JP3463176B2 - Photosensitive composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition,
More specifically, the present invention relates to a photosensitive composition suitable as a photosensitive layer of a photosensitive lithographic printing plate, a photoresist or the like. 2. Description of the Related Art A composition (cationic cationic polymerization composition) which cationically polymerizes by actinic light has been known. That is, J. Polym., Poly.Chem.Ed., 22, pp. 2105-2121 (198
4) discloses a cationic photopolymerizable composition using a compound having a vinyl ether group and a photoacid generator. JP-A-59-180543 discloses a cationic photopolymerizable composition using a compound having at least one of oxirane, thiirane, oxetane and thietane rings and a photoacid generator. [0003] However, when the above cationic photopolymerizable composition is applied to a photosensitive layer of a photosensitive lithographic printing plate, a photoresist, or the like, any of them has sensitivity and chemical resistance (photoresist resistance). At the time of etching or lithographic printing) and the mechanical strength is insufficient. Accordingly, an object of the present invention is to provide a photosensitive composition having high sensitivity and excellent in chemical resistance and mechanical strength. The structure of the present invention for achieving the above object of the present invention is as follows. A photosensitive composition having on its surface a microgel having at least one ring selected from vinyl ether groups and propenyl ether groups and at least one ring selected from oxirane, thiirane, oxetane and thietane. . Hereinafter, the present invention will be described in detail. The above-mentioned microgel is a water-insoluble, particulate dispersion capable of maintaining a stable state for several hours or more without causing dissolution, aggregation, or sedimentation in a desired solvent. The particulate dispersion useful in the present invention is not particularly limited to the type of the dispersion as long as it does not dissolve, aggregate, or settle in a desired solvent. These particulate dispersions may be used alone or in combination of two or more. Examples of such particulate dispersions include polyacrylates or copolymers thereof, polyacrylonitrile or copolymers thereof, polystyrene or copolymers thereof, polyethylene or copolymers thereof, polyvinyl chloride or copolymers thereof, polyvinylidene chloride or The copolymer, polyvinyl acetate or copolymer thereof,
Resole resins or copolymers thereof, ionomer resins,
Latex-like polymer compounds such as polymethyl methacrylate or a copolymer thereof, polybutadiene or a copolymer thereof can be given. The latex polymer compound used in the present invention is a copolymer with a monomer having a polar group in the main chain or side chain. A preferred polar group is -COOR, And the like. Particularly preferred is a copolymer with a monomer having a quaternary nitrogen atom or a quaternary phosphorus atom. Among them, a typical example including a quaternary nitrogen atom in the main chain is represented by the following general formula [1]: Some include a so-called ionene type monomer unit represented by [X ⁻ : anion, R: alkyl group or carbocyclic group, n: integer], and have a quaternary nitrogen atom in the side chain. A typical example is the following general formula [2]: A compound containing a monomer unit of methacryloxyalkylammonium represented by [X ⁻ : anion, R: alkyl group or carbocyclic group, n: integer], or a compound represented by the following general formula [3]: ] [0020] ^- those comprising monomer units of vinyl benzyl ammonium represented by [X:: anion, R an alkyl group or a carbocyclic group] or, further monomer units of the benzyl ammonium type attached through an amide group And the following general formula [4] described in JP-A-55-22766: [0022] ^- those represented by [X:: anion, R an alkyl group or a carbocyclic group]. On the other hand, an example of a monomer unit containing a quaternary phosphorus atom in the main chain is represented by the following general formula [5]: [0025] ^- It is one represented by [X:: anion, R, R 'an alkyl group or a carbocyclic group], examples including the side chain is represented by the following general formula (6) [0026] embedded image [0027] ^- those like represented by [X:: anion, R an alkyl group or a carbocyclic group] and the like. In each of the general formulas [1] to [6], specific examples of the anion represented by X ⁻ include, for example, a halogen ion, a sulfate ion, a phosphate ion, a sulfonate ion, an acetate ion and the like. And R, R '
As the alkyl group represented by, for example, each group such as methyl, ethyl, propyl, isobutyl, pentyl, hexyl, heptyl, decyl and the like, and as the carbocyclic group, for example, aryl, aralkyl, cycloalkyl For example, pendyl, phenyl, p-methylbenzyl,
Examples include groups such as cyclohexyl and cyclopentyl. And in each of the above general formulas, it binds to N ⁺ or P ⁺
The alkyl groups or carbocyclic groups represented by R may be the same or different. These latex-like polymer compounds can be obtained by emulsion polymerization. It can also be obtained by converting the synthesized polymer into a latex. In order to make it possible to use an oil-soluble ethylenically unsaturated compound and a photopolymerization initiator, these latexes are preferably dispersed in an organic solvent. Further, these latexes used in the present invention are intermolecularly cross-linked in the particles in order to increase the stability to organic solvents. That is, in a preferred embodiment, the particulate dispersion is a polyacrylate or a copolymer thereof, a polystyrene or a copolymer thereof, a polyethylene or a copolymer thereof, a polyvinyl chloride or a copolymer thereof, a polyvinylidene chloride or a copolymer thereof, a polyvinyl acetate. Or a latex of the copolymer, and preferably, the latex is a copolymer having a polar group-containing monomer represented by the following general formula. More preferably, these latexes have a quaternary nitrogen atom or a quaternary phosphorus atom in the main chain or side chain, and more preferably are intermolecularly crosslinked in the particles,
Particularly preferably, an organic solvent is used as a dispersion medium. The particle size of the particulate dispersion used in the present invention is preferably in the range of 10 nm to 1 μm. If the particle size is larger than 1 μm, the resolution of the finally obtained image will be poor, and particles smaller than 10 nm will be substantially difficult to prepare. ００３５】 ００３５ ００３５ ００３７ ００５０ ００３５ ００５０ ００４４ ００５０ ００４４ ００４４ ００５０ ００５０ ００４７ ００５０ ００５０ ００５０ ００５０ ００５０ ００５０ ００５０ In the invention according to the first aspect , a vinyl ether group and a vinyl ether group on the surface are provided. A microgel having at least one ring selected from propenyl ether groups and at least one ring selected from oxirane, thiirane, oxetane and thietane is synthesized by a method shown in the following (1) or (2). (1) A microgel having a reactive group (preferably a hydroxyl group or an amino group) is synthesized, and the functional group is introduced into the reactive group of the microgel by a chemical reaction. For example, a condensation product of a microgel having a group condensable with chloroethyl vinyl ether on the particle surface and a chloroethyl vinyl ether, a microgel having a group capable of contacting and reacting with an epoxide (eg, epihalohydrin, etc.) on the particle surface and an epoxide And reactants. The hydroxyl group-containing monomers used for producing the hydroxyl group-containing microgel include vinyl alcohol, 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N- (4-hydroxyethyl (Phenyl) methacrylamide, hydroxy-methyldiacetone (meth) acrylamide, N- (4-hydroxyphenyl) acrylamide, N-
(4-hydroxyphenyl) methacrylamide, o-, m-, p-
Hydroxystyrene, o-, m-, p-hydroxyphenyl-
Acrylate or methacrylate is exemplified. Examples of the monomer having an amino group used for producing a microgel having an amino group include acrylamide, methacrylamide, 2-aminoethyl vinyl ether, p-aminostyrene and the like. The microgel having a reactive group includes a monomer having a reactive group such as a hydroxyl group or an amino group, and another copolymerizable monomer such as an acrylate, a methacrylate, a styrene alkylene ether, a vinyl acetate, or the like. Using acrylonitrile and the like, for example, JP-A-59-6203, JP-A-59-53505, JP-A-61-36474, JP-A-62-10
It can be synthesized according to the emulsion polymerization method described in each publication of No. 2240. At this time, the crosslinking is preferably carried out with a monomer having two or more functional groups such as divinylbenzene and dimethacrylate. Further, another method for introducing a hydroxyl group or an amino group into the particle surface is described in, for example, “Chemical Reaction of Polymer (above)
(Bottom) ”written by Shin Okawara, Doujin Kagaku (1972), Fine Polymer Fine Chemicals, Ryohei Oda, Kodansha (1976),“ Reactive Polymers ”Keisuke Kurita, Yoshio Iwakura, Kodansha (1977) A method based on a molecular reaction can also be used, for example, after synthesizing a microgel having a reactive group, chemically modifying the reactive group with a compound having a hydroxyl group or an amino group, or reacting with a polymerizable monomer having a hydroxyl group or an amino group. A method of graft-polymerizing starting from a functional group can be applied. (2) The radical polymerizable monomer having a functional group is copolymerized with another copolymerizable monomer. As the radical polymerizable monomer having a functional group, glycidyl acrylate, glycidyl methacrylate, 2,3-epithiopropyl acrylate or methacrylate, a monomer represented by the following general formula, or the like is used. Embedded image (Wherein, R ₁ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 10.) Using the above monomer and the copolymerizable monomer described in the above (1), Similarly, preferably divinylbenzene,
Crosslinking is performed with a monomer having two or more functional groups such as dimethacrylate. The photosensitive composition of the invention according to claim 1 or 2 is dispersed and dissolved in a dispersion medium of a microgel and a solvent of other components, and is coated on a support by dip coating, coating rod, spinner coating, spraying. A photosensitive plate (for example, a negative photosensitive lithographic printing plate) can be manufactured by coating and drying by a known coating method such as a coat. As the dispersion / solvent, for example, cellosolves can be used. An image can be formed by exposing the photosensitive plate according to a conventional method, developing with an alkaline developer and removing the non-exposed portion. When the present invention is applied to a photosensitive layer of a photosensitive lithographic printing plate, a support generally used for a PS plate can be used. Next, the present invention will be described more specifically with reference to examples. Synthesis Example 1 An emulsion polymerization apparatus was equipped with a stirring stirrer in a 5-liter four-necked flask.
It is equipped with a 1 liter addition funnel, thermometer, nitrogen gas inlet tube, water-cooled condenser, and placed in a heating mantle. 3360 g of deionized water and 20 g of a 30% aqueous solution of sodium lauryl sulfonate were added to the flask, and the activator system was heated to 80 ° C. under a nitrogen atmosphere. At this temperature, methyl methacrylate 420
g, ethyl acrylate 240 g, p-hydroxystyrene 1
25% of a monomer mixture containing 65 g, 16 g of styrene sulfonic acid and 16 g of 1,4-butanediol diacrylate were added at once. 10 ml of 5% aqueous solution of potassium persulfate
And 10 ml of a 7% aqueous solution of potassium phosphate were added immediately. The reaction mixture became milky and exothermic to 85 ° C. 80 ~
The remainder of the monomer mixture was added over a period of 90 minutes, keeping it between 88 ° C. When the addition was completed, the reaction mixture was heated at 80-85 ° C for another 2 hours. The bluish emulsion was cooled to room temperature and coagulated by addition of methanol. The resulting slurry was filtered, washed twice with water, dried by suction and the resulting fine powder was dried in a 100 ° C. oven for 4 hours. The spherical shape of the powder particles was confirmed by microscopy. [0077] 57 g of this microgel was dispersed in 500 ml of dimethylsulfoxide, and chloroethyl vinyl ether 9.
5 g, 5 g of potassium hydroxide and 2.8 g of tetrabutylammonium bromide were added and reacted at 60 ° C. for 24 hours. After completion of the reaction, the mixture was neutralized with acetic acid and poured into 2 l of water, and the precipitated microgel was filtered, washed with water and dried in vacuo to obtain a microgel having a vinyl ether group on the surface of the target particle. [0078] Synthesis Example 2 except that instead of Synthesis Example 1 of p- hydroxystyrene with glycidyl methacrylate performed similarly to the first step of the microgel synthesis of Example 1, oxy to the particle surface
A microgel having a run ring was obtained. Synthesis Example 3 A microgel was synthesized in the same manner as in the first step of synthesis of microgel of Synthesis Example 1 except that 2,3-epithiopropyl methacrylate was used instead of p-hydroxystyrene of Synthesis Example 1. A microgel having a thiirane ring was obtained. Examples 1, 3 to 5 and Comparative Examples 2, 36 Six aluminum plates were degreased with a 10% by weight aqueous solution of sodium hydroxide, and were degreased in a 1.8% hydrochloric acid bath at 25 ° C., 30 A / dm ² ,
Electroetched under current density condition of 30 seconds, washed with water, 30%
Anodizing was performed in a sulfuric acid bath at 30 ° C. and 6.5 A / dm ² for 30 seconds. Next, a 1% by weight aqueous solution of sodium metasilicate was sealed at 85 ° C. for 30 seconds, washed with water and dried to obtain an aluminum plate as a lithographic printing plate support. The photosensitive solutions shown in Tables 1 and 2 were applied to this aluminum plate so that the coating weight after drying became 20 mg / dm ² , thereby preparing photosensitive lithographic printing plate samples. A negative film and Kodak Step Tablet No. 2 were brought into close contact with each of the obtained photosensitive lithographic printing plate samples, and exposed to idle fins 2000 (2 kW metal halide lamp, manufactured by Iwasaki Electric Co., Ltd.) for 30 seconds. The substrate was rubbed with a sponge in alkaline water having a pH of 1 for 1 minute to remove unexposed portions, thereby obtaining a printing plate having a clear image. Table 3 shows the exposure energy (sensitivity) at which three steps of curing steps were obtained and the printing results. Example 2 and Comparative Example 1 The photosensitive liquids shown in Tables 1 and 2 were applied to a copper-clad laminate for printed wiring so that the coating weight after drying was 15 mg / dm ² . After exposure and development and washing with water in the same manner as in Example 1, the copper film was removed by etching with ferric chloride, and the cured coating film on the exposed portion was peeled off to obtain a printed circuit board. Table 3 shows the exposure energy and the chemical resistance to the etching solution for obtaining three step curing steps. [Table 1] [Table 2] [Table 3] From Table 3, it can be seen that the photosensitive composition of the present invention has improved sensitivity and chemical resistance as compared with the conventional cationic photopolymerizable composition, and was used as a photosensitive layer of a photosensitive lithographic printing plate. It can be seen that the printing durability at the time is improved. According to the present invention, when the conventional cationic photopolymerization composition is applied to a photosensitive layer of a photosensitive lithographic printing plate, a photoresist, or the like, all of the sensitivity and chemical resistance (photosensitivity) It is possible to provide a photosensitive composition having improved sensitivity, etching resistance or lithographic printing, and insufficient mechanical strength, and having high sensitivity and excellent chemical resistance and mechanical strength.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI G03F 7/029 G03F 7/033 7/033 H05K 3/00 F H01L 21/027 B01J 13/02 L H05K 3/00 H01L 21 / JP-A-62-173455 (JP, A) JP-A-3-68950 (JP, A) JP-A-49-39683 (JP, A) JP-B-43-27561 (JP, B1) )

Claims (1)

(57) [Claim 1] A microgel having on its surface at least one ring selected from a vinyl ether group and a propenyl ether group and at least one ring selected from oxirane, thiirane, oxetane and thietane A photosensitive composition comprising: