JPS6076735A - Photosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain a photosetting resin composition having superior sensitivity and suitable for use as a material for a photomechanical process by blending a compound having a polymerizable ethylenic unsatd. bond with merocyanine and a diaryl iodonium salt as a photopolymn. initiator. CONSTITUTION:Merocyanine represented by formula I (where R is H or alkyl, n is 0 or 1, and a ring represented by formula II is a benzothiazoline ring or a dihydroquinoline ring), e.g., merocyanine represented by formula III or IV is combined with a diaryl iodonium salt such as diphenyl iodonium or ditolyl iodonium to prepare a photopolymn. initiator. This initiator is mixed with a compound having at least one polymerizable ethylenic unsated. bond such as 2-hydroxyethyl acrylate or diethylene glycol to obtain the desired photosetting resin composition. This composition is suitable for use in the formation of a relief.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a photocurable resin composition exhibiting excellent sensitivity, more specifically, a photocurable resin characterized in that a combination of merocyanine and a diaryliodonium salt is used as a photopolymerization initiator. The present invention relates to a composition.

Many studies have been conducted to increase the photosensitivity of photoinsoluble resins based on the principle of photopolymerization, and most of these studies concern photopolymerization initiators active in ultraviolet light. on the other hand,
Photo-insoluble resins are attracting attention not only as photoresists, inks, paints, festivals, 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, at least one trihalomethyl group conjugated to a triazine ring due to ethylenically unsaturation and at least one
A method has been proposed in which S-triazine having two chromophoric moieties is used as a photopolymerization initiator. Also, JP-A-54-15
No. 5292 proposes a composition using an unsaturated ketone conjugated with p-dialkylaminoallylidene as a photopolymerization initiator. Or, JP-A-52-1
．． No. 34692 proposes a composition containing a polycyclic quinone and a tertiary amine as a photopolymerization initiation system. Furthermore, JP-A-58-29803 discloses a photocurable resin using a combination of a cyanine dye and a triazine derivative as a photopolymerization initiator.

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

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

That is, the present invention provides a photocurable resin composition comprising a compound having at least one ethylenically unsaturated bond capable of polymerization and an fBl photopolymerization initiator. The present invention relates to a photocurable resin composition characterized in that a merocyanine represented by R represents a hydrogen atom or an alkyl group and represents an azoline or dihydroquinoline nucleus and a diaryliodonium salt as a photopolymerization initiator.

According to the present invention, it is possible to produce a photosensitive dye that is insolubilized with high sensitivity to long wavelength visible light. The constituent components of the composition will be explained below.

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, and may also be high molecular weight compounds. Specifically, acrylic acid, methacrylic acid, itaconic acid, maleic acid, acrylamide, methacrylamide, diacetone acrylamide, 2-hydroxy, ethyl acrylate, N-vinylcarbazole, N
-High-boiling monomers such as vinylpyrrolidone, as well as ethylene glycol, diethylene glycol,
, 3-propanediol, 1,4-butanediol, 1
, 5-bentanediol, ■, 6-hexanediol,
Di- or poly(meth)acrylic esters such as 1,10-decanediol, trimethylolethane, pentaerythritol, sorbitol, mannitol, etc., as well as (meth)acrylated epoxy resins, polyester acrylate oligomers, (meth)acrylated Examples include, but are not limited to, urethane oligomers and acroleinated polyvinyl alcohol.

Among the examples of merocyanine represented by the general formula (Il) and 17 constituting the photopolymerization initiator, the following are particularly preferred.

S The diaryliodonium salt as another component constituting the photopolymerization initiation system has the general formula ;1PJF・- or As
It is a compound represented by I@-). The compound represented by the general formula (2) used in the present invention includes Ma
oromoleaulea.

10, 130? The compounds described in α9?7), for example,
Chloride, bromide or borofluoride salt, hexafluorophosphate salt of iodonium such as diphenyliodonium, ditolyliodonium, phenyl(p-anisyl)iodonium, bis(m-nitrophenyl)iodonium, bis(p-tept-butylphenyl)iodonium , hexafluoroarsenate salt.

The amount of the photopolymerization initiator contained in the photocurable resin composition of the present invention is about 1:5 to about 1:500 in terms of weight ratio of merocyanine represented by general formula (I) to ethylenic compound.
It is possible to take a wide range up to 1, preferably 1
The range is from :10 to 1:100.

Also, the weight ratio of merocyanine to diaryliodonium salt 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.

As light sources suitable for the composition of the present invention, lasers such as He Ccl, Ar, and He-Ne can be used, in addition to high-pressure mercury lamps, ultra-high-pressure mercury lamps, high-pressure xenon lamps, halogen lamps, and fluorescent lamps.

The photocurable resin composition of the present invention has a sensitivity superior to 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, for printed wiring. It can be applied to a wide range of fields such as making boards.

The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to this.

Examples 1-5 1:1 of chloromethylstyrene and methyl methacrylate
1.35 g of the copolymer and 1.86 g of sodium 3,4-dihydro-2H-pyran-2-carboxylate were stirred in 20 ml of dimethylacetamide at 1,960 to 80° C. for one day, and the polymer was reprecipitated. After thorough washing with methanol, it was dissolved in dioxane again and purified by precipitation in methanol. The obtained polymer was prepared as a 7% by weight N-methylpyrrolidone solution, and this sulfate and merocyanine were each added to the polymer in amounts of 10% by weight to prepare a photosensitive solution. This was spin-coated onto an anodized aluminum plate, and the sensitivity was measured using a Kodak Step Tablet Nα1 with a xenon lamp as the light source.

The results are summarized in Table 1. Sensitivity is determined by Tokyo Ohka Kogyo (
It is shown as a relative value to the TPR of the stock.

A photoreceptor made of the composition of Example 4 was irradiated with a He Ne laser beam, and the exposure energy that gave a spot diameter equal to the beam diameter of 0.8 mm was measured.

As a result, it was found that insolubilization occurred at 10 mJ/cnl.

Table 1 Sensitivity Example 6 of a composition consisting of merocyanine-diaryliodonium group hexafluorophosphate
7. A composition consisting of 1 part of a polymer obtained by reacting a copolymer of chloromethylstyrene and methyl methacrylate with potassium methacrylate, 0.05 parts of diphenyliodonium hexafluorophosphate, and 0.05 parts of merocyanine. A dimethylformamide solution was prepared, spin coated on an anodized aluminum plate, and sensitivity was measured using a xenon lamp as a light source.

The results are summarized in Table 2.

Claims (1)

[Scope of Claims] +11 (A) A photocurable resin composition comprising a compound having at least one ethylenically unsaturated bond having polymerizability and an fBl photopolymerization initiator, which has the general formula (wherein R is a hydrogen atom) or an alkyl group and an azoline or dihydroquinoline nucleus) and a diaryliodonium salt as a photopolymerization initiator.