JP2006111843A - New polymerizable monomer, photosensitive composition containing the same and lithographic printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To find out a new photopolymerizable monomer having a high photopolymerization property and high sensitivity, and also a photosensitive composition having a sufficient film strength and eluting property on its development. <P>SOLUTION: This polymerizable monomer is characterized by having ≥2 unit structures expressed by formula (1) in its molecule, and the photosensitive composition containing the same is also provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel polymerizable monomer, and also relates to a negative photosensitive composition using the same. Applications include photosensitive resins, printing plates, inks, paints, adhesives, crosslinking agents, optical lens materials, optical fiber coatings, three-dimensional modeling, holographic recording materials, printed wiring boards, and photosensitive materials that can be used for electronic materials such as ICs. The present invention relates to a sex composition. Furthermore, it is related with the said photosensitive composition in which image formation by scanning exposure, such as a laser, is possible. Furthermore, it is related with the lithographic printing plate using the said photosensitive composition.

  Photocrosslinking systems that are sensitive to radiation and undergo a crosslinking reaction in the irradiated area are roughly classified into photoradical systems and photocationic systems based on their mechanisms. As the photoradical system, a system mainly composed of a combination of acrylates and a photoradical generator is mainly used, and one of the characteristics is that the room temperature curability is good and the curing speed is fast. Even if light irradiation is performed, the polymerization reaction rate does not reach 100%, due to the adverse effect on the physical properties of the cured product due to the remaining acrylate monomer, bleeding of the acrylate monomer from the cured product, and hydrolysis of the cured product under strong alkali conditions It has various problems such as deterioration.

  On the other hand, in the photocation system, using an onium salt-based photocation generator such as an iodonium salt or a sulfonium salt, a cationic ring-opening polymerization of an epoxy compound or a cationic polymerization of vinyl ethers is used. A similar photocrosslinking system is constructed by this method. In this case, the greatest advantage is that the polymerization is not inhibited by oxygen, and it is used for the curing reaction in air. Disadvantages are that the curing rate is often low, heat treatment (post-cure) is necessary after irradiation to promote the cross-linking reaction, and polymerization inhibition is present in the presence of basic substances. was there.

  Furthermore, with the remarkable progress of semiconductor lasers, it has become possible to easily use near-infrared laser light sources of 700 to 1300 nm, and photosensitive materials and photosensitive lithographic printing plates corresponding to the laser beams have attracted attention. .

  As a photopolymerizable composition having photosensitivity to visible light to near infrared light, JP-A-9-134007 discloses a radically polymerizable compound having an ethylenically unsaturated bond and an absorption peak at 400 to 500 nm. A lithographic printing plate material containing a photosensitizing dye and a polymerization initiator is disclosed. JP-A-62-143044, JP-A-62-1050242, JP-A-5-5988, JP-A-5-194619, JP-A-5-197069 and JP-A-2000-98603 disclose combinations of organic boron anions and dyes, and JP-A-4-31863 and JP-A-6-43633 disclose dyes and s- A combination with a triazine compound is disclosed, and JP-A-7-20629 and JP-A-7-271029 disclose a resole resin, a novolac resin, an infrared absorber and The combination of the acid generator is disclosed, JP-A-11-212252, a combination of a specific polymer and a photoacid generator and a near infrared sensitizing dyes is disclosed in JP-A-11-231535.

  Further, a polymerizable monomer having two or more vinylphenyl groups and a photosensitive composition using the same are known. For example, JP-A-2-53783 (Patent Document 1) and JP-A-2001-290271 are known. (Patent Document 2) and JP-A-2003-26744 (Patent Document 3).

  Further, as a polymerizable monomer, nitrogen-containing unsaturated monomers such as N-vinyl pyrrolidone, N-vinyl carbazole, N-vinyl acetamide, vinyl pyridine and the like can be used in the photocurable composition as disclosed in JP-A-11-106413 ( Patent Document 4). JP-A-8-297364 (Patent Document 5) describes that N-vinylpyrrolidone is used as a photopolymerizable compound having an ethylenically unsaturated group.

In the above-described photosensitive composition, a portion irradiated with light is cured, and an unexposed portion (non-cured portion) is dissolved and removed by development processing to form a relief image. However, the film strength of the photosensitive composition is increased. When it was increased, the dissolution property during the development processing was lowered, and it was difficult to satisfy the film strength and the dissolution property at the same time.
Japanese Patent Laid-Open No. 2-53783 JP 2001-290271 A JP 2003-26744 A JP-A-11-106413 (paragraph number “0056”) JP-A-8-297364 (paragraph number “0037”)

  An object of the present invention is to find a novel photopolymerizable monomer having high photopolymerizability and high sensitivity, and to find a photosensitive composition having sufficient film strength and good elution during development. Let it be an issue. In particular, it is an object to provide a negative photosensitive composition having sufficiently high sensitivity and excellent image portion strength even in scanning exposure by visible to infrared laser, and a lithographic printing plate using the same. To do.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be basically solved by using the polymerizable monomers described below.
1) A polymerizable monomer having two or more unit structures represented by the following chemical formula 1 in the molecule (hereinafter abbreviated as a polymerizable monomer of the present invention).

In the formula, VP represents a phenyl group substituted by a vinyl group, and L ¹ and L ² represent a divalent linking group.

2) A photosensitive composition comprising the photopolymerizable monomer described in 1) above.
3) The photosensitive composition as described in 2) above, which is for scanning exposure.
4) The photosensitive composition as described in 2) or 3) above, which is for exposure with a near infrared laser of 750 to 1100 nm.
5) The photosensitive composition as described in 2) or 3) above, which is for exposure with a blue semiconductor laser having a wavelength of 400 to 430 nm.
6) A lithographic printing plate using the photosensitive composition as described in any one of 2) to 5) above.

  According to the present invention, a photopolymerizable monomer having high photopolymerizability and high sensitivity can be provided. Furthermore, by using the polymerizable monomer of the present invention, it is possible to provide a photosensitive composition having sufficient film strength and good elution during development. In particular, it is possible to provide a negative photosensitive composition that has sufficiently high sensitivity even in scanning exposure with a laser of visible light to infrared light and excellent in strength of an image area, and a lithographic printing plate using the same. .

  In the formula 1 above, the phenyl group substituted by the vinyl group represented by VP is specifically represented by the following formula 2.

In the formula (2), R ¹ , R ² and R ³ may be the same or different and are each a hydrogen atom, halogen atom, carboxyl group, sulfo group, nitro group, cyano group, amide group, amino group Group, alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylamino group, arylamino group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group The alkyl group and aryl group constituting these groups are a halogen atom, carboxyl group, sulfo group, nitro group, cyano group, amide group, amino group, alkyl group, aryl group, alkenyl group, alkynyl group. , Hydroxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group O, an alkylamino group, an arylamino group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group and the like. Among these groups, those in which R ¹ and R ² are hydrogen atoms and R ³ is a hydrogen atom or a lower alkyl group having 4 or less carbon atoms (for example, a methyl group, an ethyl group, etc.) are particularly preferable.

  Furthermore, the benzene ring of Chemical Formula 2 may have other substituents. Examples include halogen atoms, carboxyl groups, sulfo groups, nitro groups, cyano groups, amide groups, amino groups, alkyl groups, aryl groups, alkenyl groups, alkynyl groups, hydroxy groups, alkoxy groups, aryloxy groups, alkylthio groups. , An arylthio group, an alkylamino group, an arylamino group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, and the like, and further, an alkyl group and an aryl constituting these groups Groups are halogen atoms, carboxyl groups, sulfo groups, nitro groups, cyano groups, amide groups, amino groups, alkyl groups, aryl groups, alkenyl groups, alkynyl groups, hydroxy groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups. Group, alkyla Amino group, an arylamino group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, may be substituted by an arylsulfonyl group.

In the formula ¹ , the divalent linking group represented by L ¹ and L ² is specifically an atom selected from a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or the like, or further hydrogen. It is a group consisting of an atomic group to which atoms are added, and among them, a hydrocarbon-based linking group such as alkylene or arylene is preferable. An alkylene group having a total carbon number of L ¹ and L ² of 6 or less is particularly preferable. These groups may have further substituents if possible.

When L ¹ and L ² described above have a substituent, examples thereof include halogen atoms, carboxyl groups, sulfo groups, nitro groups, cyano groups, amide groups, amino groups, alkyl groups, aryl groups, alkenyl groups, alkynyls. Group, hydroxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylamino group, arylamino group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group and the like.

  The polymerizable monomer of the present invention preferably has three or more unit structures represented by the chemical formula 1 as described above in a single molecule, and among them, 3 to 6 unit structures in a single molecule. What it has is especially preferable.

  Specific examples of the polymerizable monomer of the present invention are shown below, but the present invention is not limited to these examples.

  As a manufacturing method of the polymerizable monomer of this invention, it can synthesize | combine using a conventionally well-known chemical reaction. More specifically, it will be described in detail in Examples described later, but is not limited thereto.

  When the polymerizable monomer of the present invention is used for an optical material such as an optical lens, the polymerizable monomer of the present invention is preferably contained in a proportion of 20 to 80% by mass in the total polymerizable monomer composition, When it is contained in a proportion of 70% by mass, a resin excellent in hardness, weather resistance and the like is obtained, which is particularly preferable. The polymerization method for obtaining the optical material resin using the polymerizable monomer of the present invention is not particularly limited, and a conventionally known method described in JP-A-2-268170 can be employed.

  When the polymerizable monomer of the present invention is used in a photosensitive composition, it is used together with a binder resin and a photopolymerization initiator or photoacid generator. Further, a sensitizer having absorption in the wavelength region from visible light to infrared light and sensitizing the above-mentioned photopolymerization initiator or photoacid generator so as to correspond to various light sources from visible light to infrared light. It is also preferably carried out together. The polymerizable monomer of the present invention is preferably contained in an amount of 1 to 1000% by mass, more preferably 5 to 100% by mass, based on the binder resin.

  The binder resin used in the photosensitive composition containing the polymerizable monomer of the present invention is not particularly limited, and all binder resins described in JP-A-2001-290271 and other known binder resins are used. Can do. Among these binder resins, alkali-soluble resins described in JP-A No. 2001-290271 and water-soluble resins described in JP-A No. 2003-215801 are preferably used. It is particularly preferable to use an alkali-soluble resin or a water-soluble resin having a phenyl group substituted with a vinyl group in the side chain represented by 2. The molecular weight of the binder resin is preferably in the range of 1,000 to 1,000,000, and particularly preferably in the range of 10,000 to 300,000 in terms of mass average molecular weight. Binder resin may be used alone or in combination of any two or more.

  The photopolymerization initiator or photoacid generator used in the photosensitive composition containing the polymerizable monomer of the present invention is not particularly limited and may be a compound that can generate a radical or an acid upon irradiation with light or an electron beam. Any compound can be used. As examples of such photopolymerization initiators or photoacid generators, compounds exemplified in JP-A No. 2001-290271 can be used. Specifically, aromatic ketones, aromatic oniums can be used. Salt compounds, organic peroxides, hexaarylbiimidazole compounds, ketoxime ester compounds, azinium compounds, active ester compounds, metallocene compounds, trihaloalkyl-substituted compounds, organoboron compounds, aromatic diazonium salt compounds, o-nitrobenzyl esters , Sulfonic acid ester derivatives, sulfones, phosphoric acid ester derivatives and sulfonyldiazomethane compounds.

  The photopolymerization initiator and photoacid generator may be used alone or in any combination of two or more. Further, any photopolymerization initiator and any photoacid generator can be used in combination. In particular, when a trihaloalkyl-substituted compound and an organic boron salt compound are used in combination, it is preferable because sensitivity is greatly improved. The photopolymerization initiator and the photoacid generator are preferably in the range of 10 to 150% by mass, more preferably in the range of 20 to 100% by mass with respect to the polymerizable monomer.

  Various sensitizing dyes are preferably used as the sensitizer used in the photosensitive composition containing the polymerizable monomer of the present invention. Such sensitizing dyes include cyanine, phthalocyanine, merocyanine, coumarin, porphyrin, spiro compound, ferrocene, fluorene, fulgide, imidazole, perylene, phenazine, phenothiazine, polyene, azo compound, diphenylmethane, triphenylmethane, polymethine acridine, coumarin. Ketocoumarin, quinacridone, indigo, styryl, squarylium compound, pyrylium compound, thiopyrylium compound, and further, European Patent No. 0,568,993, US Patent Nos. 4,508,811, and 5,227,227. The compounds described in the publications can also be used.

  Among these sensitizers, as a sensitizer corresponding to a blue semiconductor laser having an oscillation wavelength of 400 to 430 nm developed recently, a pyrylium compound or a thiopyrylium compound is preferable. Further, as a sensitizer corresponding to scanning exposure using laser light in a wavelength range from near infrared to infrared light, that is, 700 nm or more, and further from 750 to 1100 nm, cyanine dyes, polymethine dyes, and squarylium dyes are preferable. These sensitizers are preferably contained in a proportion of 1 to 100% by mass, particularly preferably 10 to 50% by mass, based on the photopolymerization initiator or photoacid generator.

  The photosensitive composition containing the polymerizable monomer of the present invention may contain other elements for various purposes in addition to the elements described above.

  As other elements constituting the photosensitive composition, there can be mentioned a polymerizable monomer or polymerizable oligomer having a polymerizable unsaturated bond group in the molecule other than the polymerizable monomer of the present invention. In particular, it is preferable to use a polyfunctional polymerizable monomer or oligomer having two or more polymerizable unsaturated bond groups in the molecule. Examples of such polymerizable monomers include polyfunctional (meth) acrylate monomers such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetraacrylate, and 1,4-divinylbenzene. Polyfunctional styrene derivatives such as 1,4-bis (4-vinylbenzyloxy) benzene and 1,1,2,2-tetrakis [4- (4-vinylbenzyloxy) phenyl] ethane, itaconic acid ester monomers, Examples include crotonic acid ester monomers and maleic acid ester monomers.

  When the polymerizable monomer or polymerizable oligomer as described above is used in combination with the polymerizable monomer of the present invention, the polymerizable monomer of the present invention may contain 20% by mass or more based on the total amount of the polymerizable monomer. The content is preferably 30% by mass or more. The total amount of the polymerizable monomers is preferably contained in a proportion of 1 to 1000% by mass, more preferably 5 to 100% by mass with respect to the binder resin.

  As another element constituting the photosensitive composition, it is preferable to add various polymerization inhibitors for the purpose of preventing thermal polymerization or thermal crosslinking of the polymerizable unsaturated bonding group and improving the long-term storage stability. Is called. As the polymerization inhibitor in this case, compounds having various phenolic hydroxyl groups such as hydroquinones, catechols, naphthols, and cresols, quinone compounds, and the like are preferably used, and hydroquinone is particularly preferably used. In this case, the addition amount of the polymerization inhibitor is preferably 1 to 60% by mass, particularly preferably 5 to 30% by mass, based on the polymerizable monomer.

  As another element constituting the photosensitive composition, a colorant can also be preferably added. As the colorant, it is used for the purpose of enhancing the visibility of the image area after exposure and development processing, such as carbon black, phthalocyanine dye, triarylmethane dye, anthraquinone dye, azo dye, etc. These various dyes and pigments can be used, and it is preferably used in the range of 0.5 to 50% by mass with respect to the binder resin.

  About the element which comprises a photosensitive composition, another element can also be added and added for various purposes besides the above-mentioned element. For example, inorganic fine particles or organic fine particles are also preferably added for the purpose of preventing blocking of the photosensitive composition or improving the sharpness of an image after development.

  The photosensitive layer is produced by applying a coating liquid of a photosensitive composition comprising the above-described elements onto a support and drying. Various known methods can be used as the coating method, and examples thereof include bar coater coating, curtain coating, blade coating, air knife coating, roll coating, spin coating, and dip coating. Regarding the thickness of the photosensitive layer itself when used as a lithographic printing plate, it is preferably formed on the support with a dry thickness in the range of 0.5 μm to 10 μm, and more preferably in the range of 1 μm to 5 μm. Is preferable in order to greatly improve.

  Various known supports can be used as the support to which the coating liquid of the photosensitive composition is applied. Examples thereof include paper, polyethylene-coated paper, film, metal plate and the like. In particular, when used as a lithographic printing plate, a support having a hydrophilic surface is used because the support surface in the unexposed area becomes a non-image area. As a support for this purpose, an aluminum plate which has been roughened and has an anodized film is particularly preferably used.

  A suitable aluminum plate used as a support for a lithographic printing plate has a mechanical surface roughening, a chemical surface roughening, and an electrochemical surface for the purpose of improving the adhesion to the photosensitive layer and providing water retention to the non-image area. The surface is roughened by a general surface roughening or the like, and then anodized. In addition, various hydrophilization treatments and sealing treatments are performed as necessary, and examples of such hydrophilization treatments include silicate treatment using an alkali metal silicate aqueous solution, treatment with potassium fluoride zirconate, Examples thereof include treatment with polyvinylphosphonic acid.

  The photosensitive composition having the photosensitive layer formed on the support as described above is subjected to contact exposure or laser scanning exposure, and then subjected to pattern formation by removing unexposed portions with a developer. The exposed portion is cross-linked, so that the solubility in a developing solution is lowered and an image portion is formed.

  Hereinafter, although the typical synthesis example of the polymerizable monomer of this invention is given according to an Example, other exemplary compounds are compoundable by the same method. In addition to the effects, the present invention is not limited to these examples.

Synthesis of polymerizable monomer (M-5) 100.2 g of trimethylolpropane trismercaptoacetate [manufactured by Wako Pure Chemical Industries, Ltd.], 4-chloromethylstyrene [manufactured by Seimi Chemical Co., Ltd., CMS-14] 130.1 g N-nitrosophenylhydroxylamine / aluminum salt [Wako Pure Chemical Industries, Ltd.] 0.5 g and acetonitrile 1000 ml were mixed, and cooled with ice water and stirred, 96.0 g of triethylamine [Nacalai Tesque Co., Ltd.] 10 Added dropwise over a period of minutes. After completion of dropping, the mixture was cooled with ice water for 30 minutes, then returned to room temperature and further stirred for 2 hours. Subsequently, the solvent was distilled off from the reaction mixture under reduced pressure at a bath temperature of 40 ° C. or less, 600 ml of methanol was added to the residue, and the mixture was stirred at room temperature for 10 minutes. After standing, the supernatant was removed by decantation. Thereafter, this washing operation was repeated twice. Finally, 0.2 g of N-nitrosophenylhydroxylamine / aluminum salt [manufactured by Wako Pure Chemical Industries, Ltd.] was added, and the remaining solvent was distilled off under reduced pressure at a bath temperature of 35 ° C. or less. 125 g of M-5 (pale yellow oil) was obtained. ¹ H-NMR (TMS / CDCl ₃ ): 0.92 ppm (3H, t), 1.52 ppm (2H, q), 3.09 ppm (6H, s), 3.78 ppm (6H, s), 4.11 ppm (6H, s), 5.20-5.26 ppm (3H, multi), 5.68-5.77 ppm (3H, multi), 6.61-6.76 ppm (3H, multi), 7.24-7 .38ppm (12H, multi)

Synthesis of polymerizable monomer (M-10) 1,2,6-hexanetriol [manufactured by Tokyo Chemical Industry Co., Ltd.] 4.0 g, thioglycolic acid [manufactured by Tokyo Chemical Industry Co., Ltd.] 8.3 g, p-toluene 0.5 g of sulfonic acid monohydrate [manufactured by Nacalai Tesque Co., Ltd.] and 100 ml of toluene were mixed, and heated to reflux for 3 hours while removing by-product water azeotropically. Next, toluene was distilled off under reduced pressure, and the residue was 4-chloromethylstyrene [Seimi Chemical Co., Ltd., CMS-14] 13.7 g, N-nitrosophenylhydroxylamine / aluminum salt [Wako Pure Chemical Industries, Ltd. 0.1 g and 100 ml of acetonitrile were added, and 12.0 g of triethylamine [manufactured by Nacalai Tesque Co., Ltd.] was added dropwise over 10 minutes while cooling and stirring with ice water. After completion of dropping, the mixture was cooled with ice water for 30 minutes, then returned to room temperature and further stirred for 2 hours. Subsequently, the solvent was distilled off from the reaction mixture under reduced pressure at a bath temperature of 40 ° C. or less, 60 ml of methanol was added to the residue, and the mixture was stirred at room temperature for 10 minutes. After standing, the supernatant was removed by decantation. Thereafter, this washing operation was repeated twice. Finally, 0.05 g of N-nitrosophenylhydroxylamine / aluminum salt [manufactured by Wako Pure Chemical Industries, Ltd.] was added, and the remaining solvent was distilled off under reduced pressure at a bath temperature of 35 ° C. or less. 10.5 g of M-10 (pale yellow oil) was obtained. ¹ H-NMR (TMS / CDCl ₃ ): 1.35 to 1.79 ppm (6H, multi), 3.06 ppm (6H, s), 3.79 ppm (6H, s), 4.05 to 4.35 ppm ( 4H, multi), 5.10-5.26 ppm (4H, multi), 5.68-5.77 ppm (3H, multi), 6.61-6.76 ppm (3H, multi), 7.25-7. 39ppm (12H, multi)

Synthesis of polymerizable monomer (M-13) Trimethylolpropane tris (3-mercaptopropionate) [manufactured by Wako Pure Chemical Industries, Ltd.] 10.0 g, chloromethylstyrene [manufactured by Seimi Chemical Co., Ltd., CMS-P ] 11.4 g, 0.1 g of N-nitrosophenylhydroxylamine / aluminum salt [manufactured by Wako Pure Chemical Industries, Ltd.] and 100 ml of acetonitrile were mixed, and triethylamine [manufactured by Nacalai Tesque Co., Ltd.] 8.3 g with stirring at room temperature. Was added dropwise over 10 minutes. After completion of dropping, the mixture was further stirred at room temperature for 4 hours. Subsequently, the solvent was distilled off from the reaction mixture under reduced pressure at a bath temperature of 40 ° C. or less, 80 ml of methanol was added to the residue, stirred at room temperature for 10 minutes, and allowed to stand, and then the supernatant was removed by decantation. Thereafter, this washing operation was repeated twice. Finally, 0.05 g of N-nitrosophenylhydroxylamine / aluminum salt [manufactured by Wako Pure Chemical Industries, Ltd.] was added, and the remaining solvent was distilled off under reduced pressure at a bath temperature of 35 ° C. or less. 9.2 g of M-15 (pale yellow oil) was obtained. ¹ H-NMR (TMS / CDCl ₃ ): 0.80-0.95 ppm (3H, multi), 1.30-1.51 ppm (2H, multi), 2.45-2.80 ppm (12H, multi), 3.70 ppm (6H, d), 4.03 ppm (6H, d), 5.19-5.27 ppm (3H, multi), 5.67-5.79 ppm (3H, multi), 6.62-6. 76ppm (3H, multi), 7.20-7.38ppm (12H, multi)

Synthesis of polymerizable monomer (M-17) 25.4 g of dipentaerythritol [manufactured by Tokyo Chemical Industry Co., Ltd.], 55.3 g of thioglycolic acid [manufactured by Tokyo Chemical Industry Co., Ltd.], p-toluenesulfonic acid monohydrate The product [manufactured by Nacalai Tesque Co., Ltd.] 1.5 g and 300 ml of toluene were mixed, and heated and refluxed for 8 hours while removing by-product water azeotropically. Then, toluene was distilled off under reduced pressure, and the residue was 91.6 g of chloromethylstyrene [manufactured by Seimi Chemical Co., Ltd., CMS-P], N-nitrosophenylhydroxylamine / aluminum salt [manufactured by Wako Pure Chemical Industries, Ltd.] 0 0.5 g and 500 ml of acetonitrile were added, and 66.8 g of triethylamine [manufactured by Nacalai Tesque Co., Ltd.] was added dropwise over 30 minutes while cooling with ice water and stirring. After completion of dropping, the mixture was cooled with ice water for 30 minutes, then returned to room temperature and further stirred for 2 hours. Subsequently, the solvent was distilled off from the reaction mixture under reduced pressure at a bath temperature of 40 ° C. or less, 500 ml of methanol was added to the residue, and the mixture was stirred at room temperature for 10 minutes. After standing, the supernatant was removed by decantation. Thereafter, this washing operation was repeated four times. Finally, 0.1 g of N-nitrosophenylhydroxylamine / aluminum salt [manufactured by Wako Pure Chemical Industries, Ltd.] was added, and the remaining solvent was distilled off under reduced pressure at a bath temperature of 35 ° C. or less. 115.5 g of M-17 (pale yellow oil) was obtained. ¹ H-NMR (TMS / CDCl ₃ ): 3.06 ppm (12H, d), 3.42 ppm (4H, d), 3.76 ppm (12H, d), 4.18 ppm (12H, d), 5.10 -5.26 ppm (6H, multi), 5.66-5.78 ppm (6H, multi), 6.59-6.78 ppm (6H, multi), 7.21-7.39 ppm (24H, multi)

A coating solution of a photosensitive composition having the following composition was prepared. Next, the coating solution was applied on a polyethylene terephthalate film support having a gelatin undercoat layer having a thickness of 0.10 mm so as to have a dry thickness of 2.0 μm, and dried at 75 ° C. for 5 minutes to prepare a sample. .
<Coating liquid>
Binder resin (BP-1 below): 3.5 parts by mass Photopolymerization initiator (PI-1 below) 0.8 parts by mass Polymerizable monomer of the present invention (Table 1 below) 1.2 parts by mass Parts Basic Blue 7 0.1 parts by mass 1,3-dioxolane 50.0 parts by mass

  The appended numbers in the structural formulas of the binder resin (BP-1) and the binder resin (BP-2) described later represent mass% of each repeating unit with respect to the total amount of the binder resin.

(Comparative Example 1)
A sample was prepared in the same manner as in Example 5 without using the polymerizable monomer of the present invention.

A control wedge having a step wedge with a density difference of 0.15 intervals [manufactured by Fuji Photo Film Co., Ltd.] using a high-pressure mercury lamp as a light source and adjusting the amount of light so that the amount of light is 20 mW / cm ² . Then, contact exposure was performed for 15 seconds. After the exposure, an aqueous solution containing 0.7% by mass of sodium metasilicate was used as a developer, and development was performed at 30 ° C. for 20 seconds. As a result, unexposed portions were eluted, and a clear step wedge pattern was obtained. In this step wedge pattern, the maximum step number remaining as an image was obtained as sensitivity. The larger the step number, the higher the sensitivity. The results are shown in Table 1.

A coating solution of a photosensitive composition having the following composition was prepared. Next, the coating solution is applied on a grained and anodized aluminum plate having a thickness of 0.24 mm so as to have a dry thickness of 2.0 μm, and dried at 75 ° C. for 5 minutes. Produced.
<Coating liquid>
Binder resin (BP-2 below: Mass average molecular weight of about 50,000) 6.0 parts by weight Photopolymerization initiator (PI-1) 0.8 parts by weight Photopolymerization initiator (PI-2 below) 0.6 parts by weight Polymerizable monomer of the present invention (Table 2 below) 1.2 parts by mass Sensitizer (SD-1 below) 0.4 part by mass Basic Blue 7 0.1 part by mass Methanol 20.0 parts by mass 1,4-dioxane 30 .0 parts by mass

(Comparative Example 2)
A sample was prepared in the same manner as in Example 6 without using the polymerizable monomer of the present invention.

The obtained sample was exposed as follows. That is, using a contact exposure machine [Mitsubishi Paper Co., Ltd .; Hishira Copy Printer] using a tungsten lamp as a light source, a light of 3 mW / cm ² and a wavelength of 780 nm or more is passed through a filter that blocks light of 780 nm or less. Light was allowed to pass through, and exposure was performed for 30 seconds on this filter through a control wedge (manufactured by Fuji Photo Film Co., Ltd.) with a density difference of 0.15 intervals. After the exposure, development was performed for 30 seconds using tap water whose temperature was adjusted to 30 ° C. In the step wedge pattern formed on the aluminum plate after the development processing, the maximum step number remaining as an image was obtained as sensitivity. The results are shown in Table 2.

A coating solution of a photosensitive composition having the following composition was prepared. Next, the coating solution is applied on a grained and anodized aluminum plate having a thickness of 0.24 mm so as to have a dry thickness of 2.0 μm, and dried at 75 ° C. for 5 minutes. Produced.
<Coating liquid>
Binder resin (BP-1 above: mass average molecular weight of about 50,000) 3.5 parts by weight Photopolymerization initiator (PI-1 above) 1.0 part by weight Photopolymerization initiator (PI-3 below) 0.5 part by weight Polymerizable monomer (Table 3 below) 1.2 parts by mass Sensitizer (SD-1 above) 0.4 parts by mass Basic Blue 7 0.1 parts by mass 1,3-dioxolane 45.0 parts by mass

(Comparative Examples 3-5)
A sample was prepared in the same manner as in Example 7 using the following CM-1, CM-2, and CM-3 instead of the polymerizable monomer of the present invention.

  The sample produced as described above was placed in a heating chamber adjusted to a relative humidity of 65% at 38 ° C. and allowed to elapse for 2 weeks. Exposure was performed in the same manner as in Example 6, and development was performed at 30 ° C. using an aqueous solution containing 0.7% by mass of sodium metasilicate as a developing solution, and the elution time and sensitivity of the non-image area were compared. The results are shown in Table 3.

The printing performance of the sample obtained in Example 6 as a planographic printing plate was evaluated. Using an image setter [manufactured by Dainippon Screen Mfg. Co., Ltd., PTR-4000] equipped with a semiconductor laser emitting light at 830 nm, the sample before and after heating under the same conditions as in Example 7 was 2400 dpi. The exposure was performed at a drum rotation speed of 1000 rpm and a plate surface exposure energy of 70 mJ / cm ² . After the exposure, the same development processing as in Example 7 was performed, and the ink was attached to an offset printing machine [manufactured by Ryobi Corp .; Ryobi 560], and ink [manufactured by Dainippon Ink & Chemicals, Inc .; FINE INK New Champion Ink (N)] And dampening water [manufactured by Nikken Chemical Laboratory; 1% aqueous solution of Astro Mark III] was used for printing. The results are shown in Table 4. The printing durability in Table 4 is a four-stage evaluation of 200,000 sheets or more: ◎, ˜200,000 sheets: ◯, ˜70,000 sheets: Δ, 30,000 sheets or less: x. In Comparative Examples 4 and 5, as described in Example 7, since the development process after heating was impossible, printing evaluation of the sample after heating could not be performed.

A coating solution of a photosensitive composition having the following composition was prepared. Next, the coating solution is applied on a grained and anodized aluminum plate having a thickness of 0.24 mm so that the dry thickness is 2.0 μm, and dried at 75 ° C. for 5 minutes, A lithographic printing plate was prepared.
<Coating liquid>
Binder resin (BP-1 above: mass average molecular weight of about 50,000) 3.5 parts by weight Photopolymerization initiator (PI-1) 1.0 part by weight Photopolymerization initiator (PI-3) 0.5 part by weight Polymerizable monomer (M-6) 1.2 parts by mass Sensitizer (SD-2 below) 0.6 parts by mass Basic Blue 7 0.1 parts by mass 1,3-dioxolane 45.0 parts by mass

  The lithographic printing plate produced as described above was subjected to an exposure test using a blue semiconductor laser-mounted output machine; an image setter Cobalt8CTP (oscillation wavelength: 410 nm, output: 30 mW) manufactured by ESCHER GRAD. After the exposure, when an aqueous solution containing 0.7% by mass of sodium metasilicate was used as a developer and developed at 30 ° C. and developed for 20 seconds, the unexposed area was eluted, and a clear image pattern was obtained. Also, offset printing machine [Ryobi Co., Ltd .; Ryobi 560], ink [Dainippon Ink Chemical Co., Ltd .; FINE INK New Champion Ink (N)] and fountain solution [Niken Chemical Research Co., Ltd. ; Astromark III 1% aqueous solution] was used to evaluate the performance as a printing plate. As a result, up to 100,000 sheets of clear printed matter were obtained.

  As is clear from the results of Examples 5 to 9, the photosensitive composition containing the polymerizable monomer of the present invention has high sensitivity and excellent storage stability. When the photosensitive composition is used as a lithographic printing plate, it is sufficiently sensitive to scanning exposure with a laser, has good printing durability, and has good elution during development. It turns out that a thing is obtained.

  Examples of use of the present invention include photosensitive resins, printing plates, inks, paints, adhesives, cross-linking agents, optical lens materials, optical fiber coatings, three-dimensional modeling, holographic recording materials, printed wiring boards and electronic materials such as ICs. Application.

Claims (6)

A polymerizable monomer having two or more unit structures represented by the following chemical formula 1 in a molecule.

In the formula, VP represents a phenyl group substituted by a vinyl group, and L ¹ and L ² represent a divalent linking group.   A photosensitive composition comprising the photopolymerizable monomer according to claim 1.   The photosensitive composition according to claim 2, which is for scanning exposure.   The photosensitive composition according to claim 2 or 3, which is for exposure with a near infrared laser of 750 to 1100 nm.   The photosensitive composition according to claim 2 or 3, which is for exposure with a blue semiconductor laser having a wavelength of 400 to 430 nm.   A lithographic printing plate using the photosensitive composition according to any one of claims 2 to 5.