JPS63296036A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To prevent the titled composition from the formation of a chip and the generation of cold flow in a dry film by incorporating a specified compd. in the titled composition. CONSTITUTION:The titled composition contains an addition polymerizable unsatd. compd. (A), having two or more of ethylenic unsatd. double bonds in a molecule, a photopolymerization initiator (such as benzophenone) and a binding agent (B). And, the copolymer component of the component (B) is exemplified by the addition polymerizable compd. having two or more of the ethylenic unsatd. double bonds in the molecule such as a (meth)acrylic acid ester of polyol, and said exemplified compd., etc., is used for the component (A). The component capable of copolymerizing with the component (A) is exemplified by a (meth) acrylic acid ester, and can be copolymerized with a monomer having an acidic group to enable the development in a weak alkaline aqueous solution.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Application of the Invention) The present invention relates to a novel photopolymerizable composition, and particularly to a photopolymerizable composition that can be developed with a weakly alkaline aqueous solution containing no organic solvent.

(Prior Art) Photopolymerizable compositions are widely used for photoresists, letterpress printing, relief images, and the like. These are generally developed after being exposed to UV light, and depending on the developer used for this development, organic solvent type (those that can be developed with organic solvents) and alkaline aqueous type (weak alkaline aqueous solution, or those that are miscible with water) (can be developed with a mixture of a strong organic solvent and a weak alkaline aqueous solution). Initially, organic solvent type photopolymerizable compositions were mainstream, but in recent years there has been an active shift to alkaline aqueous solution type photopolymerizable compositions due to cost and pollution control considerations. In either case, however, it is generally the binder component of the photopolymerizable composition that determines the solubility and other properties of the photopolymerizable composition.

Binders used in photopolymerizable compositions that can be developed with organic solvents include binary copolymers of methyl methacrylate/ethyl acrylate, ternary copolymers of methyl methacrylate/methacrylic acid/ethyl acrylate, etc. Medel methacrylate copolymers are common.

On the other hand, there are many known binders used in photopolymerizable compositions that can be developed with weakly alkaline aqueous solutions. Akihiro j-J core/≠ issue (the binder is, for example, methyl methacrylate/methacrylic acid copolymer), Tokuko Aki!
! - Jyri No. 41 (the binder is, for example, styrene/maleic acid mono-n-7' methyl ester copolymer), share 1
[t4-JJ4cIJ (the binder is, for example, a ternary copolymer of ethyl methacrylate/ethyl acrylate/methacrylic acid), and JP-A-5R-II≠2 (the binder is, for example, a terpolymer of ethyl methacrylate/ethyl acrylate/methacrylic acid). Methacrylic acid/2-ethylhexyl acrylate terpolymer or methacrylic acid/
Methyl methacrylate/monoethylhexyl acrylate/
n-butyl methacrylate base copolymer).

Photopolymerizable compositions containing these binders are used for various purposes, and in recent years, their use as dry film resists has been expanding by 30%. This dry film resist method is described in Tokko Sho-Yo-JJ Co. No. 3/W, S, D.
e Forest Author Photoresist J Mc
Graw-Hill, New York, /ri7! ,
/A3-472 page etc.

(Problems to be Solved by the Invention) However, although photopolymerizable compositions containing the above-mentioned binders have advantages in certain applications, they have the following drawbacks, particularly when used as photoresists. It shows. Photopolymerizable compositions that are compatible with this method have, for example, good developability and resist stripping properties (but in the polymerized state, resistance to etching or plating solutions), low tackiness, high adhesion to substrates, etc., as well as moderate flexibility. Flexibility is required. If this flexibility is insufficient, small pieces of photoresist called cutting chips will scatter when the film is cut. This cutting powder itself is sticky, but it becomes sticky when it absorbs moisture, and if it adheres to the dry film laminated on the substrate attached to the mask, it will cause problems such as blurring during exposure. However, if you try to add flexibility, the problem of chips will be solved.

Cold flow occurs. The occurrence of this cold flow causes failure of the fusion at the ends of the roll during storage of the dry film. In particular, bottle dry film resists that can be developed with alkaline aqueous solutions tend to suffer from cold flow due to moisture absorption during storage. For this reason, various countermeasures have been considered, such as the Special Publication Shoj'l-212!
No. 7, Tokukai Akira! 7-2 (No. 7732, etc.) describes improvements from the binder composition. However, although these methods improve cold flow resistance, the problem of chipping occurs. It was extremely difficult to satisfy both sex and cutting power at the same time.

(Object of the Invention) An object of the present invention is to improve the cold resistance of a photopolymerizable composition free from the problem of chips.

(Means for Solving the Problems) The present inventors have discovered that the above problems can be solved by using a surface photopolymerizable composition as follows, and have arrived at the present application.

The photopolymerizable composition of the present invention contains an addition polymerizable unsaturated compound containing at least two ethylenically unsaturated double bonds in one molecule, a photopolymerization initiator, and a binder, and the Wa binder is It is characterized in that an addition polymerizable unsaturated compound containing at least two ethylenically unsaturated double bonds is used as a polymer component.

Each component of the photopolymerizable composition of the present invention will be explained below.

Examples of the addition-polymerizable unsaturated compound containing at least two ethylenically unsaturated double bonds in the molecule, which is contained as a copolymerization component in the binder, include the following compounds. Examples of ethylenically unsaturated double bonds include acryloyl groups, methacryloyl groups, vinyl groups, and the like. Examples of compounds containing an acryloyl group or a methacryloyl group include acrylic acid or methacrylic esters of polyols.

Namely, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, nato2-ethylene glycol di(meth)acrylate, nonaetelene glycol di(meth)acrylate, dodecaetelene glycol di(meth)acrylate, and tetradecaethylene. Glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpronoξtri(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol is meta(meth)acrylate Acrylate.

dipentaerythritol hexa(meth)acrylate),
/, A-hexanediol di(meth)acrylate, etc.
Alternatively, acrylamide or methacrylamide obtained from polyamines, i.e. methylene bis(meth)acrylamide, ethylene bis(meth)acrylamide, m
- xylylene bis(meth)acrylamide, etc., or a compound containing a urethane group, i.e., di(co-acryloxyethyl)-λ, 4 cm) lylene dicretane, di(co-acryloxyethyl) hexamethylene diurethane, or β-
A (meth)acrylic urethane oligomer obtained by reacting a hydroxyalkyl (meth)acrylate, for example, 1 mol of β- to a reaction product of 2 mol of 2゜hiro-tolylene diincyanate and 3 mol of ethylene glycol. Relugomer etc. obtained by reacting hydroxyethyl acrylate, or acrylic acid and methacrylic acid esters modified and derived from bisphenols, i.e. reaction products of bisphenol A-epichlorohydrin epoxy resin prepolymer and acrylic acid or methacrylic acid. , acrylic acid, methacrylic acid esters of bisphenol A fullkylene oxide adducts or hydrogenated products thereof, and esters of aromatic polyhydric carmenic acids, that is, compounds represented by the following structural formula.

Furthermore, examples of compounds containing a vinyl group as an ethylenically unsaturated double bond include divinylbenzene, diallyl phthalate, diallyl maleate, and the like.

The content of these addition-polymerizable unsaturated compounds in the binder is 0,000/mo1% to t.

Mo1% is appropriate, preferably o, o o t
It is preferably 1% to 1%, more preferably 1% to 1%, omol%.

If the content is less than 0.000/mo, the cold resistance is 7.
0- Inferior gender? ), j, Omo of 1% or more tends to cause gelation during polymerization and/or poor development.

As the monomer to be copolymerized with these addition-polymerizable unsaturated compounds, it is possible to use addition-polymerizable monomers containing one ethylenically unsaturated double bond in the molecule.

Typical monomers include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, methacrylic Wl-ethylhexyl, benzyl methacrylate, 2-hydroxyethyl methacrylate, methyl acrylate, and acrylic. Ethyl acid, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, co-hydroxyethyl acrylate, acrylonitrile, styrene, α-methylstyrene,
vinyltoluene, acrylamide, methacrylamide,
Examples include vinyl methyl ketone, vinyl propyl ketone, vinyl methyl ether, vinyl ethyl ether, vinyl hexyl ether, and vinyl acetate.

In the case of a photopolymerizable composition that can be developed with a weakly alkaline aqueous solution, it is desirable to copolymerize 10 to 60 mo1% of a monomer having an acidic group with these monomers. Examples of acidic groups include carboxyl groups, sulfonic acid groups, phosphoric acid groups, etc., and examples of monomers having carboxyl groups include acrylic acid, methacrylic acid, hexamaric acid, cinnamic acid, itaconic acid, maleic acid, etc. As a monomer having a sulfonic acid group, vinylbenzenesulfone a! , 2-7crylamide-co-methylzolonone sulfonic acid, etc., as monomers having a phosphoric acid group, registered trademarks of Hosmer M (acid phosphoxyethyl methacrylate) and Hosmer CL (J-chlorocor) manufactured by Oil Products ■ are used. Nippon Kayaku's registered trademark KAYAMER series PM-,2 (bis(
(methacryloxyethyl) 7 phosphate), PA-/
(acryloxyethyl 7m7a)), PA-co(bis(acryloxyethyl)phosphate), (registered trademark VINYE)-R, manufactured by Daiton Chemical Industry Co., Ltd., and PS-A. Binders containing these as copolymer components can be prepared by any polymerization technique known to those skilled in the art. A synthesis example is shown below.

Synthesis example (copolymer of 4/in Table 1) Methyl methacrylate 44.4P, methyl methacrylate,
ip, 2-ethylhexyl acrylate 37°rP, benzyl methacrylate/u, Jli, tetraethylene glycol diacrylate 00j4cμm, λ, 2'-asohis (2,4cm dimethylvaleronitrile) o, yztp
, methyl ethyl ketone yr.

7, l-methoxy-coprobanol P! , 71!
The mixture was placed in a 00117 flask and heated and stirred at TO0C for a required period of time under a nitrogen stream. Furthermore, λ′-azobis(-2,4&-
dimethylvaleronitrile) o, P.

After cooling, 7p of methyl ethyl ketonta Ir was added to form dimethacrylic acid/methyl methacrylate/λ-ethylhexyl acrylate/benzyl methacrylate/tetraethylene glycol diacrylate). (Jr.

l:j Hiro, ri://, 7:Il,! :0. Imol ratio)
Methyl ethyl ketone, l-methoxy-coprobanol (2
A 6% by weight solution of 4c (=7 weight ratio) was obtained. (Weight average molecular weight yzooo) Further, specific examples of copolymers preferable as the binder used in the present invention are shown in Table I, but the present invention is not limited thereto.

The content of binder in the present invention is preferably about ao-to weight percent, and more preferably about 10 to 70 weight percent, based on the total weight of the photopolymerizable composition.

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 undergoing addition polymerization. .

One or more compounds may be present as the polymerizable unsaturated compound. Preferred specific examples include Tokko Sho J-j Ori No. 3, Tokko Sho 3j-/4c7/2
No., Tokuko Shopu-λr7λ7. Acrylic or methacrylic esters of polyols, namely diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, dodecaethylene glycol di(meth)acrylate, etc. meth)acrylate, tetradecaethylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate), toIJ methylolpronone tri(meth)acrylate, trimeterolpropane di(meth)acrylate, metaerythritol tetra(meth)acrylate ) acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 6-hexanethiol di(meth)acrylate, etc., or acrylamide or methacrylamide obtained from polyamine, i.e., methylene bis(meth)acrylate, etc. ) acrylamide, ethylenebis(meth)acrylamide, m-xylylenebis(meth)acrylamide, etc., or compounds containing a urethane group, i.e., di(comethacryloxyethyl)-
λ.

Reference-tolylene diurethane, di(co-acryloxyethyl)hexamethylene diurethane, or a terminal isocyanate compound obtained by reacting a polyol with a diisocyanate in advance (further reacting with β-hydroxyalkyl (meth)acrylate) (meth)acrylic urethane oligomer 1 For example, oligomers obtained by reacting a reaction product of 3 moles of lylene diisocyanate and 3 moles of ethylene glycol with β-hydroxyethyl acrylate. or acrylic acid or methacrylic acid esters modified and derived from bisphenol A, i.e., reaction products of bisphenol-ebichlorohydrin epoxy resin sol polymer with acrylic acid or methacrylic acid, alkylene oxide adducts of bisphenol or the like. Examples include hydrogenated acrylic acid, methacrylic ester, etc., and esters of aromatic polycarboxylic acids, that is, compounds represented by the following structural formula.

Furthermore, in addition to these polymerizable unsaturated compounds, a polymerizable unsaturated compound containing seven ethylenically unsaturated double bonds in the molecule may be included. Preferred specific examples include ethylene glycol mono(meth)acrylate, triethylene glycol methyl ether (meth)acrylate,
Examples include ethylene glycol phenyl ether (meth)acrylate, tetraethylene glycol mono(meth)acrylate, diacetone acrylamide, (meth)acrylamide, N-n-butyl (meth)acrylamide, and the like.

The content of the polymerizable unsaturated compound is preferably about 7.5% based on the total weight of the photopolymerizable composition. j-jji quantity chi, and preferably about lj-hiro! Weight%.

The photopolymerization initiator suitably used in the composition of the present invention includes a single compound capable of initiating the polymerization of the polymerizable unsaturated compound, or a photopolymerization initiator system consisting of a combination of two or more compounds. Can be used. Preferably, the photoinitiator or photoinitiator system has a molecular weight of about 3000 to roo.
o^, preferably at least about in the range 3300-j000^! Contains at least one component having a molecular extinction coefficient of 0.

Preferred specific examples of the photopolymerization initiator include primary compounds. Aromatic ketones, such as benzophenone, 4! , 3'-bis(dimethylamino)benzophenone, p,l-bis(diethylamine)benzophenone, ≠-methoxyhiro'-dimethylaminobenzophenone, <z,4c'-dimethoxybenzophenone, ≠-dimethylaminobenzophenone/, hiro- dimethylaminoaceto7dinone, benzyl, anthraquinone, 2-tert
-7' thylanthraquinone, 2-methylanthraquinone, 7 enanthraquinone, xanthone, thioxanthone,
Kokroruthiosakinton, Ko, 4! - diethylthioxanthone, fluorenone, acridone and benzoin, benzoin ethers, such as hachenzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, inzoin isopropyl ether, benzoin 722yl ether, and λ,≠,1-) Realyl imidazole dimers 1 such as λ-(0-chlorophenyl)-≠,! -diphenylimidazole dimer, λ-
(0-chlorophenyl)-≠, j-di(m-methoxyphenyl)imidazole dimer, co(0-fluorophenyl)-≠,! -diphenylimidazole dimer, 2-
(0-Methoxy7enyl)-≠, j-diphenylimidazole dimer.

λ-(p-methoxyphenyl)-, j-diphenylimidazole dimer, and polyhalogen compounds such as carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethylketone, and coumarins such as J-(2 -benzofuroyl)-7-diethylaminocoumarin, J-(λ-benzo70yl)-7-(/-pyrrolidinyl)coumarin, 3-benzoyl-7-diethylaminocoumarin, J-(o-methoxybenzoyl)-7-
Diethylaminocoumarin, 3-(p-dimethylaminobenzoyl)-7-diethylaminocoumarin, 3,3'-
Carbonylbis(!, 7-di-n-flopoxycoumarin), J,! '-Carbonylbis(7-diethylaminocoumarin), 3-benzoyl-7-medoxycoumarin, J
-(λ-furoyl)-7-diethylaminocoumarin, J
-(p-diethylaminocinnamoyl)-7-diethylaminocoumarin, 7-medoxy J-(j-pyridylcarbonyl)coumarin, J-benzoyl-! .

7-dipropoxycoumarin, and amines 1 such as p
-dimethylaminobenzoic acid ether, p-dimethylaminobenzoic acid n-butyl, p-dimethylaminobenzoic acid 7-enedel, p-dimethylaminobenzoic acid co-7talimidoethyl, p-dimethylaminobenzoic acid co-methacryloyloxyethyl, penta Methylenebis(p-dimethylaminobenzoate) 1m-dimethylaminobenzoic acid 7
enethyl and pentamethylene esters, p-dimethylaminobenzaldehyde, cochrolu≠-dimethylaminobenzaldehyde, p-dimethylaminobenzyl alcohol, ethyl (p-dimethylamino) besizoyl acetate, p-pyridinoacetophenone, l-dimethylaminobenzoin, N,N-dimethyl-p-)luidine, N,N-diethyl-m-7enetidine, tribenzylamine.

Diindylphenylamine, N-me? Leu-N-phenylbenzylamine, p-,-Romu-NsN-dimethylaniline, tridodecylamine, leuco crystal violet, Kan and Tokukaisho! ! -/JJuJt issue, Tokuko Shoj
7-/r/ri issue, I! ! No. f Kosho J7-402, U.S. Patent No. Jt/jdaj! Compounds disclosed in No. A combination of two or more types, such as a combination of a 2-mercaptobenzoxazole or a leuco crystal violet, etc., with a 2-mercaptobenzoxazole or a 2-mercaptobenzoxazole or a leuco crystal violet, as described in U.S. Pat. 2. Combinations of benzophenone and benzophenone or benzoin methyl ether and benzoyl-N-methylnaphthothiazoline as described in U.S. Pat. No. 3,110. Tervis (trichloromethyl)-j
Examples include a combination of -m-methoxyphenyltriazole and a combination of dimethylthioxanthone and dialkylaminobenzoic acid ester described in JP-A-17-171 JtO.

The content of the photoinitiator or photoinitiator system is preferably about 0°/-10% by weight based on the total weight of the photopolymerizable composition.
, and more preferably from about 0.2% by weight.

The photopolymerizable composition of the present invention includes a photopolymerization initiator, an ethylenically unsaturated compound, and a binder as essential components.

If necessary, a thermal polymerization inhibitor, a plasticizer, a pigment, a color change agent, a monofunctional ethylenically unsaturated compound, an adhesion promoter to the substrate surface, and other auxiliary agents may be used in combination. Properties such as photographic properties, printout properties, and film properties of the photoresist 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, hydroquinone, and t-7.
'Tylcatechol, pyrogallol, co-6-hydroxyinzophenone, l-methoxy-co-hydroxybenzophenone, salt (tJEz copper, phenothiazine, chloranil, 7-thylamine, β-naphthol, co-,4-di-t-
Examples include butyl-p-ruzole, nitrobenzene, dinitrobenzene, picric acid, p-toluidine, and the like.

Plasticizers are added to control the physical properties of the film. For example, phthalate esters such as dibutyl phthalate, diallyl phthalate, dioctyl phthalate, and diallyl phthalate; glycols such as triethylene glycol diacetate and tetraethylene glycol diacetate. Esters; Phosphate esters such as tricresyl phosphate and triphenyl phosphate; p) Luenesulfonamide, benzenesulfonamide, N-n-
Amides such as butylacetamide; aliphatic dibasic acid esters such as diisobutyl adibate, dioctyl azide, dimethyl sepacate, dioctyl azelate, dibutyl maleate; triethyl citrate, tributyl citrate, glycerin triacetyl ester, laurin Butyl acid, Ri.

! -diepoxycyclohexane/, dioctyl 2-dicarboxylate, and the like.

Examples of pigments are brilliant green, eosin, cucine, phenolphthalein, l,3-di7-dirutriazine, alizarin red S, thymolphthalein, methyl violet JB, quinaldine red, rose bengal, methanil yellow, Thymol sulfophthalein, xylenol blue.

Methyl orange, orange ■, diphenylthiocarbazone, 2,7-dichlorofluorescein, paramethyl red, Congo red, benzopurpurin ginseng B, α-su 7
Terretsud, Nile Blue-A.

7 enacetarin, methyl violet, malachite clean, e7 fuchsin, oil blue ≠ 603 [manufactured by Orient Chemical Industry ■], Victoria Pureb #-BOH,
These include Spilon Blue GN (manufactured by Hodogaya 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, diethylaniline, diphenyl-p-phenylenediamine, p-toluidine, 4/-
, biphenyl diamine, o-chloroaniline, leuco crystal violet, leucomalachite green, leucoaniline, leucomethyl violet and the like.

Specific examples of adhesion promoters include benzimidazole, benzthiazole, benzoxazole, and benztriazole. Compound described in No. 0-ta/77, 2-
Compounds such as mercaptobenzthiazole and comelkabutopenzimidazole described in JP-A-13-702 are used.

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. Solvents used in this case include ethylene dichloride, monochlorobenzene, cyclohexanone, methoxypropanol, toluene, xylene, etc. alone or in mixtures.

The photopolymerizable composition of the present invention is suitable as the 7th photoresist layer of a dry film resist. In that case, the appropriate thickness of the photoresist layer is from O6lμ to 100μ, and preferably from /μ to 200μ for l#. Further, when producing a photosensitive lithographic printing plate using the photopolymerizable composition of the present invention, the coating amount is generally 0.000. /-
10.0g7m2 is suitable, particularly preferably 0.1-
j.

This is Ogl Exhibition 2.

When the photopolymerizable composition of the present invention is used as a dry film resist, a suitable support is selected from films such as polyamides, polyolefins, polyesters, vinyl polymers, and cellulose esters having a thickness of 3μ to 100μ. Things are good. Particularly suitable support films have a thickness of about i.

A transparent polyethylene terephthalate film having a thickness of 2 to 2 Iμ. In this case, polyolefins are preferably used as the protective film, and particularly preferred are λO~co! Mention may be made of polyethylene films with a thickness of μ.

(9) When the photopolymerizable composition of the present invention is used to produce a photomask film, suitable supports include polyethylene terephthalate films deposited with aluminum, aluminum alloys, and chromium, and polyethylene terephthalate films provided with colored layers. can be mentioned.

Further, when the photopolymerizable composition of the present invention is used as a photosensitive layer of a photosensitive lithographic printing plate, suitable supports include hydrophilically treated aluminum plates, such as silicate-treated aluminum plates, anodized aluminum plates, Examples include grained aluminum plates, silicate electrodeposited aluminum plates, zinc plates, stainless steel plates, chrome-treated copper plates, and hydrophilic plastic films and paper.

In addition, when the photopolymerizable composition of the present invention is used for producing color proofs for printing, films for overhead projectors, and films for second original drawings, suitable supports include polyethylene terephthalate film, cellulose triacetate film, etc. Examples include transparent films and plastic films whose surfaces have been chemically or physically roughened.

The photopolymerizable composition of the present invention can be prepared by using an organic solvent such as /eerl)'J dichlorothane, a weak alkaline aqueous solution such as a sodium carbonate aqueous solution, or a semi-solvent aqueous solution consisting of a weak alkaline aqueous solution and an organic solvent miscible with water. Can be developed.

Examples are shown below to explain the present invention in more detail.

Example-1 A Hiro O weight% solution of the copolymer of Table 7 (the solvent was methyl ethyl keto/, l-methoxy-pronocenol (
1 weight ratio)) 37.17 Undecapropylene glycol 7. O6f diacrylate tetradecaethylene glycol no, 944F diacrylate ethyl Michler's ketone O0Oμ! Inciphenone o, ajyλ, 3-diethylthioxane) 0. /llnp-dimethylaminobenzoic acid di0.2tertribromomethylphenylsul a,/19honj,4-bis(diphenylamino,o1))fluoran l-phenyl-3-morpholino 0,0 /p methyl-I, 3. Dirt Triazole-λ-Theon Victoria Vinia Blue BOHO, 0/1p A photosensitive liquid having the above composition is used as i! jlin and rod coater, 2
! It was coated on a μ-thick polyethylene terephthalate film so that the dry film thickness was approximately jθμ, and dried in an oven at 100°C for 2 minutes.

The dry film resist thus obtained was leveled and placed on the dried copper-clad laminate using an Aλ≠ type laminator (Du Pknt) so that the coating surface was in contact with the copper surface.
It was laminated using TSO 0c (manufactured by Co., Ltd.). The wiring pattern (a high-contrast transparent image in which a conductor pattern (line width 100 μ) appears as a transparent part on an opaque background) was exposed at l16 m J/0 M2 (j
KW ultra-high pressure mercury lamp double-sided simultaneous exposure device HMW-j-N type (
Made of oak)>. The polyethylene terephthalate film was peeled off to obtain 1% by weight sodium carbonate of JOc'C.

In addition, the results of evaluating the chipping and cold resistance of this dry film resist are shown in Table 1.

Example 1 A dry film resist was obtained in the same manner as in Example 7 except that copolymer A in Table 7 was used as the binder.

By side-lighting and developing this dry film resist in the same manner as in Example 7, a good resist pattern image was obtained. Table 2 shows the results of evaluating the cutting dust and cold resistance of Makuko's dry film resist.

Example 3 A dry film resist was obtained in the same manner as in Example 7, except that the copolymer of JIIL3 shown in Table 7 was used as the binder. A good resist pattern image was obtained by subjecting this dry film resist to tremor and light imaging in the same manner as in Example 7. In addition, the results of evaluating the chipping and cold resistance of this dry film resist are shown in Table 1.

Comparative Example-/A dry film resist was obtained in the same manner as in Example-7 except that the following binder was used as the binder.

Methacrylic acid/methyl methacrylate/coethylhexyl acrylate/benzyl methacrylate (21, r:!!
:// , 7:4I# mol ratio) - Original copolymer This dry film resist chips, cold resistance 70
- The results of evaluating the performance are shown in Table-C.

(Evaluation method for cutting chips) A KA-2 laden type laminator (manufactured by Pont) was used to make sure that the coated surface of the dry film resist was in contact with the steel surface on a leveled and dried copper-clad laminate. Laminated at 120°C. The resist is cut along the copper-clad laminate using a cutter, and the condition of the cut surface (does it cut smoothly) is visually evaluated.

(O: Good Δ: Fair ×: Poor) (Evaluation of cold flow resistance) After laminating dry film resist with polyethylene film! Cut at a declination angle. After stacking 10 of these sheets, a load of 2 Kf was applied between the steel plates. ao
It was stored at 0cro%RH and evaluated based on the number of days the photosensitive layer started to seep out.

Table 2: Comparison of cutting dust and cold flow resistance (effects of the invention) The photopolymerizable composition containing the binder of the present invention has particularly excellent cold flow resistance and is free from the problem of cutting dust.

Claims (1)

[Claims] In a photopolymerizable composition containing an addition polymerizable unsaturated compound containing at least two ethylenically unsaturated double bonds in the molecule, a photopolymerization initiator, and a binder, as a copolymer component of the binder A photopolymerizable composition comprising at least one addition polymerizable unsaturated compound having at least two ethylenically unsaturated double bonds in the molecule.