JPH0469936B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a novel photopolymerizable composition. More specifically, the present invention uses 1-cyano-2 as a sensitizer.
- Photopolymerization containing a photoinitiator or photoinitiator system in combination with a (P-dialkylaminophenyl)-ethylene derivative and a 1-cyano-4-(P-dialkylaminophenyl)-1,3-butadiene derivative The present invention relates to a sexual composition. BACKGROUND OF THE INVENTION Photopolymerizable compositions have been widely used in many applications, such as printing, copying, resist formation, and other commercial applications. These compositions generally contain an ethylenically unsaturated compound or other type of polymerizable compound, a photoinitiator or photoinitiator system, and preferably a solvent-soluble or aqueous or alkali-soluble organic polymeric binder compound. Many known useful photopolymerizable compositions have limited utility. This is because the initiators are not as active as desired and/or these initiators are not activated outside the ultraviolet region of the spectrum. Chambers (see U.S. Pat. No. 3,479,185) discloses photopolymerizable compositions containing ethylenically unsaturated monomers, free radical generators such as leukotriphenylamine dyes and hexaphenyl biimidazole. There is. These compositions are photoinitiable in the ultraviolet region of the spectrum. However, Mr. Chambers found that the addition of energy transfer dyes of the xanthene and acridine groups extended the sensitivity of the photopolymerizable composition into the visible spectral region with an increase in the rate of polymerization. Mr. Chiyoung (see U.S. Patent No. 3,549,367)
discloses a photopolymerizable composition containing a hexaarylbiimidazole and a P-aminophenyl ketone (e.g., Michler's ketone), which reduces the spectral sensitivity of the composition only slightly in the visible region of the spectrum. It has been extended to Messrs. Baum and Henry (U.S. Patent No.
No. 3,652,275) enhances the efficiency of hexaarylbiimidazole systems in photopolymerizable compositions through the use of selected bis(P-dialkylaminobenzylidene) ketone sensitizers. Messrs. Duuber and Link (Unexamined Japanese Patent Publication No. 59-74551)
(see specification) enhance the efficiency of various photoinitiators in photopolymerizable compositions through the use of selected N-alkylindolylidene and N-alkylbenzothiazolylidene alkanone sensitizers. There is. (Problems to be Solved by the Invention) Although the composition provides the visible light sensitivity of the photopolymer composition, the sensitivity in the visible region is still insufficient and the sensitivity range is narrow. (Means for Solving the Problem) The inventors of the present invention have made extensive research and efforts to solve the above problems, that is, to improve sensitivity in the visible range and expand its range. We have finally completed the present invention. That is, the present invention provides (A) at least one ethylenically unsaturated compound that is non-gaseous at room temperature, (B) hexaarylbiimidazole, 4-trichloromethyl-4-methyl-
At least one photoinitiator selected from the group consisting of 2,5-cyclohexadienone, quinone, alkylaryl ketone, benzophenone, and peroxy ester compound, and (C) the following general formula ()
1-cyano-2-(P-dialkylaminophenyl)-ethylene derivative or 1-cyano-4-(P-dialkylaminophenyl)-1,
A photopolymerizable composition characterized by containing at least one sensitizer selected from 3-butadiene derivatives. (In the formula, R ₁ and R ₂ are alkyl groups having 1 to 4 carbon atoms, R ₃ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ₄ is a hydrogen atom, a substituted or unsubstituted aryl group, or 1 is an integer of 0 to 4, n is 0 or 1, and m is an integer of 0 to 2. ) The ethylenically unsaturated compound used in the present invention is
Monomers suitable for free radical initiated chain growth addition reactions, such as pentaerythritol triacrylate, polyethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol dimethacrylate, tetraethylene glycol dimecacrylate, trimethylolpropane triacrylate,
Examples include trimethylolpropane trimethacrylate. Useful types of photoinitiator compounds include hexaarylbiimidazole compounds, 4-trichloromethyl-4-methyl-2,5-cyclohexadienone, quinones, alkylaryl ketones, benzophenones, and peroxy ester compounds. Biimidazole is photodissociable to the corresponding triarylbiimidazolyl residue. These hexaarylbiimidazoles have a maximum absorption in the 255-275 nm range and usually exhibit some absorption, albeit to a lesser extent, in the 300-375 nm range. Absorption bands tend to tail and encompass longer wavelengths of about 430 nm, but they typically require light rich in wavelengths from 255 to 375 nm for dissociation. Hexaarylbiimidazole has the formula [wherein A, B and D are the same or different carbocyclic or heterocyclic unsubstituted or do not inhibit the dissociation of the hexaarylbiimidazole to the triarylimidazolyl radical, or are optionally present leuco dyes represents an aryl group that may be substituted with a substituent that does not inhibit the oxidation of (that is, two conjugates = double bond)]. The aryl groups of B and D can each be substituted with 0 to 3 substituents, and the aryl group of A can be substituted with 0 to 4 substituents. Useful 2,4,5-triarylimidazolyl dimers are disclosed in U.S. Pat. No. 3,652,275, which is incorporated herein by reference. Useful quinone types are camphorquinones, substituted or unsubstituted polynuclear quinones which are compounds having two endocyclic carbonyl carbon atoms in a conjugated carbocyclic ring system, such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloro Anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiary butylanthraquinone, octamethylanthraquinone, 1,4-naphthoquinone,
9,10-phenanthrenequinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3
-dichloronaphthoquinone, 1,4-dimethylanthraquinone, 2,3-dimethylanthraquinone,
2-phenylanthraquinone, anthraquinone α
-sodium salt of sulfonic acid, 3-chloro-2-
methylanthraquinone, retenquinone, 7,8,
9,10-tetrahydronaphthacenequinone, 1,
2,3,4-tetrahydronaphthacenequinone and 1,2,3,4-tetrahydrobenz(a) anthracene-7,12-dione. Useful alkylaryl ketones include vicinal ketoaldonyl alcohols such as benzoin, pivaloin, acryloin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzoin tertiary butyl ether, benzoin secondary butyl ether, α Including benzoin isobutyl ether, benzoin n-butyl ether, α-methylbenzoin, α-allylbenzoin and α-phenylbenzoin.
-hydrocarbon-substituted aromatic acrylosones, benzoin dialkyl ketals such as benzyl dimethyl ketal, benzyl ethylene glycol ketal, benzyl, benzoin esters such as 0-acetylbenzoin and 0-acylated oxyiminoketones such as 1-phenyl-1,2-propanedione. 2-0-benzoyloxime is mentioned. Benzophenones useful as photoinitiators include benzophenone, 4,4'-dichlorobenzophenone, fluorenone, anthrone, thioxanthone, Michler's ketone, 4-dimethoxyaminobenzophenone, and 4-morpholinobenzophenone. 4-Trichloromethyl-4-methyl-2,5-cyclohexadienone compounds useful in the present invention are disclosed in U.S. Pat.
It is disclosed in specification No. 4341860. Useful such compounds include 4-methyl-4-trichloromethyl-2,5-cyclohexadienone,
3,4-dimethyl-4-trichloromethyl-2,
5-cyclohexadienone, 2,6-di(tert-butyl)-4-methyl-4-trichloromethyl-
Other useful compounds include 2,5-cyclohexadienone and the like, and 4-dichloromethyl-2,5-cyclohexadienone substituted as above. Peroxyester-type organic peroxides useful in the present invention have the formula [In the formula, Ar is an unsubstituted phenyl group or a carbon number of 1 to
4 represents a phenyl group substituted with an alkoxy group, a phenyl group, an amino group, or a halogen atom], such as t-butyl-peroxybenzoate, di-t-butyl-
Examples include diperoxyisophthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, and the like. 1-cyano-2- useful in photopolymerizable compositions
The sensitizer of (P-dialkylaminophenyl)-ethylene derivative or 1-cyano-4-(P-dialkylaminophenyl)-1,3-butadiene derivative is represented by the above general formula (), and specifically is 1-
Cyano-1-phenyl-2-(4-dimethylaminophenyl)-ethylene, 1-diano-1-(4chlorophenyl)-2-(4-dimethylaminophenyl)-ethylene, 1-cyano-1-( 3-Biridyl)-2-(4-dimethylaminophenyl)-ethylene, 1-cyano-1-phenyl-2-(4-diethylaminophenyl)-ethylene, 1-cyano-1-phenyl-2-(2 -methyl-4-dimethylaminophenyl)-ethylene, 1-cyano-1
-Phenyl-4-(4-dimethylaminophenyl)
-1,3-butadiene, 1-cyano-1-(4-
Chlorophenyl)-4-(4-dimethylaminophenyl)-1,3-butadiene, 1-cyano-1-
(3-methoxyphenyl)-4-(4-dimethylaminophenyl)-1,3-butadiene, 1-cyano-1-(2-cyanophenyl)-4-(4-dimethylaminophenyl)-1, 3-butadiene, 1
-cyano-1-(3-biridyl)-4-(4-dimethylaminophenyl)-1,3-butadiene, 1
-cyano-1-(3-thiophene)-4-(4-dimethylaminophenyl)-1,3-butadiene,
1,4-bis[1-(1-cyano-4-dimethylaminophenyl)-13-butadiel]-benzene,
1,10-di(4-dimethylaminophenyl)-4,
Examples include 7-diano-1,3,5,7,9-decapentaene, 1-cyano-2-(4-dimethylaminophenyl)1,3-butadiene, and the like. Preferably, a thermoplastic high molecular weight organic polymeric binder is present in the compositions of the invention. Examples of polymer binders include (a) copolyesters containing terephthalic acid, isophthalic acid, sebacic acid, adipic acid, and hexahydroterephthalic acid as acid components, (b) polyamides, (c) vinylidene chloride copolymers, (d ) ethylene/vinyl acetate copolymer, (e)
Cellulose ethers, (f) polyethylene, (g) synthetic rubbers, (h) cellulose esters, (i) polyvinyl esters, including polyvinyl acetate/acrylates and polyvinyl acetate/methacrylate copolymers, (j) polyacrylates and polyalpha-alkyls. Acrylate esters such as polymethyl methacrylate and polyethyl methacrylate, (k)
High molecular weight ethylene oxide polymer having a weight average molecular weight of 4,000 to 4,000,000, (l) polyvinyl chloride and its copolymer, (m) polyvinyl acetal,
(n) polyformaldehyde, (o) polyurethane, (p) polycarbonate and (q) polystyrene. In particularly preferred embodiments of the invention, the photopolymerizable coating is soluble in primarily aqueous solutions, such as alkaline solutions, but relatively insoluble therein after exposure to actinic radiation. Choose a binder. Polymers that typically meet these requirements are carboxylated polymers, such as vinyl addition polymers containing free carboxylic acid groups. Preferred binders include styrene/maleic anhydride (1:1) copolymers having an acid number of about 190 and a weight average molecular weight of about 10,000 partially esterified with isobutanol mixtures, and styrene/maleic anhydride copolymers partially esterified with isobutanol mixtures. Examples include combinations of polymers and terpolymers of ethyl acrylate/methyl methacrylate/acrylic acid. Other preferred groups of binders include polyacrylate esters and polyα-alkyl acrylate esters, especially polymethyl methacrylate. Leuco dyes can optionally also be present in the photopolymerizable composition. "Leuco dye"
is a colorless form (i.e., reduced form) of a dye compound that can be oxidized to its colored form by a triarylimidazolyl radical.
Leuco dyes are disclosed in U.S. Pat. No. 3,652,272, column 7, line 24 to column 11, line 32. In preferred positive-acting photopolymerizable compositions, a nitroaromatic photoinhibitor as disclosed in Belgian Patent No. 852,517 is present, and 0,
These compounds, which may be present in an amount of 5 to 15 parts by weight, have the formula [In the formula, R ¹ is H, R ⁴ is H, R ² and
^R3 is the same or different, OH, halogen, _NO2 ,
CN, alkoxy of 1 to 18 carbon atoms, aryl containing 6 to 18 carbon atoms, benzyl, halogen-substituted phenyl, containing 2 to 18 carbon atoms and 1 to 6 oxygen atoms polyester, dialkylamino where each alkyl is of 1 to 18 carbon atoms, thioalkyl where alkyl is of 1 to 18 carbon atoms, or thioaryl where aryl is of 6 to 18 carbon atoms or any two of R ¹ , R ² , R ⁵ and R ⁴ together form a residue of a second benzene nucleus bonded to the benzene nucleus, provided that one of R ² and R ³ no more is OH or NO ₂ and R ⁵ is H, alkyl containing 1 to 18 carbon atoms, halogen, phenyl or alkoxy where alkyl is of 1 to 18 carbon atoms , R ⁶ is H, OH, alkyl containing 1 to 18 carbon atoms, phenyl, where the alkyl is 1 to
Alkoxy containing 18 carbon atoms with the proviso that only one of R ⁵ and R ⁶ is H, or R ⁵ and R ⁶ taken together =0, =CH ₂ , -
0-CH ₂ −, = NC ₆ H ₅ , = NC ₆ H ₄ N (alkyl) ₂
(wherein each alkyl is of 1 to 18 carbon atoms), -0-CH ₂ H ₄ -0-, =N (hydrocarbylene) (wherein the hydrocarbyn group is of 1 to 18 carbon atoms) or - ^CR7 = ^CR8 -NH- ^CR9 = ^CR10 - (wherein ^R8 and ^R9 are the same or and R ⁷ and R ¹⁰ are the same or different -CN, -
COR''(R'' is alkyl containing 1 to 5 carbon atoms) or -COOR ¹² (wherein R ¹² is alkyl containing 1 to 6 carbon atoms, optionally interrupted by an oxygen atom) , alkenyl of 2 to 5 carbon atoms, alkynyl of 2 to 5 carbon atoms) or R ⁷ and R ⁸ taken together,
or R ⁹ and R ¹⁰ together complete a 6-membered carbon ring containing a keto group. Active hydrogen donors, which act as promoters or reducing agents such as oxygen scavengers and chain transfer agents, are useful additives in compositions that lead to improved photographic speed. Oxygen scavengers that have been found to be useful are phosphines, phosphonates, phosphites, stannous salts and other compounds that are readily oxidized by oxygen. Useful chain transfer agents are N-phenylglycine, trimethylparbituric acid, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole and other compounds having hydrogen that is easily removed by radicals. A wide variety of non-polymerizable plasticizers are effective in achieving improved exposure and development latitudes. When a high molecular weight binder is present in the layer, the choice of plasticizer is based on compatibility with it and with the monomers, dimers, ketones, and other components, as is well known in the art. Regarding acrylic binders,
For example, dibutyl phthalate and other esters of aromatic acids, esters of aliphatic polyacids such as diisooctyl phthalate, nitrate esters, etc., glycols, polyoxyalkylene glycols, aliphatic polyols, and other aromatic or aliphatic acid esters, Alkyl and aryl phosphates, low molecular weight polyesters of poly-α-methylstyrene, chlorinated paraffins, and sulfonamide types can be used.
Although generally water-insoluble plasticizers are preferred for greater high-humidity storage stability, but are not necessarily required to obtain improved latitude, other inert additives such as dyes, pigments and fillers may be used. Known to those skilled in the art. These additives are generally present in small amounts and should not interfere with exposure of the photopolymerizable layer. The photopolymerizable compositions described herein can be coated onto a wide variety of substrates. By "substrate" is meant any natural or synthetic support, preferably in the form of a flexible or rigid film or sheet. For example, the substrate can be a metal sheet or foil, a sheet or film of synthetic organic resin, cellulose paper, fiberboard, etc. or a composite of two or more of these materials. Specific substrates include alumina-plast aluminum, anodized aluminum, alumina-plast polyethylene terephthalate film, polyethylene terephthalate film such as resin-subbed polyethylene terephthalate film, electrostatic discharge treated polyethylene terephthalate film, polyvinyl alcohol coated paper, cross-linked polyester coatings. Examples include paper, nylon, glass, cellulose acetate film, and others. The particular substrate will generally be determined by the application purpose involved. For example, if printed circuits are to be manufactured, the substrate may be a copper coated plate on fiberboard. In the manufacture of lithographic printing plates, the substrate is anodized aluminum. Preferably, the layer of photopolymerizable composition has a thickness in the range of 0.0001 inch (0.0003 cm) to about 0.01 inch (0.025 cm), and the photopolymerizable layer has a thin flexible layer that is transparent to the active radiation. Adhered to a flexible polymeric film support with low to moderate adhesion. A protective cover layer or cover sheet can be adhered thereto. The sheet has less adhesion to the layer than the adhesion between the film support and the layer. A particularly preferred support is a transparent polyethylene terephthalate film having a thickness of about 0.001 inch (~0.0025 cm).
0.001 inch (~0.0025) polyethylene is the preferred cover sheet. A polyvinyl alcohol coating is a preferred cover layer. In the composition of the present invention, 1-cyano-2-(P-
A sensitizer that is a dialkylaminophenyl)-ethylene derivative or a 1-cyano-4-(P-dialkylaminophenyl)-1,3-butadiene derivative has a wavelength in a spectral region that overlaps with the absorption band of the sensitizer. Any conventional activating radiation source can be used to activate the photopolymerizable composition by radical formation, imaging, and photoinitiation. This light can be natural or artificial, monochromatic or polychromatic, incoherent or coherent. 405, 436 and 546nm as normal light sources
Fluorescent lamps, mercury vapor lamps, metal-doped lamps, and arc lamps provide narrow or broad bands of light centered at the (Hg) wavelength. Interference light sources include pulsed xenon, argon ion, helium-cadmium, and ionizing neon lasers. Visible light emitting cathode ray tubes, commonly used in printout systems, are also useful with the compositions of the present invention. These generally include an internal coating of ultraviolet or visible light-generating phosphor as a means of converting electrical energy into light energy.
It also includes an optical fiber face plate as a means for directing the radiation to the light sensitive target. The photopolymerizable compositions of this invention are useful in offset and letterpress printing plates, industrial drafting films, photoresist production in printed circuit manufacturing or chemical mills, and as solder masks. In printing plate applications, an important use is in positive-negative dual-exposure imaging systems of positive photopolymer lithographic printing plates. The compositions are also useful in positive working photopolymer lithographic films. This composition can be used for producing colored images from color separation negatives suitable for color proofing. It can be used to make copies by thermal transfer of images formed from elements made using the composition to a substrate. 1-cyano-2-(P-dialkylaminophenyl)-ethylene derivatives and 1-cyano-4-(P-dialkylaminophenyl)-1,
Photopolymerizable compositions containing 3-butadiene derivatives unexpectedly exhibit improved visible light sensitization. Increased speed results in energy and related cost savings. This is because lower energy exposure sources can be used or because a larger number of elements can be exposed and developed in a given time. Alternatively, the photopolymerizable layer can be exposed with an exposure source held at a greater distance than is usual for known sensitizing elements. This makes it possible to collimate the exposure radiation, which has particular advantages in the form of half-torido dots with substantially vertical sides.
A wide sensitization range combined with sensitization effectiveness using specific nitroaromatic photoinhibitors allows for double exposure techniques, first imagewise in the ultraviolet region of the spectrum and then globally in the visible part of the spectrum. This allows a useful positive image to be formed. (Function) The sensitizer used in the present invention is activated by efficiently absorbing visible light that the photoinitiator used in the present invention cannot absorb or exhibits only very low absorbance. In this state, the sensitizer of the present invention acts on the photoinitiator used in the present invention, resulting in the generation of active radicals, which attack the ethylenically unsaturated compound in the composition and cause a polymerization reaction. is starting. (Example) The present invention will be specifically explained with reference to the following examples, where parts and percentages are based on weight. The components shown below were mixed, each composition was applied onto a 125 μm thick transparent polyethylene terephthalate film having a subbing layer, and dried with hot air to obtain a 5 μm thick coating film. Tetraethylene glycol dimethacrylate 40 parts Poly(methyl methacrylate/methacrylic acid, 70/
30 molar ratio) 45 parts carbon black 3 parts bis(2-0-chlorophenyl-4.5-diphenyl)imidazole 10 parts sensitizer shown in Table 1 2 parts Next, 10% polyvinyl alcohol (completely saponified, polymerized) A 2 μm overcoat layer was provided by applying an aqueous solution of 500° C. to obtain a sensitivity test piece. 21√ as a negative film on the above sensitivity test piece
Two step plates (gray film scale manufactured by Dainippon Screen Co., Ltd.) are stacked, and an interference filter (KL-44 or KL-49 manufactured by Toshiba Corporation) and a colored glass filter are placed on top of a xenon lamp (UXL-500D-O manufactured by Ushio Inc.). (Toshiba Y-42 or Y-
45), exposed for a certain period of time from a distance of 15 cm, washed with water, immersed in a 1% sodium carbonate aqueous solution at 30℃ for 10 seconds, washed with water again, dried, and then 21√2 gray scale. The sensitivity of the composition of the present invention was determined by examining the number of stages at which exposure and development were completed. The numbers in the table indicate the sensitivity in grayscale steps.
The higher the number, the higher the sensitivity.

【table】

[Table] From Table 1, Examples 1 to 5 and 13 have a wavelength of 490 nm.
Although the sensitivity range up to
It can be seen that it has high sensitivity. In Example 6, 10 parts of each of the photoinitiators shown in Table 2 were used, and everything was the same as in Example 6 except that a sensitizer was used or not. The results are also listed in Table-2.

[Table] As is clear from Table 2 above, when there is no photoinitiator or when there is no sensitizer, the sensitivity is either very low compared to the examples of the present invention, or the sensitivity is essentially It can be seen that it has no photosensitivity to visible light. (Effect of the invention) 1-cyano-2(P-dialkylaminophenyl)-ethylene derivative or 1-cyano-4-(P-dialkylaminophenyl)-1,3 of the present invention
- The photosensitive composition containing the butadiene derivative is He
-High sensitivity to 440nm light, which corresponds to the oscillation wavelength of a Cd laser, and 490nm light, which corresponds to the oscillation wavelength of an Art laser. Therefore, by using the composition of the present invention, not only is exposure to visible light possible, but also a light source with considerably lower output power can be used effectively.

Claims (1)

[Claims] 1 (A) at least one ethylenically unsaturated compound that is non-gaseous at room temperature, (B) hexaarylbiimidazole, 4-trichloromethyl-4-methyl-2,
At least one photoinitiator selected from the group consisting of 5-cyclohexadienone, quinone, alkylaryl ketone, benzophenone, and peroxyester compound, and (C) 1-cyano-represented by the following general formula (). 2-(P-dialkylaminophenyl)-ethylene derivative or 1-cyano-
4-(P-dialkylaminophenyl)-1,3-
A photopolymerizable composition comprising at least one sensitizer selected from butadiene derivatives. (In the formula, R ₁ and R ₂ are alkyl groups having 1 to 4 carbon atoms, R ₃ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ₄ is a hydrogen atom, a substituted or unsubstituted aryl group, or 1 is an integer of 0 to 4, n is 0 or 1, and m is an integer of 0 to 2. )