JPH0236604B2 - HIKARIKOKAJUSHISOSEIBUTSU - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a photocurable resin composition exhibiting excellent sensitivity,
More specifically, the present invention relates to a photocurable resin composition characterized in that a combination of an aminophenyl compound and an active halogen compound is used as a photopolymerization initiator.

Many studies have been carried out to increase the photosensitivity of photoinsoluble resins based on the principle of photopolymerization, and most of them are related to photopolymerization initiators active in ultraviolet light. On the other hand, photoinsoluble resins are attracting attention not only as photoresists, inks, paints, varnishes, and printing plate materials, but also as image forming materials using laser light and photosensitive materials in place of silver salts. Conventional materials have extremely insufficient photosensitive characteristics for use in lasers. Therefore, it is necessary to expand the photosensitive wavelength range and dramatically increase the photosensitive speed.

Several proposals have been made for photopolymerizable resins that are sensitive to visible light. In JP-A-48-36281, S having at least one trihalomethyl group conjugated to a triazine ring due to ethylenic unsaturation and at least one chromophore moiety
- A method using triazine as a photopolymerization initiator has been proposed. Furthermore, Japanese Patent Application Laid-Open No. 155292/1983 proposes a composition in which an unsaturated ketone conjugated with p-dialkylaminoallylidene is used as a photopolymerization initiator. Or, JP-A-52-134692
In the publication, a composition using a polycyclic quinone and a tertiary amine as a photopolymerization initiation system is proposed.

All of these can provide materials that are sensitive to longer wavelength light than conventional photopolymerizable resins, but even higher photosensitive speeds are desired for use as photosensitive materials for lasers or silver salt substitute materials. .

The present invention was completed based on the discovery that aminophenyl compounds efficiently sensitize the photodecomposition of iodonium salts in the process of investigating the sensitized decomposition reaction of diaryliodonium salts that generate acid through photolysis. It is something that

That is, the present invention provides a photoinsoluble resin composition comprising a photopolymerization initiator and a compound having at least one ethylenically unsaturated bond having polymerizability, which has the general formula () (R ₁ and R ₂ in the formula represent an alkyl group, and n is 0
or 1, and X may have a substituent 1-
(representing an azoniaphenyl group or a 1-azonianaphthyl group, and Y represents an acyl group, a cyano group, or an alkoxycarbonyl group) and an active halogen compound as a photopolymerization initiator. The present invention relates to a cured resin composition.

As the aminophenyl compound represented by the general formula () constituting the photopolymerization initiator, the following compounds can be exemplified.

In these compounds, the 1-azoniaphenyl group or 1-azonianaphthyl group may have a substituent, and the substituent may be a polymeric substance. In particular, when the substituent is a polymeric substance, not only the sensitivity is significantly increased, but also the decrease in sensitivity caused by the polymerization inhibiting effect of oxygen in the atmosphere is reduced. The polymer material for this purpose is the general formula () (In the formula, R ₁ , R ₂ , Y, and n have the same meanings as above, and Z ^- represents a halogen ion.) A vinyl polymeric polymer material having at least one photosensitive structural unit represented by the following is particularly desirable. .
A vinyl polymeric polymer material containing a photosensitive structural unit represented by the general formula () can be produced from a vinylpyridine copolymer in the following manner. That is, by reacting a vinylpyridine copolymer with a halomethyl compound, the general formula () Let the constituent unit be expressed as . Next, a condensation reaction may be performed with p-dialkylaminobenzaldehyde or p-dialkylaminocinnamaldehyde.

The iodonium salt as an active halogen compound, which is another component constituting the photopolymerization initiation system, has the general formula () (R ₃ and R ₄ in the formula are hydrogen atoms, lower alkyl groups,
It represents a methoxy group or a nitro group, and X ^- represents a halogen ion, BF ₄ ^- , PF ₆ ^- or A _S F ₆ ^- . The compounds represented by the general formula () used in the present invention include:
Macromolecules, 10, 1307 (1977). Mention may be made of iodonium chloride, bromide or borofluoride salts, hexafluorophosphate salts, and hexafluoroarsenate salts.

Alternatively, as an active halogen compound,
s-triazines substituted with at least one mono-, di- or trihalomethyl group, e.g.
2,4,6-tris(trichloromethyl)-s-
Triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-methyl-
4,6-bis(trichloromethyl)-s-triazine is also suitable for the present invention.

The compound having at least one ethylenically unsaturated bond constituting the photocurable resin composition of the present invention includes oligomers in addition to vinyl monomers,
Furthermore, a high molecular weight compound may be used. Specifically, acrylic acid, methacrylic acid, itaconic acid, maleic acid, acrylamide, methacrylamide, diacetone acrylamide, 2-hydroxyethyl acrylate, N-vinylcarbazole,
There are high-boiling monomers such as N-vinylpyrrolidone, as well as ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4
-butanediol, 1,5-pentanediol,
Di- or poly(meth)acrylic esters such as 1,6-hexanediol, 1,10-decanediol, trimethylolethane, pentaerythritol, sorbitol, mannitol, and
Examples include (meth)acrylated epoxy resins, polyester acrylate oligomers, (meth)acrylated urethane oligomers, and acroleinated polyvinyl alcohol, but are not limited thereto.

The amount of the photopolymerization initiator contained in the photocurable resin composition of the present invention is about 1:5 to about 1 in terms of the polymerization ratio of the aminophenyl compound represented by the general formula () to the compound having an ethylenically unsaturated bond. :500, preferably in the range 1:10 to 1:100. The weight ratio of aminophenyl compound to active halogen compound ranges from about 10:1 to about 1:10, preferably from about 2:1 to about 1:5.

If desired, known additives such as a binder, a thermal polymerization inhibitor, and a plasticizer may be added to the photocurable resin composition of the present invention.

Suitable light sources for the compositions of the invention include high-pressure mercury lamps, ultra-high pressure mercury lamps, high-pressure xenon lamps, halogen lamps, fluorescent lamps, as well as He-Cd, Ar, He-
Lasers such as Ne can be used.

The photocurable resin composition of the present invention has a sensitivity superior to that of conventional photopolymerizable compositions, so it can be used as a plate-making material for planography or letterpress, for the production of reliefs, for the production of non-silver salt images, and for printed wiring boards. It can be applied to a wide range of fields such as creating .

The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.

Example 1 3.56 g of 1-phenacylpyridinium bromide and 1.5 g of p-dimethylaminobenzaldehyde were dissolved in 30 ml of acetic anhydride, and the mixture was reacted at 130° C. for 30 minutes. After concentrating the reaction solution using an evaporator,
The red pasty product was dissolved in 40 ml of distilled water. This aqueous solution was heated to 50° C., and 1.89 g of potassium hexafluorophosphate was added thereto and stirred. The precipitated yellowish precipitate is recrystallized from hot water,
3.3 g (yield 71%) of the compound represented by the following formula was obtained. The melting point was 120-122°C. 10mg of this compound
was added to 1.00 g of a 10% by weight solution of polyglycidyl methacrylate in dioxane, and A photosensitive solution was prepared by mixing and dissolving 70 mg of lythritol triacrylate and 10 mg of diphenyliodonium hexafluorophosphate. This was diluted with 1.2 ml of dimethylformamide and then spin-coated onto an aluminum plate. After drying the coating film, a 10% polyvinyl alcohol aqueous solution was spin-coated to form a top coat layer. A xenon lamp (0.9 mW/cm ² ) was applied through the Eastman Kodak Co., Ltd. step tablet No. 1A.
Irradiated for 20 seconds. When the PVA membrane was removed with water and developed with dioxane, up to 7 layers were insolubilized. This corresponds to approximately 32 times the sensitivity of polyvinyl cinnamate-based sensitive materials.

Example 2 In the photosensitive solution prepared in Example 1, 10 mg of 2-methyl-4,6-bis(trichloromethyl)-s-triazine was used in place of diphenyliodonium hexafluorophosphate. The photosensitivity of this material was evaluated in the same manner as in Example 1, and as a result, it showed about 8 times the sensitivity of the polyvinyl cinnamate-based sensitive material.

Claims (1)

[Scope of Claims] 1. A photoinsoluble resin composition comprising a compound having at least one ethylenically unsaturated bond having polymerization ability and a photopolymerization initiator, which has the general formula (R ₁ and R ₂ in the formula represent an alkyl group, and n is 0
or 1, and X may have a substituent 1-
The combination of a compound having a conjugated dialkylaminophenyl group (representing an azoniaphenyl group or a 1-azonianaphthyl group, and Y represents an acyl group, a cyano group, or an alkoxycarbonyl group) and an active halogen compound is used as a photopolymerization initiator. A photocurable resin composition characterized by: 2. The photocurable resin composition according to claim 1, wherein the active halogen compound is a diaryliodonium salt or an s-triazine substituted with at least one mono-, di-, or trihalomethyl group.