JPH01949A - Photopolymerizable composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention "Field of Industrial Application" The present invention relates to a novel photopolymerizable composition,
More specifically, the present invention relates to an improved photopolymerizable composition that can be developed with a weakly alkaline aqueous solution containing no organic solvent.

"Prior Art" Alkali-developable photopolymerizable compositions basically consist of a photopolymerization initiator, a polyfunctional monomer, and a polymer binder having an alkali-solubilizing group in the molecule. Insoluble in aqueous solution.

Taking advantage of this property, it is widely used in photography, printing, metal surface processing, ink, paint, etc. (J. Kosar, "
Light 5intensive Systems J
J.

Wiley k 5ons, , New York,
/Pt! Annual, /! (see page 93) Various types have been developed depending on the purpose.

For example, after manufacturing a printed wiring board, a solid film-like photoresist layer is basically heat-pressed onto a substrate (hereinafter simply referred to as the substrate) such as a glass epoxy board covered with steel foil. Regarding the so-called dry film resist method, which includes a process of laminating layers, the special public Sho 4T! −
2! It is stated in Ko No. 31. In reality, the solid film-like photoresist layer (hereinafter simply referred to as photosensitive layer) is
A nine-structure photosensitive dry film resist material is used sandwiched between a film support and a protective film.

The method for using the photosensitive dry film resist material is to remove the protective film and then heat and press (laminate) the photosensitive layer so that it is in contact with the copper surface of the substrate. Image exposure is then carried out by stacking a film original with a negative image on the film-like support and exposing it to light.The film-like support is then removed and the unexposed areas are removed with a liquid (referred to as development). ) Form a resist image on the copper surface. The next etching process (dissolving and removing the copper surface part) and plating process (depositing powder, copper, etc. on the copper surface part)
In this step, the steel surface of the portion in close contact with this resist image is protected. Next, the resist@ is peeled off with a liquid (and further etched in some cases), and a printed wiring board is manufactured.

As a photosensitive layer, a so-called alkaline development type in which unexposed areas are removed (developed) with an alkaline aqueous solution, and a so-called solvent development type in which the unexposed areas are removed with an organic solvent are known. The alkaline developing type has attracted attention in recent years because it is advantageous in terms of occupational safety and health and the cost of the processing agent is low.

The following can be cited as representative documents regarding photopolymerizable compositions suitable for use as an alkali-developable photosensitive layer. (Since the main performance of the photosensitive layer is mainly determined by the binder contained therein, it is expressed as a binder.) It is a terpolymer of ethylhexyl/methacrylic acid), Shikosho 1l-31
No. P4/ (the binder is, for example, styrene/maleic acid mono-
n-butyl ester copolymer), Tokukosho! Section-2
IP17 (the binder is, for example, a quaternary copolymer of styrene/methyl methacrylate/ethyl acrylate/methacrylic acid), JP-A-12-29110 (the binder is, for example, a benzyl methacrylate/methacrylic acid copolymer) )
, Machikosho 111-/2!77 (the binder is, for example, a terpolymer of acrylonitrile/lambda-ethylhexyl methacrylate/methacrylic acid) and Tokkosho! ! -t
No. 10 (the binders are, for example, a terpolymer of methyl methacrylate/ethyl acrylate/acrylic acid and a partially esterified nine-styrene/maleic anhydride copolymer with imprononol).

``Problems to be solved by the invention'' Alkaline development photosensitive dry using these photosensitive layers
Despite the above-mentioned advantages, film resist materials still have many performance problems. That is, when the glass transition temperature of these dry film resist materials exceeds uo 0c,
Problems such as insufficient flexibility result in insufficient adhesion to the steel surface (substrate), chips are generated when cutting with a cutter knife, etc., and cause problems during exposure, and development time becomes longer. Jiru. In order to solve these problems, the copolymerization elements and composition ratio of the binder, ffi of the polymerizable unsaturated compound! The above problem can be solved by lowering the glass transition point of the dry film resist material to 4AO0C or lower by changing the ratio of binder and polymerizable unsaturated compound, or by adding a plasticizer, but storage When cold claw occurs, adhesion failure occurs at the edge of the photosensitive material, making it unsuitable for practical use. In this way, with conventional technology, it is not possible to solve the above performance problems at the same time, and the balance of each practical performance is considered, and the practical performance necessary for use is only barely satisfied. .

An object of the present invention is to provide a photopolymerizable composition that can be developed with an alkaline aqueous solution by improving each of the competing practical performances of the conventional technology to a practically sufficient level. It's about doing. In other words, it does not generate chips when cutting, has sufficient flexibility to be laminated to the substrate, has a high degree of adhesion to the substrate, has strong film strength before exposure, and has a low surface tackiness. It does not cause cold claws during storage, yet can be developed with a weak alkaline aqueous solution, has excellent swelling resistance to developing solutions in areas polymerized by image exposure, and has excellent adhesion to tents obtained by the tenting method. Another object of the present invention is to provide a photopolymerizable composition that can be peeled off by treatment with a dilute aqueous strong alkali solution containing no organic solvent.

A further object of the present invention is to faithfully reproduce a resist image on a manuscript (7 Ototools) and to achieve high resolution.

"Means for Solving the Problems" The present inventors have discovered that these objects can be achieved by using the following photopolymerizable composition, leading to the present application. That is, 1) a copolymer having an acidic group, 2) an addition-polymerizable unsaturated compound containing at least two ethylenically unsaturated double bonds in the molecule, and 3) containing at least seven types of photopolymerization initiators. The glass transition point is 0°
In the photopolymerizable composition of C or less, the photopolymerizable composition has the characteristic of further adding a metal compound containing a divalent or higher metal ion.

Using this composition, it is possible to suppress the occurrence of cold claw without degrading other properties such as lamination properties, chips, and development speed. It has an incredible effect of having sufficient resistivity against etching solutions such as ferric aqueous solution and ammonium persulfate aqueous solution, as well as in solder plating, birophosphate steel plating, copper sulfate plating, and other ordinary plating processes. The following turns out to be obtained.

Here, the glass transition point of the photopolymerizable composition was determined using Pyblon (DDV-nW) manufactured by Orientic Co., Ltd.
It is a ratio value measured under the conditions of temperature increase of 0 Hz and 2°C/min.

The copolymer having acidic groups used in the present invention is used as a binder for other components in the photosensitive layer, and determines the main performance of the photosensitive dry film resist.

As this binding agent (binder), the following are suitable. Special Publication No. 31-/≠06J- (the binder is a side chain oxygen acid-containing polymer), Special Publication No. 32711 No. 32711
No. I (the binder is, for example, methyl methacrylate/methacrylic acid copolymer), Machikoaki! ≠-3μ327 (the binder is, for example, a terpolymer of methyl methacrylate/no-ethylhexyl methacrylate/methacrylic acid),
Special Publication No. 61 (Binding agent is styrene/
maleic acid mono-n-butyl ester copolymer)
, Tokko Sho It-33μ13 (the binder is, for example, a terpolymer of ethyl methacrylate/ethyl acrylate/methacrylic acid), Tokko Sho! ≠-2! ? ! No. 7 (the binder is, for example, a quaternary copolymer of styrene/methyl methacrylate/ethyl acrylate/methacrylic acid), JP-A-Sho!
Coater 2r70 (the binder is, for example, benzyl methacrylate/methacrylic acid copolymer), Shikosho sr-/2
No. J'77 (the binder is, for example, a terpolymer of acrylonitrile/methacrylic acid-noethylhexyl/methacrylic acid), Tokkosho! ! No.-6210 (the binders are, for example, methyl methacrylate/ethyl acrylate/acrylic acid ternary copolymer and nine-styrene/maleic anhydride copolymer partially esterified with isochloro A-nol)
, and Machikai Showa 11-//4c (the binder is, for example, methyl methacrylate/methacrylic acid/coethylhexyl acrylate terpolymer or methacrylic acid/methyl methacrylate/2-ethylhexyl acrylate). / n-butyl methacrylate quaternary copolymer).

Maku, waiting for the show 60-2! IJi! No. 2 (Binder is methacrylic ester/acrylic ester/methacrylic acid/
is a quaternary copolymer of acrylic acid).

The polymerizable unsaturated compound suitably used in the photopolymerizable composition of the present invention may be one containing at least two ethylenically unsaturated double bonds in the molecule and capable of addition polymerization. . And /ffi or more compounds can be present.

Preferred specific examples include acrylic acid or methacrylic acid esters of polyols, that is, diethylene glycol diethylene (meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(
meth)acrylate, nonaethylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol is meth(meth)acrylate, dipentaerythritol hexa(meth)acrylate
), /, 4-hexanediol di(meth)acrylate, etc., or bis(meth)acrylamides, i.e., methylenebis(meth)acrylamide, ethylenebis(meth)acrylamide, m-xylylenebis(meth)acrylamide, etc., or urethane group. Compounds containing, i.e., di(comethacryloxyethyl) J, 4 cm)
It can be obtained by further reacting β-hydroxyalkyl (meth)acrylate with a terminal incyanate compound obtained by reacting lylene diurethane, di(-monoacryloxyethyl)hexamethylene diurethane, or a polyol with a diisocyanate in advance. (meth)acrylic urethane oligomer, NJ, tld', 2 mols of Hiro-tolylene diisocyanate and 3 mols of ethylene glycol
Corbis(hydroxyethyl)pronone, moss 2-bis(
Examples include diacrylates such as hydroxyethoxyphenyl) furonone, co, and λ-bis(hydroxyethoxyethoxyphenyl)propane.

The content of the polymerizable unsaturated compound is preferably about 7.7-43% by weight, and more preferably about 1j-≠j% by weight, based on the total weight of the photopolymerizable composition.゛The photopolymerization initiator suitably used in the composition of the present invention is a single compound that can initiate the polymerization of the polymerizable unsaturated compound, or preferably a photopolymerization initiator that is a combination of two or more compounds. All systems can be used. Preferably, the photoinitiator or photoinitiator system has a molecular weight of about 3000 to roo.
oh, preferably at least one component having a molecular extinction coefficient of at least about 10 within the range of 3300 to zooo^.

Preferred specific examples of the photopolymerization initiator include the following compounds. Aromatic ketones, e.g. evabenzophenone, l-bis(dimethylamino)benzophenone, ≠14A'-bis(diethylamine)benzophenone, ≠-methoxyhiro'-dimethylaminobenzophenone, μIμ'-dimethoxybenzophenone, ≠-dimethylamino Benzophenone, μm dimethylaminoacetophenone, benzyl, anthraquinone, 2-tert-butylanthraquinone, co-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, cochloro-thioxanthone, co-, hiro-dimethylthioxanthone, λ, ≠-diethylthioxanthone, Fluorenone, acridone and benzoin, benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal and co, Hiro,! - triarylimidazoles, such as co(〇-chlorophenyl)-1,j-diphenylimidazole, co(0-chlorophenyl)-1,j-diphenylimidazoles;
-chlorophenyl)-Hiroshi.

! -di(m-methoxyphenyl)imidazole dimer,
λ-(0-fluorophenyl)-4A, j-diphenylimidazole dimer s'('-methoxyphenyl)
-U,j-diphenylimitasol ditL λ-(p-
methoxyphenyl)-≠, j-diphenylimidazole dimer, and polyhalogen compounds, such as carbon tetrabromide, phenyl) IJ dibromotylsulfone, phenyl trichloromethyl ketone, and Machikai Sho 13-/J34t
λr number, special public show j7-/II number, special public show t7-405
'J, US Patent No. 367! Compounds disclosed in each publication. A combination of two or more types, e.g.

≠、! - a combination of a triarylimidazole dimer and 2-mercaptobenzoxazole or leuco crystal violet, or a combination of ≠, ≠'-bis(dimethylamino)benzophenone and benzophenone described in U.S. Pat. No. 31427/l/; benzoyl-N-methylnaphthothiazoline in combination with benzoin methyl ether and as described in U.S. Pat.

≠-Bis(trichloromethyl)-4, Hiro-methoxyphenyl) IJ azole combination, 7tWg Kaisho! 7-
The combination of dimethylthioxanthone and Hiro-dialkylamine benzoate described in IJ 40λ is exemplified.

The content of the photopolymerization initiator or photoinitiator system is preferably from about o, i to 10 parts by weight based on the total weight of the photopolymerizable composition.
t% and more preferably from about 0.2 to t%.

The metals forming the metal compound suitably used in the photopolymerizable composition of the present invention include metals such as aluminum, tal, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, copper, zinc, cadmium, and aluminum. , gallium, indium, germanium, tin, lead, antimony, bismuth, etc., which form divalent or higher ions.

Further, metal compounds include metal oxides, metal salts, metal hydroxides, metal complexes, chelates, organometallic compounds, and the like.

Specifically, for example, zinc acetate, zinc oxide, zinc acetylacetonate, zinc benzoate, zinc carbonate, zinc chloride,
Zinc citrate, zinc di-n-butyldithiocarbamate, zinc diethyldithiocarbamate, dimethyldithiocarbamine! Zinc N-ethyl-N-phenyldithiocarbamate, zinc formate, zinc hydroxide, zinc lactate, zinc oleate, zinc oxalate, zinc perchlorate, zinc peroxide, zinc phosphate, zinc phthalocyanine, piperidine/ -N-
Zinc dithiocarbamate, zinc pyrophosphate, zinc salicylate, zinc silicate, zinc sulfate, zinc tartrate, zinc thiocyanate, toluene-3,≠-zinc dithiol, zinc butylade, etc.; zirconium acetylacetate $-t, zirconium oxide, zirconium oxychloride, zirconium sulfate, zirconocene dichloride, zirconyl chloride, ? il [zirconium compounds such as zirconyl, zirconium propylade, zirconium butylade; barium acetate, barium aluminate, 1
Barium borate, barium bromide, barium carbonate, barium chloranilate, barium chlorate, barium chloride,
Barium chromate, barium 2-cyanoethyl phosphate, barium cyclohexanebutyrate, barium ≠-diphenylamine sulfonate, barium formate, barium hydroxide,
Barium lactate, barium nitrate, barium oxalate, barium oxide, barium peroxide, barium phosphate, barium stearate, barium sulfate, barium thiocyanate,
Barium compounds such as barium thiosulfate, barium titanate, etc.; calcium acetate, calcium benzoate, calcium bromide, calcium carbonate, calcium chloride, calcium λ-ethylhexanoate, calcium formate, calcium gluconate, calcium glycerophosphate, hydrogen phosphate Calcium, calcium hydroxide, calcium lactate, calcium nitrate, calcium oleate, calcium oxalate,
Calcium oxide, calcium palmitate D, 4
Calcium compounds such as calcium nitrate, calcium phosphate, calcium phosphite, calcium pyrophosphate, calcium salicylate, calcium silicate, calcium stearate, calcium sulfate, calcium sulfite, calcium tartrate, calcium thiocyanate; magnesium acetate, magnesium phosphate, magnesium benzoate , magnesium bromide, basic magnesium carbonate, magnesium chloride, magnesium cyclohexane butyrate, magnesium hexafluorosilicate, magnesium lactate, magnesium oleate, magnesium oxalate, magnesium oxide, magnesium perchlorate, magnesium phosphate, magnesium phthalocyanine, silica. Magnesium compounds such as magnesium acid, magnesium stearate, magnesium sulfate, magnesium compounds), magnesium ethylate, magnesium propylate, iron acetylacetonate, iron alum, iron citrate, iron oxalate, iron benzoylacetonate, Iron bromide, iron chloride, iron citrate, iron hydroxide, iron lactate, iron naphthenate, iron nitrate,
iron oxalate, iron oxide, iron perchlorate, iron phosphate, iron sulfate,
Iron compounds such as methyl titanate, ethyl titanate,
Propyl titanate, butyl titanate, coethylhexyl titanate, stearyl titanate, cresyl titanate, octylene glycol titanate, titanium chloride, titanium oxide, titanium oxyacetylacetonate, titanium potassium oxalate, titanium tetrabutoxide, titanium tetraline propoxide, titanium compounds such as; tin compounds such as tin acetate, tin bromide, tin chloride, tin oxalate, tin oxide, tin sulfate, Fukumi i-Higashi;!
Antimony compounds such as antimony chloride, antimony bromide/antimony oxide; indium compounds such as indium chloride, indium oxide, indium hydroxide, indium sulfate; aluminum acetate, aluminum borate, aluminide, toxide, aluminum chloride, cyclohexane Aluminum butyrate, aluminum 2-ethylhexanoate, aluminum hydroxide, aluminum impropoxide, aluminum lactate, aluminum laurate,
Aluminum monostearate, aluminum nitrate, aluminum oleate, aluminum sulfate, aluminum oxide, aluminum chloride 7-talocyanine, potassium aluminum sulfate, aluminum stearate, aluminum triethoxide, aluminum triphenyl,
Aluminum compounds such as acetic acid steel, cupric carbonate, cupric chloride, citric acid steel, cupric formate, cupric oxalate, steel oxide, cupric perchlorate, steel pyrophosphate, tartaric acid Examples include, but are not limited to, divalent copper compounds such as cupric thiocyanate, cupric thiocyanate, and copper xanthate.

Among these, weakly acidic and neutral salts are preferred.

WK zinc compounds, calcium compounds, aluminum compounds, zirconium compounds, titanium compounds, and tin compounds are preferred, and zinc compounds, aluminum compounds, and zirconium compounds are particularly preferred.

The above-mentioned metal compound may be dissolved in an organic solvent and added and mixed to a mixture of a polymer having an acidic group, an addition polymerizable unsaturated compound, and a photopolymerization initiator, or it may be added and mixed in the form of a powder. It's okay. At this time, two or more kinds of metal compounds may be mixed and used.

The amount of the ta metal compound added is as follows. In the case of a polymer having a heptavalent acidic group, the amount of the divalent metal compound added is 171,000 to 773 mol of the acidic group, preferably /
/ j 00-/ / / 0 mol, preferably 7730 to 7710 mol. The amount of trivalent metal compound added is about 27 J for each divalent metal compound, about 1/2 of the amount for a covalent metal compound for each divalent metal compound, and so on. Further, in the case of a polymer having a tetravalent acidic group, the amount of the metal compound added is, for example, one times the amount added in the case of having a polymer having a heptavalent acidic group.

The photopolymerizable composition of the present invention contains a metal compound containing a metal ion having a covalent value or higher, a photopolymerization initiator, a polyfunctional ethylenically unsaturated compound, and a binder as essential components, and may optionally prevent thermal polymerization. Agents, plasticizers, dyes, color change agents, monofunctional ethylenically unsaturated compounds, adhesion promoters to the substrate surface, and other auxiliary agents may be used in combination, thereby improving the desired photographic properties of the photoresist. Properties such as bakeout properties and film properties can be adjusted.

The thermal polymerization inhibitor is added to prevent thermal polymerization or temporal polymerization of the photopolymerizable composition of the present invention, and examples thereof include p-methoxyphenol, hydroquino-7, t-butylcatechol, and pyrogallol. , λ-hydroxybenzophenone, ≠-methoxycohydroxybenzophenone, phenothiazine, chloranil, naphthylamine, β
-su7toll,co,4-di-t-butyl-p-cresol, nitrobenzene, dinitrobenzene, hyfuric acid,
p-) luidine and the like.

Plasticizers are added to control the film properties of the photosensitive layer and resist image, and include, for example, dibutyl 7 tallate, dibutyl 7 tallate, dioctyl 7 tallate,
7-thalic acid esters such as diallyl phthalate 5) Glycol esters such as lyethylene glycol diacetate and tetraethylene glycol diacetate; Noric acid esters such as tricresyl phosphate and triphenyl phosphate; p-toluenesulfonamide, benzenesulfonamide, Amides such as N-n-butylacetamide; aliphatic dibasic acid esters such as diisobutyl azide, dioctyl adipate, dimethyl sepacate, dioctyl azelate, dibutyl maleate; triethyl citrate, tributyl citrate, glycerin Examples include tria heptyl ester, butyl laurate, 4Llj-jepoxycyclohexane-/, dioctyl 2-dicarboxylate, and the like.

Examples of pigments are brilliant green, eosin, ethyl violet, erythrosin B, methyl green, crystal violet, pacific tuxin, phenolphthalein, 3-diphenyl triazine, alizarin red S1 thymolphthalein, methyl violet JB, quinal. Gin red, rose bengal, methanyl
Yellow, thymol sulfo-7 thalein, xylenol blue, methyl orange, orange ■, diphenylthiocarbazone, 2,7-dichlorofluorescein, paramethyl red, Congo red, benzopurvalin φB1 benzopurpurin B, α-su7 thalein , Nile Blue A, Phenacetarin, Methyl Violet, Malachite Green, / 7 Kushin, Oil Blue @dos (
Manufactured by Orient Chemical Industry ■, Victoria Pure Blue B
These include OH, Spironzolu 〇N (manufactured by Hoshidani Chemical Industry Co., Ltd.), Rhodamine B, Rhodamine 6G, and the like.

A color change agent is added to the photopolymerizable composition so that it can provide a visible image upon exposure to light. Specific examples of these include, in addition to the above dyes, diphenylamine, dibenzylaniline, triphenylamine, cyxylaniline, diphenyl-p-phenylenediamine, p-toluidine, 4C
, l-biphenyldiamine, o-10 loaniline, D*
Examples include D'*D"-hexamethyltriaminotriphenylmethane, p,p'-tetramethyldiaminotriphenylmethane, p,p',p"-triaminotriphenylcarbinol, and leucomethyl violet.

Specific examples of the adhesion promoter include benzimidazole, benzthiazole, benzoxazole, benztriazole, and other compounds described in Japanese Patent Publication No. Sho-to-ylZy, Komel Kabutobenzthiazole, Komel Kabutobenzimidazole, and the like. ! Examples include the compounds described in No.-702.

The photopolymerizable composition of the present invention is used by dissolving the above-mentioned various components in a solvent and applying the solution onto a desired support by a known method. In that case, the solvents used are ethylene dichloride, monochlorobenzene, cyclohexanone, methyl ethyl keto/, acetone, methylcerone acetate, ethyl acetate, methyl acetate, methanol, ethanol, n-propanol, impropanol, n-butanol, Methyl selonulf, toluene, xylene, etc. alone or as a mixture.

The photopolymerizable composition of the present invention can be developed with a weak alkaline aqueous solution. Add a small amount of organic solvent that is miscible with Makusui (approximately 20%
may also contain

Suitable bases to be added are selected from alkali metals or heptammonium, fluoroammonium hydroxides, carbonates, bicarbonates, silicates, phosphates, pyrophosphates, acetates and amines. Specific examples of these include lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, trimethylbenzylammonium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, phosphorus Examples include sodium acid, potassium phosphate, sodium pyrophosphate, sodium acetate, jetanolamine, and triethanolamine. Firstly, a solution of sodium carbonate is preferred.

The photopolymerizable composition of the present invention has excellent flexibility during film formation, excellent adhesion to the substrate, and easy resist peelability, and also provides faithful reproducibility of original images and high resolution. That's surprising. As a result, the substrate can be processed with high precision.

The photopolymerizable composition of the present invention is suitable as a photosensitive layer of a photosensitive dry film resist material. In this case, the thickness of the photosensitive layer is suitably in the range of o, iμ to 200μ, preferably in the range of 7μ to 200μ. Suitable supports are selected from films of polyamides, polyolefins, polyesters, vinyl polymers, cellulose esters, etc., and have a thickness of 3 microns to 700 microns. A flexible support suitable for holding is approximately It is a transparent polyethylene terephthalate film with a thickness of μ.

Suitable protective films include polyolefins, and particularly preferred are polyethylene films with a thickness of 20 to 21 microns.

Although the compositions of the invention are particularly applicable to photoresists, they are also advantageous for other applications. For example, it can also be used to produce a lithographic printing plate (28 plate) to which photosensitivity has been imparted in advance. In this case, the coating radius is generally o, i when drying.
~10.0? /m2 is suitable, particularly preferably 0.1
-j, 017 m2. Suitable supports include hydrophilic treated aluminum plates, silicate treated solid aluminum laminate plates, anodized aluminum plates, grained aluminum plates, and silicate electrodeposited aluminum plates. In addition to that, we also produce zinc plates, stainless steel plates,
Examples include chromium-treated copper plates, hydrophilic-treated plastic films and paper.

When the photopolymerizable composition of the present invention is used to produce color proofs for printing, overhead projector films, and films for second original drawings, suitable supports include polyethylene terephthalate film, cellulose triacetate film, etc. Examples include transparent films such as these, and those obtained by chemically or physically matting the surface of these plastic films.

When the photopolymerizable composition of the present invention is used to produce a film for a photomask, a suitable support is a polyethylene terephthalate film on which aluminum, an aluminum alloy or chromium is vapor-deposited, and a colored layer is formed on a polyethylene terephthalate film. Films can be mentioned.

L, Ho1liday! It is known that when metal ions are added to organic polymers containing acidic groups, the physical properties change. 1rIon
ic PolymersJ (Applied 5cie
ncePublishers Ltd, London,
/ri7j, published in 2013). 1*, Japanese Patent Publication No. 47-
No. 2341sr discloses that an alkali metal hydroxide is added to a photopolymerizable composition containing a binder having a carboxylic acid group to increase the flexibility of the photosensitive layer and also to improve the development and stripping speed. Techniques for increasing this are disclosed.

On the other hand, the present inventors have developed a composition that has excellent flexibility, development speed, stripping properties, etc. and has a glass transition point of ≠00C or lower, by adding a metal compound with a covalent value or higher. It has been found that the properties are significantly improved, and such an effect is completely unexpected from the above-mentioned known technology. The reason why the present invention suppresses the occurrence of cold claws is thought to be because the ionic bond between the binder and metal ions stops the binder molecular chain from slipping, but this ionic bond is weak in the case of m ions such as alkali metals. It seems that it has no effect.

Hereinafter, the present invention will be explained in more detail based on Examples and Comparative Examples, but the present invention is not limited to these Examples.

[Examples and comparative examples]

Example 1 ~ Comparative Example ~ Using each binder in Table I, each metal compound in Table I was added to the photosensitive solution shown below, and coated with a rod coater. Dry film thickness on μm thick polyethylene terephthalate film is approx.! Apply to 0μm, 10
Dry in OOC oven for 2 minutes.

A solution of the binder (listed in Table I) in 4tO wt % methyl ethylcarbonate j7. jf ethyl Michler's ketone 0, 0449 benzophenone o, 4try tribromomethyl phenyl sulfone o, izy polypropylene glycol diacrylate (Mw=r12) 7. Of polyethylene glycol diacrylate (MW=74L2) 2 , 0 t3.
6-bis(diphenylamine)fluorane 0.0? ? /-722-3-morpholinomethyl-/, J, 41 monotriazole-corchion 0. θ/2 Victoria Pure Blue BOHO, 0/f Unexposed film characteristics were evaluated using K as shown below.

To evaluate the degree of generation of chips, after laminating the unexposed film to the substrate, quickly tear and cut the area around the substrate with the back of a cutter knife, and judge by whether or not powdery chips are generated. ``flj adhesion strength was evaluated with the substrate unexposed.Cold flow property was evaluated by sandwiching the unexposed film between a film support and a retention film and leaving it at 7+?, !0vsX!I
Cut into squares of ts, stack 30 to 30 pieces, place a non-deformable plate on top of this so that the load is evenly applied, put a weight on top of it, 4co 0C, to 7 Changes in the edges were observed for days. Those with no change in the edges are ranked with ○, those with slight K oozing are marked with 9, and those where the resist protrudes beyond the edges are ranked with an X mark.

Developing suitability is determined by peeling off the protective film, laminating the unexposed film on the substrate, then peeling off the polyethylene terephthalate film that is the film support, and using an alkaline micro-developing machine. Next, spray a 7% by weight aqueous sodium carbonate solution of IO'C at a pressure of 7 m''/kg. By this operation, the entire surface can be dissolved and cleaned in the shortest possible time without leaving any unexposed laminated films. Find this and use it as the development speed.

Image formation characteristics after exposure, etc. were evaluated as follows.

After smoothing the surface and drying it, apply an A-shaped laminator (Du, Fo) so that the coating surface contacts the copper surface.
Laminated at t2o 0c using T-T (manufactured by NT).

Wiring pattern (high-contrast transparent image gR in which a conductor noturn (line width iooμ) appears as a transparent part on an opaque background) is exposed to lμOmJ/crIL2 through t&: (J kW ultra-high pressure mercury lamp double-sided simultaneous exposure device HMW) −
1-N type (made of oak ■) is used). Peel off the polyethylene terephthalate film and add a 1% by weight aqueous solution of 306C sodium carbonate. Remove the unexposed areas by spraying with 9/cut2. Observe the image formation status and line breakage of the obtained resist, and also measure the thickness of the line width. Next, I printed a resolution chart in place of the wiring pattern, removed the unexposed areas in the same way as above, and observed the line width that would allow me to distinguish the resist image to determine the resolution. In the same way, resist films were laminated on both sides of a double-sided steel-clad laminate having 100 through holes with an inner diameter of 2.1 ms, and a 3 kW ultra-high pressure mercury lamp double-sided simultaneous exposure device 1HMW-≦-N type (made by Oak ■) was used. Then, a circular pattern with a land diameter of 3.0 mm was printed on the through hole, and the unexposed portion was removed in the same manner as above to form a pattern. The ninth step in evaluating the strength of a tent is this board! Yu/12
After passing through the hot water spray, count the number of tents that remain without tearing, and calculate the survival rate (chi) of the tents.

After baking and developing the conductor pattern, the nine steel clad laminates were sprayed with a 3I% aqueous solution of ferrous chloride (≠o'C).

/ , j 'Q/art 2) etching friend. Etching is performed until the steel in areas not covered by the resist lines is completely dissolved. The etched plate is washed with water and dried to obtain a steel conductor pattern still covered with resist. This resist was immersed in a 3% potassium hydroxide aqueous solution of ZO 0C, and the time required to peel it off from the steel surface (peeling speed) was carefully examined.

These results are shown in Table ■.

As is clear from the results in Table H, when a hard binder is used as in Comparative Example 1, cold 70- does not occur, but chips are generated and the TE development speed is slow. If a binder is used after softening as in Comparative Example 3 and ≠, no chips are generated and the development speed is fast, but cold claw occurs. In this way, simply changing the properties of the binder and changing the ratio cannot overcome the competitive relationship between multiple physical properties. On the other hand, when the material is suitably softened, a binder is used, and the metal compound disclosed in the present invention is added as in the example, no chips are generated and no cold flow occurs. The primary and developing speeds are well within the practical range. Further, the quality of the resist image is good, the reproducibility of the image width is excellent, and high resolution can be obtained. Furthermore, the strength of the tent is high and the peeling speed is also good.

Claims (1)

[Scope of Claims] 1) a copolymer having an acidic group, 2) an addition polymerizable unsaturated compound containing at least two ethylenically unsaturated double bonds in the molecule, 3) a photopolymerization initiator at least 1. A photopolymerizable composition comprising one type of photopolymerizable composition having a glass transition point of 40° C. or lower, further comprising a metal compound containing a divalent or higher metal ion.