JPS5849940A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a water-developable photosensitive composition suitable for use in the manufacture of a printing plate such as a lithographic plate or a letterpress plate, or a printed circuit by adding a photo-sensitive high molecular compound contg. specified groups as a crosslinking component in the principal chain or the side chain together with diazo resin and a water-softenable high molecular compound. CONSTITUTION:A photosensitive liq. is prepared by adding a photosensitive high molecular compound contg. groups represented by the formula (where R is H, CN or halogen) as a cross-linking component in the principal chain or the side chain together with diazo resin and a water-softenable high molecular compound such as cellulose, a polyvinyl alcohol deriv. or poly(meth)acrylamide and by further adding a necessary pigment, etc. The liq. is applied to an Al plate or the like and dried to form a printing plate such as a lithographic plate. The resulting photosensitive layer can be developed with water after exposure and has superior shelf stability before use. The printing plate has high resolving power and wear resistance and is not affected by O2. Said photosensitive liq. is also suitable for use in the manufacture of a printed circuit.

Description

[Detailed description of the invention] The present invention relates to a photosensitive composition.

More specifically, the present invention relates to a water-curable photosensitive composition useful in the production of printing plates such as lithographic plates and letterpress plates, photoresists used in the production of graphic art elements, and printing paths.

Conventionally, photosensitive compositions that can be developed with water include (1) compositions comprising a water-soluble polymer compound and dichromate salts, and (2) compositions comprising a water-soluble polymer compound and a water-soluble diazo resin. (3) A composition comprising a water-soluble polymer compound and a water-soluble azide compound, (4) A water-soluble photopolymerizable composition, and the like are known. Since the photosensitive layers obtained by preparing these photosensitive compositions are all water-soluble, great care must be taken not to touch the surface with damp hands when handling them. For this reason, work efficiency is seriously reduced. Furthermore, it is extremely susceptible to the effects of moisture in the air, making it impossible to store it for long periods of time.

Furthermore, since the photocured film is hydrophilic and brittle, when used as a printing plate, for example, it has poor affinity for printing during printing, and its suitability for printing is extremely poor.

Also, as a photoresist, it has poor water resistance, so the resist machine iii! has not yet been achieved.

In order to solve the above-mentioned problems, an attempt was made to form a nuclide in a water-soluble photosensitive layer and an oil-based resin photosensitive layer, and the surface properties of the photosensitive layer were improved to be hydrophobic. However, these compositions F
Because of the iz layer system, manufacturing is complicated and costly, and the resolution is poor. Several improvements have been attempted in order to solve the above-mentioned problems in single-layer systems as well. For example, JP-A-52-2520 discloses a composition consisting of an aqueous emulsion of a lipophilic resin and a water-soluble diazo resin, but since this composition uses an aqueous emulsion, it is not affected by moisture. It was easy to use and had poor storage stability. Furthermore, for example, JP-A-55-120028 discloses a composition comprising a homogeneous mixture of an oily film-forming resin, a free radical polymerizable unsaturated compound, a lipophilic diazo compound, a water-soluble resin, and an initiator. There is. However, this composition was easily affected by atmospheric oxygen and had poor storage stability. Furthermore, JP-A-55-
Publication No. 159433 discloses a composition comprising an epoxy resin and a lipophilic diazo resin, but storage stability was poor due to dark reaction during storage of the epoxy resin. At present, there is currently no known photosensitive composition that can be processed with water, has good resolution and printing durability, is not affected by oxygen, and has good storage stability.

The present invention has been made to solve the problems faced by the above-mentioned prior art.

An object of the present invention is to provide a photosensitive composition that has excellent storage stability, lipophilicity, resolution, and abrasion resistance, and can be developed with water without being affected by build-up. be.

Another object of the present invention is to provide a lithographic printing plate which has excellent storage stability, oil resistance, resolution, and printing durability, and which is unaffected by M elements and can be printed with water.

As a result of intensive research, the present inventors have found that the above object can be achieved by using a photosensitive composition having the following structure.

That is, the water-dispersible photosensitive composition of the present invention has [A]
Diazo resin, [B] water-softening polymer compound, and [C]
-CH-C-C0 as main chain or IIIK linkage component
The photosensitive composition according to the present invention is characterized in that it contains a photosensitive polymer compound containing a - group (representing R, a cyano group, or a halogen atom). Since 6 is added with a certain photosensitive polymer compound, the skin III strength is significantly increased, and when the photosensitive composition according to the present invention is used in a lithographic printing III plate, printing durability is significantly improved. .

Next, the present invention will be explained in detail.

As the diazo resin, for example, U.S. Pat. No. 2,06363
Diphenylamine-p-diazonium salt, which is a reaction product of the diazonium salt disclosed in the specifications of No. 1 and No. 2667415, and an organic condensing agent containing a reactive carbonyl group such as aldol or acemer, and form Condensates with aldehydes, fft These water-soluble diazo compounds are used in the katana GK j F) BF4-, PF6-. 5iF6
-'', 8bF6-''''.

Included are halogenated Lewis acid salts such as those substituted with an anionic component of BaF2.

The amount of the diazo resin added is 1 to 50 weight equivalents based on the total weight of the photosensitive layer made of the photosensitive composition, and 3.
~301i amount is preferred.

The water-softening polymer compound used in the present invention is a water-soluble polymer compound that is also soluble in polar organic solvent systems, and preferably has a moisture absorption rate (water vapor) of 5 to 60 at relative humidity wIL80'lVc. It is.

Although it does not depend on the amount of the water-softening polymer compound added, when the moisture absorption rate is 60% or less, it is even better in that a water-resistant and lipophilic photosensitive composition can be obtained. , storage stability is also improved.

Further, when the number is 5 or more, the developability with water becomes extremely excellent. #The moisture absorption rate was measured by the weighing bottle method as described in "Handbook of Materials and Moisture" (edited by the Society of Polymer Science and Technology, Kyoritsu Publishing, 1968) ill, page 77.

Among the water-softening polymer compounds of the present invention, preferred are cellulose tsuba conductor, polyvinyl alcohol n-conductor, polyvinyl vicritone, polyhydroxystyrene, and acrylic acid, methacrylic acid, acrylamide type, methacrylamide type, and those having no hydroxyl group. At least one selected from the group consisting of homopolymers or copolymers containing acrylic ester-based or methacrylic ester-based monomer units containing hydroxyl groups.

Typical cellulose derivatives used in the present invention include those having a structure in which at least one of the water Ia atoms in the hydroxyl group of cellulose is replaced with an alkyl group, a hydroxyalkyl group, and/or an acyl group. Specific examples of the core cellulose enzyme conductor include hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose phthalate, hydroxypropylmethylcellulose hexahydrophthalate, methylcellulose, ethylcellulose, propylcellulose, and the like.

Specific examples of the polyvinyl alcohol sieve conductor used in the present invention include polyvinyl alcohol with saponification of 1120 to 5 degrees, 2H5H (each having a molecular weight of 1,000 to 100,000), and the like.

Examples of the acrylamide type, methacrylamide type, hydroxyl group-containing acrylic ester type and hydroxyl group-containing methacrylamide type monomer units in the present invention include those represented by the following general formula [T].

General formula [I] 1 -CH2-C- C202 Monomers that provide the monomer unit represented by the above general formula [T] include, for example, acrylamide, p-hydroxyphenyl methacrylamide, hydroxymethyl methacrylate, Examples include hydroxyethyl methacrylate and hydroxypropyl methacrylate.

In the present invention, copolymers containing acrylic acid, methacrylic acid, acrylamide type, methacrylamide type, acrylic ester type having a hydroxyl group, or methacrylic ester type having a hydroxyl group as monomer units are At least 181 body units
It is sufficient if it is included.

Further, the ratio of these monomer units in the copolymer is preferably on a 30-weight plate.

Specific examples of homopolymers or copolymers containing at least one of the above structural units include the following.

The numbers in parentheses represent the weight ratio of monomer units.

[13 Polyhydroxyethyl methacrylate [2]
Poly-p-hydroxyphenylmethacrylamide [3] Copolymer of hydroxyethyl methacrylate/butyl acrylate/styrene (40:15:35) [4] Hydroxyethyl methacrylate/butyl acrylate/acrylic acid/styrene (40:25) :to
:25) copolymer [5] p-hydroxyph, enylmemethrylamide/acrylonitrile/butyl acrylate/acrylic acid (2
0:20:40:20) copolymer [6] Petitilme! Copolymer of acrylate/acrylic acid/styrene (25:50:25) [7] Copolymer of methyl methacrylate/butyl acrylate/acrylic acid/styrene (10:10:50:30) [8] Butyl acrylate/acrylic copolymer of acid/hydroxyethyl acrylate (30:30:40) [9] phthyl acrylate/methacrylic acid (SO:50)
) Photosensitive polymer compounds used in the present invention include the following.

n: 8 to 200), for example, as shown in JP-A-55-40415, there is a polyester compound consisting of phenylene diethyl acrylate, bisphenol A to which water has been added and triethylene glycol.

Examples include styryl I, polyether, polyvinyl rarefrecol, polyhydroxyphenyl amide/acrylate, polyhydroxystyrene, novolak resin, etc.
The one that reacts with the conductor is the one, and the specific color is, for example, d
The following can be mentioned:

CN [Iro, top & l: +ll to α, m, n/ri integer, l 00 ) −) 0.01. ] It is preferable to use a sensitizer when using the above photosensitive polymer compound. As a sensitizer, a nidroaryl compound,
Anthrones, diaminobenzophenonimides, diaminodiphenylmethanes, diaminodiphenylketones, diaminodiphenylcalpitols, and the like are preferably used.

The sensitizer is used in an amount of 0 per 100 parts by weight of the photosensitive polymer compound.
．． 1 to 50 parts by weight are used. When irradiated with active light, the photosensitive polymer compound self-crosslinks and/or reacts with expanded decomposed diazo to form a network structure and harden.

The photosensitive composition according to the present invention contains two types of photosensitive compounds. That is, they are a diazo resin and a photosensitive polymer compound.

Alkaline-current photosensitive compositions made of diazo resins and lipophilic resins are well known, but they suffer from the disadvantage of not being able to provide high printing durability when used as lithographic printing plates. However, alkaline-current photosensitive compositions comprising a photosensitive polymer compound and a lipophilic resin are also well known, but they generally have the drawback of low sensitivity.

By combining a diazo resin, a photosensitive polymer compound, and a water-softening polymer compound, the present inventors have developed
A photosensitive composition made of IAlt that has extremely excellent abrasion resistance and can be developed with water has been completed.

When the photosensitive composition is used as a printing plate, it is very advantageous to obtain a printing plate that has high sensitivity, high printing durability, and can be washed with water.

It is desirable that a filler is added to the photosensitive composition according to the present invention. The filler 1i is a material that transmits active light IIt and is inert to traps such as diazo resin and water-softening polymer compounds. Specific examples include inorganic fillers such as asbestos, alumina, attapulgite, kaolin clay, graphite, finely divided silicic acid, diatomaceous earth, titanium oxide, silicon oxide, quartz powder, and talc, such as 7-talocyanine, dioxazine, and anthraquinone. Organic pigments such as
There are hydrophobic polymers dispersed in an organic solvent as described in Japanese Patent No. 149326.The particle size of the filler is suitably 1 mm to 100μ, and lrnp to I
on is preferably used. Deleting the above inorganic element, #i
Preferably, the material used is one in which the water-softening polymer compound described above is dispersed in an organic solvent as a preservative.

It has been known in the past that the addition of a filler improves the sensitivity and 1I9IJ degree, but the present inventors have discovered that the addition of a filler improves the water extensibility. This fact is thought to be because the addition of the filler reduces the intermolecular force between the polymer compounds constituting the photosensitive composition, but it is not clear. The amount of the above-mentioned filling is 1 to 60 liters of the total weight of the photosensitive layer, and 3 to 4 liters of the total weight of the photosensitive layer.
5 weight ratio is preferable.

The water developability is greatly influenced by the moisture absorption rate of the water-softening polymer compound and the amount thereof added, as well as the amount of the Km photosensitive polymer compound added.

The water-softening polymer compound, the photosensitive polymer compound, and the respective additive amounts Fi should be adjusted so that the performance of the ice-water softening polymer compound in terms of detection, storage stability, abrasion resistance, developability, etc. is maximized. Generally, a't of one photosensitive layer is determined by
The amount of the water softening polymer compound added to r i is 10
The amount of the photosensitive polymer compound added is preferably 10 to 8011%, preferably 30 to 701% by weight.

The photosensitive composition of the present invention can contain various additives as necessary. Exposure visualization agents for visualizing the exposure fIt image, such as dyes such as acridine dyes, cyanine dyes, merocyanine dyes, styryl dyes, and triphenylmethane dyes, and pigments such as the aforementioned 7-talocyanine, dioxazine, anthraquinone, etc. For example, combinations of aromatic and, carbonyl azide, sulfonyl azide, polyhalomethyl compounds, etc. and leuco dyes, etc., such as those described in Japanese Patent Publication No. 44-6413,
A spiropyran compound or the like that changes color depending on the tip of the tube can be added. The amount of addition thereof varies depending on the desired degree of opacity, but is approximately 1 to 5% by weight based on the total weight of the photosensitive layer. In addition, when an organic pigment is used as a filler, the above-mentioned exposed visible image agent is not particularly required. Furthermore, stabilizers, surfactants, plasticizers, thickeners, leveling agents, etc. can also be added as appropriate.

The photosensitive composition according to the present invention can be used as a photosensitive layer by disposing it on a support. Supports include paper, plastic films (e.g. cellulose diacetate, triacetate
! Cellulose, polyethylene terephthalate, polystyrene), aluminum plates, lead plates, copper plates, chrome-plated iron plates, etc. are preferably used.

In addition, in the case of a support having a surface of metal, especially aluminum, bag surface treatment such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphorus 1, etc., or anodizing treatment, etc. It is preferable that the As described in U.S. Patent No. 2,714,066, an aluminum plate is grained and then immersed in an aqueous sodium silicate solution; 1. After anodizing an aluminum plate, an alkali metal silicon plate immersed in an aqueous salt solution is preferably used.

The coating amount of the photosensitive layer provided on the support varies depending on the purpose of use of the photosensitive composition according to the present invention, but is about 0.5q/
d- to about 100 q/dm' is suitable, preferably about 5.0 my/dm' to about 501111/drp/t1b OIII cloth method can be performed using known coating methods such as dip coating, low 5111 cloth. , rotation coating, air knife I
11 cloth, spray coating, etc. can be used. Coating liquid lII modified Fi is determined from the coating method, coating conditions, and coating amount.

A water-soluble compound layer or a water-soluble photosensitive layer may be provided as an undercoat layer between the photosensitive layer obtained from the photosensitive composition according to the present invention and the support for the purpose of improving so-called opacity. However, if the amount of seeds in the undercoat layer is large, it will lead to poor storage stability and low resolution. ~5q/d is appropriate.

The photosensitive sodium bicarbonate-forming material thus produced is then developed with water.

The light source used for image gI is one that includes light in the wavelength range to which the photosensitive layer is sensitive. Generally, 300-45
A lamp including a wavelength of Q nm is suitable; for example, a mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, etc. are used.

The optically rotating portion of the photosensitive layer does not change during development, but the optically rotating portion is easily removed by lightly rubbing the surface with, for example, absorbent cotton or a sponge.

A lipophilic and hydrophobic resin image is thus formed on the support.

Hereinafter, the unexploded 8J4 will be described in detail as a nail based on an example, but the embodiments of the present invention are not limited thereto. Note that the moisture absorption rates shown below are values at relative f1180%.

Synthesis Example L 30g of polyhydroxystyrene (Maruzen Petrochemical 2 molecular weight approximately 10,000) t4007! (Completely dissolved in a mixed solvent of D dry pyridine and r-butyrolactone 60-,
α-cyanocinnamic acid chloride 9.8 at 50°C
5 g i was added little by little, and after the addition was completed, the reaction was allowed to proceed at 50° C. for 5 hours, and the reaction mixture turned into a pale yellow transparent solution. After leaving this overnight at room temperature, ice water 31 and IIk hydrochloric acid 8
0- into a mixed solution under stirring to generate a precipitate,
After suction filtration, washing with water, and drying, 35 g of polymer (photosensitive polymer compound) was obtained.

@Example 2 30g of polyvinyl alcohol [manufactured by Nippon Gosei Kagaku Kogyo ■, GL-05] was completely dissolved in 400d of a mixed solution of dry pyridine and r-butyrolactone 60-ts, kept at 50°C, and α- Cyanocinnamic acid chloride 6.18 g
was added little by little, and after the addition was completed, the reaction mixture was allowed to react at 50° C. for 5 hours, and the reaction mixture turned into a pale yellow transparent solution. After leaving this overnight at room temperature, it was poured into a mixed solution of 3 tons of ice water and #SO- under vigorous stirring to form a precipitate, which was filtered with suction.
Washed with water and dried 920g of polymer (g photopolymerization @ thing)
I got it.

Example 1 Ifo, the surface of 24 38 aluminum plates was grained using a nylon brush and a 400 mesh pumice stone water suspension, washed with water, and heated at 50°C in a 10 mm sodium hydroxide aqueous solution. Etching my friend for 20 seconds. This was desmutted by immersing it in a nitric acid solution for 20 seconds at room temperature, and then in a mimic acid solution at a temperature of 40° C. and a voltage of tOV.

Anodic oxidation treatment was performed at a current density of 2 A/dm' for 5 minutes. Next, III! It was immersed in a sodium silicate solution at a temperature of 80° C. for 5 minutes to seal the holes. The grain roughness of the obtained aluminum plate was RZ=4.5a (D
IN standard), anodized skin IItFi1511t/
It was d-.

A photosensitive solution having the following composition was coated on this substrate using a spin coating surface so that the weight of the coating after drying was 27 to 30 F/dm', and then dried at 55°C for 1 hour. A lithographic mortar plate was obtained.

Photosensitive solution] A negative film was bonded onto the above lithographic printing plate, and after exposure for 40 seconds at a distance of 1 m and a plate surface strength of 8 mW/- using an Idolfin 2000 [manufactured by Ichizaki Kame Kiku ■, 2 KW metal halide lamp], approximately The edges were immersed in tap water at 18° C. for 30 seconds, then gently wiped with absorbent cotton for 1 minute, and the non-printed areas were removed. After drying,
After performing gumming treatment by exposing for 2 minutes using the above exposure machine, this printing plate was set in sheet-fed offset printing*@Komori Sprint L-25B', and Ultra King (manufactured by Toyo Ink) red printing ink was used. When I printed it,
More than 100,000 good prints with good ink quality were obtained.

Comparative Example 1 As a comparative example, the following composition was prepared using a free radical polymerizable polyethylenically unsaturated compound and a 7-radical photopolymerization initiator as a photopolymerization system in place of the photosensitive polymer compound of the present invention. The photosensitive solution was applied to a K1ml cloth in the same manner as in Fabrication Example 1 and dried.

[Photosensitive liquid]

The printing plate of the above comparison and the printing plate of the present invention of Example 1 were each divided into three parts and subjected to forced storage at a water temperature of 55°C and a humidity of 3 to 4 degrees RH for 3 days, 6 days, and 9 days, respectively. . Thereafter, Kodak Step Meplet-2 was brought into close contact with the upper 1 pyro type lithographic printing plate, and exposed in the same manner as in Example 1. 1
After immersing it in tap water at 8°C for 30 seconds, it was lightly rubbed with absorbent cotton for 60 seconds to remove dust. Table 1 shows the number of solid steps of the current step tablet. In addition, after the Inkuri version was treated with T-gumming, the offset printing machine was added with additional markings, and the printed matter after printing 500 sheets was evaluated on the following three levels. ○: Good, Mu: Slightly dirty, X: Stained. The results f: are shown in Table 1.

Table I As is clear from Table 1, the comparative printing plate using the photopolymerization system 1 shows significant deterioration due to heat, but the printing plate which is an embodiment of the photosensitive composition according to the 2F invention has a good shelf life. It can be seen that it is excellent.

Example 2 The same procedure as in Example 1 was carried out except that the photosensitive solution having the above composition was used and the post-exposure after exposure was omitted. When 80,000 copies were printed using this printing plate, printed matter faithful to the original image was obtained.

Example 3 The same procedure as in Example 1 was carried out except that photosensitive tf& having the above composition was used. As in Example 1, when this printing plate was printed, more than 90,000 prints faithful to the original were obtained.

Example 4 A photosensitive solution having the above composition was applied to the aluminum plate of Example 1 in the same manner as in Example 1, dried, exposed to light, and developed with tap water. As a result, a lithographic printing plate with excellent resolution and ink receptivity was obtained. Over 80,000 copies were obtained.

Example 5 500 μm of aluminum was vacuum vaporized on one side of a polyethylene terephthalate film with a thickness of 1004 m, and the photosensitive solution of Example 1 was coated on the aluminum surface with a coating weight of 3 after drying.
It was coated using a rotary coater so that the coating was 0 q/d-. After drying at 55° C. for 1 hour, a negative film was adhered onto the photosensitive film and exposed in the same manner as in Example 1.

After immersing in tap water at 18° C. for 1 minute, the tip of the tube was removed by rubbing with absorbent cotton for 1 minute, and the aluminum in the lower layer was calculated.

Next, it was immersed for 1 minute in a solution containing 20 wt of phosphoric acid in 100 m of water, washed with water, and dried. As a result, a positive film with extremely high itgIIl optical properties without pinholes was obtained.

Horror Example 6 Spinning a photosensitive solution with the following composition on the copper surface of a copper/plastic plate so that the coating weight after drying is 30w/diK.
It was coated using II.

[Photosensitive liquid]

After drying at 55° C. for 1 hour, a negative film for printed wiring was brought into close contact with the photosensitive copper plate, and exposure and exposure were performed in the same manner as in Example 1 to calculate the copper plate of the lower layer. Next, when the board was immersed in 40 g of ferric chloride aqueous solution for corrosion, a good printed wiring board with no defects was obtained.

Patent applicant Konishi Roku Photo Industry Co., Ltd. Agent Patent attorney Akira Oshin Saka (a or 1 person) Procedural amendment (Issue) 1-'JSeptember 29, 1957! T! i Mr. Kazuo Sugi, Director-General of the Office of the Director General 1 ° II I'
1 Indication 1982 Patent Application No. 100626 2. Name of the invention 111s1 r'L'”;', (?+M・) (127) Roku Konishi Photo Industry Co., Ltd. 4, Agent 〒105/6 The number of inventions increased by 8 due to the amendment. Contents of the amendment V. Contents of the amendment 1 The words "aldol and acetal" are deleted from lines 11 to 12 of the central cylinder of the specification.

2. On page 9, lines 6 to 7, the phrase "methacrylamide-based monomer" is corrected to "methacrylic ester-based car body."

3 Same stop 1 negative 11th line r40: 15: 35
J is corrected to r50: 15: 35J.

4 On the 8th line of the 13th car, l'f: CHO-, NH,
1 [R: 11-, CHO-, N)l-J
and correct it.

and correct it.

1-6 On page 23, lines 9 and 10, the phrase ``No change, but'' is corrected to ``Not removed, but J.''

7. On page 25, line 12, ``6 Fuji J'' is corrected to read ``aqueous solution''.

8 In the first line of page 26 of the same document, the phrase ``baradiphenylamine'' is corrected to ``paradiazodiphenylamine J.''

Above 2 - Procedural amendment (direction: November 4, 1980 Kazuo Wakasugi, Commissioner of the Patent Office, 1, Indication of the case, Patent Application No. 100626 filed in 1982, 2, Inventors: 0, Photosensitive composition, 3, Make amendments) Relationship with the Patent Applicant's Case Patent Applicant 4/Agent 105 6, Number of Inventions Increased by Amendment 7, Subject of Amendment/Contents of Amendment to Procedural Supplementary Statement Submitted on September 29, 1980, 1 .1 Contents of amendment as per paper 8u 1 In the contents of the amendment to the procedural amendment submitted on January 4, 1981, paragraph 1 was changed to ``In the 5th paragraph lines 11 to 12 of Specification 1''.
Delete "like aldol or acetal."

” he exclaims.

that's all

Claims (1)

[Scope of Claims] [A] Diazo resin, [B] water-softening polymer compound, and (C) -CH as a crosslinking component in the main chain or 1lIl@
= C-Co- group (represented by Rti hydrogen atom, cyano group/% Loken atom t-).