JP2884741B2 - Photocurable composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a photocurable composition, and more particularly, to a photocurable composition having sensitivity characteristics at wavelengths from an ultraviolet region to an infrared region.

[Conventional technology]

Conventionally, for example, a photosensitive recording medium formed by applying a photocurable composition to the surface is irradiated with light based on image information, and only the lighted area is photocured to record an image on the photosensitive recording medium. Things are going on.

As the photocurable composition used in such a medium, various types are already known. Generally, a radical polymerizable unsaturated group-containing compound is used as a base material, and a photopolymerization initiator and a sensitizer are used. Are blended. In this case, as the photopolymerization initiator, those used alone such as benzyl, Michler's ketone, diethylthioxanthone, benzophenone, and acetophenone, and composite photopolymerization initiators such as a composite initiator system of a dye and an aliphatic amine (Japanese Patent Publication No. -20189), a complex system composed of hexaarylbiimidazole, a radical generator and a dye (Japanese Patent Publication No. 45-37377), and a complex system of hexaarylbiimidazole and p-dialkylaminobenzylidene ketone (Japanese Unexamined Patent Publication No. No. 2528), a complex system of a cyclic cis-α-dicarbonyl compound and a dye (JP-A-48-84183), a complex system of a carbonyl compound and a tertiary amine (JP-A-52-134692), substitution -Compound system of triazine and merocyanine dye (JP-A-54-
No. 151024), a complex system of biimidazole and indanone (JP-A-54-155292), a complex system of hexaarylbiimidazole and a p-dialkylaminostilbene derivative (JP-A-57-21401), hexaary A complex system of rubiimidazole and a p-alkylaminocinnamylidene derivative (JP-A-58-19315), a complex system of a triazine derivative and a cyanine dye (JP-A-58-29803),
Complex system of triazine derivative and thiapyrylium salt
58-40302), hexaarylbiimidazole and n-dialkylaminostilbenzene derivatives or p-
A complex system of a dialkylaminophenylbutadienyl derivative and a thiol compound (JP-A-59-56403) and a complex system of a ketone-substituted derivative and an organic peroxide (JP-A-60-32)
Photopolymerization initiators such as a complex system of α-diketone and mercaptocarboxylic acid (Japanese Patent Laid-Open No. 61-258802) and a complex system of α-diketone and polysulfide (Japanese Patent Laid-Open No. 61-258803). It has been known.

[Problems to be solved by the invention]

However, photocurable compositions using these single or composite photopolymerization initiators have problems such as poor photocuring sensitivity and slow curing speed due to slow curing.

The present invention has been made to solve the above-described problems, and its object is to increase the curing type sensitivity having sensitivity characteristics at any wavelength from the ultraviolet light region to the infrared light region,
An object of the present invention is to provide a photocurable composition that can shorten the curing time.

[Means for solving the problem]

Using a radical polymerizable unsaturated group-containing compound as a base material, adding an appropriate amount of an iron arene compound as a photopolymerization initiator thereto, and further as a sensitivity sensitizer N, N-dialkylaniline or a group having no unsaturated bond or It is obtained by adding a small amount of an N, N-dialkylaniline compound in which a halogen is substituted on a benzene ring.

The radical polymerizable unsaturated group-containing compound used in the present invention is not particularly limited, but is generally N-vinyl-2-pyrrolidone, bisphenol A diacrylate and methacrylate, tripropylene glycol diacrylate and methacrylate, polyethylene Glycol diacrylate and methacrylate, pentaerythritol triacrylate and methacrylate,
Examples include dipentaerythritol hexaacrylate and methacrylate, trimethylolpropane triacrylate and methacrylate, oligoester acrylate and methacrylate, and the like. Further, these radical polymerizable unsaturated group-containing compounds may be used alone or as a mixture of two or more.

Such radically polymerizable unsaturated group-containing compounds include:
A photopolymerization initiator is contained. Examples of the photopolymerization initiator include benzyl, Michler's ketone, diethylthioxanthone, benzophenone, acetophenone, and metal arene compounds. Among them, metal arene compounds are particularly preferred. These photopolymerization initiators may be used alone or 2
It may be a mixture of more than one species. The metal arene compound which is the most preferred embodiment as a photopolymerization initiator is represented by the following general formula (1).

Here, M _t represents a metal such as Fe. X is a group containing at least one benzene ring, preferably benzene. Y ^- is ^{_{BF 4 -, PF 6 -,}} AsF 6 - illustrates a basic ion substance such.

Such a metal arene compound is contained in an amount of 0.01 to 20% by weight, more preferably 1 to 10% by weight, based on the radical polymerizable unsaturated group-containing compound. When this value exceeds 20% by weight, there is a disadvantage that the monomer does not disperse.
When the content is less than 0.01% by weight, there is a disadvantage that the composition is not cured.

Further, the radical polymerizable unsaturated group-containing compound contains an aniline-based compound as a sensitivity sensitizer.

Such an aniline compound is not particularly limited, but preferably has an alkyl group. Such aniline-based compounds include, for example, N, N-dimethylaniline, 4-cyano-N, N-dimethylaniline, 4-acetyl-N, N-dimethylaniline, 4-bromo-N, N-dimethylaniline , Ethyl 4-
(N, N-dimethylamino) benzoate, 3-chloro-N, N-dimethylaniline, 4-chloro-N, N-dimethylaniline, 3-ethoxy-N, N-dimethylaniline,
-Fluoro-N, N-dimethylaniline, 4-methyl-N, N
-Dimethylaniline, 4-ethoxy-N, N-dimethylaniline, N, N-dimethylthioanisidine, 4-amino-
N, N-dimethylaniline, 3-hydroxy-N, N-dimethylaniline, N, N, N ', N'-tetramethyl-1,4-dianiline, 4-acetamido-N, N-dimethylaniline, etc. .

The aniline-based compound having an alkyl group is 0.01 to 50% by weight based on the radical polymerizable unsaturated group-containing compound,
More preferably, the content is 1 to 15% by weight. When this value exceeds 50% by weight, there is a disadvantage that the composition is not cured, and when this value is less than 0.01% by weight, there is a problem that the sensitization is insufficient.

[Action]

According to the photocurable composition of the present invention having the above configuration, when the photopolymerization initiator receives light, the photoinitiator I is radicalized as shown in the following formula (3), and a radical R is generated. The generated radical R • forms a polymer by a chain reaction with the radical polymerizable unsaturated group-containing compound M as shown in the following formula (4).

Here, if oxygen O ₂ is present in the reaction system, the radical R · reacts with oxygen to form RO ₂ · as shown in the following formula (5). Are not formed, and the polymerization reaction rate is suppressed.

The addition of aniline compound in the reaction system in the presence of oxygen, as in the following equation (6), hydrogen H aniline compound R'H is added to RO ₂ ·, RO ₂ H and the newly radicals R '
Are generated, and the radical R '. Starts a chain reaction again to form a polymer, so that the rate of the polymerization reaction is hardly suppressed by oxygen.

I → R ・ ・ ・ ・ (3) R ・ + M + M + M + ・ ・ ・ → RMM ・ + M + M + ・ ・ ・ → RMM ・ + M + ・ ・ ・ (4) R ・ + O ₂ → RO ₂・ ・ ・ ・ (5) RO ₂ + R'H → RO ₂ H + R '・ (( 6) [wherein I: polymerization initiator R .: radical generated from the polymerization initiator M: radical polymerizable unsaturated group-containing compound O ₂ : oxygen molecule R'H: aniline compound R ':: from aniline compound Examples of generated radicals] [Examples] Hereinafter, the present invention will be described in more detail with reference to Examples.

Experimental Example 1 (Invention) N, N-dimethylaniline was used as the aniline-based compound.

As a radical polymerizable unsaturated group-containing compound, a mixture of two kinds of polyethylene glycol diacrylate and dipentaerythritol hexaacrylate is used as a base material, and an iron arene compound (X is benzene, Y is RF ₆ ^- ).

 The compounding amounts (ratio) are as shown below.

As the orientation method, the above-mentioned two types of radically polymerizable unsaturated group-containing compounds were mixed at the above-mentioned mixing ratio, and an iron arene compound as a photopolymerization initiator and N, N- as a sensitivity sensitizer were added thereto. Dimethylaniline was mixed at the above mixing ratio. Then, while mixing and stirring by ultrasonic irradiation, 100
The composition was heated and kneaded at a heating temperature of about 15 ° C. for about 15 minutes to obtain the composition of the present invention. The heating temperature is suitably room temperature (20 ° C.) or more and 200 ° C. or less, preferably 50-150 ° C., and the time required for heating and kneading is 10 minutes or more.

Experimental Example 2 (Comparative Example) The sensitivity sensitizer of Experimental Example 1 was replaced with 2,2-dimethoxy-2-
The same procedures as in Experimental Example 1 were carried out except that phenylacetophenone was used (the amount was 0.1 g per 10 g of radically polymerizable unsaturated group-containing compound).

Experimental Example 3 (Comparative Example) Except that the sensitivity sensitizer of Experimental Example 1 was changed to thioxanthone (the amount was 0.1 g per 10 g of a radical polymerizable unsaturated group-containing compound according to Experimental Example 1). It was the same as in Experimental Example 1.

Experimental Example 4 (Comparative Example) The sensitivity sensitizer of Experimental Example 1 was replaced with naphthalene (the compounding amount corresponded to that of Experimental Example 1 and a radical polymerizable unsaturated group-containing compound was used).
Except that the amount was changed to 0.1 g per 10 g).

Experimental Example 5 (Comparative Example) The sensitivity sensitizer of Experimental Example 1 was replaced with benzyl (the compounding amount corresponded to that of Experimental Example 1;
except that the amount was changed to 0.1 g per g).

Experimental Example 6 (Comparative Example) The sensitivity sensitizer of Experimental Example 1 was changed to acridine (the compounding amount corresponds to that of Experimental Example 1, and the compound containing a radical polymerizable unsaturated group was used).
Except that the amount was changed to 0.1 g per 10 g).

Experimental Example 7 (Comparative Example) The same operation as in Experimental Example 1 was performed except that no sensitivity sensitizer was added.

Using the compositions obtained in each of the above experimental examples, the photocurability of each composition was actually examined. The experimental method was carried out by applying the obtained composition to the surface of a polyester sheet and measuring the photocuring energy with a spectral sensitivity meter. Table 1 shows the results.

As is clear from Table 1, according to the composition of the experimental example according to the present invention, the photocuring energy value of the composition of the present invention is higher than that of the composition of the present invention.
The value was relatively lower than that of the composition, and the curing speed was found to be fast.

It should be noted that the present invention is not limited to the above embodiment,
Various modifications can be made without departing from the spirit of the invention. For example, a wavelength sensitizer can be added to the photocurable composition of the above example so that the composition can be cured at an arbitrary wavelength.

〔The invention's effect〕

As is apparent from the above detailed description, according to the photocurable composition of the present invention, upon photocuring polymerization of the radical polymerizable unsaturated group-containing compound, synergistic curing of the photopolymerization initiator and the aniline compound is performed. Thereby, the photocuring sensitivity can be increased, so that the photocuring treatment time can be shortened. Further, since the aniline-based compound does not have wavelength selectivity, there is an effect that it can be used at any wavelength from the ultraviolet region to the infrared region.

Continuation of the front page (56) References JP-A-2-263803 (JP, A) JP-A-2-291 (JP, A) JP-A-2-249 (JP, A) JP-A-61-304453 (JP) JP-A-61-114234 (JP, A) JP-A-63-221110 (JP, A) JP-A-62-90648 (JP, A) JP-A-63-258903 (JP, A) JP-A-1-304453 (JP, A) JP-A-2-2562 (JP, A) JP-A-63-146903 (JP, A) JP-A-2-868 (JP, A) A) JP-A-63-91130 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03F 7/004-7/031 C08F 2/48-2/50

Claims (2)

(57) [Claims] 1. A radical polymerizable unsaturated group-containing compound as a base material, which has at least an iron arene compound as a photopolymerization initiator and no N, N-dialkylaniline or an unsaturated bond as a sensitivity sensitizer. A photocurable composition comprising an N, N-dialkylaniline compound in which a benzene ring is substituted for a group or halogen. 2. The method according to claim 1, wherein said iron arene compound is present in an amount of 0.01 to 20% by weight based on said radical polymerizable unsaturated group-containing compound.
The photocurable composition according to claim 1, wherein the composition contains 0.01 to 50% by weight of an N-dialkylaniline or an N, N-dialkylaniline-based compound.