JPS61123603A - Photo-polymerizable composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a photopolymerizable composition. More specifically, the present invention relates to a stable photopolymerization initiation system exhibiting high sensitivity.

<Prior art> Many methods of forming image formations using photopolymerization systems have been known in the past.
For example, compounds containing addition-polymerizable ethylenic double bonds.
A photopolymerizable composition consisting of a photopolymerization initiator, an organic polymer binder, a thermal polymerization inhibitor, a colorant, a plasticizer, etc., which are used as desired, is prepared, and this photopolymerizable composition is processed without a solvent. Alternatively, a photosensitive material is prepared by applying a layer of a photopolymerizable composition to a solution and a Klr cloth on a support, imagewise exposing the desired image, polymerizing and curing the exposed areas, and dissolving and removing the unexposed areas. There is a method of curing and forming a leaf image. In addition, the above-mentioned photosensitive material is one in which a layer of a photopolymerizable composition is provided between two supports, at least one of which is transparent, and the transparent support is exposed imagewise from the side to cause a change in adhesive strength due to light. There are a method of forming a cross-sectional image by peeling off the support after the irradiation, and a method of forming an image that utilizes changes in the toner adhesion resistance of the photopolymerizable composition layer due to light. Conventionally, benzoin, benzoin alkyl ether, benzophenone, anthraquinone, benzyl, Michler's ketone, etc. have been used as photopolymerization initiators for photopolymerizable compositions applied to such methods. However, these photopolymerization initiators are not necessarily sufficient in terms of sensitivity, and attempts have been made to further increase the sensitivity. After that, it became possible to obtain a certain degree of satisfactory sensitivity by using a composite initiation system that uses one or more kinds of compounds in combination. For example, the combination of benzophenone and Michler's ketone is a typical example (British Patent No. 1.OPO, 1142). Currently, various studies are being conducted and reports have been made to aim for even higher sensitivity, but improvements in sensitivity often result in a decrease in storage stability, and there are still no products with sufficient performance. That is the reality.

Hexaarylbiimidazole and p as photopolymerization initiation system
- U.S. Pat. No. 35
≠Described in the specification of No. 2367. Furthermore, combinations of hexaarylbiimidazole and various sensitizers have been reported, and US Patent No. 3J33727 describes hexaarylbiimidazole and a coumarin compound. However, these had low photosensitivity to light having a wavelength of μHonm or more. US Patent gJtj227Jr
No. Specification O J1. In the specification of It/42/42, a combination of hexaarylbiimidazole and p-dialkylaminobenzylidene ketone is described as being particularly sensitive to light with a wavelength of 4 nm or more; Sensitization was desired.

The use of a 3-keto substituted coumarin compound in a photopolymerization initiation system is described in US Pat.
Also, a combination of a 3-keto-substituted coumarin compound and an amine compound, an acetic acid derivative, or an alkoxypyridinium salt (P
olym, Eng.

Sci, , , -2j (/r) t (/r3)], combination with active halogen compound [JP-A-5R
-irsoJ Publication] is known.

<Problem that the invention seeks to solve> However, further improvements were desired in terms of sensitivity and stability.

Therefore, the present invention aims to obtain a photopolymerization initiation system with high sensitivity and excellent storage stability.

Means for Solving the Problems> The present invention makes it possible to solve the above problems using a novel photopolymerization initiation system that combines a hexaarylbiimidazole and a 3-keto-substituted coumarin compound.

That is, the gist of the present invention is to provide an addition-polymerizable compound having at least one ethylenically unsaturated double bond and a hexaarylimidazole as a photopolymerization initiation system.
The photopolymerizable composition is specially designed to contain a marine compound instead of f.

The present invention will be explained in detail below.

Addition-polymerizable compounds having at least one ethylenically unsaturated double bond (hereinafter referred to as "compounds having ethylenically unsaturated double bonds") are included as the first essential component in the photopolymerizable composition of the present invention. ) is a photopolymerizable composition that is cured by addition polymerization due to the action of the photodecomposition product of the photopolymerization initiation system, which is the second essential component, when the photopolymerizable composition is irradiated with actinic rays. It is a monomer having an ethylenically unsaturated double bond or a polymer having an ethylenically unsaturated double bond in the side chain or the main chain, which causes insolubilization.

Examples of monomers having ethylenically unsaturated bonds include unsaturated carboxylic acids, esters of unsaturated carboxylic acids and aliphatic polyhydroxy compounds, esters of unsaturated carboxylic acids and aromatic polyhydroxy compounds, and unsaturated carboxylic acids. Examples include esters obtained by an esterification reaction between a polyhydric carboxylic acid and a polyhydroxy compound.

Specific examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pe/taerythritol diacrylate, and pe/taerythritol diacrylate. Acrylic acid esters such as /taerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate; triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate,
Trimethylolethane trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate,
Methacrylic acid esters such as dipentaerythritol trimethacrylate and dipentaerythritol tetramethacrylate; other examples include itaconic acid esters, crotonic acid esters and maleino acid esters of aliphatic polyhydroxy compounds.

Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.

Although not necessarily a single ester, typical examples include a condensate of acrylic acid, phthalic acid and ethylene glycol, a condensate of acrylic acid, maleic acid and diethylene glycol, methacrylic acid, terephthalic acid and penta Examples include condensates of erythritol, acrylic acid, adipic acid, butanediol, and glycerin.

Examples of compounds having ethylenically unsaturated double bonds used in the invention include acrylamides such as ethylenebisacrylamide, allyl esters such as diallyl phthalate and their prepolymers, and vinyl group-containing compounds such as divinyl phthalate. Useful.

Polymers having ethylenically unsaturated bonds in the main chain include, for example, polyesters obtained by the polycondensation reaction of unsaturated dicarboxylic acids and dihydroxy compounds, and polyesters obtained by the polycondensation reaction of unsaturated dicarboxylic acids and diamines. There are polyamides etc.

Polymers having ethylenically unsaturated bonds in their side chains include condensation polymers of dicarboxylic acids having unsaturated bonds in their side chains, such as itaconic acid, propylidene succinic acid, ethylidene malonic acid, etc., and dihydroxy or diamine compounds. . In addition, polymers having reactive functional groups such as hydroxyl groups and halogen/methyl chloride groups in their side chains, such as polyvinyl alcohol, poly(2-hydrodiethyl methacrylate),
Polymers obtained by polymer reaction of epoxy resins, phenoxy resins, polyepichlorohydrin, etc., and unsaturated carboxylic acids such as (meth)acrylic acid and crotonic acid can also be suitably used.

Among the compounds having an ethylenically unsaturated double bond described above, monomers of acrylic esters or methacrylic esters can be particularly preferably used.

Next, the photopolymerization initiation system, which is the second essential component of the photopolymerizable composition of the present invention, will be explained. The photopolymerization initiation system generates radicals by irradiation with actinic rays and also reduces the addition polymerization reaction of the above-mentioned compounds having ethylenically unsaturated bonds. The photopolymerization initiation system of the present invention consists of a novel combination of at least two components, the seventh component (5) of which is hexaarylbiimidazole. This is 2, Hiro, j-)
It is also called a realyl imidazolyl dimer and has a structure of the following formula in which two imidazoles are linked by one covalent bond.

Various isomers of the above compounds can be used in the present invention.

The aryl group is preferably a phenyl group. Such a phenyl group may have a substituent, and in particular, the ortho positions of the phenyl group at the 2- and 2'-positions are substituted with a fluorine atom, and the chlorine atom is substituted with a halogen atom such as a bromine atom, a nitro group, or a methyl group. Hexaarylbiimidazole is advantageous in terms of thermal stability and photoreaction rate.

As a specific example of hexaarylbiimidazole, Te1l-1
,2. λ′-bis(o-10lofenyl) ”-”tφ
/, r, j/-tetraphenylbiimidazole (
Hereinafter abbreviated as [a-/J], 2,2'-bis(0-bromophenyl)-Hiroshi, 4C', ! ,! '-tetraphenylbiimidazole (hereinafter abbreviated as r, -JJ), J,
2'-bis('+P-dichlorophenyl)-Hiro, Hiro',
! ,! '-Tetraphenylbiimidazole, 2.2'
-bis(0-chlorophenyl)-≠, 4c', z, r'
-tetra(m-methoxyphenyl)biimidazole,
2.2'-bis(o,o'-dichlorophenyl)-≠,
≠1. j, 11-tetraphenylbiimidazole, λ′-bis(0-nitrophenyl)-”*≠’*l!
' f t57 x nylbiimidazole, λ, λ'-
Bis(0-methylphenyl) -a, 4c', s, z'
-tetraphenylbiimidazole and the like.

These intermediate thearylbiimidazoles include, for example, Bu
ll, Chew, Sac, Japan, 33,
j 4 j (/940) Lolbi, r, Org, Ohe
m,, Jt (/6) can be easily synthesized by the method disclosed in Jt (/6).

The second component (6) of the photopolymerization initiation system is a 3-monovalent coumarin and is represented by the following general formula (1).

[In the formula, R1 and moieties may be different, and a hydrogen atom,
It represents a dialkylamino group or an alkoxy group, R3 represents an alkyl group or a phenyl group, R4 represents a hydrogen atom, a dialkylamino group or an alkoxy group, and R1 and R2 have the same meanings as above. ) is shown. ] Preferred specific examples include 3-acetylcoumarin, 3-acetyl-7-dinithylaminocoumarin, 3-penzoylcoumarin 97, and J-pe/soil-7-dinithylaminocoumarin (hereinafter abbreviated as rb-/J). , 3-benzoyl-7-medki7ris/, 3-benzoyl-! , 7-Simethoxycoumarin (hereinafter abbreviated as "b-JJ"), 3.3'-carbonylbiscoumarin (hereinafter abbreviated as "b-≠"), 3.3'-
Carbonylbis(7-dinithylaminocoumarin (hereinafter “
h-2''), J, 3'-carbonylbis (7-medoxycoumarin), J, J'-carbonylbis (r, 7
-cymethoxycoumarin) (hereinafter abbreviated as "6-IJ"), 7
-Dinithylamino-J-(Hiro-dimethylaminocinnamoyl)coumarin and the like. In particular, 3,3'-carbonylbis(7-dinithylaminocoumarin) is preferred because it has high sensitivity up to long wavelengths.

The photopolymerization initiation system of the present invention is based on a novel combination of λ type compounds of component (tz) and component (6). -NH- is shown. A thiol compound or/and a thiol compound represented by the general formula % [wherein R1%R2 and Rs represent a hydrogen atom or a hydrocarbon group which may have a substituent. ] By containing the amine compound represented by! The fI degree can be improved. A specific example of this thiol compound is Komelkabutobenzothiazole (r, -,
/J), comelcabutopenzoxazole (hereinafter abbreviated as "c-2"), and λ-mercaptobenzimidazole.

In the amine compound represented by the above general formula, R1 and R2 are alkyl groups such as methyl and ethyl, substituted alkyl groups such as cordimethylamino and hydroxymethyl, phenyl, a7tylphenyl, be/diylphenyl, and alkoxycarbonyl. Phenyl, pe/dioquina
I) Aryl group such as phenyl group substituted with ru or benzothiazolyl group Examples of Hs include alkyl groups such as methyl, substituted alkyl groups such as hydroxymethyl, and aryl groups such as phenyl.

Preferred specific examples include ethyl p-dimethylaminobenzoate (hereinafter abbreviated as ra-JJ), N,N-diethylaniline, triethanolamine, N,1! -diethylglycine, N-phenylchrycine, tribenzylamine, dibenzylamine, leucomalachite green, p-dimethylaminoacetophenone, p-dimethylaminobenzophenone, p,p'-bis(diethylamino)benzophenone s 1) tP'-bis (dimethylamino)pe/
Siphenon, ethyl p-dimethylaminobenzoate, p-
Inamyl dimethylaminobenzoate, N, N, N', N
'-nato2methylethylenediamine, co-(p-dimethylaminophenyl)benzoxazoles'-(p-diethylaminophenyl)benzoxazole, -1(p-dimethylaminophenyl)benzoxazole
-diethylaminophenyl)pe/dithiazole, etc., and dialkylaminophenyl group-containing compounds are particularly preferred. These thiol compounds or amine compounds can achieve improved sensitivity even if they do not have a substantial ability to absorb irradiated light, and in particular, 3-keto-substituted coumarins absorb irradiated light, so they only absorb light at shorter wavelengths. Absorption is desirable.

The preferred amount of the photopolymerization initiation system of the present invention to be used is 0.00% of component (a) relative to the compound having an ethylenically unsaturated double bond. j
~J 0% by weight, preferably /-/! t4#chi, component<h) 0. /~lj weight - preferably o, r~10% by weight. The thiol compound and/or amine compound preferably has a weight of 0.2 to 15 thiol.

In addition to the above-mentioned components, the photopolymerizable composition of the present invention may further contain an organic polymeric substance as a binder in order to modify the composition and improve the physical properties after photocuring. The binder may be appropriately selected depending on the purpose of improving compatibility, film-forming properties, developability, adhesion, etc. Specifically, for improving aqueous developability, #''t (mep) acrylic acid copolymer, itaconic acid copolymer, partially esterified maleic acid copolymer, and acidic cellulose modified with a carboxyl group in the side chain are used. polyethers of shrimp chlorohydrin and bisphenol A, soluble nylon, polyalkyl methacrylates such as polymethyl methacrylate, and polyacrylics to improve film strength and adhesion. Shun alkyl, copolymer of alkyl methacrylate and acrylonitrile, acrylic acid, methacrylic acid, vinyl chloride, vinylidene chloride, styrene, etc., copolymer of acrylonitrile and vinyl chloride, vinylidene chloride, vinylidene chloride, chlorinated polyolefin, chloride Copolymer of vinyl and vinyl acetate, polyvinyl acetate, copolymer of acrylonitrile and styrene, copolymer of acrylonitrile and butadiene, styrene, polyvinyl alkyl ether, polyvinyl alkyl ketone, polystyrene/, polyamide, polyurethane, polyethylene Examples include tere-7-thalerate, iso-7-thalerate, acetyl cellulose, and polyvinyl butyral.

The weight ratio of these binders to the compound having an ethylenically unsaturated double bond is 200% or less.

Preferably, it can be added and mixed in a range of 100% or less.

The photopolymerizable composition of the present invention may further contain a thermal polymerization inhibitor, a colorant, a plasticizer, a surface protective agent, a smoothing agent, a coating aid, etc., if necessary.

Examples of thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, pyrogallol, catechol, λ, t-
D-t-butyl-p-cresol, β-naphthol, etc. Coloring agents include pigments such as 7-thalocyanine pigments, azo pigments, carbon black, titanium oxide, etc.
Triphenylmethane dyes such as ethyl violet and crystal violet, azo dyes, anthraquino/
There are dyes based on cyanine and dyes based on cyanine.

The theoretical amounts of these thermal polymerization inhibitors and colorants added are 0.0% to 1% of the total weight of the compound having an ethylenically unsaturated double bond and the binder, 0% of the colorant, 1% to λ0chi is preferred. Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol caprylate, dimethyl glycol heptatarate, tricresyl phosphate, diocteradipate, dibutyl sepacate, glycerol triacetate, etc., which have an ethylenically unsaturated double bond group. For the total weight of the compound and binder with! −
The following can be added.

The photopolymerizable composition of the present invention can be used to form a photosensitive material in the absence of a solvent, or can be dissolved in a suitable solvent to form a solution, which is coated on a support and dried to prepare a photosensitive material. Examples of the solvent include methyl ethyl ketone, cyclohexanone, butyl acetate, amyl acetate, ethyl propionate, toluene,
xylene, monochlorobenze/, carbon tetrachloride, trichloroethylene, trichloroethane, dimethylformamide, methyl cellosolve, ethyl cellosolve/, tetrahydrofuran, pentoxone (≠-methyl-Hiro-methoxy 2
-Pentano/) etc.

Examples of the support used when preparing a photosensitive material using the photopolymerizable composition of the present invention include metals such as aluminum, magnesium, copper, zinc, chromium, nickel, and iron, or alloys containing these as main components. sheets, high-quality paper, art paper, paper such as release paper, glass, inorganic sheets such as ceramics, polyethylene terephthalate, polyethylene, polymethyl methacrylate, polyvinyl chloride, vinyl chloride-vinylidene chloride copolymer, polyethylene, 6 −
These include polymer sheets such as nylon, cellulose triacetate, and cellulose acetate butyrate.

In addition, the photopolymerizable composition of the present invention can be further processed using known techniques to prevent adverse effects such as a decrease in sensitivity and deterioration of storage stability due to oxygen, such as providing a removable transparent cover sheet on the photosensitive layer or A coating layer made of a waxy material, water-soluble polymer, etc. with low permeability may also be provided.

Suitable exposure light sources that can be applied to the composition of the present invention include carbon arc, low-pressure and high-pressure mercury lamps, xenon lamps, metal halide lamps, fluorescent lamps, argon ion lasers, krypton lasers, helium cadmium lasers, etc. obtain.

<Effects of the Invention> The photopolymerizable composition of the present invention containing a polymerization initiation system with high sensitivity and excellent storage stability is useful in a wide range of application fields, such as the preparation of printing plates for lithography and letterpress, printed wiring, etc. Engineering C%L
It can be used for photoresist for F3 production, dry film, image formation such as relief images and image duplication, photocurable ink, paint, adhesive, etc.

<Examples> The present invention will be specifically explained below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Example/-10 and Comparative Example 1-4 A partially esterified product of an equimolar copolymer of styrene and maleic anhydride having a weight average molecular weight of about rooo (CM-λ, manufactured by Ohka Kasei Co., Ltd., trade name)! ? , trimethylolpropane triacrylate j? Then, predetermined amounts of each component of the photopolymerization initiation system shown in Table 1 were dissolved in methylceronolp, and the sample photosensitive solution was placed on a grained and anodized aluminum sheet using a whirler until the dry film thickness was 2. It was coated to a thickness of .04 m and dried at 60° C. for 5 minutes. Furthermore, polyvinyl alcohol (GL-0 manufactured by Nippon Gosei Kagaku Co., Ltd.)
7. Apply an aqueous solution of (trade name) to a dry film thickness of /, 0 μm,
An overcoat layer was provided.

The resulting photosensitive sample had an optical density step of 0. / J step tablets were stacked and irradiated for 75 seconds from an ultra-high pressure mercury lamp in a vacuum baking frame at a distance of 2 cm, then developed with a sodium silicate ix*% aqueous solution, and the sensitivity was determined by the number of curing stages. A was measured.

Furthermore, for some samples, step tablets were similarly stacked/interference filters KL-
After irradiating light with a wavelength of around 100 nm for 15 seconds through a bright colored glass filter Y-≠7 (all manufactured by Toshiba Glass Co., Ltd.), the number of curing stages was determined by developing in the same manner. did.

The results are shown in Table 1 for component (G) and component (6).
The photopolymerization initiation system based on the new combination of the following showed high sensitivity.

Moreover, when b-2 was used, it was wide and had high sensitivity to light around onm.

In addition, the photosensitive sample was heated at 0°C, /week or 4cO°C.
The samples containing the photopolymerization initiation system of the present invention showed no change in sensitivity or developability and had excellent storage stability.

On the other hand, components (,) only, components (&) alone, components (α) or components (6) in combination with thiol compounds or amine compounds have low sensitivity, and therefore components (6) and (h) High sensitivity was achieved for the first time with the new combination K.

Claims (2)

[Claims] (1) A photopolymerizable composition containing an addition-polymerizable compound having at least one ethylenically unsaturated double bond and a hexaarylbiimidazole and a 3-keto-substituted coumarin compound as a photopolymerization initiation system. . (2) Furthermore, there are the following general formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, Z represents -O-, -S-, -NH-. ] or/and the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R^1, R^2 and R^3 have a hydrogen atom, a carboxyl group or a substituent. Indicates a good hydrocarbon group. ] The photopolymerizable composition according to claim 1, which contains an amine compound represented by the following.