JP2652095B2 - Photosensitive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition suitably used in the production of lithographic printing plates, IC circuits, photomasks and the like. More specifically, the present invention relates to a negative photosensitive composition containing a photocrosslinkable polymer compound and surface-modified silica fine particles and having excellent sensitivity and abrasion resistance during exposure.

[0002]

2. Description of the Related Art Photocrosslinkable materials which are crosslinked by a cycloaddition reaction are well known, and many of them are major components of photosensitive compositions used in the production of photosensitive lithographic printing plates and the like. Used. Of these,
Examples of the photocrosslinkable polymer compound include a polymer compound having a maleimide group in a side chain, a cinnamyl group having an unsaturated double bond capable of photodimerization adjacent to an aromatic nucleus, a cinnamylidene group or a chalcone group in a side chain or a main chain. Is useful, and a polymer compound having a maleimide group is particularly useful in terms of high sensitivity.

A photosensitive composition containing such a polymer compound containing a maleimide group is disclosed in
No. 988, No. 52-3055, No. 55-160010
However, none of the photosensitive compositions has sufficient sensitivity, and a sufficient image cannot be obtained with a short exposure time. Further, the photosensitive lithographic printing plate obtained from such a photosensitive composition has a disadvantage that only a lithographic printing plate having low printing durability can be obtained.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a negative photosensitive composition having a high sensitivity, capable of forming a sufficient image even with a short exposure time, and having a high film strength in an image area and excellent abrasion resistance.

[0005]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that these objects can be achieved by using a novel photosensitive composition. Reached. That is, the present invention provides a photocrosslinkable polymer compound having a photocrosslinkable group represented by the following general formula (I) and at least one photocrosslinkable polymer compound represented by the following general formula (II)
A photosensitive composition comprising surface-modified silica fine particles in which various types of functional groups are linked to the particle surface by a chemical bond.

[0006]

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In the formula, T ¹ and T ² are each a hydrogen atom,
Represents a halogen atom, an alkyl group or an aryl group,
T ¹ and T ² may form a ring together.

[0008]

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In the formula, R represents a divalent linking group consisting of two or more atoms selected from C, H, N, O, S, and Si;
Is at least

[0010]

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Wherein Q ¹ and Q ² each represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and Q ¹ and Q ² together form a ring; Is also good. Hereinafter, the present invention will be described in detail. Surface-modified silica fine particles The surface-modified silica fine particles used in the present invention, in which at least one kind of functional group represented by the above general formula (II) is linked to the particle surface by a chemical bond, preferably have the following general formula (III) The surface of silica fine particles is modified by using at least one of the silane coupling agents represented by the formulas (1) to (V), or the silica fine particles modified with the silane coupling agent obtained as described above are further treated with amines, alcohols and carboxylic acids. And the like.

[0012]

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Wherein R ¹ , R ² and R ³ are each C,
A divalent linking group consisting of two or more atoms selected from H, N, O, S and Si, wherein Y ¹ , Y ² and Y ³ are each

[0014]

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And M ¹ represents a halogen atom;
M ² represents a hydrogen atom or a metal or a C _{1 to} C ₁₅ hydrocarbon group which may have a substituent; Q ¹ and Q ² each represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group; , Q ¹ and Q ² may together form a ring.

Q ³ represents a hydrogen atom or a C ₁ -C ₁₅ hydrocarbon group which may have a substituent, and Q ⁴ represents a C ₁ -C ₁₅ hydrocarbon which may have a substituent. Represents a group. X ¹ ,
X ² and X ³ are each a hydrogen atom, a halogen atom, -OQ
⁵ shows a ^{-O-CO-Q 5, -N} (Q 6) (Q 7) , or -OSO ₂ CF _3. Q ⁵ represents a C ₁ -C ₁₅ which may have a substituent.
Q ⁶ represents a hydrogen atom or a C ₁ -C ₁₅ hydrocarbon group which may have a substituent, and Q ⁷ represents
It represents a C ₁ -C ₁₅ hydrocarbon group which may contain Si.

Also, X^ThreeAnd Y¹Are linked to form a ring structure
May be. However, depending on the silane coupling agent used
And at least one is Y¹, Y^Two, Y ^ThreeAt least one of
Tsuga

[0018]

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It is assumed that it has the following structure. Among these, as silane coupling agents that can be particularly preferably used, X ¹ , X ² , and X ³ are each a halogen atom or —OQ ⁵ (Q ⁵ is a C _{1 to} C ₁₅ which may have a substituent. A hydrocarbon group.). As the silane coupling agent suitably used in the present invention, for example,

[0020]

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[0021]

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These silane coupling agents may be used together with the following silane coupling agents for the purpose of improving alkali developability. For example,

[0023]

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[0024]

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And the like. In the formula, preferred Q ¹ and Q ² are a hydrogen atom, a chlorine atom, a bromine atom, a C ₁ -C ₆ alkyl group and a phenyl group which may have a substituent, and Q ₁ and Q ² May together form a ring. Alternatively, Q ⁸ represents a hydrogen atom or —CH ₃ . Z ¹ and Z ² are each -S-,
-O- or -NH- is shown. n ^{1 to} n ^{14 each} represent an integer of 1 or more.

The silica fine particles used for the above-mentioned modification are particles containing silicic anhydride (SiO ₂ ) as a main component, and can be easily obtained as various commercial products. The particle size of the silica particles preferably ranges from about 1 nm to 500 nm. It is more preferably 100 nm or less. Specifically, Snowtex OL manufactured by Nissan Chemical Industry Co., Ltd. (20% colloidal aqueous solution of silica having a particle size of 45 nm), AEROSIL130 manufactured by Nippon Aerosil Co., Ltd. (silica having a particle size of 16 nm), Mizukasil P- manufactured by Mizusawa Chemical Industries, Ltd. 527U
(Silica having a particle size of 60 nm).

The above-mentioned silica particles modified with a silane coupling agent can be produced by a conventionally known surface modification method. Specifically, Noboru Suzuki, Nobuko Yuzawa, Atsushi Endo, and Hiroshi Utsuki "Coloring Materials" 57 , 429 (198)
4), Hiroshi Yoshioka, Masayuki Ikeno “Surface” 21 , 33 (198)
3), Hiroshi Utsugi "Surface" 16, 525 (1978), K.
Tanaka, et al., Bull. Chem. Soc. Jpn., 53 , 12
42 (1980), ML Hair, W. Hertl. J. Phys. C
hem., 77 , 1965 (1973), Ya. Davydov. et.
al., Chromatographia, 14 , 13 (1981), K. U.
nger. et al., Colloid polym. Sci., 252 , 317
(1974), R. Burwell, O. Leal, J. Chem. Soc. C
hem. Commun., 342 (1974); W. Stoeber, Koll.
oid-Z. 149 , 39 (1956), Franz. Pat. 136876
The compound can be synthesized according to a method described in a review such as 5 DAS 1163784 and the references and patents thereof.

Further, the treatment of the modified silica fine particles obtained by these methods with an amine, an alcohol, a carboxylic acid or the like specifically includes the following reactions.

[0029]

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Wherein A ¹ is a hydrogen atom or S, N, O, P
Represents a C ₁ -C ₃₀ hydrocarbon group which may contain
² , A ³ and A ⁴ are C which may contain S, N, O and P
₁ represents a hydrocarbon group -C _30. The amount of the modified silica fine particles used in the present invention is 0.1 to 0.1% based on the total weight of the photosensitive composition including the photocrosslinkable polymer compound and the modified silica particles.
It is 60% by weight, preferably 0.3 to 25% by weight. 0.1
When the amount is less than 60% by weight, the effect of the modified silica fine particles is hardly recognized, and when the amount is more than 60% by weight, the film strength is reduced. Photocrosslinkable Polymer Compound The photocrosslinkable polymer compound having a photocrosslinkable group represented by the above general formula (I) of the present invention is preferably a polymer having a structural unit derived from a monomer shown in Group A below. It may be a union and may contain the monomers shown in groups B (1) to (15) as copolymer components. Group A:

[0031]

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[0032]

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[0033] In the formula, each of T ¹ and T ² are a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group, a phenyl group which may have a substituent ^{_{C 1 ~C 6, T 1,}} T ^Two
May together form a ring. Q ⁸ ,
Q ⁹ represents a hydrogen atom or —CH ₃ , and Z ³ represents —O
-Or -NH- is shown. n ^{1 to} n ^{9 each} represent an integer of 1 or more.

Further, monomers described in JP-A-52-988 and the like are also preferable. Group B: (1) Acrylamides, methacrylamides, acrylates, methacrylates and hydroxystyrenes having an aromatic hydroxyl group, such as N- (4-hydroxyphenyl) acrylamide or N- (4-hydroxyphenyl) ) Methacrylamide, o-, m-, p
-Hydroxystyrene, o-, m-, p-hydroxyphenyl-acrylate or methacrylate, (2) acrylates and methacrylates having an aliphatic hydroxyl group, for example, 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate , 4-
Hydroxybutyl methacrylate, (3) acrylic acid, methacrylic acid, maleic anhydride, unsaturated carboxylic acid such as itaconic acid, (4) methyl acrylate, ethyl acrylate,
Propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate, N
(Substituted) alkyl acrylates such as dimethylaminoethyl acrylate; ) Alkyl methacrylate, (6) acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide and the like Acrylamide or methacrylamide, (7) ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether,
Vinyl ethers such as propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether; (8) vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, and vinyl benzoate; and (9) styrene, α-methylstyrene, and chloroform. Styrenes such as methylstyrene, (10) methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone,
Vinyl ketones such as phenyl vinyl ketone, (11) olefins such as ethylene, propylene, isobutylene, butadiene, isoprene, (12) N-vinylpyrrolidone,
N-vinyl carbazole, 4-vinyl pyridine, acrylonitrile, methacrylonitrile and the like (13) maleimide,
N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N-
Unsaturated imides such as (p-chlorobenzoyl) methacrylamide, (14) N- (o-aminosulfonylphenyl)
Methacrylamide, N- (m-aminosulfonylphenyl) methacrylamide, N- (p-amino) sulfonylphenylmethacrylamide, N- (1- (3-aminosulfonyl) naphthyl) methacrylamide, N- (2-aminosulfonyl) Ethyl) methacrylamides such as methacrylamide, and acrylamides having the same substituents as above, and o-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate,
Unsaturated sulfonamides such as methacrylates such as 1- (3-aminosulfonylnaphthyl) methacrylate and acrylates having the same substituents as described above, and (15) crosslinkable to side chains such as vinyl cinnamate Unsaturated monomer having a group.

Further, a monomer copolymerizable with the above monomer may be copolymerized. Examples include, but are not limited to, those obtained by modifying a copolymer obtained by copolymerization of the above monomers with, for example, glycidyl methacrylate, glycidyl acrylate, or the like. More specifically, the photocrosslinkable polymer compound preferably contains the unsaturated carboxylic acid listed in Group B (3) as a copolymer component, and the copolymer preferably has a carboxylic acid value of 0. ~
It is 4 meq / g, more preferably 0.5-3.5 meq / g.

Further, among the monomers shown in Groups A and B (1) to (15), the following monomers
That is, as a monomer having a photocrosslinkable group listed in the above group A,

[0037]

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(Wherein n ¹⁰ , n ¹¹ and n ^{12 each} represent an integer of 1 or more).
Monomers having an aromatic hydroxyl group or a sulfonamide group of groups (1) and (14), monomers of groups B (4) and (5) above, especially ethyl acrylate, butyl acrylate, benzyl acrylate, methyl methacrylate; Copolymers containing ethyl methacrylate, butyl methacrylate or benzyl methacrylate are preferred.

The above photocrosslinkable polymer compound is
It has two or more photocrosslinkable groups on the side chain on average, and the weight average molecular weight is preferably 1,000 or more, more preferably in the range of 2000 to 300,000. Further, the number average molecular weight is preferably 800 or more, more preferably 1000
２５250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, more preferably 1.1.
-10.

The photocrosslinkable polymer compound used in the present invention is usually contained in the solid content of the photosensitive composition in an amount of 40 to 99% by weight, preferably 50 to 95% by weight. Other Additives The photosensitive composition of the present invention can contain a photosensitizer as needed.

As the photosensitizer, a triplet sensitizer having a maximum absorption which actually allows sufficient light absorption in a range of 300 nm or more is preferable. Preferred triplet sensitizers include benzophenone derivatives, benzanthrone derivatives, quinones, aromatic nitro compounds, naphthothiazoline derivatives, benzothiazoline derivatives, thioxanthones, naphthothiazole derivatives, ketocoumarin compounds, benzothiazole derivatives, benzodithiol derivatives, naphthofuranone Compounds, pyrylium salts, thiapyrylium salts and the like can be mentioned. Specifically, Michler's ketone, N, N'-diethylaminobenzophenone, benzanthrone, (3-
Methyl-1,3-diaza-1,9-benz) anthrone picramide, 5-nitroacenaphthene, 2-chlorothioxanthone, 2-isopropylthioxanthone, dimethylthioxanthone, methylthioxanthone-1-ethylcarboxylate, 2-nitrofluorene , 2-dibenzoylmethylene-3-methylnaphthothiazoline, 3,3
-Carbonyl-bis (7-diethylaminocoumarin),
2,4,6-triphenylthiapyrylium perchlorate, 2- (p-chlorobenzoyl) naphthothiazole,
2- (5-t-butyl-1,3-benzodithiol-2
-Ylidene) -1,3-diethylthiobarbituric acid;

Also, Japanese Patent Application Laid-Open No. 3-54566 and Japanese Patent Application Laid-Open
Compounds described in JP-A-236552, JP-A-2-173646, JP-A-2-131236 and the like are also preferable. The addition amount of these sensitizers is 1 to 20 of the total composition.
%, Preferably 3 to 10% by weight.

In addition to the above, a diazo resin having a negative action can be added as necessary. Such diazo resins include 4-diazo-diphenylamine, 1-diazo-4-N, N-dimethylaminobenzene, 1-diazo-4-N, N-diethylaminobenzene, 1-diazo-
4-N-ethyl-N-hydroxyethylaminobenzene, 1-diazo-4-N-methyl-N-hydroxyethylaminobenzene, 1-diazo-2,5-diethoxy-
4-benzoylaminobenzene, 1-diazo-4-N-
Benzodylaminobenzene, 1-diazo-4-N, N-
Dimethylaminobenzene, 1-diazo-4-morpholinobenzene, 1-diazo-2,5-dimethoxy-4-p
-Tolylmercaptobenzene, 1-diazo-2-ethoxy-4-N, N-dimethylaminobenzene, p-diazo-dimethylaniline, 1-diazo-2,5-dibutoxy-4-morpholinobenzene, 1-diazo- 2,5-diethoxy-4-morpholinobenzene, 1-diazo-
2,5-dimethoxy-4-morpholinobenzene, 1-
Diazo-2,5-diethoxy-4-morpholinobenzene, 1-diazo-2,5-diethoxy-4-p-tolylmercaptobenzene, 1-diazo-3-ethoxy-4-
N-methyl-N-benzylaminobenzene, 1-diazo-3-chloro-4-N, N-diethylaminobenzene,
1-diazo-3-methyl-4-pyrrolidinobenzene, 1
-Diazo-2-chloro-4-N, N-dimethylamino-
5-methoxybenzene, 1-diazo-3-methoxy-4
Diazos such as -pyrrolidinobenzene, 3-methoxy-4-diazodiphenylamine, 3-ethoxy-4-diazodiphenylamine, 3- (n-propoxy) -4-diazophenylamine, 3-isopropoxy-4-diazodiphenylamine The monomer and a condensing agent such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, and benzaldehyde are each in a molar ratio of 1: 1 to 1: 0.5, preferably 1: 0.8 to 1: 0.6. And a reaction product of an anion with a condensate obtained by condensing the product by an ordinary method. As anions, tetrafluoroboric acid, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 5-nitro-o-toluenesulfonic acid, 5-sulfosalicylic acid,
2,5-dimethylbenzenesulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-fluorocaprylnaphthalenesulfonic acid, dodecylbenzenesulfonic Acid, 1-naphthol-5-sulfonic acid, 2-methoxy-4-hydroxy-
Examples thereof include 5-benzoyl-benzenesulfonic acid and p-toluenesulfonic acid. Among them, alkyl aromatic sulfonic acids such as hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid and 2,5-dimethylbenzenesulfonic acid are particularly preferable.

A reaction product of the above-mentioned diazo monomer, a aldehyde having a carboxylic acid and / or a phenol or an acetal thereof (and, if necessary, the above-mentioned condensing agent) and the above-mentioned anion, JP 1
The diazo resins described in JP-A-102456 and JP-A-1-102457 are also suitably used in the present invention.

The amount of these diazo resins to be added to the total composition is generally preferably from 0.1 to 15% by weight, more preferably from 0.3 to 5% by weight. Further, these diazo resins can be used as an intermediate layer between the photosensitive layer and the support. In the photosensitive composition of the present invention, further, for example, a polymer compound described in JP-A-52-988,
Known alkali-soluble polymer compounds such as phenol formaldehyde resin, cresol formaldehyde resin, phenol-modified xylene resin, polyhydroxystyrene, and polyhalogenated hydroxystyrene can be contained. Such an alkali-soluble polymer compound is used in an amount of 70% by weight or less of the total composition.

Further, the photosensitive composition of the present invention preferably contains a thermal polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-butyl.
Cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t
-Butylphenol), 2,2'-methylenebis (4-
Methyl-6-t-butylphenol), 2-mercaptobenzimidazole and the like are useful, and in some cases, a dye or pigment or a pH indicator or the like as a printing agent can be added for the purpose of coloring the photosensitive layer. .

As a printing-out agent, a combination of a photosensitive compound which releases an acid upon exposure and an organic dye which can form a salt can be mentioned as a representative. Further, as a stabilizer of the diazo resin, phosphoric acid, phosphorous acid, tartaric acid, citric acid,
Malic acid, dipicolinic acid, polynuclear aromatic sulfonic acids and salts thereof, sulfosalicylic acid, and the like can be added as necessary.

The photosensitive composition of the present invention may contain a plasticizer and the like. As a plasticizer, dibutyl phthalate, dialkyl phthalate such as dihexyl phthalate, oligoethylene glycol alkyl ester,
The photosensitive composition of the lithographic printing plate present invention using the photosensitive composition of the present invention which can be used plasticizers of phosphoric acid ester may, for example, 2-methoxyethanol, 2-methoxyethyl acetate, propylene Glycol monomethyl ether, 3-methoxypropanol, 3-methoxypropyl acetate, methyl ethyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, ethylene dichloride, acetone, methanol, ethanol, butanol, water, methyl lactate, It is coated on a support by dissolving or dispersing in an appropriate solvent such as ethyl lactate alone or in a mixed solvent in which these are appropriately combined. The coating amount in the range of 0.1g / m ² ~10g / m ² in weight after drying are suitable, preferably from 0.5 to 5 g / m ^2.

When a lithographic printing plate is produced using the photosensitive composition of the present invention, an aluminum plate is preferred as a support. Aluminum plates include pure aluminum and aluminum alloy plates. Various aluminum alloys can be used, for example, silicon, copper, manganese,
An alloy of a metal such as magnesium, chromium, zinc, lead, bismuth, and nickel and aluminum is used. These compositions also contain some negligible amount of impurities in addition to some iron and titanium.

The aluminum plate is subjected to a surface treatment as required. For example, surface treatment such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, or the like, or anodic oxidation treatment is preferably performed. Also, as described in U.S. Pat. No. 2,714,066, an aluminum plate grained and then immersed in an aqueous solution of sodium silicate, and an aluminum plate as described in U.S. Pat. Those that have been immersed in an aqueous solution of an alkali metal silicate after the oxidation treatment are also suitably used. The anodizing treatment, for example, phosphoric acid, chromic acid, sulfuric acid, an inorganic acid such as boric acid, or oxalic acid, an organic acid such as sulfamic acid or an aqueous solution or a non-aqueous solution of these salts alone or in combination of two or more. It is carried out by flowing a current in an electrolyte using an aluminum plate as an anode.

Further, silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective. These hydrophilization treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions with the photosensitive composition provided thereon and to improve the adhesion with the photosensitive layer. It is applied to improve.

Prior to graining the aluminum plate, if necessary, the surface may be subjected to a pretreatment to remove rolling oil on the surface and to expose a clean aluminum surface. For the former, solvents such as trichlene, surfactants and the like are used. For the latter, a method using an alkali etching agent such as sodium hydroxide or potassium hydroxide is widely used.

As the graining method, any of mechanical, chemical and electrochemical methods is effective. Examples of the mechanical method include a ball polishing method, a blast polishing method, and a brush polishing method in which an aqueous dispersion slurry of an abrasive such as pumice is rubbed with a nylon brush, and the chemical method is disclosed in JP-A-54-31187. A method of immersing in a saturated aqueous solution of an aluminum salt of a mineral acid as described in the official gazette is suitable, and as an electrochemical method, a method of alternating current electrolysis in an acidic electrolyte such as hydrochloric acid, nitric acid or a combination thereof is used. Is preferred. Among such surface roughening methods, in particular, a surface roughening method combining mechanical surface roughening and electrochemical surface roughening as described in JP-A-55-137993 is described.
This is preferable because the adhesive force of the oil-sensitive image to the support is strong.

The graining by the above-mentioned method is performed when the center line surface roughness (Ra) of the surface of the aluminum plate is 0.3 to 1.0 μm.
It is preferable that the application is performed in such a range as follows. The aluminum plate thus grained is washed with water and chemically etched as required. The etching solution is usually selected from aqueous solutions of bases or acids that dissolve aluminum. In this case, the etched surface
A coating different from aluminum derived from the etchant component must not be formed. Preferred examples of the etching agent include sodium hydroxide, potassium hydroxide, trisodium phosphate, disodium phosphate, tripotassium phosphate, and dipotassium phosphate as basic substances; and sulfuric acid and persulfuric acid as acidic substances. , Phosphoric acid, hydrochloric acid, and salts thereof. Metals having a lower ionization tendency than aluminum, such as salts of zinc, chromium, cobalt, nickel, and copper, are not preferable because they form unnecessary films on the etched surface.

Most preferably, these etching agents are used so that the dissolution rate of the aluminum or alloy used is 0.3 to 40 g / m ² per one minute of immersion time at the setting of the concentration and temperature for use. But you can go above or below this. Etching is performed by immersing the aluminum plate in the above-mentioned etching solution or by applying an etching solution to the aluminum plate, etc., and may be processed so that the etching amount is in the range of 0.5 to 10 g / m ^2. preferable.

As the above-mentioned etching agent, it is desirable to use an aqueous solution of a base because of its high etching rate. In this case, since a smut is generated, a normal desmutting process is performed. As the acid used for the desmut treatment, nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, borofluoric acid and the like are used. The etched aluminum plate is optionally washed with water and anodized. The anodic oxidation can be performed by a method conventionally used in this field. Specifically, when direct current or alternating current is passed through aluminum in an aqueous solution or a non-aqueous solution in which sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, or the like or a combination of two or more thereof, aluminum An anodized film can be formed on the surface of the support.

The anodizing treatment conditions cannot be determined unequivocally because they vary depending on the electrolytic solution to be used. However, in general, the concentration of the electrolytic solution is 1 to 80% by weight, and the liquid temperature is 5 to 70%.
° C, current density 0.5-60A / dm ² , voltage 1-100V,
An electrolysis time of 30 seconds to 50 minutes is appropriate. Among these anodizing treatments, in particular, the method of anodizing at a high current density in sulfuric acid described in British Patent No. 1,412,768 and the method of electrolyzing phosphoric acid described in U.S. Pat. No. 3,511,661. A method of anodizing as a bath is preferred.

The aluminum plate which has been roughened and anodized as described above may be subjected to a hydrophilic treatment, if necessary. Preferred examples thereof are disclosed in US Pat. Nos. 2,714,066 and 3,181,461. Alkali metal silicates such as, for example, aqueous sodium silicate or potassium fluorozirconate disclosed in JP-B-36-22063 and polyvinyl sulfonic acid disclosed in U.S. Pat. No. 4,153,461. There is a way to handle it.

Further, after these treatments, a water-soluble resin,
For example, polymers and copolymers having a polyacrylic acid or sulfonic acid group in the side chain, other low-molecular compounds soluble in an alkaline aqueous solution, triethanolamine salts, and those coated with an alanine compound are also suitable. The photosensitive composition of the present invention coated on a support is exposed through a transparent original having a line image, a halftone dot image, and the like, and then developed with an aqueous alkaline developer to form a negative relief image on the original. give.

The light source used for exposure includes a carbon-arc lamp, a mercury lamp, a xenon lamp, a metal halide lamp, a strobe, an ultraviolet ray, a laser beam and the like. The developer used for the developing treatment may be any known one. For example, developers such as those described in U.S. Pat. Nos. 4,259,434 and 4,186,006 are exemplified.

[0061]

The photosensitive composition of the present invention has excellent sensitivity at the time of image exposure, a sufficient image can be obtained even with a short exposure time, and the obtained image portion has a high film strength and excellent abrasion resistance. It will be. Therefore, work efficiency in printing plate manufacturing, etc.,
Cost and the like are remarkably improved.

[0062]

The present invention will be described in more detail with reference to Synthesis Examples and Examples, but the present invention is not limited thereto. Synthesis Example 1 of Silane Coupling Agent Having Photocrosslinkable Group
In a 1-liter flask equipped with an SC-1 stirrer and a condenser, 2,3-
126 g (1 mole) of dimethylmaleic anhydride, 131 g (1 mole) of 6-aminocaproic acid and toluene 600
Then, the mixture was stirred at 100 ° C. for 1 hour while heating. Next, a Dean-Stark water separator was attached, and the mixture was stirred for 3 hours while removing water under reflux of toluene. After the reaction was completed, the mixture was cooled and then crystallized in 1.5 liter of hexane. The resulting solid was reslurried in 1.5 liters of water by filtration and drying.

By filtering and drying, 231 g of the following compound (i) as a white solid was obtained.

[0064]

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Next, 57.4 g (0.24 mole) of the compound (i) and 29.7 g (0.25 mole) of thionyl chloride were placed in a 300 ml flask equipped with a stirrer and a condenser, and stirred at room temperature for 1 hour. . Further, the mixture was stirred for 1 hour while heating to 80 ° C. After completion of the reaction, the mixture was cooled and 150 ml was added. Next, a dropping funnel was attached to the flask, and while cooling the reaction mixture in an ice water bath, 44.8 g (0.25 mole) of 3-aminopropyltrimethoxysilane and 25.5 g of triethylamine were added.
(0.25 mole), and a mixture of 50 ml of THF was added dropwise using a dropping funnel over about 30 minutes. After the completion of the dropwise addition, the mixture was stirred in an ice water bath for 2 hours.

After the completion of the reaction, 50 ml of hexane was added to increase the cloudiness, which was filtered through filter paper. The filtrate was concentrated under reduced pressure to give 95 g of a liquid of the following compound (SC-1).
was gotten.

[0067]

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A silane coupling agent having a photocrosslinkable group
Synthesis Example 2: In a 1-liter flask equipped with an SC-2 stirrer and a condenser, 2,3-
163.2 g (1 mole) of dimethyl maleimide potassium salt,
181.1 g (1 mole) of 6-bromo-1-hexanol and 500 ml of dimethylformamide were added and stirred for 1 hour while heating to 90 ° C. After completion of the reaction, the mixture was cooled, filtered, and the filtrate was concentrated under reduced pressure. Thereto was further added 100 ml of ether, the mixture was filtered, and the filtrate was concentrated under reduced pressure to obtain 201.0 g of a liquid of the following compound (ii).

[0069]

Embedded image

Next, 81.2 g of 2- (4-chlorosulfonylphenyl) ethyltrimethoxysilane was placed in a 300 ml flask equipped with a stirrer, a condenser and a dropping funnel.
5 mol) and 150 ml of THF, and compound (ii)
56.3 g (0.25 mole), triethylamine 25.5 g
(0.25 mole), and a mixture of 50 ml of THF was added dropwise using a dropping funnel over about 30 minutes. After dropping, add hexane 5
When 0 ml was added, cloudiness increased, which was filtered through filter paper, and the filtrate was concentrated under reduced pressure to give the following compound (SC-
115.6 g of the liquid of 2) were obtained.

[0071]

Embedded image Synthesis Examples 3 to 3 of silane coupling agents having photocrosslinkable groups
8: SC-3 to SC-8 SC-3 to SC-8 shown below in the same manner as in Synthesis Examples 1 and 2.
C-8 was synthesized.

[0072]

Embedded image

[0073]

Embedded image Synthesis Example 1: Silane Coupling Agent Modified Silica Fine Particles
In a G-1 high - speed stirrer, 10 g of silica fine particles (Mizukasil P-527U manufactured by Mizusawa Chemical Industry Co., Ltd.), 8 g of photocrosslinkable silane coupling agent (SC-1), 1 g of benzooxasilepin dimethyl ester, 5 g of 25% aqueous ammonia solution , Toluene (200 ml) were added, and the mixture was stirred and mixed at 18000 rpm for 1 hour.

The mixture was placed in a flask equipped with a stirrer, a condenser, and a dehydrating trap, and heated and stirred at the reflux temperature of toluene for 2 hours. After stirring, the contents of the flask were separated into a toluene solution and a sediment by a centrifuge at 7000 rpm for 30 minutes. This deposit is washed with acetone 40
The mixture was dispersed in 0 ml using an ultrasonic disperser, and after the dispersion, separated by a centrifuge again. This operation of washing with acetone was further repeated twice, and the obtained deposit was air-dried to obtain 15.1 g of a white powder. The carbon content was measured by elemental analysis and found to be C (%): 18.1, and the particle size was found to be 60 nm by observation with an electron microscope. Synthesis example 2: Silane coupling agent-modified silica fine particles: M
A G-2 high - speed stirrer was charged with 10 g of silica fine particles (Mizukasil P-527U manufactured by Mizusawa Chemical Industry Co., Ltd.) and 8 g of a photocrosslinkable silane coupling agent (SC-1).
Stir and mix for hours. The mixture was placed in a flask equipped with a stirrer, a condenser equipped with a trap containing alkali, and a dehydration trap, and heated and stirred at the reflux temperature of toluene for 2 hours. After stirring, the temperature was returned to room temperature, 2 g of 2- (4-chlorosulfonylphenyl) ethyltrichlorosilane and 3 g of water were added to the flask, and the mixture was stirred at room temperature for 1 hour.
The mixture was heated and stirred at the reflux temperature of toluene for 2 hours. After stirring, the contents of the flask were separated into a toluene solution and a sediment by a centrifuge at 7000 rpm for 30 minutes.

The precipitate is ultrasonically placed in 400 ml of acetone.
Disperse using a disperser, and after dispersion, use a centrifuge again.
separated. Repeat this acetone washing operation two more times.
After drying, the obtained sediment is air-dried to white
15.7 g of a powder were obtained. Measure carbon content by elemental analysis
As a result, C (%) was 18.5.
Observation revealed a particle size of 60 nm.Synthesis Example of Silane Coupling Agent Modified Silica Fine Particles 3,
4: MG-3 and MG-4 Silica particles (Mizuzu manufactured by Mizusawa Chemical Industry Co., Ltd.)
Casil P-527U) 10g, photocrosslinkable silane coupling
Agent (SC-2) 10 g, 3-glycidoxypropyl
Trimethoxysilane 2g, 25% ammonia aqueous solution 5
g, 200 ml of toluene and 1 hour at 18000 rpm
During the stirring and mixing. This mixture is stirred, cooled, and drained.
Place in a flask equipped with a water trap,
Heating and stirring were performed at reflux temperature. After stirring, the flask
The contents are centrifuged at 7000 rpm for 30 minutes.
Separated into Ruen solution and sediment. The sediment is
In 400 ml using an ultrasonic disperser, and after dispersion,
It was separated again by a centrifuge. This acetone cleaning operation
After repeating the crop two more times, the resulting sludge is allowed to air dry.
By drying, 16.8 g of a white powder (MG-3) was obtained.
Was.

When the carbon content was measured by elemental analysis, the C (%) was 20.8%, and the particle size was 60 nm when observed with an electron microscope. This white powder (MG-
3) 16.8 g was placed in a flask equipped with a stirrer and a condenser, and 1 g of p-hydroxyaniline and 2 g of toluene were added.
Then, the mixture was heated and stirred at the reflux temperature of toluene for 2 hours. After stirring, the contents of the flask were separated into a toluene solution and a sediment by a centrifuge at 7000 rpm for 30 minutes.

This deposit was dispersed in 400 ml of acetone by using an ultrasonic disperser, and after the dispersion, separated by a centrifuge again. The operation of washing with acetone was further repeated twice, and the obtained deposit was air-dried to obtain 16.9 g of a white powder. The carbon content measured by elemental analysis was C%: 21.5%, and the particle size was 60 nm when observed with an electron microscope. Synthesis Examples 5-1 of Silane Coupling Agent-Modified Silica Fine Particles
0: Modified silica fine particles MG-5 to MG-10 were synthesized using the silane coupling agents and amines shown in Table 1 in the same manner as in Synthesis Examples 1 to 4 for MG-5 to MG-10 modified silica fine particles.

In observation with these electron microscopes, the particle diameter was 60 nm in all cases.

[0079]

[Table 1]

[0080]

[Table 2]

[0081]

[Table 3] Example 1 A 0.30 mm thick aluminum plate was coated with a nylon brush and 40
The surface was sand-grained using a 0-mesh pumistone aqueous suspension, and then thoroughly washed with water. After etching by dipping in 10% sodium hydroxide at 70 ° C. for 60 seconds, the substrate was washed with running water, neutralized with 20% HNO ₃ , and washed with water. This was subjected to electrolytic surface roughening treatment in a 1% nitric acid aqueous solution at an anode-time electricity quantity of 160 clones / dm ² using a sinusoidal alternating waveform current under the condition of V _A = 12.7 V. When the surface roughness was measured, it was 0.6 μ (Ra indication). Followed by 3
After immersion in 0% H ₂ SO ₄ aqueous solution and desmutting at 55 ° C. for 2 minutes, current density 2A in 20% H ₂ SO ₄ aqueous solution
Thickness at / dm ² was anodized for 2 minutes so that 2.7 g / m ^2.

The following photosensitive solutions [V] -1 to [V] -10 were applied to the aluminum plate obtained as described above using a wheeler and dried at 80 ° C. for 2 minutes. Dry weight is
It was 1.0 g / m ² . Incidentally, the photosensitive solutions [V] -1 to [V]-
Table 2 shows the modified silica fine particles of the present invention used in No. 10.
The following P-1 was used as a photocrosslinkable polymer compound to be added to these photosensitive solutions.

Photocrosslinkable polymer compound (P-1):

[0084]

Embedded image Photosensitive solution [V] : 0.5 g of the modified silica fine particles of the present invention (Table 2) 4.5 g of polymer compound (P-1) • Sensitizer represented by the following structural formula

[0085]

Embedded image -50 g of propylene glycol monomethyl ether-50 g of methyl ethyl ketone-0.03 g of Megafac F-177 (a fluorinated nonionic surfactant manufactured by Dainippon Ink Co., Ltd.)-10% plasticizer of copper phthalocyanine pigment (CI Pigment Blue 15) Dispersion 1.0 g Next, as a comparative example, instead of the modified silica fine particles of the present invention in the photosensitive solution [V], unmodified silica fine particles and hydrophobic silica fine particles usually used as a filler were used. The photosensitive solutions [M] -1 and [M] -2 containing the compound (A) and the reduced amount (0.5 g) of the polymer compound (P-
A photosensitive solution [W] supplemented by the increase in 1) was prepared, coated and dried in the same manner. These are shown in Table 2.

Each photosensitive lithographic printing plate [V] -1 obtained using the photosensitive liquids [V] -1 to [V] -10 and [W], [M] -1 and [M] -2. [V] -10 and [W],
Fuji Photo Film Co., Ltd. on [M] -1 and [M] -2
Barkey Printer (Iko Adalx,
2 kW), immersed in a developer [S] shown below at room temperature for 1 minute, and lightly rubbed the surface with absorbent cotton to remove unexposed portions.

Developing solution [S]. 25 g of sodium silicate having a SiO ₂ / Na ₂ O molar ratio of about 1.2. 1000 g of water. The pH of the developing solution [S] was 13.1. The sensitivity of the obtained lithographic printing plate to the amount of exposure was visually read from the number of solid portions. Table 2 shows the results.

Further, using these lithographic printing plates,
High quality with commercially available inks on a KOR type printing machine manufactured by Leberg
Printed on paper. The printing durability at this time is adjusted by the modified silica fine particles.
Based on the final print number of the comparative example [W] without additive,
The result calculated for each printing plate as 100% printing durability is
It is shown in Table 2. Table 2 改 質 Modified silica fine particles used in photosensitive lithographic printing plate Development Printing durability after printing (%) Number of solid sections ─────────────────────────────────── [V] -1 MG-1 6140 [V] -2 MG-2 6140 [V] -3 MG-3 6140 [V] -4 MG-4 6150 [V] -5 MG-5 5.5 140 [ V] -6 MG-6 5 135 [V] -7 MG-7 6 150 [V] -8 MG-8 5 125 [V] -9 MG-9 4 125 [V] -10 MG-10 5 130 [V] -6 W] (Comparative example) 3 100 [M] -1 (Comparative example) 395 Mizukasil P-527U (unmodified silica) manufactured by Mizusawa Chemical Industry Co., Ltd. [M] -2 (Comparative example) Nippon Aerosil ( 5 100 Aerosil R-972 (hydrophobic fiber) Rica) か ら Based on these results, the modified silica fine particles of the present invention I was exposed
Compare all lithographic printing plates [V] -1 to [V] -10
From the photosensitive printing plates [W], [M] -1, and [M] -2 of the examples
Large number of steps, high sensitivity, and high printing durability
It was a printing press. Example 2 According to the method disclosed in JP-A-56-28893.
A substrate was prepared. That is, an aluminum plate 0.24 mm thick
The nylon brush and 400 mesh pumice water suspension
Use a turbid solution, grain the surface, and wash well with water
did. Then in 10% sodium hydroxide at 70 ° C for 60 seconds
After immersion for etching, rinse with running water and wash with 20% HNO
_ThreeAnd then washed with water. When the anode voltage is 12.7
The ratio of the quantity of electricity at the cathode to the quantity of electricity at the anode when V is 0.8.
In a 1% nitric acid aqueous solution using a sinusoidal alternating current
160 clones / dm^Two Electrolytic surface roughening treatment
Was done. The surface roughness measured at this time was 0.6.
μ (Ra indication). Then in 30% sulfuric acid
After immersion and desmutting at 55 ° C for 2 minutes, 20%
In sulfuric acid, current density 2A / dm^Two 2.7 g / m in thickness^Two
For 2 minutes. Then at 70 ° C
It was immersed in a 2.5% aqueous solution of sodium silicate for 1 minute, washed with water and dried.
The following photosensitive liquid is placed on the substrate thus prepared.
[N] -1 to [N] -10 are applied using a wheeler,
Dried at 80 ° C. for 2 minutes. Dry weight is 1g / m^TwoSo
Was.

Table 3 shows the modified silica fine particles of the present invention used in the photosensitive solutions [N] -1 to [N] -10. The following P-1 was used as a photocrosslinkable polymer compound to be added to these photosensitive solutions. Photocrosslinkable polymer compound (P-1):

[0090]

Embedded image Photosensitive solution [N] :-0.5 g of the modified silica fine particles of the present invention (Table 3)-4.5 g of polymer compound (P-1)-4-n of 4-diazodiphenylamine or a condensate of phenoxyacetic acid and formaldehyde -Dodecylbenzene sulfonic acid salt 0.1 g-Malic acid 0.05 g-Sensitizer represented by the following structural formula

[0091]

Embedded image -50 g of propylene glycol monomethyl ether-50 g of methyl ethyl ketone-0.03 g of Megafac F-177 (a fluorinated nonionic surfactant manufactured by Dainippon Ink Co., Ltd.)-10% of plasticizer of copper phthalocyanine pigment (CI Pigment Blue 15) Dispersion 1.0 g Next, as a comparative example, instead of the modified silica fine particles of the present invention in the photosensitive solution [N], unmodified silica fine particles and hydrophobic silica fine particles usually used as a filler. And the light-sensitive solutions [L] -1 and [L] -2 containing no fine particles, and the reduced amount (0.5 g) was added to the polymer compound (P-
A photosensitive solution [Q] supplemented by the increase in 1) was prepared, and coated and dried in the same manner. These are shown in Table 3.

Each photosensitive lithographic printing plate [N] -1 obtained using the photosensitive liquids [N] -1 to [N] -10 and [Q], [L] -1 and [L] -2. [N] -10 and [Q],
Fuji Photo Film Co., Ltd. on [L] -1 and [L] -2
Barkey Printer (Iko Adalx,
2 kW), immersed in the above-mentioned developer [T] for 1 minute at room temperature, and lightly rubbed the surface with absorbent cotton to remove unexposed portions.

Developer [T] : 5 g of sodium sulfite 30 g of benzyl alcohol 5 g of ethanolamine 35 g of sodium isopropylnaphthalenesulfonate 35 g of water 1000 g The sensitivity of the obtained lithographic printing plate to the exposure was visually read from the number of solid portions. . Table 3 shows the results.

Further, using these lithographic printing plates,
High quality with commercially available inks on a KOR type printing machine manufactured by Leberg
Printed on paper. The printing durability at this time is adjusted by the modified silica fine particles.
Based on the final print number of the comparative example [Q] without additive,
The result calculated for each printing plate as 100% printing durability is
It is shown in Table 3. Table 3 改 質 Modified silica fine particles used in photosensitive lithographic printing plate Development Post-press life (%) Number of solid sections ─────────────────────────────────── [N] -1 MG-1 6135 [N] -2 MG-2 6 135 [N] -3 MG-36 135 [N] -4 MG-4 6145 [N] -5 MG-5 5 135 [N] -6 MG-6 5130 [N] -7 MG-7 5.5 125 [N] -8 MG-8 5 125 [N] -9 MG-9 4 125 [N] -10 MG-10 5 130 [ Q] (Comparative example) 3 100 [L] -1 (Comparative example) 395 Mizukasil P-527U (unmodified silica) manufactured by Mizusawa Chemical Industry Co., Ltd. [L] -2 (Comparative example) 3100 Aerosil R-972 (hydrophobic) Rica) か ら Based on these results, the modified silica fine particles of the present invention I was exposed
All of the lithographic printing plates [N] -1 to [N] -10 are compared
From the photosensitive printing plates [Q], [L] -1, and [L] -2 of the examples
Large number of steps, high sensitivity, and high printing durability
It was a printing press. Example 3 The photosensitive lithographic printing plate [N] -1, obtained according to Example 2,
On [N] -2 and [Q], [L] -1, [L] -2
Grayscale tablet manufactured by Fuji Photo Film Co., Ltd.
US Barkey Technical Barkey Printer
(Iko Adalux, 2kW)
After immersing in liquid [U] for 1 minute at room temperature, lightly rub the surface with absorbent cotton.
The unexposed part was removed.

Developer [U] : 10 g of sodium hydrogen carbonate 20 g of sodium carbonate 50 g of sodium isopropylnaphthalenesulfonate 50 g of water 1000 g The sensitivity of the obtained lithographic printing plate to the amount of exposure was visually read from the number of solid portions. Table 4 shows the results.

Using these lithographic printing plates, printing was performed on high quality paper with a commercially available ink using a KOR type printer manufactured by Heidelberg. The printing durability at this time was calculated for each printing plate based on the final number of printed sheets of Comparative Example [Q] in which the modified silica fine particles were not added, and the printing durability was set to 100%. Table 4 ────────────────────────────── Photosensitive lithographic printing plate Number of solid sections after development Printing durability (%) ────────────────────────────── [N] -1 6 140 [N] -2 5.5 140 [Q] ( Comparative Example) 3 100 [L] -1 (Comparative Example) 3 100 [L] -2 (Comparative Example) 3 105 ───────────────────────よ り From Table 4, the photosensitive lithographic printing plates [N] -1 and [N] -2 using the modified silica fine particles of the present invention were both photosensitive printing plates [Q] of Comparative Examples. , [L] -1 and [L] -2, the number of steps was larger, the sensitivity was higher, and the printing durability was higher.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-55-160010 (JP, A) JP-A-61-264341 (JP, A) JP-A-61-275834 (JP, A) JP-A-62 52548 (JP, A) JP-A-63-261253 (JP, A) JP-A-1-197744 (JP, A) JP-A-1-253730 (JP, A)

Claims (1)

(57) [Claims] 1. A photo-crosslinkable polymer compound having a photo-crosslinkable group represented by the following general formula (I) and the following general formula (II)
A photosensitive composition comprising surface-modified silica fine particles in which at least one kind of functional group represented by the formula is connected to the particle surface by a chemical bond. Embedded image (In the formula, T ¹ and T ² each represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and T ¹ and T ² may be combined with each other to form a ring.) ] (Wherein, R represents a divalent linking group consisting of two or more atoms selected from C, H, N, O, S, and Si, and Y represents at least Wherein Q ¹ and Q ² each represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group;
Q ¹ and Q ² may together form a ring. )