JP3473259B2 - Photopolymerizable composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photopolymerizable composition. Particularly, the present invention relates to a photopolymerizable composition suitable for image formation.

[0002]

2. Description of the Related Art Conventionally, many image forming methods utilizing a photopolymerizable composition are known. For example, a photopolymerizable composition is prepared from a compound having an addition-polymerizable ethylenic double bond, a photopolymerization initiator, and optionally an organic polymer binder, and the photopolymerizable composition is used as a support. A light-sensitive material having a layer of the photopolymerizable composition coated thereon is prepared, and a desired image is imagewise exposed to this to polymerize and cure the exposed portion, and then the unexposed portion is dissolved and removed to cure and cure a relief image. There is known a method of forming the. Further, the above-mentioned photopolymerizable composition is provided in a layer form between two supports, at least one of which is transparent, and image exposure is performed from the transparent support side to cause a change in adhesive strength by light, and then the support is A method of forming an image by peeling is known. Furthermore, a microcapsule having a photopolymerizable composition and a color material such as a leuco dye in its content is applied to a support to prepare a photosensitive material provided with a microcapsule layer, and this is imagewise exposed to form a capsule in an exposed portion. A method for forming a colored image by photocuring, then destroying the unexposed portion of the capsule by pressure treatment or heat treatment, and contacting the color material with a color developer to form a colored image, a method of forming a photopolymerizable composition layer An image forming method and the like utilizing changes in toner adhesion due to light are also known.

Conventionally, benzoylalkyl ether, benzyl ketal, benzophenone, anthraquinone, Michler's ketone, etc. have been used as the photopolymerization initiator of the photopolymerizable composition applied to these methods. However, when these photopolymerization initiators are used for the preparation of a photopolymerizable composition having a high concentration of a pigment that does not have an oxygen gas barrier, such as a pigment-dispersed resist for a color filter, it has a practical sensitivity. There is a problem that can not be obtained. Further, these photopolymerization initiators are compared with the photopolymerization initiation ability with respect to light in the ultraviolet region of 400 nm or less,
It is remarkably low for light in the visible region above 400 nm, so that the application range of photopolymerizable compositions containing them is limited.

In recent years, with the development of image forming technology, there has been a strong demand for a photopolymer having a high adaptability to light rays in the visible region. For example, it is a light-sensitive material suitable for non-contact type projection exposure plate making, laser plate making by visible light laser, and the like. For example, a plate making method using an 488 nm oscillation beam of an argon ion laser is considered to be one of the most promising techniques in the future.

Several proposals have hitherto been made for a photopolymerizable composition containing a photopolymerization initiation system which is sensitive to light rays in the visible light region. Examples of such a photopolymerization initiation system include a system of hexaarylbiimidazole and a radical generator and a dye (Japanese Patent Publication No. 45-37377), a system of hexaarylbiimidazole and (p-dialkylaminobenzylidene) ketone ( JP-A-47-25
28, JP-A-54-155292, JP-A-56-1
No. 66154), systems of cyclic cis-α-dicarbonyl compounds and dyes (JP-A-48-84183), systems of substituted triazines and merocyanine dyes (JP-A-54-1).
51024), a system of ketocoumarin and an activator (JP-A-52-112681, JP-A-58-15503,
JP-A-60-88005), systems of substituted triazines and sensitizers (JP-A-58-29803, JP-A-58-58003).
40302), hexaarylbiimidazole, styrene derivative and thiol system (JP-A-59-5).
6403), a system of an organic peroxide and a dye (Japanese Patent Laid-Open No. Sho 5).
9-140203, JP-A-59-189340).

It is also known to use a titanocene compound in a photopolymerization initiation system (JP-A-59-15239).
6, JP-A-61-151197, and JP-A-63-10.
No. 602, JP-A-63-41484, JP-A-2-29
No. 1, JP-A-3-12403), and a system of titanocene and 3-ketocoumarin dye (JP-A-63-221).
110 gazette) In addition, for titanocene and xanthene dye,
Furthermore, a system in which an addition-polymerizable ethylenic saturated double bond-containing compound having an amino group or a urethane group is combined (Japanese Patent Laid-Open No. 221958 and No. 4-219756) and the like are also known.

[0007]

However, although these conventionally known polymerization initiation systems are certainly effective for light in the ultraviolet to visible region, they are not very sensitive and, from a practical standpoint, A more sensitive polymerization initiation system has been demanded. A photopolymerization initiation system comprising a sensitizing dye having a julolidine skeleton and a hexaarylbiimidazole compound is also known (Japanese Patent Publication No. 2-50492). Although this polymerization initiation system has high sensitivity, it has a low solubility in a solvent, so that there is a problem in that the solvent for coating the photopolymerizable composition on the support is limited. Further, with the passage of time after coating, the sensitizing dye crystallizes and the sensitivity decreases, that is, the temporal stability of the photosensitive material tends to be low.

Further, it is expected that the solubility of a sensitizer having a tetrahydroquinoline skeleton in a coating solvent and the stability over time of a light-sensitive material formed by coating will be improved. Introduced two methyl groups (USP. 4,736,032,
4,794,184, JP-A-7-258566).
Or a phenyl group introduced at the 2-position (Tetr
ahedron Vol. 51, No. 21, P611
5-6132, 1955) are known. However, a compound having two methyl groups at the 4-position of the tetrahydroquinoline skeleton is difficult to cyclize an alkylamino group of a dialkylaniline which does not have a hydroxyl group or an alkoxy group at the meta position with respect to an amino group. Therefore, the compounds that can be synthesized are limited. Further, a compound having a phenyl group at the 2-position is easy to synthesize, but has a problem that sensitivity is not so high.

Accordingly, it is an object of the present invention to provide a photopolymerizable composition with high sensitivity. Another object of the present invention is to provide a photopolymerizable composition using a sensitizer which is excellent in solubility in a coating solvent and in stability over time of a light-sensitive material formed by coating. Still another object of the present invention is to create a black matrix of a color filter or to perform laser plate making with an argon ion laser, which enables a higher speed plate making work by using a lower output laser such as an air-cooled argon ion laser. And a photopolymerizable composition.

[0010]

The photopolymerizable composition according to the present invention is a photopolymerizable composition containing an addition polymerizable compound having at least one ethylenically unsaturated double bond and a photopolymerization initiation system. The photopolymerization initiation system is characterized by containing a sensitizer represented by the general formula (1) and an activator capable of generating an active radical upon irradiation with light in the presence of the sensitizer. .

[0011]

[Chemical 4]

(In the formula, R ¹ and R ² are each independently a hydrogen atom, a chlorine atom, a bromine atom, a hydroxyl group, an alkoxy group having 1 to 15 carbon atoms, an acyloxy group having 2 to 15 carbon atoms, or a phenyl group. A vinyl ether group or a vinyl group which may be substituted with a vinyl group represents an alkyl group having 1 to 15 carbon atoms in the longest chain and 1 to 30 carbon atoms in total in the carbon chain,
Alternatively, R ¹ and R ² are bonded to each other to form a 6-membered ring which may have a substituent. R ³ represents a hydroxyl group, a chlorine atom, a bromine atom, a vinyl ether group or an acyloxy group having 2 to 15 carbon atoms. R ⁴ represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms or an acyloxy group having 2 to 15 carbon atoms, or R ⁴ and R ⁵ are bonded to each other to give a compound represented by the general formula (2 Or a ring structure of the general formula (3) is formed.

[0013]

[Chemical 5]

R ⁷ , R ⁸ and R in the general formulas (2) and (3)
R ⁵ when it does not form a ring structure by combining with ⁴ is 2
A 2-cyanoethenyl group which may further have a substituent at the carbon atom at the -position, or a substituent which may have a substituent on the ring 1
To a 5-ring monocyclic or condensed polycyclic residue or a residue having a linking group having 1 to 4 carbon atoms bonded thereto. R ⁶ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. )

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. At least one ethylenically unsaturated double bond contained as the first essential component in the photopolymerizable composition of the present invention is used.
The compound capable of addition polymerization (hereinafter, abbreviated as “ethylenic compound”) means that when the photopolymerizable composition is exposed to actinic rays, it acts by the action of the photopolymerization initiation system that is the second essential component. A compound having an ethylenically unsaturated double bond capable of undergoing addition polymerization and curing, for example, a monomer having the above double bond, or an ethylenically unsaturated double bond in a side chain or a main chain. It is a polymer having. In addition, the monomer in the present invention is a concept facing a so-called polymer substance, and therefore includes not only a narrowly defined monomer but also a dimer, a trimer and an oligomer.

Examples of the monomer having an ethylenically unsaturated bond include unsaturated carboxylic acids, esters of aliphatic polyhydroxy compounds with unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds with unsaturated carboxylic acids; Examples thereof include an ester obtained by an esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and the aforementioned polyvalent hydroxy compound such as an aliphatic polyhydroxy compound and an aromatic polyhydroxy compound.

Specific examples of the ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, Pentaerythritol triacrylate, pentaerythritol tetraacrylate,
Acrylic acid esters such as dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, methacrylic acid esters in which the acrylic acid portion of these esters is replaced with methacrylic acid,
Similarly, itaconic acid ester replaced with itaconic acid, crotonic acid ester replaced with crotonic acid, maleic acid ester replaced with maleic acid and the like. Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.

The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound is often a mixture. Typical examples are acrylic acid, phthalic acid and Examples thereof include condensates of ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin.

Other useful ethylenic compounds used in the present invention include acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinylphthalate. The polymer having an ethylenically unsaturated bond in the main chain, for example, polyester obtained by polycondensation reaction of an unsaturated divalent carboxylic acid and a dihydroxy compound, by a polycondensation reaction of an unsaturated divalent carboxylic acid and a diamine There are obtained polyamides and the like.

As the polymer having an ethylenically unsaturated bond in the side chain, a divalent carboxylic acid having an unsaturated bond in the side chain,
For example, there are condensation polymers of itaconic acid, propylidene succinic acid, ethylidene malonic acid and the like with a dihydroxy or diamine compound. Further, a polymer having a functional group having a reactive activity such as a hydroxy group or a methyl halide group in the side chain,
For example, a polymer obtained by reacting polyvinyl alcohol, poly (2-hydroxyethyl methacrylate), polyepichlorohydrin or the like with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid or crotonic acid can also be preferably used.

Among these ethylenic compounds, acrylic acid ester or methacrylic acid ester monomers are particularly preferably used. Next, the photopolymerization initiation system which is the second essential component of the photopolymerizable composition of the present invention will be described.
The photopolymerization initiation system of the present invention is composed of a combination of two components, and the first component thereof is the sensitizer represented by the above general formula (1).

The sensitizer used in the present invention has a structure in which a substituent is bonded to the tetrahydroquinoline skeleton, and in terms of solubility in a coating solvent, stability and sensitivity in a light-sensitive material formed by coating. Is also excellent. Among the compounds represented by the general formula (1), those in which R ¹ and R ² are bonded to form a julolidine structure having a substituent represented by the general formula (4) are excellent in photosensitivity and The effect of increasing the solubility in the coating solvent by the substituent and the stability in the photosensitive material formed by coating is large.

[0023]

[Chemical 6]

(In the formula, R ³ represents a hydroxyl group, a chlorine atom, a bromine atom, a vinyl ether group or an acyloxy group having 2 to 15 carbon atoms. R ⁴ represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or a carbon number. It represents an alkoxy group having 1 to 15 or an acyloxy group having 2 to 15 carbon atoms, or R ⁴ and R ⁵ are bonded to each other to form a ring structure as shown in the general formula (5) or (6).

[0025]

[Chemical 7]

[0026] R ^7, R ⁸ and R ⁵ when R ⁴ combine with do not form a ring structure are each independently 2-position of which may have a substituent on the carbon 2 A cyanoethenyl group or a monocyclic or condensed polycyclic residue having 1 to 5 rings which may have a substituent on the ring, or a carbon number of 1 in this residue
The groups to which the linking groups of 4 are bonded are shown. R ⁶ and R ¹⁰ are
Each independently represents a hydrogen atom or an alkyl group having 1 to 15 carbon atoms. R ⁹ is a hydrogen atom, a hydroxyl group, a chlorine atom, a bromine atom, a vinyl ether group, an acyloxy group having 2 to 15 carbon atoms, or the longest chain which may have a substituent has 1 to 1 carbon atoms.
It shows an alkyl group having a total carbon number of 1 to 30 and an alkyl group having a carbon number of 1 to 30 or an alkoxy group having a carbon number of 1 to 15 and optionally having a substituent. Preferably, R ³ is independently a hydroxyl group, a chlorine atom, a bromine atom, a vinyl ether group, or a carbon number of 2 to
15 represents an acyloxy group, and R ^9's each independently represent a hydroxyl group, a chlorine atom, a bromine atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, or 2 carbon atoms.
~ 15 represents an acyloxy group, wherein R ⁹ may be a hydrogen atom. Further, R ⁹ and R ¹⁰ are not an alkyl group at the same time. Similarly, R ⁴ is preferably a hydrogen atom or bonded to R ⁵ to form a ring.

When the compound having a substituent on the tetrahydroquinoline skeleton represented by the general formula (1) does not form a julolidine structure, the following general formula (7) to
It is preferably represented by the formula (9). (7)
In formula (9), R ¹¹ has 1 to 15 carbon atoms in the longest chain.
And an alkyl group having 1 to 30 total carbon atoms is shown.

[0028]

[Chemical 8]

Some of the compounds represented by these general formulas are exemplified as A series in Table 1 below.

[0030]

[Table 1]

[0031]

[Table 2]

Preferred examples of those forming the julolidine structure are shown in Table 2 below as the BD series. Of these, the B series is R ⁴ and R ⁵
Is an example of those in which and do not combine to form a ring structure,
In the C series, R ⁴ and R ⁵ are bonded to each other to form a ring structure represented by the general formula (2), and in the D series, R ⁴ and R ⁵ are bonded to each other, the general formula (3) It is an example of forming a ring structure represented by.

[0033]

[Table 3]

[0034]

[Table 4]

[0035]

[Table 5]

[0036]

The substituents R ⁵ , R ⁷ and R ⁸ in the structures of the compounds exemplified above are described in JP-B 2-5046.
2, JP-A-52-112681, 58-15503, 6
0-84304, JP-A-3-239703, 6-289.
335, 6-295061, 6-329654, etc., that is, a 2-position carbon atom may further have a substituent such as a cyano group, an alkoxy group or an alkoxycarbonyl group 2- A cyanoethenyl group,
Or, a monocyclic or condensed polycyclic residue having 1 to 5 rings, or a residue in which a connecting group having 1 to 4 carbon atoms is bonded to the residue can be mentioned. Some of these substituents are listed in Table 3 below.
For example. The E series is an example of a 2-cyanoethenyl group which may further have a substituent at the 2-position carbon atom, and the F series is an example of a monocyclic or condensed polycyclic residue. G
Series has 1 to 4 carbon atoms in aromatic hydrocarbon ring or heterocycle
Is an example in which the linking group of is bonded. The H series is an example of a condensed polycyclic residue in which a linking group having 1 to 4 carbon atoms is bonded. The linking group preferably contains an unsaturated bond, and when the linking group consists of one carbon, the linking group is preferably a carbonyl group (-CO-) or a methine group (-CH =). Further, when the linking group is composed of two or more carbons, the linking group preferably has a carbon-carbon double bond therein.

These substituents can be introduced into a compound having a tetrahydroquinoline or julolidine structure by condensing a carboaldehyde compound having a tetrahydroquinoline or julolidine structure with a compound having an active methyl group.

[0039]

[Chemical 9]

Further, an acylated product having a tetrahydroquinoline or julolidine structure may be condensed with a compound having a carboxaldehyde group.

[0041]

[Chemical 10]

[0042]

[Table 7]

[0043]

[Table 8]

[0044]

[Table 9]

[0045]

[Table 10]

[0046]

[Table 11]

General formula (1) used as a sensitizer in the present invention
The compound represented by can be produced by a known synthesis method. For example, the formation of a julolidine structure is described by De
gutis, J .; Dubinskaite, D .; , K
him. Geterotsikl. Soedin. 19
72, (1), 41-4 (Russ), by reacting anilines with (methyl) epichlorohydrin, a compound of the general formula (4) in which R ³ and R ⁹ are hydroxyl groups. Is obtained.

[0048]

[Chemical 11]

By reacting this compound with phosphorus oxychloride, the hydroxyl group can be replaced with a chlorine atom.

[0050]

[Chemical 12]

[0051]

[0052]

[0053]

[0054]

Some of the compounds having a julolidine structure suitable for use as a sensitizer in the present invention are shown in the table below.
An example is shown in FIG.

[0056]

[Table 12]

[0057]

[Table 13]

[0058]

[Table 14]

[0059]

[Table 15]

[0060]

[Table 16]

[0061]

[Table 17]

The second component constituting the photopolymerization initiation system used in the present invention is an activator which generates active radicals upon irradiation with light in the presence of the above-mentioned sensitizer. Examples of such activators include halogenated hydrocarbon derivatives, diaryl iodonium salts, organic peroxides, and JP-A-59-
Examples include various titanocene compounds described in JP-A-152396, 61-151197 and various hexaarylbiimidazole compounds described in JP-B-6-29285. In particular, titanocene compounds and hexaarylbiimidazole compounds are preferable because they exhibit high photosensitivity.

Specific examples of the titanocene compound include di-
Cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-
Pentafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-
Bis-2,4,6-trifluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-cyclopentadienyl-T
i-bis-2,4-di-fluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,
4,5,6-Pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5
6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,6-difluoro-3-
(Pyr-1-yl) -phen-1-yl.

Specific examples of the hexaarylbiimidazole compound include 2,2'-bis (o-chlorophenyl).
-4,4'5,5'-tetraphenylbiimidazole,
2,2'-bis (o-chlorophenyl) -4,4'5
5'-tetra (p-carboethoxyphenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,
4'5,5'-tetra (p-bromophenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,
4'5,5'-tetra (o, p-dichlorophenyl) biimidazole, 2,2'-bis (o-bromophenyl)
-4,4'5,5'-tetraphenylbiimidazole,
2,2'-bis (o, p-dichlorophenyl) -4,
4'5,5'-tetraphenylbiimidazole, 2,
2'-bis (o-chlorophenyl) -4,4'5,5 '
-Tetra (m-methoxyphenyl) biimidazole,
2,2'-bis (o, p-dichlorophenyl) -4,
4'5,5'-tetraphenylbiimidazole, 2,
2'-bis (o-nitrophenyl) -4,4'5,5 '
-Tetraphenylbiimidazole, 2,2'-bis (o
-Methylphenyl) -4,4'5,5'-tetraphenylbiimidazole and the like.

In the polymerization initiation system used in the present invention, in addition to the above-mentioned sensitizer and activator, a radical such as an alkylamino compound or an aromatic mercapto compound is added for the purpose of further improving sensitivity and stability with time. A chain transfer agent may be included. These radical chain transfer agents, the absorption of excitation light is lower than the light absorption of sensitizers and radical generators, mainly by chain transfer of radicals generated from the sensitizer and radical generator, It has the function of generating radicals with good polymerization efficiency of ethylenic compounds.

Examples of the alkylamino compound include compounds having a dialkylaminophenyl group and alkylamine compounds described in JP-A-6-19240 and JP-A-6-19249, and specifically, dialkyl As a compound having an aminophenyl group, p-
Compounds such as ethyl dimethylaminobenzoate and dialkylaminophenylcarbaldehydes such as p-diethylaminobenzcarbaldehyde and 9-jurolidylcarbaldehyde, and alkylamine compounds include triethanolamine, diethanolamine and triethylamine. Of these, compounds having a dialkylaminophenyl group are preferred because they have higher sensitivity.

Examples of the aromatic mercapto compound are 2-mercaptobenzthiazole, 2-mercaptobenzoxazole and 2-mercaptobenzthiazole described in JP-A-59-56403.
Mercaptobenzimidazole, 2-mercaptonaphthothiazole, 2-mercaptonaphthoxazole, 2-
Examples include mercaptonaphthoimidazole and the like. If desired, the photopolymerizable composition according to the present invention may further contain an organic polymer substance to improve compatibility, film-forming property, developability, adhesiveness and the like.

Examples of such organic polymer compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth). An alkyl ester which may have a substituent of (meth) acrylic acid such as acrylate, hydroxypropyl (meth) acrylate and benzyl (meth) acrylate; hydroxyphenyl (meth) acrylate, methoxyphenyl (meth) acrylate and the like ( (Meth) acrylic acid phenyl ester which may have a substituent; acrylonitrile; vinyl acetate,
Vinyl esters of carboxylic acids such as vinyl versatate, vinyl propionate, vinyl cinnamate, vinyl pivalate; styrene; (co) polymers such as α-methylstyrene,
Examples thereof include polyether of epichlorohydrin and bisphenol A, soluble nylon, polyvinyl alkyl ether, polyamide, polyurethane, polyethylene terephthalate isophthalate, acetyl cellulose, polyvinyl formal, polyvinyl butyral and the like.

In the present invention, of the above organic polymer substances, those having a carboxylic acid group, for the purpose of enhancing the film strength, coating solvent resistance and substrate adhesion of the resulting coating film,
A part or all of the carboxylic acid group may be reacted with glycidyl (meth) acrylate or (3,4-epoxy-cyclohexyl) methyl (meth) acrylate to give a photopolymerizable organic polymer substance.

In the present invention, as particularly preferable organic polymer substances, styrene, α-methylstyrene, benzyl (meth) acrylate, hydroxyphenyl (meth) acrylate and methoxyphenyl (meth) are used for the purpose of improving the adhesion to the substrate. ) Acrylate, hydroxyphenyl (meth) acrylamide, hydroxyphenyl (meth)
Containing a comonomer having a phenyl group such as acrylsulfoamide in an amount of 10 to 80 mol%, preferably 20 to 70 mol%, more preferably 30 to 60 mol%,
Copolymer containing other (meth) acrylic acid in an amount of 2 to 50% by weight, preferably 5 to 40% by weight, more preferably 5 to 30% by weight, or 2 to 50% based on all copolymerized monomers. Desirably, the reaction product has a mole%, preferably 5 to 40 mol%, and more preferably 10 to 30 mol% epoxy (meth) acrylate added thereto.

The weight average molecular weight (Mw) of the organic polymer substance is 1,000 to 1,000,000, preferably 2,000 to 500,000, and more preferably 3,0.
The range is from 00 to 200,000. If the molecular weight of the organic polymer substance is significantly lower than this range, the film portion of the image-forming portion will develop during development. Conversely, if the molecular weight of the organic polymer substance is extremely high, the non-image-forming portion will be defective during development.

The photopolymerizable composition according to the present invention may further contain various additives which are commonly used, if desired. For example, when a colored image is formed using the photopolymerizable composition of the present invention or a black matrix of a color filter is formed, a color material, that is, a dye or a pigment is contained. The color materials are usually red, green, and blue color materials, but black color materials are also used when forming a black matrix. Further, metal powder, white pigment, fluorescent pigment and the like can be further used depending on the application.

Specific examples of dyes and pigments include Victoria Pure Blue (42595) and Auramine O (4100).
0), Catillon Brilliant Flavin (Basic 1
3), Rhodamine 6GCP (45160), Rhodamine B (45170), Safranine OK 70: 100 (50
240), Erioglaucine X (42080), No.
120 / Rionol Yellow (21090), Rionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4
T-564D (21095), Shimla Fast Red 4015 (12355), Lionol Red 7B44
01 (15850), Fast Gen Blue TGR-L
(74160), Lionol Blue SM (2615
0), Mitsubishi Carbon Black MA100, Mitsubishi Carbon Black # 40, Rionol Blue ES (Pigment Blue 15: 6), Rionogen Red GD (Pigment Red 168), Rionol Green 2YS (Pigment Green 36) and the like. In addition, the above ()
The numbers inside indicate the color index (C.I.).

Further, regarding other pigments, C.I. I. When it is indicated by a number, for example, C.I. I. Yellow pigment 20, 2
4, 86, 93, 109, 110, 117, 125, 1
37, 138, 147, 148, 153, 154, 16
6, C.I. I. Orange pigment 36, 43, 51, 55, 5
9, 61, C.I. I. Red pigment 9, 97, 122, 12
3, 149, 168, 177, 180, 192, 21
5, 216, 217, 220, 223, 224, 22
6, 227, 228, 240, C.I. I. Violet pigment 19, 23, 29, 30, 37, 40, 50, C.I.
I. Blue pigment 15, 15: 1, 15: 4, 22, 60,
64, C.I. I. Green pigment 7, C.I. I. Brown pigment 2
3, 25, 26 etc. can be mentioned. These color materials are added so that their proportion in the total solid content is 90% by weight or less. It is preferably added in an amount of 70% by weight or less, particularly 60% by weight or less.

Ratio of the ethylenic compound in the total of the ethylenic compound, the sensitizer and the activator which are the essential components of the photopolymerizable composition according to the present invention and the radical chain transfer agent and the organic polymer compound which are the optional components. Is preferably 20 to 90% by weight, particularly preferably 30 to 80% by weight. Similarly, the organic polymer compound is 0 to 80% by weight, especially 10 to 6%.
0% by weight is preferable, and the photopolymerization initiation system is 0.1%.
-40% by weight, in particular 0.5-30% by weight, is preferred.

Most preferably, the photopolymerization initiation system is from 0.5 to
It accounts for 20% by weight. Further, in the photopolymerization initiation system,
The sensitizer, relative to the activator, is 1 to 1000% by weight, especially 5 to
It is preferably 500% by weight, the radical chain transfer agent is preferably 0 to 1000% by weight, particularly preferably 200 to 500% by weight. To prepare a photosensitive material using the photopolymerizable composition according to the present invention, the photopolymerizable composition is dissolved in a solvent so that the solid content concentration is 5 to 50% by weight, preferably 10 to 3%.
The solution may be a 0% by weight solution, which may be applied to an appropriate support and dried. As the solvent, methyl cellosolve, ethyl cellosolve, butyl cellosolve, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, chloroform, dichloromethane, ethyl acetate, methyl lactate, ethyl lactate, methanol, ethanol, propanol. , Butanol, tetrahydrofuran and the like.

As the support, for example, a sheet of metal such as aluminum, magnesium, copper, zinc, chromium, nickel, iron or an alloy containing them as a main component, upper paper quality, art paper, paper such as release paper, Inorganic sheets such as glass and ceramics, polyethylene terephthalate, polyethylene, polymethylmethacrylate, polyvinyl chloride, vinyl chloride-vinylidene chloride copolymer, polystyrene, 6
-Polymer sheets such as nylon, cellulose triacetate, cellulose acetate butyrate and the like.

In producing a light-sensitive material with the photopolymerizable composition of the present invention, known techniques for preventing adverse effects such as sensitivity decrease and storage stability deterioration due to oxygen, for example,
A peelable transparent cover sheet may be provided on the photosensitive layer, or a coating layer made of a waxy substance having a low oxygen permeability, a water-soluble polymer or the like may be provided. As an exposure light source applicable to the composition of the present invention, carbon arc, ultrahigh pressure mercury lamp, high pressure mercury lamp, xenon lamp, metal halide lamp, fluorescent lamp, ultraviolet argon ion laser, HeNe laser, HeCd laser, ruby laser, YAG laser, semiconductor A general-purpose light source including a laser can be preferably used. INDUSTRIAL APPLICABILITY The photopolymerizable composition of the present invention is useful in a wide range of application fields.
It can be used for dry film, image formation such as relief image and image duplication, photocurable ink, paint, adhesive and the like.

[0079]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Synthesis Example 1 (Synthesis of 2-hydroxyjulolidine) 1,2,3,4-tetrahydroquinoline (20 g) and epichlorohydrin (16.7 g) were mixed with each other in a nitrogen atmosphere at 130
Reaction was carried out at 0 ° C for 20 hours. Concentrated hydrochloric acid 50 g and water 5 in the reaction solution
After adding 0 g and maintaining at 80 degreeC for 8 hours, it cooled to room temperature and isolate | separated into the water layer and the oil layer. Sodium hydroxide was added to the aqueous layer to make the liquid alkaline. The precipitated oily substance was extracted with toluene by adding toluene. After the extract was dried over sodium sulfate, toluene was distilled off to obtain 19 g of 2-hydroxyjulolidine.

[0080]

[Chemical 15]

Synthesis Example 2 (Synthesis of bis (2-hydroxyjulolidyl) methane) 2-Hydroxyjulolidine (10.7 g), 37% formalin aqueous solution (1.74 g) and concentrated hydrochloric acid (0.1 g) were equipped with a reflux condenser. The mixture was placed in a 500 ml three-necked flask, reacted under reflux for 9 hours, and then cooled to room temperature. Aqueous ammonia was added to the solution to make it alkaline, and the solution was left for 10 hours. Then, the aqueous phase was removed, the precipitate was washed with water three times and then dried to obtain 5.2 g of bis (2-hydroxyjulolidyl) methane.

[0082]

[Chemical 16]

Synthesis Example 3 (Synthesis of bis (2-hydroxyjulolidyl) ketone) Bis (2-hydroxyjulolidyl) methane 13.5
g, chloranil 18.8 g and dry ethanol 80
g was placed in a flask equipped with a reflux condenser, reacted for 10 hours under reflux, and then cooled to room temperature. Sodium hydroxide was added to this to make the liquid alkaline and left for 10 hours. Then ethanol is distilled off and chloroform 500
g was added and the mixture was washed 3 times with water. The brown chloroform solution thus obtained was dried over sodium sulfate, and after decolorizing by adding activated clay, chloroform was distilled off to obtain 4.2 g of bis (2-hydroxyjulolidyl) ketone.

[0084]

[Chemical 17]

Examples 1 to 6 and Comparative Examples 1 to 4 Preparation of photopolymerizable composition solution; 60 parts by weight of trimethylolpropane triacrylate Methyl methacrylate-methacrylic acid copolymer 40 parts by weight (polymerization molar ratio 9: 1 , Weight average molecular weight 5 × 10 ⁴ ) Crystal Violet 3 parts by weight Sensitizer 5 parts by weight Activator 5 parts by weight Chain transfer agent 5 parts by weight Propylene glycol monomethyl ether acetate 400 parts by weight

After mixing the above respective samples, they were stirred for 30 minutes at 25 ° C. using a magnetic stirrer. The presence or absence of undissolved sensitizer in the obtained solution was visually inspected to evaluate the solubility of the sensitizer in the coating solvent. Preparation of photosensitive material: After filtering the above solution, it was coated on a grained and anodized aluminum sheet with a wire bar coater to a dry film thickness of 2 μm, and dried at 80 ° C. for 1 minute. . Next, polyvinyl alcohol (GL-03, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
8% aqueous solution to a dry film thickness of 1 μm,
By drying at 0 ° C. for 2 minutes to form an overcoat layer, a light-sensitive material was manufactured.

Exposure and development of a light-sensitive material; a high-pressure mercury lamp (manufactured by Ushio Inc .; UMH-3000) was added to the above light-sensitive material.
As an exposure light source and a spectral irradiation device (manufactured by Narumi; RM
-23) was used for exposure. Then sodium silicate 0.5
Development was carried out using an aqueous solution containing 0.5% by weight of an anionic surfactant (Perox NBL manufactured by Kao Corporation) and the minimum cured image forming light energy value was determined. The smaller the energy value, the higher the sensitivity of the photosensitive material. The results are shown in Table-5.

[0088]

[Table 18]

In Table 5, the symbols for the S series of sensitizers are the same as those in Table-4. CS-1 to CS-
4, K-1 to K-3, and P-1 and P-2 represent the following compounds. The solubility and the stability of the light-sensitive material over time were evaluated as follows.

[0090]

[Chemical 18]

K-1: dicyclopentadienyl-Ti-
Bis-2,6-difluoro-3- (pyr-1-yl)-
Phen-1-yl K-2: 2,2'-bis (o-chlorophenyl) -4,
4 ′, 5,5′-tetraphenylbiimidazole K-3: 2,2′-bis (o-chlorophenyl) -4,
4 ', 5,5'-tetra (o, p-dichlorophenyl)
Biimidazole

[0092]

[Chemical 19]

Evaluation of Solubility: After dissolving the polymerizable composition in a solvent with a magnetic stirrer at 25 ° C. for 30 minutes, the amount of undissolved sensitizer in the solution was visually determined. A: The sensitizer is completely dissolved. B: 10% or less of the sensitizer is undissolved and suspended. C: More than half of the sensitizer is undissolved, and the sensitizer is deposited on the bottom of the container. Stability of Photosensitive Material with Time: The photosensitive material stored at 25 ° C. for 2 months was exposed to the whole surface with the minimum curing image forming energy, and then developed in the same manner as in Example to form a fully cured image. Observe the surface of this image with a microscope with 400x magnification,
10-100μ generated by crystallization of sensitizer
The number of m pinhole-like defects was examined. A: No pinhole-like defect was observed on the image surface of 1 cm ² . B: 1 to 10 pinhole-like defects were observed on the image surface of 1 cm ² . C: 11 to 99 pinhole defects were observed on the image surface of 1 cm ² . D: 100 or more pinhole-like defects were observed on the image surface of 1 cm ² .

Example 7 50 parts by weight of dipentaerythritol hexaacrylate 50 parts by weight of the following polymer compound 50 parts by weight of carbon black (MA220 manufactured by Mitsubishi Chemical Corporation) 50 parts by weight of S-7 5 parts by weight of K-1 5 parts by weight of propylene glycol monomethyl 400 parts by weight of ether acetate The above respective samples were mixed to prepare a polymerizable composition solution.
This solution was dried on a glass substrate having a thickness of 1 mm to give a dry film thickness of 1.
It was applied so as to have a thickness of 5 μm and dried at 80 ° C. for 1 minute.
Using this photosensitive material, the minimum cured image forming light energy was determined in the same manner as in Example 1 and found to be 300 mJcm ^−2.
/ 366 nm, which shows high practical sensitivity without an oxygen barrier layer. Polymer compounds;

[0095]

[Chemical 20]

Example 8 A photosensitive material was prepared and an exposure test was conducted in the same manner as in Example 2 except that S-16 of the sensitizer was changed to S-16. The minimum cured image forming light energy was as high as 0.2 mJcm ⁻² / 488 nm.

[0097]

The photopolymerizable composition according to the present invention has an ultraviolet to
It is extremely sensitive to light in the visible region. Further, it has excellent solubility in a solvent, and a light-sensitive material produced using this material has excellent stability over time. Therefore, the photopolymerizable composition according to the present invention is useful in a wide range of applications, for example, production of printing plates such as planographic, intaglio and letterpress, production of color filters, photoresist for producing printed wiring and IC, and dry. It can be used for film, image formation such as relief image and image duplication, photocurable ink, paint, adhesive and the like.

Continuation of the front page (56) Reference JP-A-6-332172 (JP, A) JP-A-8-62838 (JP, A) JP-A-7-258566 (JP, A) JP-A-6-192309 (JP , A) JP-A-6-107719 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F 7/004 G03F 7/027 G03F 7/028 G08F 2/50

Claims (4)

(57) [Claims] 1. A photopolymerizable composition comprising an addition polymerizable compound having at least one ethylenically unsaturated double bond and a photopolymerization initiation system, wherein the photopolymerization initiation system is represented by the general formula (1). A photopolymerizable composition comprising a sensitizer represented and an activator capable of generating an active radical upon irradiation with light in the presence of the sensitizer. [Chemical 1] (In the formula, R ¹ and R ² are each independently a hydrogen atom, a chlorine atom, a bromine atom, a hydroxyl group, an alkoxy group having 1 to 15 carbon atoms, an acyloxy group having 2 to 15 carbon atoms, a phenyl group or a vinyl ether group. Or an alkyl group having 1 to 15 carbon atoms in the longest chain and 1 to 30 carbon atoms in the carbon chain, which may be substituted with a vinyl group, or R ¹ and R
² and are bonded to each other to form a 6-membered ring which may have a substituent. R ³ represents a hydroxyl group, a chlorine atom, a bromine atom, a vinyl ether group, or an acyloxy group having 2 to 15 carbon atoms. R ⁴ represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms or an acyloxy group having 2 to 15 carbon atoms, or R ⁴ and R ⁵ are bonded to each other to give a compound represented by the general formula (2 Or a ring structure of the general formula (3) is formed. [Chemical 2] R ⁵ in the general formulas (2) and (3) in the case of not forming a ring structure by combining with R ⁷ , R ⁸ and R ⁴ has a substituent at the 2-position carbon atom. A 2-cyanoethenyl group which may be substituted, or a monocyclic or condensed polycyclic residue having 1 to 5 rings which may have a substituent on the ring, or this residue having 1 to 4 carbon atoms
The linking group of is bonded. R ⁶ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ) 2. The photopolymerizable composition according to claim 1, wherein the sensitizer is represented by the general formula (4). [Chemical 3] (In the formula, R ^{3 to} R ⁶ are the same as those in the general formula (1). R ⁹ is a hydrogen atom, a hydroxyl group, a chlorine atom, a bromine atom, a vinyl ether group, an acyloxy group having 2 to 15 carbon atoms, or a substituent. The longest chain which may have is C1-C15, and the total number of carbon atoms of a carbon chain is a C1-C30 alkyl group or a C1-C15 alkoxy group which may have a substituent is shown. R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.) 3. The photopolymerizable composition according to claim 1, which contains a hexaarylbiimidazole compound and / or a titanocene compound as an activator. 4. The sensitizer has the general formula (1) or (4):
K R ^Four Is a hydrogen atom, an alkyl group having 1 to 15 carbon atoms,
Alkoxy group having 1 to 15 carbon atoms or 2 to 15 carbon atoms
R is an acyloxy group of ^Five But at the 2-position carbon atom
2-cyanoethenyl group which may further have a substituent or
Is a monocyclic ring of 1 to 5 rings which may have a substituent on the ring.
Or a condensed polycyclic residue or a chain of 1 to 4 carbon atoms to this residue.
The bond according to any one of claims 1 to 3, wherein the bonding group is bonded.
The photopolymerizable composition described.