JPH06105355B2 - Photosensitive composition - Google Patents

Description

The present invention relates to a photosensitive composition suitable for producing a lithographic printing plate, an IC circuit and a photomask. For more details,
The present invention relates to a photosensitive composition comprising a photosensitive compound such as an o-naphthoquinonediazide compound and a polymer which is soluble in an alkaline aqueous solution or an alkaline solvent containing water as a main component (hereinafter referred to as alkaline water soluble).

[Conventional technology]

BACKGROUND ART A photosensitive composition comprising an o-naphthoquinonediazide compound and a novolac type phenol resin has been industrially used as a very excellent photosensitive composition for producing a lithographic printing plate and a photoresist.

However, due to the nature of the novolac type phenolic resin used as the main component, the adhesion to the substrate is poor, the film is brittle, the abrasion resistance is poor, and the printing durability when used for lithographic printing plates is not sufficient. There was a point to be solved and there was a limit in application.

Various polymers have been investigated as binders in order to solve such problems. For example, the polyhydroxystyrene or hydroxystyrene copolymer described in JP-B-52-41050 has certainly improved the film forming property, but has the drawback of being inferior in abrasion resistance. Further, JP-A-51-34711 proposes to use a polymer having a structural unit of an acrylic acid derivative in the molecular structure as a binder, but such a polymer is said to have a narrow range of appropriate developing conditions. There was a problem.

[Problems to be solved by the invention]

Accordingly, it is an object of the present invention to provide a photosensitive composition which gives a lithographic printing plate having a wide range of suitable developing conditions and a large printing durability. Another object of the present invention is to provide a photosensitive composition having good adhesion to a substrate and giving a flexible film.

[Means for solving problems]

As a result of various studies, the inventors of the present invention have invented the following photosensitive composition useful for achieving the above object.

That is, the present invention provides a positive photosensitive composition containing a polymer having an active imino group and insoluble in water and soluble in alkaline water.

Further, in a preferred embodiment of the present invention, the polymer has a structural unit represented by the following general formula [I] or [II].

[However, in the formula, A is a hydrogen atom, a halogen atom or a carbon number 1
Represents an alkyl group of 4; B represents an alkylene group, a phenylene group, a substituted alkylene group or a substituted phenylene group.
X is Represents Y is Represents -C≡N or -NO ₂ (provided that R ¹ is an alkyl group,
It represents a phenyl group, a substituted alkyl group or a substituted phenyl group. ). m represents 0 or 1, and n represents 1. ] (However, E in the formula is a hydrogen atom, a halogen atom, or a carbon number of 1 to
4 represents an alkyl group or a phenyl group. F and G each independently represent an alkylene group or a substituted alkylene group.
X is Represents p and p'represent 0 or 1 and q and q'represent 1) The polymer of the present invention is characterized in that it has an active imino group in its molecular structure. Dissolves in a developer. The active imino group in the present invention has a dissociation degree (pKa) of 4 to 11, more preferably 5 to 9. If pKa is larger or smaller than this range, the range of appropriate developing conditions becomes narrow.

It was truly surprising that the polymer of the present invention gives a photosensitive composition having good adhesion to a substrate, excellent abrasion resistance, and a wide range of appropriate developing conditions (wide development tolerance). .

The preferred structure of the polymer in the invention is represented by the above general formula [I] or [II].

A in the general formula [I] is a hydrogen atom, a halogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group.

B is an alkylene group, a phenylene group, a substituted alkylene group or a substituted phenylene group, more preferably a phenylene group or m = 0.

X is Is represented, but more preferably, Is.

Y is It represents -C≡N or -NO ₂ , but more preferably And R ¹ is preferably a phenyl group, a naphthyl group, a cyclohexyl group or an alkyl group having 1 to 4 carbon atoms.

E in the general formula [II] is a hydrogen atom, a halogen atom,
It represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, and more preferably a hydrogen atom.

F and G each independently represent an alkylene group or a substituted alkylene group, more preferably a methylene group or p
= P '= 0.

X is Is represented, but more preferably, Is.

The molecular weight of the polymer in the present invention may be in a wide range, but when measured by gel permeation chromatography using polystyrene as a standard, the weight average molecular weight (w) is preferably 500 to 1,000,000, and It is preferably 4,000 to 300,000. The amount of the polymer having an active imino group in the photosensitive composition of the present invention is 3 to 90% by weight, more preferably,
15 to 50% by weight. The polymer having an active imino group in the present invention is a polymer having a repeating structure of only the structural unit of the general formula [I] or [II] or the general formula [I]
The copolymer of [II] and [II] may be used, but a multi-component copolymer having a repeating structure in which one or more of vinyl monomers that are usually used are combined may be used. In the case of such a multi-component copolymer, the structural units represented by the general formula [I] or [II], alone or in combination, are preferably contained in an amount of 10 mol% or more, more preferably 20 mol% or more.
Examples of the structural unit used in combination with the structural unit represented by the general formula [I] or [II] include ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene, and isobutylene, for example, styrene and α-methylstyrene. , O-methylstyrene, m-methylstyrene, p-methylstyrene, o-chlorostyrene, p-chlorostyrene, and other styrenes, such as acrylic acid, methyl acrylate, ethyl acrylate, iso-butyl acrylate, and acrylic. Acrylic acid and its esters such as n-butyl acid, hexyl acrylate, octyl acrylate, 2-hydroxyethyl acrylate, 2-cyanoethyl acrylate, glycidyl acrylate, dimethylaminoethyl acrylate, for example, methacrylic acid, methacrylic acid Methyl, Ethyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid Methacrylic acid and its esters such as 2-hydroxyethyl, 2-hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate and allyl methacrylate, for example vinyl acetate, propion Vinyl esters such as vinyl acetate, vinyl butyrate, vinyl caproate, and vinyl benzoate, for example, nitriles such as acrylonitrile and methacrylonitrile, For example, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether, cyclohexyl vinyl ether, for example, acrylamide, N-methyl acrylamide, N, N-dimethyl acrylamide, N-tert-butyl acryl aminoxide, N-octyl. Acrylamides such as acrylamide and diacetone acrylamide, for example, unsaturated double bonds of vinyl monomers such as N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, and N-vinylpyrrolidone. What is shown by a cleaved structure, and others
Substituted styrenes having a phenolic hydroxyl group, which are disclosed in Japanese Patent Laid-Open Publication No. H11-242, can be cited.

Next, typical specific examples of the polymer having an active imino group in the present invention will be shown.

[Exemplified compound] Next, representative synthetic examples of the polymer having an active imino group in the present invention will be shown, but the present invention is not limited to these examples.

Synthesis Example 1 N-methacrylylsulfonamide 10.0 g (0.044 mol), methyl methacrylate 4.46 g (0.044 mol)
Mol) in 22 ml of 2-methoxyethanol, V-65 [2,
2'-azobis- (2,4-dimethylvaleronitrile) 0.02
Copolymerization was carried out using 13 g of an initiator. After stirring at 60 ° C for 7 hours, 60 ml of 2-methoxyethanol was added,
Re-precipitated in 2 liters of water. The obtained polymer was dissolved in 100 ml of tetrahydrofuran and then reprecipitated in 1.5 l of methanol to obtain 10.2 g of polymer of Exemplified Compound No. 1.
(W = 200,000, 70% yield) Polymer composition ratio is ¹ H-NMR
Decided by.

(Same below) Synthesis Example 2 N-methacrylylsulfonamide 15.78 g (0.070 mol), benzyl methacrylate 12.35 g (0.070 mol),
Copolymerization was carried out using 0.173 g of V-65 in 47 ml of ethyl acetate as an initiator. After stirring at 60 ℃ for 6 hours, 1.5l of hexane
Reprecipitated in, the resulting polymer was tetrahydrofuran 15
By dissolving in 0 ml and reprecipitation in 2 l of methanol,
23.4 g of polymer of Exemplified Compound No. 2 was obtained. (W = 6500
0, yield 83%) Synthesis Example 3 N-methacrylylsulfonamide 11.28 g (0.055 mol) and ethyl acrylate 13.74 g (0.15 mol) were mixed with ethyl acetate 65 ml using V-65 0.235 g as an initiator. Polymerization was carried out. After stirring at 60 ° C. for 6 hours, 50 ml of ethyl acetate was added, and the mixture was reprecipitated in 2 l of hexane. The obtained polymer was dissolved in 150 ml of ethyl acetate and reprecipitated in 1.5 l of hexane to obtain 23.9 g of a polymer of Exemplified Compound 3. (
w = 60,000, yield 96%) Synthesis Example 4 N-methacrylylsulfonamide 11.27 g (0.050 mol), acrylic acid-n-butyl 13.74 g (0.107 mol) were started with V-65 0.195 g in ethyl acetate 65 ml. Copolymerization was performed as an agent. After stirring at 60 ℃ for 6 hours, 1.5l of hexane
After reprecipitation, 20.6 g of a polymer of Exemplified Compound 4 was obtained.
(W = 83,000, yield 82%) Synthesis Example 5 14.58 g (0.15 mol) of maleimide, 1 methyl methacrylate
5.04 g (0.15 mol) was copolymerized with 0.371 g of V-65 in 69 ml of 1-acetoxy-2-methoxyethane as an initiator. After stirring at 60 ° C for 2 hours, 1-acetoxy-2-
By adding 50 ml of methoxyethane and reprecipitating in 2 l of water, 23.7 g of a polymer of Exemplified Compound 5 was obtained. (W = 590
00, yield 80%) Synthesis Example 6 Maleimide 9.75 g (0.10 mol), benzyl methacrylate 1
7.62 g (0.10 mol) was copolymerized in 64 ml of 1-acetoxy-2-methoxyethane with 0.125 g of V-65 as an initiator. After stirring at 60 ° C for 4 hours, 1-acetoxy-
30 ml of 2-methoxyethane was added and reprecipitated in 2 l of water. The obtained polymer is 1-acetoxy-2-methoxyethane
After dissolving in 150 ml and reprecipitating in 2 l of water, 22.5 g of a polymer of Exemplified Compound 6 was obtained. (W = 84000, yield 82
%) Synthetic Example 7 11.28 g (0.055 mol) of N-methacrylylsulfonamide, 3.30 g (0.033 mol) of ethyl acrylate and 5.77 g (0.050 mol) of n-butyl acrylate in V-65 0.171 in 75 ml of ethyl acetate. Copolymerization was carried out using g as an initiator. 60 ° C
After stirring for 6 hours, the mixture was reprecipitated in 1.5 l of hexane to obtain 18.7 g of a polymer of Exemplified Compound 7. (W = 76000, yield
92%) As the positive-working photosensitive compound used in the present invention, an o-naphthoquinonediazide compound is preferable, and a 1,2-diazonaphthoquinonesulfonic acid chloride described in JP-B-43-28403 is used. Most preferred is an ester with pyrogallol-acetone resin. Other suitable orthoquinonediazide compounds are the esters of 1,2-diazonaphthoquinone sulfonic acid chloride with phenol-formaldehyde resins described in US Pat. Nos. 3,046,120 and 3,188,210. Other useful o-naphthoquinonediazide compounds have been reported and known in numerous patents.
For example, Japanese Patent Laid-Open Nos. 47-5303, 48-63802 and 48-
63803, 48-96575, 49-38701, 48-13
No. 354, Japanese Patent Publication No. 41-11222, No. 45-9610, No. 49-174
81 gazette, U.S. Pat.Nos. 2,797,213, 3,454,400,
No. 3,544,323, No. 3,573,917, No. 3,674,495
No. 3,785,825, British Patent No. 1,227,602, No. 1,
No. 251,345, No.1,267,005, No.1,329,888, No.1
Examples thereof include those described in each specification such as 1,330,932 and German Patent No. 854,890.

Further, as a photosensitive compound or a photosensitive mixture which acts as a positive type without using an o-naphthoquinonediazide compound, for example, a polymer compound having an orthonitrocarbinol ester group described in the specification of JP-B-56-2696 is also available. It can be used in the present invention.

Further, a photosensitive mixture of a compound which generates an acid by photolysis and a compound having a C—O—C group or a C—O—Si group which is dissociated by an acid can be used in the present invention.

For example, a combination of a compound that generates an acid by photolysis and an acetal or an O, N-acetal compound (Japanese Patent Laid-Open No. 48-8).
9003), a combination with an orthoester or amide acetal compound (JP-A-51-120714), a combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-120714).
-133429), a combination with an enol ether compound (JP-A-55-12995), a combination with an N-acyliminocarbonate compound (JP-A-55-126236), and a polymer having an orthoester group in the main chain. Combination (JP-A-56-17345), combination with a silyl ester compound (JP-A-60-10247) and combination with a silyl ether compound (JP-A-60-37549).
And JP-A-60-121446).

The amount of the positive-working photosensitive compound or photosensitive mixture in the photosensitive composition of the present invention is 10 to 50% by weight.
And more preferably 20 to 40% by weight.

The composition of the present invention contains a known alkali-soluble polymer compound such as phenol formaldehyde resin, cresol formaldehyde resin, phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, etc. in addition to the polymer of the present invention. Can be made. Such an alkali-soluble polymer compound is used in an amount of 70% by weight or less based on the total composition.

In the composition of the present invention, a cyclic acid anhydride may be added to enhance the sensitivity, a printout agent for obtaining a visible image immediately after exposure, a dye or other filler as an image colorant may be added. Examples of the cyclic acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and 3,6-as described in U.S. Pat.No. 4,115,128.
Endoxy-Δ ⁴ -tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic acid and the like. By containing 1 to 15% by weight of these cyclic acid anhydrides in the total composition, the sensitivity can be increased up to about 3 times. As a printing-out agent for obtaining a visible image immediately after exposure, a combination of a photosensitive compound which releases an acid upon exposure and an organic dye capable of forming a salt can be mentioned as a representative example. Specifically,
Nos. 50-36209 and 53-8128, combinations of o-naphthoquinonediazide-4-sulfonic acid halogenide and salt-forming organic dyes, and Japanese Patent Laid-Open Nos. 53-36223 and 53-36223 The combination of the trihalomethyl compound and the salt-forming organic dye described in JP-A-54-74728 can be mentioned. In addition to the salt-forming organic dyes described above, other dyes can be used as the image colorant. Suitable dyes including salt-forming organic dyes include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 10
1, oil yellow # 130, oil pink # 312, oil green BG, oil blue BOS, oil blue # 603, oil black BY, oil black BS, oil black T-
505 (above, manufactured by Orient Chemical Industry Co., Ltd.), crystal violet (CI42555), methyl violet (C
I42535), Rhodamine B (CI45170B), Malachite Green (CI42000), Methylene Blue (CI52015) and the like.

The composition of the present invention is dissolved in a solvent that dissolves each of the above components and applied onto a support. As the solvent used here,
There are ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, toluene, ethyl acetate, etc. Solvents may be used alone or as a mixture. The concentration (solid content) in the above components is 2 to 50% by weight. Although the coating amount varies depending on the use, for example, in the case of a photosensitive lithographic printing plate, it is generally preferable that the solid content is 0.5 to 3.0 g / m ² . Although the photosensitivity increases as the coating amount decreases, the physical properties of the photosensitive film deteriorate.

In the case of producing a lithographic printing plate using the photosensitive composition of the present invention, the support thereof may be a hydrophilized aluminum plate, for example, a silicate-treated aluminum plate, an anodized aluminum plate, a grained aluminum plate, or a silicate electrode. There is a coated aluminum plate, and other examples include a zinc plate, a stainless plate, a chrome-treated steel plate, and a hydrophilized plastic film or paper.

The developer for the photosensitive composition of the present invention includes sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium triphosphate, dibasic sodium phosphate, tribasic ammonium phosphate, Aqueous solutions of inorganic alkaline agents such as ammonium diphosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. are suitable and their concentration should be 0.1-10% by weight, preferably 0.5-5% by weight. Is added.

If necessary, an organic solvent such as a surfactant or alcohol can be added to the alkaline aqueous solution.

〔Example〕

Next, the present invention will be described in more detail with reference to examples. All percentages in the following examples are% by weight unless otherwise specified.

Examples 1 to 7 An aluminum plate having a thickness of 0.30 mm was grained on its surface using a nylon brush and an aqueous suspension of 400 mesh pumice, and then washed thoroughly with water. To 10% sodium hydroxide
After immersing at 70 ℃ for 60 seconds and etching, rinse with running water
It was neutralized and washed with 20% HNO ₃ . This was subjected to electrolytic surface-roughening treatment in an aqueous 1% nitric acid solution at an anodic electricity of 160 clones / dm ² using a sinusoidal alternating current under the condition of V _A = 12.7V. The surface roughness was measured to be 0.6μ (Ra indication), followed by immersion in 30% H ₂ SO ₄ aqueous solution and desmutting at 55 ° C for 2 minutes, then in 20% H ₂ SO ₄ aqueous solution. , And anodized so that the thickness was 2.7 g / m ² at a current density of 2 A / dm ² .

The following photosensitive solution was applied onto the aluminum support thus obtained using a whiler and dried at 100 ° C. for 2 minutes.

Naphthoquinone- (1,2) -diazido- (2) -5-sulfonyl chloride Esterification reaction product of cresol novolac resin 0.75 g m-cresol novolac resin 1.40 g Tetrahydrophthalic anhydride 0.15 g Polymers shown in Table 1 0.70g 2- (p-butoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine 0.02g naphthoquinone-1,2-diazide-4-sulfonyl chloride 0.03g crystal violet 0.01g oil blue # 603 0.015g (Orient Chemical Co., Ltd.) Ethylene dichloride 18 g 2-methoxyethyl acetate 12 g The coating amount after drying was 2.1 g / m ² . Each of these photosensitive lithographic printing plates was exposed for 40 seconds through a positive transparent original image from a distance of 1 m with a 2 KW metal halide lamp. The exposed photosensitive lithographic printing plate was immersed in a 4% aqueous solution of sodium metasilicate for 1 minute to develop it, and then processed according to a conventional method to obtain a lithographic printing plate. The lithographic printing plate thus obtained was printed on an offset printing machine to test the printing durability. If the number of sheets with poor printing durability is small, the image area will be worn out and ink will not adhere, and normal printed matter cannot be obtained.

Further, in order to examine the range of suitable developing conditions (development acceptability), the change in tone reproducibility when immersed in the above developing solution for 5 minutes and developed and immersed for 1 minute and developed was examined. Those with almost no change are indicated with a circle, those with a large change are indicated with a cross, and the middle thereof is indicated with a triangle. Further, in order to examine the adhesion and flexibility of the photosensitive composition to the substrate, a constant load was applied to the image area with a diamond stylus after exposure, and after development, printing was performed to examine the ease of scratching. Good for scratches ○, very easy for ×, middle △
Displayed in. The results are shown in Table 1.

As apparent from Table 1, the photosensitive composition of the present invention is
It can be seen that it has excellent performance.

Examples 8 to 11 The following photosensitive solution was applied onto a support prepared in the same manner as in Examples 1 to 7 using a whiler and dried at 100 ° C for 2 minutes.

Naphtoquinone- (1,2) -diazido- (2) -5-sulfonyl chloride ester compound with pyrogallol-acetone resin 0.90 g (described in US Pat. No. 3,635,709, Example 1) The coating amount after drying was 2.5 g / m ² . The results of evaluating these photosensitive lithographic printing plates by the same method as in Examples 1 to 7 are shown in Table 2. From Table 2, it can be seen that the photosensitive composition of the present invention has excellent performance.

[Effect of the Invention] The photosensitive composition containing the polymer having an active imino group of the present invention has good developability and printing durability, and also has excellent adhesion to a substrate.

Claims (2)

[Claims] 1. A positive photosensitive composition comprising a water-insoluble and alkaline water-soluble polymer having a structural unit having an active imino group represented by the general formula [I] or [II]. [However, in the formula, A is a hydrogen atom, a halogen atom or a carbon number 1
Represents an alkyl group of 4; B represents an alkylene group, a phenylene group, a substituted alkylene group or a substituted phenylene group.
X is Y is Represents -C≡N or -NO ₂ (provided that R ¹ represents an alkyl group, a phenyl group, a substituted alkyl group or a substituted phenyl group). m represents 0 or 1, and n represents 1. ] (However, E in the formula is a hydrogen atom, a halogen atom, or a carbon number of 1 to
4 represents an alkyl group or a phenyl group. F and G each independently represent an alkylene group or a substituted alkylene group.
X is p and p'represent 0 or 1, and q and q'represent 1. ) 2. The photosensitive composition according to claim 1, wherein the dissociation degree (pKa) of the active imino group is 4 to 11.