphine, trinaphthylphosphine, and tri (p
-Chlorophenyl) phosphine, tributylphosphine, tricyclohexylphosphine, methyldiphenylphosphine, dibutylphenylphosphine, 1,2-bis (diphenylphosphino) ethane, bis (diphenylphosphino) methane and the like.

Embedded image

Among the above organic phosphine compounds, a second phosphine or a tertiary phosphine is preferable, and a tertiary phosphine is particularly preferable. The reason for this is that the tertiary phosphine itself is the most stable of the organic phosphine compounds and, when incorporated in a photocurable composition, at a higher polymerization rate, the ethylenically unsaturated compound (A) This makes it possible to carry out photopolymerization of The organic phosphine compound (C) may be used alone or
More than one kind can be used in combination, and the compounding amount is suitably in the range of 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the ethylenically unsaturated compound (A). Range of parts. If the compounding amount of the organic phosphine compound is too small than the above range, a sufficient polymerization rate cannot be obtained, and conversely, if the compounding amount is more than the above range, the organic phosphine compound remains after the photocuring of the composition and the cured product has There is a possibility that the characteristics are deteriorated.

In the photocurable composition of the present invention, the other photopolymerization initiator (D) that can be used in combination with the bisacylphosphine oxide compound (B) is not particularly limited. Hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2- (Hydroxy-2-propyl) ketone, 2,2
-Dimethoxy-2-phenylacetophenone, 2,2-
Diethoxyacetophenone, trichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2
-Methyl-1- [4- (methylthio) phenyl] -2-
Morpholinopropan-1-one, 2-benzyl-2-
Dimethylamino-1- (4-morpholinophenyl)-
Butanone-1, benzophenone, benzyl, methylbenzoyl formate, o-benzoylmethylbenzoate, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether,
Examples include benzoin isobutyl ether, xanthone, thioxaton, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-ethylanthraquinone, tetramethylthiuram monosulfide, and the like. In addition, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide,
2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, 2,6-dimethylbenzoyldiphenylphosphine oxide, 4-methylbenzoyldiphenylphosphine oxide, 4-ethylbenzoyldiphenylphosphine oxide Acyl such as 4-isopropylbenzoyldiphenylphosphine oxide, 1-methylcyclohexanoylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, and 2,4,6-trimethylbenzoylphenylphosphinic acid isopropyl ester And phosphine oxide compounds.

In addition, titanocene compounds which are photopolymerizable radical polymerization initiators at a light absorption wavelength of 400 to 700 nm, for example, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2- (1- Pyr-1-yl) ethyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-
((2,5-dimethyl-1-pyr-1-yl) methyl)
Phenyl] titanium, bis (cyclopentadienyl)
-Bis [2,6-difluoro-3-((2-isopropyl-5-methyl-1-pyr-1,6-yl) methyl) phenyl] titanium, bis (cyclopentadienyl)-
Bis [2,6-difluoro-3-((3-trimethylsilyl-2,5-dimethyl-1-pyr-1-yl) methyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6- Difluoro-3-((2,5-dimethyl-3- (bis (2-methoxyethyl) aminomethyl) -1-pyr-1-yl) methyl) phenyl] titanium, bis (cyclopentadienyl) -bis [ 2,6-
Difluoro-3-((2,5-bis (morpholinomethyl) -1-pyr-1-yl) methyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,3
5,6-tetrafluoro-4- (3- (1-pyr-1-
Yl) propyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-
(2- (4,5,6,7-tetrahydro-isoindol-2-yl) ethyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3
-(6- (9-carbazol-9-yl) hexyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (3- (2,3,4,
5,6,7,8,9-octahydro-1-carbazole-
9-yl) propyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3
-(2- (N-allylmethylsulfonylamino) ethyl) phenyl] titanium, bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole- 1-yl) phenyl) titanium and the like can also be used.

Among the above photopolymerization initiators (D), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxy-cyclohexylphenylketone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- Phenyl ketone compounds such as (4-morpholinophenyl) -butanone-1 and titanocene compounds are preferred. The other photopolymerization initiators (D) as described above can be used alone or in combination of two or more,
The compounding amount of the ethylenically unsaturated compound (A) 10
The amount is suitably 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 0 parts by weight. When the blending amount of the other photopolymerization initiator is less than 0.01 part by weight, it is difficult to obtain the above-described effect by using the bisacylphosphine oxide compound in combination, and on the other hand, the amount is more than 10 parts by weight. However, it is not economical because the effect is saturated and the composition is not economical. On the contrary, the composition may remain after photocuring and deteriorate the properties of the cured product, which is not preferable.

The amine compound of the component (E) which can be added to the photocurable composition of the present invention includes a tertiary amine represented by the following general formula (3) and a secondary amine represented by the following general formula (4) An amide represented by the following general formula (5) is used.

Embedded image Although these amine compounds are not particularly limited, tertiary amines are preferable among them. Specific examples of the tertiary amine include, for example, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine, tri-n -Butylamine, N-methyldiethanolamine, N-ethyldiethanolamine, triisopropanolamine, dimethylaminoethylbenzoate,
Dimethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminomethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diisopropylaminomethyl (meth) acrylate, and the like. These may be used alone or in combination of two or more. Can be used in combination. An appropriate amount of such an amine compound (E) is about 0.01 to 5 parts by weight per 100 parts by weight of the ethylenically unsaturated compound (A). If the amount of the amine compound is less than the above range, the above-described effects due to the addition of the amine compound cannot be obtained.

The photocurable composition of the present invention may contain additives as appropriate in addition to the components described above. For example, an organic or inorganic filler can be blended from the viewpoints of reducing the cure shrinkage, reducing the thermal expansion coefficient, improving the dimensional stability, improving the elastic modulus, adjusting the viscosity, improving the thermal conductivity, improving the strength, improving the toughness, and the like. As such a filler, polymers, ceramics, metals, metal oxides, metal salts, and the like can be used, and the shape is not particularly limited to a particle shape, a fibrous shape, and the like. In addition, when blending the above polymer, it is also possible to dissolve, semi-dissolve or microdisperse in the photocurable composition as a polymer blend or a polymer alloy instead of as a filler. Further, a colorant such as an organic or inorganic pigment or dye may be blended as an additive into the photocurable composition of the present invention, and the composition may be used for applications such as paints and inks. Further, in the photocurable composition of the present invention, as other additives, a softener, a plasticizer, a flame retardant, a storage stabilizer, an antioxidant, an ultraviolet absorber, a thixotropic agent, a coupling agent, a dispersant A stabilizer, a fluidity-imparting agent and the like can be appropriately compounded. In addition, it is also possible to prepare the above-mentioned essential components and, if necessary, these additives by dissolving them in an appropriate solvent.

As described above, in the photocurable composition of the present invention, desired properties can be imparted by blending the above essential components and appropriate additives, and polymerization by irradiation with visible light is possible. Due to this, it has a number of advantages as described above. Therefore, the photocurable composition of the present invention can be applied to a wide range of applications such as adhesives, coating agents, paints, molding materials, human body-related materials, and image forming materials. In addition, various modes can be adopted as the application form. For example, when utilizing the photocurable composition of the present invention as an adhesive, it can be prepared as a one-part adhesive and stored in a light-impermeable container,
A liquid composition (1) containing an ethylenically unsaturated compound (A) and a bisacylphosphine oxide compound (B) or another photopolymerization initiator (D), and an ethylenically unsaturated compound (A) And a liquid composition (2) containing an organic phosphine compound (C) or an amine-based compound (E) to prepare a two-part adhesive, and, in use, a liquid composition (1) on one of the adherend surfaces. And applying the liquid composition (2) to the surface of the other adherend, and bonding these adhesive-coated surfaces together to form a joint. In this case, since the photocurable rate of the photocurable composition of the present invention is extremely high and the degree of polymerization is high, the two adherends can be firmly bonded to each other in a very short time.

Further, the photocurable composition of the present invention has a sensitivity to ultraviolet light as high as that of visible light or more, and shows a sufficient polymerization rate. Therefore, the photocurable composition of the present invention,
It can be cured by irradiation with any of visible light and ultraviolet light. For example, when a cured product is manufactured by using a visible light irradiation device and an ultraviolet light irradiation device in combination, the photocuring is cured when the visible light is used as a light source but is not cured when the ultraviolet light is used as a light source. In the case of a composition, a photocurable composition having high sensitivity to ultraviolet light must be separately prepared, and a different photocurable composition must be used for each apparatus, which complicates the process. In contrast, the photocurable composition of the present invention has excellent sensitivity to both visible light and ultraviolet light, so that it is not necessary to use a different photocurable composition for each device, and It is extremely effective.

[0032]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but it goes without saying that the present invention is not limited to the following Examples.

Example 1 97.33 parts by weight of trimethylolpropane triacrylate and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Ciba Specialty.
Chemicals Co., Ltd., Irgacure 819) 2.67 parts by weight was mixed to prepare a photocurable composition solution (a).
A solution (b) is prepared by mixing 97.36 parts by weight of trimethylolpropane triacrylate and 2.64 parts by weight of triphenylphosphine. In use, the solution (a) and the solution (b) are mixed at a ratio of 3: 1. Used as a mixture.

Example 2 97.33 parts by weight of trimethylolpropane triacrylate and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Ciba Specialty Co., Ltd.)
Chemicals, Irgacure 819) 1.34 parts by weight and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Ciba Specialty Chemicals, Irgacure 369)
The photocurable composition solution (a) was prepared by mixing 34 parts by weight, while trimethylolpropane triacrylate 9
A solution (b) was prepared by mixing 7.36 parts by weight and 2.64 parts by weight of triphenylphosphine, and the solution (a) and the solution (b) were mixed at a ratio of 3: 1 for use. .

Example 3 97.33 parts by weight of trimethylolpropane triacrylate and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Ciba Specialty.
1.34 parts by weight of Chemicals, Irgacure 819) and bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl)- Phenyl) titanium (Irgacure 784, manufactured by Ciba Specialty Chemicals)
The photocurable composition solution (a) was prepared by mixing 1.34 parts by weight, while 97.36 parts by weight of trimethylolpropane triacrylate and 2.64 of triphenylphosphine were prepared.
The solution (b) was prepared by mixing parts by weight, and the solution (a) and the solution (b) were mixed at a ratio of 3: 1 for use.

Example 4 97.33 parts by weight of trimethylolpropane triacrylate and Irgacure 1850 bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide manufactured by Ciba Specialty Chemicals 2.67 parts by weight of a 1: 1 mixture of 1-hydroxy-cyclohexyl-phenyl ketone was mixed to prepare a photocurable composition solution (a), while 97.36 parts by weight of trimethylolpropane triacrylate and A solution (b) was prepared by mixing 2.64 parts by weight of phenylphosphine, and the solution (a) and the solution (b) were mixed with the solution (3) at the time of use:
The mixture was used at a ratio of 1.

Example 5 97.33 parts by weight of trimethylolpropane triacrylate and Irgacure 1800 (manufactured by Ciba Specialty Chemicals) {bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide 2.67 parts by weight of a 1: 3 mixture of 1-hydroxy-cyclohexyl-phenyl ketone was mixed to prepare a photocurable composition solution (a), while 97.36 parts by weight of trimethylolpropane triacrylate and A solution (b) was prepared by mixing 2.64 parts by weight of phenylphosphine, and the solution (a) and the solution (b) were mixed with the solution (3) at the time of use:
The mixture was used at a ratio of 1.

Example 6 97.33 parts by weight of trimethylolpropane triacrylate and Irgacure 1700 (bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide manufactured by Ciba Specialty Chemicals) 2-hydroxy-2-methyl-1-phenyl-
A photocurable composition solution (a) was prepared by mixing 2.67 parts by weight of a 1: 3 mixture of propan-1-one, while 97.36 parts by weight of trimethylolpropane triacrylate and triphenylphosphine 2 were prepared. .64 parts by weight were mixed to prepare a solution (b), and the solution (a) and the solution (b) were mixed at a ratio of 3: 1 for use.

Example 7 97.33 parts by weight of trimethylolpropane triacrylate and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Ciba Specialty.
Chemicals Co., Ltd., Irgacure 819) 2.67 parts by weight was mixed to prepare a photocurable composition solution (a).
97.36 parts by weight of trimethylolpropane triacrylate, 2.64 parts by weight of triphenylphosphine and p-
A solution (b) was prepared by mixing 1 part by weight of dimethylaminobenzoic acid isoamyl ester (manufactured by Nippon Kayaku Co., Ltd., KAYACURE DMBI), and the solution (a) and the solution (b) were mixed at a ratio of 3: 1 when used. They were used in a mixed ratio.

Example 8 97.33 parts by weight of trimethylolpropane triacrylate and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Ciba Specialty Co., Ltd.)
Chemicals Co., Ltd., Irgacure 819) 2.67 parts by weight was mixed to prepare a photocurable composition solution (a).
A solution (b) was prepared by mixing 97.36 parts by weight of trimethylolpropane triacrylate, 2.64 parts by weight of triphenylphosphine and 1 part by weight of triethylamine.
At the time of use, the solution (a) and the solution (b) were mixed and used at a ratio of 3: 1.

Example 9 97.33 parts by weight of trimethylolpropane triacrylate and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Ciba Specialty Co., Ltd.)
Chemicals Co., Ltd., Irgacure 819) 2.67 parts by weight was mixed to prepare a photocurable composition solution (a).
A solution (b) was prepared by mixing 97.36 parts by weight of trimethylolpropane triacrylate, 2.64 parts by weight of triphenylphosphine and 1 part by weight of diallylamine, and the above solution (a) and solution (b) were mixed at the time of use. : 1 was used by mixing.

Example 10 97.33 parts by weight of trimethylolpropane triacrylate and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Ciba Specialty.
Chemicals Co., Ltd., Irgacure 819) 2.67 parts by weight was mixed to prepare a photocurable composition solution (a).
97.36 parts by weight of trimethylolpropane triacrylate, 2.64 parts by weight of triphenylphosphine and a reactive aromatic polyamide resin (manufactured by Tomagawa Manufacturing Co., Ltd., ME-
(type) was mixed with 1 part by weight to prepare a solution (b), and the solution (a) and the solution (b) were mixed at a ratio of 3: 1 before use.

Comparative Example 1 For comparison, 99.33 parts by weight of trimethylolpropane triacrylate and 0.67 parts of triphenylphosphine were used.
The solution was prepared by mixing parts by weight.

Comparative Example 2 98 parts by weight of trimethylolpropane triacrylate and 2 parts by weight of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure 819, manufactured by Ciba Specialty Chemicals) were mixed. A photocurable composition was prepared.

Comparative Example 3 98 parts by weight of trimethylolpropane triacrylate, 1 part by weight of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure 819, manufactured by Ciba Specialty Chemicals) and 2-benzyl One part by weight of 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Irgacure 369, manufactured by Ciba Specialty Chemicals) was mixed to prepare a photocurable composition.

Comparative Example 4 98 parts by weight of trimethylolpropane triacrylate, 2 parts by weight of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure 819, manufactured by Ciba Specialty Chemicals) and p-dimethyl 0.25 parts by weight of aminobenzoic acid isoamyl ester was mixed to prepare a photocurable composition.

Comparative Example 5 98 parts by weight of trimethylolpropane triacrylate and bis (η ⁵ -2,4-cyclopentadien-1-yl)
-Bis (2,6-difluoro-3- (1H-pyrrole-
2 parts by weight of 1-yl) -phenyl) titanium (Irgacure 784, manufactured by Ciba Specialty Chemicals) was mixed to prepare a photocurable composition.

Comparative Example 6 A photocurable composition was prepared by mixing 97 parts by weight of trimethylolpropane triacrylate, 3 parts by weight of camphorquinone and 1 part by weight of dimethylaminoethyl methacrylate.

Using the samples obtained in Examples 1 to 8 and Comparative Examples 1 to 6, the following characteristics were tested. (1) Gel time 0.2 ml of each sample was dropped on a glass plate having a thickness of 3 mm.
A halogen lamp (100 V, 300 W × 1 lamp, manufactured by Marox Japan Co., Ltd.) was used as an irradiation light source, and 3 lamps above the sample were used.
It was set at a position of 2.5 cm, and irradiated through a UV cut filter (SK-HEIGHT HD-25 manufactured by Soken Chemical Co., Ltd., film thickness 25 μm). Meanwhile, the time until the sample gelled was measured while stirring the sample with a toothpick.

(2) Gel fraction (a) Measurement 1: 27 mmφ × 55 m whose weight was measured in advance
m, a container that does not transmit ultraviolet light (manufactured by Nidec Rika Glass Co., Ltd.
2 ml of the sample was placed in a brown screw-necked bottle SV-20), and the weight of the sample was measured. Then, a high pressure mercury lamp (USHIO spot cure UIS-251 manufactured by Ushio Inc.)
02, detector: USHIO UNI METER UI
T-102), placed at a position 10 cm above the container, and passed a UV cut filter to obtain an integrated light amount of 150 mJ.
/ Cm ² or 500 mJ / cm ² . The obtained cured product is immersed in acetone for 24 hours to dissolve the uncured product, and the acetone-insoluble cured product is removed by a hot air drier.
After drying at 0 ° C., the weight of the cured product was measured. The percentage of the weight of the cured product relative to the weight of the sample thus obtained was calculated, and this was defined as the gel fraction (%). (B) Measurement 2: A halogen lamp (100 V, 300 W × 1 lamp manufactured by Marox Japan) was used as a light source, the irradiation distance was 32.5 cm, and the irradiation time was 3 minutes, except that
The gel fraction was determined in the same manner as in Measurement 1 described above.

(3) Surface curability A 1 m sample was placed in a small can whose upper surface was previously measured and whose weight was measured.
1 and the weight of the sample was measured. Next, use a halogen lamp (100 V, 300 W × by Marox Japan).
1 light) at 32.5 cm above the sample, and UV
Irradiated through cut filter for 2 minutes. The obtained cured product was washed with acetone, dried at 70 ° C. with a hot air drier, and the weight of the cured product was measured. The percentage of the weight of the cured product relative to the weight of the sample thus obtained was calculated, and this was defined as the degree of surface curing (%).

(4) Depth of cure As shown in FIG. 1, a black ring-shaped resin is placed on the bottom of a 27 mmφ × 55 mm container (Nippon Denka Kagaku Co., Ltd., brown screw hole bottle SV-20) 1 which does not transmit ultraviolet rays. A sealing material (outside diameter 15 mm, inside diameter 5 mm) 2 is applied, and the sample S
Add an appropriate amount of Next, the irradiation spot 4 at the tip of the optical fiber 3 of a high-pressure mercury lamp (USHIO spot cure UIS-25102 manufactured by Ushio Inc.) was brought into close contact with the sealing material 2 at the bottom of the container, and irradiation was performed for 14 seconds. After the obtained cured product was washed with acetone, the height of the cured product was measured.

Table 1 shows the results of the above test.

[Table 1] As is clear from comparison of the results of Comparative Example 2 and Comparative Example 6, when only the bisacylphosphine oxide compound was used as the photopolymerization initiator, the degree of surface hardening was slightly higher than when camphorquinone was used. , Other properties are inferior. In Comparative Example 5 using only a titanocene compound as a photopolymerization initiator, the surface curing degree was high, but other characteristics were inferior. On the other hand, in Example 1 in which the photopolymerization initiator bisacylphosphine oxide compound was used in combination with the organic phosphine compound, excellent results were obtained in all the properties of gel time, gel fraction, surface hardening degree and hardening depth. Was. Further, as is clear from comparison of the results of Example 1 and Examples 2 and 4 to 6, when another photopolymerization initiator is used in combination with the bisacylphosphine oxide compound, the gel time, the gel fraction and the curing depth are reduced. It turns out that it improves further. Also, the results of Example 3 show that when a titanocene compound is used in combination with the bisacylphosphine oxide compound, the gel time, the surface curability, and the curing depth are improved. Furthermore, the results of Examples 7 to 10 show that the gel time can be improved by using a tertiary amine, a secondary amine or an amide together with the bisacylphosphine oxide compound.

[0054]

As described above, the photocurable composition of the present invention has excellent sensitivity to visible light, shows a sufficient polymerization rate when irradiated with both ultraviolet light and visible light, and has a very short time. It is excellent in both surface curability and curing depth. In addition, visible light can be used as a light source and can be applied to various uses, and its industrial value can be said to be extremely large.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram of a curing depth measuring device used in a test example.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Container 2 Ring-shaped resin sealing material 3 Optical fiber 4 Irradiation spot S Sample

Claims (3)

[Claims] (A) an ethylenically unsaturated compound, (B)
A photocurable composition comprising a bisacylphosphine oxide compound represented by the following general formula (1) and (C) an organic phosphine compound. Embedded image 2. The photocurable composition according to claim 1, further comprising a photopolymerization initiator other than the bisacylphosphine oxide compound (B). 3. The photocurable composition according to claim 1, further comprising at least one compound selected from the group consisting of tertiary amines, secondary amines, and amides.