JP3428301B2 - Photopolymerizable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a photopolymerizable composition.
It is about. Especially for light in the visible range
The present invention relates to a highly sensitive photopolymerizable composition. [0002] 2. Description of the Related Art Conventionally, an image forming method using a photopolymerization system has been known.
Many are known. For example, addition polymerizable ethylenic
A compound containing a double bond and a photopolymerization initiator, and
Photopolymerizable composition consisting of organic polymer binders used
Product, and apply the photopolymerizable composition on a support.
Create a photosensitive material provided with a layer of a photopolymerizable composition,
The image is exposed to light to polymerize and cure the exposed part, and the unexposed part is
For forming a cured relief image by dissolving and removing
Method, two sheets of the above-mentioned photosensitive material at least one of which is transparent
A layer of a photopolymerizable composition is provided between supports of
Image exposure from the transparent support side to induce changes in adhesive strength due to light
After raising, the image is formed by peeling the support.
Method, other toner adhesion of photopolymerizable composition layer by light
There is an image creation method utilizing a change in gender. These people
The photopolymerization initiator of the photopolymerizable composition applied to the method
Conventionally, benzoyl, benzoin alkyl ether, ben
Zirketal, benzophenone, anthraquinone, ben
Jill or Michler's ketone has been used.
However, these photopolymerization initiators are less than 400 nm.
Compared to the photopolymerization initiation ability for light in the ultraviolet region of
It is remarkable for light in the visible light region of 400 nm or more.
Application range of photopolymerizable compositions containing them
Has been limited. In recent years, with the development of image forming technology, the visible region
Photopolymer with high adaptability to
It has come to be requested. They are, for example,
Tactile projection exposure plate making and laser with visible light laser
It is a photosensitive material suitable for plates and the like. Sensitive to light rays in the visible light range
Photopolymerizable composition containing responsive photopolymerization initiation system
In the past, several proposals have been made. For example,
Hexaarylbiimidazole and a radical generator;
Dye system (JP-B-45-37377), hexaa
Reelbiimidazole and (p-dialkylaminobenzyl)
Ridene) ketone system (JP-A-47-2528, JP-A-47-2528)
54-155292), cyclic cis-α-dicals
A system of a bonyl compound and a dye (JP-A-48-84183)
Report), a system of substituted triazine and merocyanine dye (JP-A
No. 54-151024), between ketocoumarin and activator
System (Japanese Patent Application Laid-Open No. 52-112681, Japanese Patent Application Laid-Open No. 58-155)
03, JP-A-60-88005), substituted tris
System of azine and sensitizer (JP-A-58-29803, JP-A-58-29803)
No. 58-40302), biimidazole, styrene
A system of a len derivative and a thiol (JP-A-59-56403)
Gazette), a system of an organic peroxide and a dye (JP-A-59-140)
No. 203, JP-A-59-189340).
Can be Further, titanocene is used for a photopolymerization initiation system.
For example, Japanese Patent Application Laid-Open Nos. Sho 59-152396 and
1-1151197, JP-A-63-10602, JP-A-63-10602
JP-A-63-41484, JP-A-2-291, JP-A-3-291
-12403, JP-A-3-20293 and JP-A-3-20293
27393, JP-A-3-52050, and
Titanocene and xanthene dyes plus amino groups or urea
Containing addition-polymerizable ethylenic double bond with tan group
A system combining compounds (JP-A-4-221958,
JP-A-4-219756), Argon ion ray
A light source with excellent sensitivity to light around 488 nm emitted by the laser
A system of tanocene and a 3-ketocoumarin dye (JP-A-63-2
No. 21110), having a heterocyclic group at the 3-position with titanocene
Coumarin dye system (JP-A-6-289335,
JP-A-3-239703), for holography
Pyran dyes and diali dyes used in photopolymerizable compositions
Halomethyl salt, halomethyl-s-triazine, bis
Imidazole derivatives, halogen compounds or organic peroxides
(JP-A-6-329654)
Is mentioned. However, the above photopolymerization system is certainly visible
Sensitive to light in the area, but small air-cooled argon
Laser plate making using on-laser and semiconductor laser
Insufficient sensitivity to do, even more sensitive light
A polymerization system has been desired. [0005] SUMMARY OF THE INVENTION The present invention relates to
Photopolymerizable composition with higher sensitivity to such long wavelength light
And a sensitizer for a specific dye.
Active radicals can be generated during light irradiation in the presence of sensitizers
By using a titanocene compound, argon ion
Sensitive to light around 488 nm, which is the laser oscillation wavelength
Excellent in solubility, and also soluble in coating solvents
It is possible to provide an excellent photopolymerizable composition. [0006] SUMMARY OF THE INVENTION The present inventors have developed a high sensitivity
Study to obtain an excellent photopolymerizable composition having
As a result, at least a compound capable of addition polymerization and photopolymerization initiation
A photopolymerizable composition comprising a system,
Compound having one or more ethylenic double bonds
In the sensitizer wherein the photopolymerization initiation system has a specific skeleton
And active radicals upon irradiation with light in the presence of the sensitizer.
By containing a possible titanocene compound,
It has been found that practicality increases with sensitivity, and
Was. That is, the present invention relates to a compound capable of addition polymerization and
And a photopolymerizable composition containing a photopolymerization initiator system.
The polymerizable compound has at least one ethylenic double.
Having a bond, and the photopolymerization initiator system is represented by the following general formula (a):
A sensitizer represented by (I), and (b) in the presence of the sensitizer.
Titanocene compounds capable of generating active radicals upon light irradiation
And (c) a compound represented by the following general formula (II) or (III)
Photopolymerizable group comprising at least one of the following:
The subject is a gist. [0008] Embedded image [In the formula (I), R¹ And R^Two Are independent
A hydrogen atom, an optionally substituted
Alkyl group (as the substituent, a fluorine atom, a chlorine atom,
Bromine atom, hydroxyl group, alkoxy group having 1 to 15 carbon atoms, carbon
Acyloxy group having 2 to 16 primes, ant having 6 to 12 carbon atoms
Oxy group, hydroxycarbonyl having 3 to 10 carbon atoms
Acyloxy group, alkoxycarbonyl having 4 to 10 carbon atoms
Racyloxy)), R^Three And R^Four
Are each independently a hydrogen atom or an alkyl having 1 to 10 carbon atoms.
Represents a hydroxyl group. Also, R¹ And R^Three , And R^Two And R^Four Are each other
Directly or through an oxygen or sulfur atom
A ring may be formed. R^Five Is a complex having 3 to 17 carbon atoms
A ring residue;⁶ And R⁷ Are each independently a cyano group,
C2 to C10 alkoxycarbonyl group, C1 to C1
10 acyl groups, phenylcarbo which may be substituted
Nyl group or optionally substituted naphthylcarbonyl group
(As the substituent, a fluorine atom, a chlorine atom, a bromine atom
, Hydroxyl group, alkoxy group having 1 to 15 carbon atoms, 2 carbon atoms
To 16 acyloxy groups). However,
R⁶ And R⁷ At least one of them is a cyano group. formula
In (II) and (III), R⁸ ~ R¹⁴Are each replaced
Represents an optionally substituted alkyl group (as the substituent, halo
Gen atom, aryl group, acyl group, carboxyl group,
Alkoxy group). ] [0010] BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
I do. First essential component in the photopolymerizable composition of the present invention
At least one ethylenic double bond contained as
Addition-polymerizable compound (hereinafter referred to as “ethylenic compound
Abbreviated as "product") means that the photopolymerizable composition
The second essential component, the photopolymerization initiation system,
Ethylenic double bond that undergoes addition polymerization and cures
A compound having, for example, an ethylenic double bond
Monomers, or ethylenic dimers in the side chain or main chain
It is a polymer having a heavy bond. Note that the unit of the present invention
The meaning of a monomer is a general term for a so-called polymer substance.
Remember, therefore, that dimers, trimers
And oligomers. As a monomer having an ethylenic double bond
Are, for example, unsaturated carboxylic acids and their alkyl esters
, An aliphatic polyhydroxy compound and an unsaturated carboxylic acid
Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids
Esters with boric acid; unsaturated carboxylic acids and polycarboxylic acids
Acids and the aforementioned aliphatic polyhydroxy compounds,
S with polyvalent hydroxy compounds such as rehydroxy compounds
Esters obtained by a tellurization reaction are exemplified. Unsaturated carboxylic acids and their alkyl esters
As acrylic acid, methacrylic acid, itaconic acid,
Crotonic acid, maleic acid and carbon number of these carboxylic acids
Alkyl esters of 1 to 5;
, Ethyl, propyl, butyl esters, as well as acrylic
Esters in which luic acid is replaced with methacrylic acid are exemplified. [0013] The aliphatic polyhydroxy compound and unsaturated
The ester with the carboxylic acid is not limited, but specific examples and
Are ethylene glycol diacrylate, triethylene
Lenglycol diacrylate, trimethylolpropa
Triacrylate, trimethylolethane triacrylate
Rate, pentaerythritol diacrylate, penta
Erythritol triacrylate, pentaerythritol
Letetraacrylate, dipentaerythritol tetra
Acrylate, dipentaerythritol pentaacryle
, Dipentaerythritol hexaacrylate,
Acrylic esters such as lyserol acrylate
Changed the acrylate of the exemplified compound to methacrylate
Methacrylic acid esters, similarly to itaconate
Crotonic acid instead of taconate and crotonate
Maleate ester replaced with stele or maleate
Etc. Aromatic polyhydroxy compound and unsaturated carboxylic acid
Hydroquinone diacrylate as an ester with boric acid
Rate, hydroquinone dimethacrylate, resorcinol
Diacrylate, resorcin dimethacrylate, pyroga
Roll triacrylate and the like. Unsaturated carbo
Acid and polycarboxylic acid and polyhydroxy compound
The ester obtained by the esterification reaction must be
Is not a single thing, but a typical example is
Condensates of phosphoric acid, phthalic acid and ethylene glycol,
Condensation of acrylic acid, maleic acid and diethylene glycol
Compound, methacrylic acid, terephthalic acid and pentaerythr
Litol condensate, acrylic acid, adipic acid, butanedi
And condensates of all and glycerin. Other ethylenic compounds used in the present invention
Examples of such materials include acrylics such as ethylenebisacrylamide.
Luamides; Allyl esters such as diallyl phthalate;
Useful compounds containing vinyl group such as divinyl phthalate
It is. A polymer having an ethylenic double bond in the main chain
For example, an unsaturated divalent carboxylic acid and a hydroxy compound
Polyesters obtained by the polycondensation reaction with
Obtained by polycondensation reaction between divalent carboxylic acid and diamine
Polyamide and the like. Has an ethylenic double bond in the side chain
Polymers are divalent carboxylic acids with double bonds in the side chain, such as
For example, itaconic acid, propylidene succinic acid, ethylidenemaro
Polycondensation of dihydroxy or diamine compounds
There is coalescence. In addition, hydroxy groups and halogenated methyl
Polymer having a functional group having a reactive activity such as
Polyvinyl alcohol, poly (2-hydroxyethyl)
(Methacrylate), polyepichlorohydrin, etc.
Unsaturated carboxylic acids such as luic acid, methacrylic acid, crotonic acid
Polymers obtained by a polymer reaction with
obtain. Of the ethylenic compounds described above,
When the monomer of acrylate or methacrylate is
It can be used particularly preferably. Next, the photopolymerizable composition of the present invention
The photopolymerization initiation system, which is the second essential component, will be described.
The photopolymerization initiation system of the present invention comprises a combination of two components.
Wherein the first component is (a)
A sensitizer represented by the general formula (I)
It is. The sensitizer corresponds to, for example,
Coumarin and a cyanomethyl compound
Can be obtained by condensation using
You. [0017] Embedded image In the general formula (I), R¹And R^Two
Are each independently a hydrogen atom, an optionally substituted carbon number
1 to 16 alkyl groups (for the substituent, a fluorine atom
Atom, chlorine atom, bromine atom, hydroxyl group,
Lucoxy group, acyloxy group having 2 to 16 carbon atoms, carbon number
6 to 12 aryloxy groups, C3 to C10 hydro
An oxycarbonylacyloxy group having 4 to 10 carbon atoms;
Selected from oxycarbonylacyloxy groups)
Has a carbon number of 1 to 8 which may be substituted
Alkyl groups are preferable, and the substituents include a hydroxyl group and chlorine.
Atom, bromine atom, acyloxy group having 2 to 5 carbon atoms, carbon
A hydroxycarbonylacyloxy group of the number 3 to 6, carbon
Alkoxycarbonylacyloxy groups of formulas 4 to 7 are preferred
New R^ThreeAnd R^FourAre each independently a hydrogen atom or carbon
The alkyl groups represented by the formulas 1 to 10 are represented by
Children are preferred. Also, R¹And R^Three, And R^TwoAnd R^FourAre
Directly or through an oxygen or sulfur atom
May form a ring,¹And R^Three, And R^TwoWhen
R^FourThe ring structure formed by the quinoline ring or
Is preferably an alicyclic amine ring such as a julolidine ring. R^Five
Represents a heterocyclic residue having 3 to 17 carbon atoms.
A condensed ring nitrogen-containing aromatic heterocyclic residue having 3 to 11 carbon atoms is preferred.
Preferably, benzothiazolyl group, benzoxazolyl group,
Or a benzimidazolyl group is particularly preferred. Also, R⁶
And R⁷Are each independently a cyano group, an alkyl group having 2 to 10 carbon atoms.
Lucoxycarbonyl group, acyl group having 2 to 10 carbon atoms,
Optionally substituted phenylcarbonyl group, substituted
An optionally substituted naphthylcarbonyl group (as the substituent,
Fluorine atom, chlorine atom, bromine atom, hydroxyl group, carbon number 1
15 alkoxy groups, acyloxy groups having 2 to 16 carbon atoms
Wherein R is selected from the group consisting of⁶And R⁷Of which,
One of them is a cyano group. Of these, a cyano group,
An alkoxycarbonyl group having 2 to 5 carbon atoms or 2 carbon atoms
To 5 acyl groups, preferably a cyano group, or ethoxyca
A rubonyl group is particularly preferred. In the general formula (I)
Thus, if each substituent is the preferred one described above, the sensitivity
Particularly effective for improvement. Note that R⁶And R⁷Geometric if different
Although isomers exist, such geometric isomers usually
Obtained as a mixture in the course of the formation. Therefore, the present invention
The sensitizer used in formula (I) is represented by R⁶
And R⁷Also includes the ones that have been replaced. Used in the present invention
Preferred specific examples of the sensitizer obtained are shown in Table 1 below.
However, the present invention is not limited to these. In the present invention
One or more of these sensitizers,
The above can be mixed and used. [0020] [Table 1][0021] [Table 2]The second component constituting the photopolymerization initiation system of the present invention.
The increase is represented by (b) in the present invention.
Generates active radicals when irradiated with light in the presence of sensitizer
Is a titanocene compound. The titanocene compound
Is not particularly limited, but is described, for example, in JP-A-59-1523.
No. 96, JP-A-61-151197, JP-A-6-41
Various titanocene compounds described in Japanese Patent Publication No. 170
Can be appropriately selected and used. More specifically
Is di-cyclopentadienyl-Ti-dichloroyl
, Di-cyclopentadienyl-Ti-bis-phenyl
, Di-cyclopentadienyl-Ti-bis-2,3,
4,5,6-pentafluorophenyl-1-yl, disucci
Lopentadienyl-Ti-bis-2,3,5,6-tet
Lafluorophenyl-1-yl, di-cyclopentadie
Nyl-Ti-bis-2,4,6-trifluorophenyl
-1-yl, di-cyclopentadienyl-Ti-bis-
2,6-di-fluorophenyl-1-yl, di-cyclo
Pentadienyl-Ti-bis-2,4-difluoro
Enyl-1-yl, di-methylcyclopentadienyl-
Ti-bis-2,3,4,5,6-pentafluorophen
Ni-1-yl, di-methylcyclopentadienyl-Ti
-Bis-2,3,5,6-tetrafluorophenyl-1-
Yl, di-methylcyclopentadienyl-Ti-bis-
2,6-difluorophenyl-1-yl, di-cyclope
Nantadienyl-Ti-bis-2,6-difluoro-3-
(Pyr-1-yl) -phenyl-1-yl, bis [cyclo
Pentadienyl] bis [6-chloro-2-i-butylthio
O-4- (3-Methylbut-1-oxy) pyrimidini
Titanium, bis [cyclopentadienyl] bis [2
4-bis (1,1-dimethylpropoxy) pyrimidyl]
Titanium and the like can be mentioned. Generating radicals other than the titanocene compound
Activators can also be used in combination.
No. 56403, s-triazine compound, JP
The thiol compounds described in JP-A-58-29803,
Or amine compounds and the like, and particularly preferred additives.
As a dialkylamine derivative compound,
Specifically, Michler's ketone, dialkylaminophenyl
And the like. Dialkylamino
As the compound containing a phenyl group, for example, the following general
Compounds of formulas (II) to (IV) are mentioned. [0024] Embedded image In the general formulas (II) to (IV), R⁸~ R
¹⁸Each represents an alkyl group;⁸, R⁹, R¹¹~
R¹⁸Is preferably a lower alkyl group, particularly preferably
An alkyl group having 1 to 4 carbon atoms;^TenIs more specific
Represents an alkyl group having 1 to 20 carbon atoms.
They may be linear or have a branched structure.
R^TenAlkyl group further has a substituent, for example, a halogen atom,
Aryl group, acyl group, carboxyl group, alkoxy group
And so on. Compounds represented by general formulas (II) to (IV)
Is specifically exemplified by, for example, p-dimethylamino
Benzoic acid ethyl ester, p-diethylaminobenzoic acid
Ethyl ester, p-dimethylaminobenzoic acid isopro
Pill ester, p-dimethylaminobenzoic acid-n-buty
Ester, p-dimethylaminobenzoic acid-n-octy
Ester or p-di-n-butylaminobenzoic acid
Alkyl dialkylaminobenzoates such as tyl esters
Stele; 4,4'-bis (dimethylamino) benzofe
Non, 4,4'-bis (diethylamino) benzopheno
Or 4,4'-bis (diisopropylamino) benzene
Bisaminobenzophenones such as zophenone; 4,4'-
Bis (dimethylamino) benzyl or 4,4'-bis
Bisaminobenzyl such as (diethylamino) benzyl
No. Of these, general formula (II) or (III)
Compounds represented by the following, especially dialkylaminobenzoic acid
Kill esters are preferred. For use in the photopolymerizable composition of the present invention described above.
Sensitizers and active radica that constitute the photopolymerization initiation system used
The suitable amount of the compound capable of generating a compound is not particularly limited.
However, the sensitizer is added to 100 parts by weight of the ethylenic compound.
Preferably 0.05 to 20 parts by weight, more preferably 0.1 to 20 parts by weight.
2 to 10 parts by weight of a compound capable of generating an active radical
Generally, 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight.
Parts by weight, more preferably 0.5 to 10 parts by weight. The photopolymerizable composition of the present invention comprises each of the components described above.
To improve the composition and improve the physical properties after photocuring.
It is preferable to add an organic polymer substance as a mixture.
No. Binders are compatible, film-forming, developable, adhesive, etc.
What is necessary is just to select suitably according to the improvement objective. Specifically,
For example, acrylic acid copolymers and methacrylic
Luic acid copolymer, itaconic acid copolymer, partially esterified
Maleic acid copolymer, acidic with carboxyl group in side chain
Modified cellulose, polyethylene oxide, polyvinyl
And pyrrolidone. For improvement of film strength and adhesion,
Polyether of drin and bisphenol A;
Iron; polymethacryl such as polymethyl methacrylate
Alkyl acrylates and polyalkyl acrylates; methacrylic acid
Alkyl and acrylonitrile, acrylic acid, methacryl
Co-polymerization with acid, vinyl chloride, vinylidene chloride, styrene, etc.
Coalescence: acrylonitrile and vinyl chloride, vinylidene chloride
With vinyl; vinylidene chloride, chlorinated polyolefin
Copolymer of vinyl chloride and vinyl acetate; polyvinyl acetate
Nyl; a copolymer of acrylonitrile and styrene;
Copolymer of rilonitrile with butadiene and styrene;
Rivinyl alkyl ether; polyvinyl alkyl keto
Polystyrene; polyamide; polyurethane;
Tylene terephthalate isophthalate; acetone cellulose
And polyvinyl butyral.
You. These binders are in weight with respect to the ethylenic compound.
Generally, the ratio is 500% or less, preferably 200% or less.
It can be added and mixed in the following range. [0030] The photopolymerizable composition of the present invention may be modified if necessary.
Thermal polymerization inhibitors, coloring agents, plasticizers, storage stabilizers,
Add protective agents, leveling agents, coating aids and other additives
Can be. As a thermal polymerization inhibitor, for example, hydroquino
, P-methoxyphenol, pyrogallol, catechol
, 2,6-t-butyl-p-cresol, β-naphtho
And coloring agents such as phthalocyanine
Pigments, azo pigments, carbon black, titanium oxide
Which pigment, ethyl violet, crystal violet
G, azo dyes, anthraquinone dyes, cyanine dyes
There is a fee. The addition amount of these thermal polymerization inhibitors and coloring agents is as described above.
When a binder is used, the ethylenic compound and the binder
0.01 to 3% of thermal polymerization inhibitor based on total weight, colorant
Is preferably 0.1 to 20%. As the plasticizer, for example, dioc
Tyl phthalate, didodecyl phthalate, triethylene
Glycol dicaprylate, dimethyl glycol phthale
Phosphate, tricresyl phosphate, dioctyl adipate
, Dibutyl sebacate, triacetylglycerin, etc.
Yes, when used with a binder, binds to ethylenic compounds
10% or less based on the total weight of
You. When using the photopolymerizable composition of the present invention,
Form the photosensitive material without solvent or use a suitable solvent
Dissolve to form a solution, apply it on a support, and dry to
Optical materials can be prepared. As the solvent, for example,
Methyl ethyl ketone, cyclohexanone, butyl acetate,
Amyl acetate, ethyl propionate, toluene, xylene
, Monochlorobenzene, carbon tetrachloride, trichloroethyl
Len, trichloroethane, dimethylformamide, methyl
Lucerosolve, ethyl cellosolve, tetrahydrofura
, Bentoxone, propylene glycol monomethyl ester
Or one or more of them in combination
be able to. Photosensitive material using the photopolymerizable composition of the present invention
The support applied when preparing is commonly used
May be any. For example, aluminum, magnesium
Metals, such as copper, zinc, chromium, nickel, iron, etc.
Sheets of alloys based on these; fine paper, art paper,
Papers such as release paper; inorganic sheets such as glass and ceramics
G; polyethylene terephthalate, polyethylene, poly
Methyl methacrylate, polyvinyl chloride, vinyl chloride
Vinylidene chloride copolymer, polystyrene, 6-nylo
, Cellulose triacetate, cellulose acetate
Polymer sheets such as butyrate are exemplified. The photopolymerizable composition of the present invention may further comprise an acid
Prevents adverse effects such as loss of sensitivity and storage stability
Publicly known technology for, for example, transparent and peelable on the photosensitive layer
A wax-like material with a small oxygen permeability and a cover sheet
Coating layer of high quality, water soluble polymer, etc.
You. As the exposure light source applicable to the composition of the present invention,
Without limitation, carbon arc, high pressure mercury lamp, xeno
Lamp, metal halide lamp, fluorescent lamp, tongue
Stainless lamp, helium cadmium laser, algo
Ion laser, YAG laser etc.
A general-purpose light source including visible light can be more preferably used. [0035] Next, the present invention will be described in more detail with reference to Examples.
The present invention will be described below, unless the gist of the present invention is exceeded.
It is not limited to the embodiment. Examples 1-4 and Comparative Examples a, 1-5 On grained and anodized aluminum sheet
Then, using a wheeler, the photosensitive composition coating solution of the following composition
Coated to a dry film thickness of 2 μm, and further on the surface
The polyvinyl alcohol aqueous solution is dried to a dry film thickness of 3 μm.
To prepare a photosensitive material sample. [0036] (Photosensitive composition coating solution)   50 parts of methyl methacrylate / methacrylic acid / methyl acrylate copolymer   (Weight average molecular weight 45,000, copolymerization ratio 80/10/10)   Trimethylolpropane triacrylate 50 parts   Methyl cellosolve 500 parts   500 parts of propylene glycol monomethyl ether acetate   Sensitizers; compounds described in Table 2 Compounding amounts described in Table 2   Active radical generator; compounds described in Table 2 Compounding amounts described in Table 2 Next, the following items were evaluated. Table 2 shows the results
Shown in (Sensitivity) A photosensitive material sample was added to a key made by Ushio Electric
Senon lamp: Spectroscopy manufactured by Narumi using UI-501C
The horizontal axis is wavelength and the vertical axis is logarithmic light intensity by the sensitivity measurement device.
Irradiated for 10 seconds so that the light was weakened. The exposed sample was carbonate
1% by weight of thorium and an anionic surfactant (manufactured by Kao Corporation)
Perex NBL) with an aqueous solution containing 0.5% by weight
Image and height of the cured image obtained at 488 nm
Calculates the minimum exposure required for photocurable image formation
And the sensitivity of the photosensitive composition. [Solubility of Sensitizer]
Put 20 ml of cloth solution into a 30 ml sample bottle,
mm Teflon stirrer tip 300 rpm
When stirred, the sensitizer in the photosensitive composition coating solution is completely
The solubility of the sensitizer was evaluated based on the time until dissolution. [0039] [Table 3][0040] [Table 4] * 1: The amount in parentheses indicates the amount (parts by weight) in the photosensitive composition coating solution. In Table 2, among the abbreviations in the column of the sensitizer, S-1,
S-2 and S-7 represent the compounds described in Table 1 respectively.
You. Further, T-1 and T-2 represent the following compounds. [0042] Embedded imageIn Table 2, abbreviations in the column of active radical generator
(B-1, C-1, C-2, D-1, D-2, D-3)
Represents the following compounds, respectively. [0044] Embedded image [0045] According to the present invention, the photopolymerizable composition of the present invention is
Extremely high sensitivity, cost and time
In addition to enabling extremely advantageous plate making operations,
Shorter liquid preparation time due to excellent solubility in coating solvents
And achieve high productivity. Therefore, the composition
Is useful for a wide range of applications, such as lithography, intaglio,
For making printing plates such as letterpress, printing wiring and IC
Photoresist, dry film, relief image and image duplication
Image forming, photocurable ink, paint, adhesive, etc.
It is very useful industrially because it can be used for

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03F ^7/ 00-7/42

Claims (1)

(57) [Claim 1] In a photopolymerizable composition containing a compound having at least one addition-polymerizable ethylenic double bond and a photopolymerization initiation system, the photopolymerization initiation system is , (A)
At least one chromene dye represented by the following general formula (I): [Wherein, R ¹ and R ² each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 16 carbon atoms (for the substituent, a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group,
From an alkoxy group having 1 to 15 carbon atoms, an acyloxy group having 2 to 16 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, a hydroxycarbonylacyloxy group having 3 to 10 carbon atoms, and an alkoxycarbonylacyloxy group having 4 to 10 carbon atoms R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Also,
R ¹ and R ³ and R ² and R ⁴ may be bonded to each other directly or via an oxygen atom or a sulfur atom to form a ring. R ⁵ is a heterocyclic residue of 3-17 carbon atoms, R ⁶
And R ⁷ are each independently a cyano group, an alkoxycarbonyl group having 2 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, an optionally substituted phenylcarbonyl group or an optionally substituted naphthylcarbonyl group ( Examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, an alkoxy group having 1 to 15 carbon atoms, and an acyloxy group having 2 to 16 carbon atoms. However, at least one of R ⁶ and R ⁷ is a cyano group. ], (B) at least one titanocene compound, and (c) the following general formula (II)
Or a photopolymerizable composition comprising at least one compound represented by (III) . Embedded image [Wherein, R ^{8 to} R ¹⁴ each represent an optionally substituted
Represents a alkyl group (as the substituent, a halogen atom,
Reel group, acyl group, carboxyl group, alkoxy group
Selected from). ]