JPH02269721A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which can give a finely disintegrated film when it is released in alkali development and is useful for dry film resist by mixing a mixture comprising a specified combination of compounds having photopolymerizable, ethylenically unsaturated double bonds with a carboxylated thermoplastic polymer binder and a photopolymerization initiator system. CONSTITUTION:A mixture of three monomers having two photopolymerizable/ ethylenically unsaturated double bonds in the molecule of the formula, i.e., component (a) (wherein n-4; R1 is CH3; and R2 is H), component (b) (wherein n is 9-14; and R1-2 are each H) and component (c) (wherein n is 7-12; R1 is H; and R2 is CH3) in a mixing ratio falling on or inside the lines of a pentagon defined by points A, B, C, D and E in the diagram is mixed with a carboxylated thermoplastic polymer binder (e.g. methyl methacrylate/methacrylic acid/2- ethylhexyl acrylate/benzyl methacrylate copolymer) and a photopolymerization initiator system which can initiate the photopolymerization of the above monomer mixture (e.g. benzophenone).

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a photopolymerizable composition that can be polymerized and cured by irradiation with actinic rays, which is useful for producing printed wiring boards and the like. More specifically, we use a dry film photoresist that can be rapidly developed and peeled off with alkali, and when peeled off with alkali, the peeled film becomes fine and the film after photopolymerization is soft and highly flexible. The present invention relates to photopolymerizable compositions useful for making. [Prior Art] In the manufacture of printed wiring boards, dry film resists are laminated onto copper-clad laminates (substrates). Actinic light is irradiated through the document having the wiring pattern, and then the unexposed areas are dissolved and removed using a developer such as a weak alkaline aqueous solution. Using the resulting exposed image as a resist, the exposed copper can be etched, plated,
or anodizing) to form printed circuits. Then, the resist that is no longer needed is peeled off from the substrate by treatment with a strong alkali such as caustic soda. However, at this time, if the resist piece simply swells and is peeled off from the substrate, the peeled piece will become entangled with the conveyance roller in the peeling device, and if this number increases, it will be difficult to properly feed the substrate. Therefore, in order to remove the peeled pieces, the peeling device must be stopped periodically, which causes a significant decrease in work efficiency. For such problems, for example, JP-A-64-102
As seen in JP-A No. 35 and JP-A-56-19752, in the monomer represented by the general formula (1), (R1 and R2 are H or CH31n is an integer from 1 to 23), It is stated that the peeled pieces can be made finer. It is true that within the scope of implementation in this publication, it is possible to make the peeling pieces finer, but at the same time (as a very characteristic property of these monomers) the time required for peeling becomes extremely slow. However, this alone will result in worsening the actual peeling workability. In addition, monomers of types disclosed in the publication but not implemented, such as R in general formula (I), may also be used.
Even if the test is carried out using monomers in which 2 = CH3 and n = 12 or more, the peeled pieces do not become small pieces. Furthermore, even if monomers are used within the range practiced in the publication, as in the examples in the publication, even if the monomer is used alone, other properties that the resist must have (for example, the resist's performance after exposure) There is no one that satisfies all requirements (flexibility, development time, sensitivity, etc.). Moreover, as seen in the specification of JP-A-63-184744, in the general formula (I), R2=H and n
It is also known to use monomers of 2 to 20 in combination with urethane acrylates as disclosed in that publication. However, even in this publication, there is no mention of the above-mentioned delay in peeling time. Also, Japanese Patent Application Laid-Open No. 62-24246, U.S. Patent No. 449
A suitable monomer for the dry film resist is a so-called (meth)acrylic acid ester of polypropylene glycol in which R2=CH3 in the general formula (T) as seen in Japanese Patent No. 5271. It is also disclosed that it can be used in However, even if the monomer disclosed in the publication was used, it was still insufficient in terms of making the peelable pieces into fine pieces. Furthermore, as a monomer having a chemical structure similar to general formula (1), a monomer shown in general formula (n) is disclosed in Japanese Patent Application Laid-open No. 61
It is disclosed in Japanese Patent No.-228007. (R+ is H or CHa) However, even if the monomer disclosed in the publication was used, it was still insufficient in terms of making the peeled pieces into fine pieces. [Problems to be Solved by the Invention] Therefore, the object of the present invention is to solve the various problems mentioned above. Immediately, the peeled pieces become small pieces without slowing down the peeling time,
The object of the present invention is to provide a photopolymerizable composition that is sufficiently satisfactory in other performances such as resist flexibility after exposure, development time, and sensitivity.

[Between ff1. ．． Means for Solving Problem 1 The present inventors have discovered that the present inventors can achieve exfoliation by using a specific combination of monomers having a photopolymerizable ethylenically unsaturated double bond in one molecule, as shown in general formula (1). A dry film suitable for use in the manufacture of printed wiring boards, with fast aR time, peeling into small pieces, excellent flexibility of renost after exposure, fast development time, and excellent sensitivity, resolution, and adhesion. We have discovered a photopolymerizable composition that is excellent for forming resists. That is, the objects of the present invention are at least (1) to (3)
This was achieved using a photopolymerizable composition whose vf characteristic is that it contains (1) Carboxyl group-containing thermoplastic polymer binder. (2) What about the following general 2 (1) that has two photopolymerizable ethylenically unsaturated double bonds in one molecule? 2 of the monomers
A mixture consisting of the mixing ratio on and inside the pentagon represented by the point ABCDEA in FIG. However, component a: n = 4. R,=CH, and R2=Hb
Ingredients: n = 9-14. R,=H, and R,=I C component: n =7-12. R,=H, and R2=C
H. (3) A photopolymerization initiator system capable of initiating photopolymerization of the monomer mixture of (2) for 1 m using actinic light. In the photopolymerizable composition of the present invention, a-b and cfl
l, min each at least 1 f! Although it is necessary to contain 11, there is no problem even if two or more types of b or C components are contained. In the monomer of general formula (1), the main purpose of using a component such as a in particular is due to the discovery that the 77mer can significantly speed up the development time.
This is because if the monomer content is 5% or less, the development time becomes slow even if monomer 1) and C are used. Also,
When the monomer content is 60 mol % or more, the flexibility of the renost after exposure is significantly deteriorated. Further, in the monomer of the general formula (1), the main purpose of using a component such as 1] is to break the peeled pieces into small pieces, and to improve the visibility of the renost. Therefore, if the monomer is present at 5 mol % or less, these performances are impaired. Moreover, when the monomer content is 50 mol % or more, the peeling time becomes noticeably slow. Furthermore, if the length of this type of monomer; 1 is shorter than 9, the IJ membrane, which cannot be optimized even in combination with C777-, becomes brittle, and the flexibility of Rennost deteriorates significantly. Furthermore, if the length n of this type of roller is longer than 14, the development time becomes unduly slow and the sensitivity, adhesion and resistivity are impaired, which is unsuitable. Furthermore, in the monomer of general formula (1), the main purpose of using a component such as C in particular is to significantly shorten the peeling time, improve the flexibility of Rennost, and improve the plating properties required for Rennost. This is due to the discovery that it satisfies many performance requirements in a well-balanced manner. Therefore, when the monomer content is 10% or less, there arises a drawback that the peeling time is not particularly shortened. Further, when the monomer is present in an amount of 90 mol% or more, the peeled pieces are not broken into small pieces. Furthermore, if fjk 'b n of this type of moamer is shorter than 9, the film becomes brittle, similar to the 1,'j characteristic in monomer 1], and the renostability deteriorates. Further, if the length +1 of this type of mower 7- is longer than 12, it is not suitable because the developing time becomes significantly longer, similar to the characteristic of monomer b. As mentioned above, in the ternary mixture of monomers represented by general formula (1), the range of the quantitative ratio of the components (a, b and C) is defined by the molar fraction. FIG. 1 shows this using so-called three-dimensional coordinates. The range of the quantitative ratio of the three components of the monomer of general formula (1) in the present invention is points A, B, and C in FIG. Let D and E be the vertices. It exists within the range indicated by the pentagon (points on the line of pentagon ABCDE are included). Moreover, this molar ratio preferably exists within the range indicated by the square FGHI (points on the line of the square FGHI are included). The coordinates of 9 points A-1 in FIG. 1 (ratio of component a [mol %], ratio of component b [mol % L, ratio of component c [mol %]) are as follows. Point A (5%, 6%, 90%) Point B (60%, 5%, 35%) Point C (60%, 30%, 10%) Point D (40%, 50%, 10%) Point E (5%, 50%, 45%) Point F (5%, 10%, 85%) Point G (30%, 10%, 60%) Point H (30%, 30%, 40%) Point R (5 %, 30%, 65%) The following monomers can be used as the monomer of general formula (I) in the present invention. Component a: Dimethacrylate of polyethylene glycol with a weight average molecular member of approximately 200 Commercially available products that can be easily prepared by hand include: NK Ester manufactured by Shin-Nakamura Chemical Co., Ltd. 4Light Ester manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd. 4EC Mitsubishi Rayon Co., Ltd. Acryester 4D Somar Co., Ltd.! ! Examples include tetraethylene glycol dimethacrylate. Component b: polyethylene glycol diacrylate having a weight average molecular weight of about 400 to about 600. A commercially available product that can be easily made by hand is Aronix M-245 (manufactured by Toagosei Chemical Industry Co., Ltd.).
n=9) Shin Nakamura Chemical Co., Ltd. INK Ester A-400 (n=9) Shin Nakamura Chemical Co., Ltd. NK Ester A-600 (n
=14) Light ester 9EG manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.
-A (n=9) Light ester 14E manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.
G-A (n=14) KAYARAD PEG400 manufactured by Nippon Kayaku Co., Ltd.
DA (n=9) Polyethylene glycol (400) manufactured by Somar Co., Ltd.
Diacrylate (n = 9) manufactured by Somar Co., Ltd. Polyethylene glycol (600) Diacrylate (n
=14). Component C: Polypropylene glycol diacrylate having a weight average molecular layer of about 400 to about 700. A readily available commercially available product is NK Ester APC-400 manufactured by Shin-Nakamura Chemical Co., Ltd. In the present invention, monomer component a of general formula (I). The content of (2), which is the sum of b and C, is 10 to 60% by weight, preferably 30 to 60% by weight, based on the total weight of the photopolymerizable composition.
It is 50% by weight. With 10% by weight ungrooved, good image quality cannot be obtained because the difference in solubility between exposed and unexposed areas is small. If it exceeds 60% by weight, when the composition is made into a dry film, the fluidity of the unexposed area is too high and the physical storage stability is poor, so that it is not suitable for the purpose of the present invention. The carboxyl group-containing thermoplastic polymer binder (hereinafter referred to as binder) suitable for the photopolymerizable composition of the present invention is soluble in an aqueous alkaline solution, or at least swellable. Specific examples include the following. Special Public Service (1977)
-32714 (the binder is, for example, methyl methacrylate/methacrylic acid copolymer), Japanese Patent Publication No. 54-34
No. 327 (the binder is, for example, a ternary copolymer of methyl methacrylate/2-ethylhexyl methacrylate/methacrylic acid); ), Japanese Patent Publication No. 56-33413 (the binder is, for example, a ternary copolymer of methyl methacrylate/ethyl acrylate/methacrylic acid), Japanese Patent Publication No. 1983
-25957 (the binder is, for example, a quaternary copolymer of styrene/methyl methacrylate/ethyl acrylate/methacrylic acid), and JP-A-52-99810 (the binder is, for example, a hensyl methacrylate/methacrylic acid copolymer). ), Japanese Patent Publication No. 58-12577 (the binder is, for example, a ternary copolymer of acrylonitrile/2-ethylhexyl methacrylate/methacrylic acid), and Japanese Patent Publication No. 55-6210 (the binder is, for example, a terpolymer of methyl methacrylate/acrylic acid). Styrene partially esterified with ethyl/acrylic acid terpolymer and isopropanol/
It is a mixture of two types of maleic anhydride copolymer), JP-A-58-1142 (the binder is, for example, a quaternary copolymer of methyl methacrylate/methacrylic acid/2-ethylhexyl acrylate/n-butyl methacrylate). and JP-A-63-147159 (the binder is, for example, a quaternary copolymer of late methyl methacrylate/2-ethylhexyl acrylate/hensyl methacrylate/methacrylic acid). The content of the group-containing binder is preferably 40 to 90% by weight, more preferably 50 to 90% by weight, based on the total weight of the photopolymerizable composition.
It is 70% by weight. If it is less than 40% by weight, the fluidity is too high and creep phenomenon is likely to occur, so that it is not suitable for the purpose of the present invention. If it exceeds 90% by weight, the difference in solubility between exposed and unexposed areas is too small, making it impossible to obtain good image quality. As the photopolymerization initiator suitably used in the present invention, a single compound or a photopolymerization initiator system consisting of a combination of two or more compounds capable of initiating the photopolymerization of the above-mentioned ethylenically unsaturated group-containing compound is used. can all be used. However, preferably the photoinitiator or photoinitiator system has a wavelength of about 300-800 nm, more preferably 330-50 nm.
It contains at least one component having a molecular extinction coefficient of at least about 50 in the 0 nm range. Otherwise, they will not be sufficiently sensitive to commonly used actinic light sources. Specific examples of these include the following compounds. Aromatic ketones, such as benzophenone, 4゜4'-bis(dimethylamino)benzophenone, 4-methoxy-
4'-dimethylaminohensiphenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl anthraquinone, 2-tert-butylanthraquinone, 2-methylanthraquinone, xanthone, thioxanthone, 2 - Chlorthioxanthone, 2,4-diethylthioxanthone, fluorenone, acridone; benzoin and benzoin ethers, such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin phenyl ether;
2. 4. 5-) Realyl imidazole dimer, for example 2-(0-chlorophenyl)-4,5-diphenylimidazole 2'Ik form/2-(o-chlorophenyl)
-4,5-di(m-methoxyphenyl)imidazole 2
m-form・2-(0-fluorophenyl)-4,5-diphenylimidazole dimer・2-(0-methoxyphenyl)-4,5-diphenylimidazole dimer・2-(p
-methoxyphenyl)-4,5-diphenylimidazole dimer; polyhalogen compounds such as carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethylketone and JP-A-53-133428, JP-B-Sho 57-1819 , No. 57-6096, U.S. Patent No. 3
There are compounds described in No. 615455 and the like. Furthermore, a combination of two or more types of compounds is known as a photopolymerization initiator system. For example, 2, 4. 5
-) A combination of only two realyl imidazole derivatives and mercaptobenzoxazole or leuco crystal violet, etc.; a combination of 4,4'-bis(dimethylamino)benzophenone and benzophenone or benzoin methyl ether described in U.S. Pat. No. 3,427,161; Combination of benzoyl-N-methylnaphthothiazoline and 2,4-bis(trichloromethyl)-6-(4'-methoxyphenyl)-triazole described in U.S. Pat. No. 4,239,850, JP-A-57-23602 The combination of dialkylaminobenzoic acid ester and dimethylthioxanthone described in JP-A-59-78339, and the combination of 4,4'-bis(dimethylamino)benzophenone, benzophenone, and polyhalogenated methyl compound described in JP-A-59-78339. can be mentioned. More preferred examples include a combination of 4,4'-bis(diethylamino)benzophenone and benzophenone;
Combination of 4-diethylthioxanthone and ethyl 4-dimethylaminobenzoate, 4°4'-bis(diethylamino)benzophenone and 2, 4. 5-) A combination of 211 realyl imidazoles is mentioned. The content of the photopolymerization initiator (system) is preferably 0.5% based on the total weight of the photopolymerizable composition. 1-10% by weight, more preferably 0. It is 2 to 6% by weight. If it is less than 0.1% by weight, the sensitivity will be insufficient, and if it exceeds 10% by weight, no increase in sensitivity can be expected. As mentioned above, the photopolymerizable composition of the present invention contains a novel polyfunctional monomer, a carboxyl group-containing binder, and a photopolymerization initiator or an initiator system as essential components, but if necessary, a thermal polymerization inhibitor, Plasticizers, dyes, color change agents, adhesion promoters and other auxiliary agents may be used in combination, and with these, a wide range of target photoresists, resin letterpresses, lithographic printing plates, photomasks, color proofs, etc. can be prepared. sell. A thermal polymerization inhibitor can be further added to the photopolymerizable composition of the present invention. Thermal polymerization inhibitors are added to prevent thermal polymerization and polymerization over time of photopolymerizable compositions, thereby improving the chemical stability of photopolymerizable compositions during preparation and storage. can be increased. Examples of thermal polymerization inhibitors include p-methoxyphenol, hydroquinone, alkyl- or aryl-substituted hydroquinone, benzoquinone, 0-torquinone, p-torquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-
2-hydroxybenzophenone, cuprous chloride, phenothiazine, floranil, chloranil, naphthylamine, pyridine, p-toluidine, β-naphthol, 2,6-di-t-butyl-p-cresol, nitrobenzene, dinitrobenzene, picric acid, N -Aluminum salt or ammonium salt of nitrosophenylhydroxylamine, methylene blue organic copper, methyl salicylate, aryl phosphite and the like. i! ! ! The amount of the polymerization inhibitor added is preferably 0.001 to 10% by weight, more preferably 0.01 to 3% by weight, based on the total weight of the photopolymerizable composition. 0.001 wt% ungrooved 7 has poor thermal stability, 10 wt%
Sensitivity decreases when the value is exceeded. The plasticizer is added to adjust the film quality, other physical properties, photosensitivity, etc. of the photopolymerizable composition before and after photocuring. Examples of plasticizers include dibutyl phthalate, diallyl phthalate,
Phthalate esters such as dioctyl phthalate and diallyl phthalate, triethylene glycol diacetate,
Glycol esters such as tetraethylene glycol diacetate, acid amides such as p-)luenesulfonamide, benzenesulfonamide, N-n-butylbenzenesulfonamide, diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dioctyl azelate, Aliphatic dibasic acid esters such as dibutyl maleate,
Examples thereof include tributyl citrate, glycerin triacetyl ester, butyl laurate, and dioctyl 4,5-jepoxycyclohexane-1°2-dicarboxylate. The preferred amount of the plasticizer added is 0.001 to 50% by weight based on the total weight of the photopolymerizable composition, and more preferably,
It is 0.01 to 20% by weight. If it exceeds 20% by weight, developability will be adversely affected. Dyes are added to color the photopolymerizable composition. Examples of pigments include malachite green, methyl green, brilliant green, methyl violet, crystal violet, ethyl violet, Victoria Pure Blue BOH, oil blue #603 (manufactured by Orient Chemical Industry Co., Ltd.), eosin, and erythrosin 81.
Rose Bengal, Rhodamine B1 Rhodamine 6C
;, 2. 7-dichlorofluorescein, phenolphthalein, alizarin red S1 thymol phthalein, quinaldine red, methanyl yellow thymol sulfophthalein, diphenyl triazene, xylenol blue methyl congo red, benji■, diphenylthiocarbazone, rose methyl red, Examples include Congo red, benzobrulin 4B, α-naphthyl red, Nile blue A, phenacetaline, paratuxin, and peisic tuxin. The amount of the dye added is preferably 0.001 to 10% by weight, more preferably 0.01 to 10% by weight based on the total weight of the photopolymerizable composition.
It is 5% by weight. If it exceeds 10% by weight, it tends to have an adverse effect on sensitivity. The color change agent is added so that a visible image is obtained when the photopolymerizable composition is exposed to light through a photomask. In addition to the above dyes, examples of color changing agents include diphenylamine, dibenzylaniline, triphenylamine, diethylaniline, diphenyl-p-phenylenediamine, p-
Toluidine, 4.41-Biphenyldiamine, 0-chloroaniline, p, p', p''-hexamethyldiaminotriphenylmethane, p, p' -tetramethyldiaminotriphenylmethane, p, p', p''- Triaminotriphenyl carbinol and the like are mentioned, and the preferable amount of the color change agent added is 0.00 based on the total IIT of the photopolymerizable composition.
It is 1 to 10% by weight, more preferably 0.01 to 6% by weight. If it exceeds 10% by weight, desensitization and fogging over time are likely to occur. The adhesion promoter is added to enhance the adhesion of the photopolymerizable composition to the surface of a copper or silicon substrate, anodized aluminum plate, plastic plate, or the like. Examples of adhesion promoters include benzimidazole, benzthiazole, benzoxazole, and benztriazole described in JP-B No. 50-9177, and JP-A-53-702.
2-mercaptobenzthiazole and mercaptobenzimidazole described in JP-A-59-113432
No. 59-165051, No. 60-12543,
Compounds described in JP 60-12544, JP 61-172139, etc. can be mentioned. The adhesion promoter is preferably added in an amount of 0.001 to 10% by weight, more preferably 0.001% by weight, based on the total weight of the photopolymerizable composition.
01 to 5% by weight. If it exceeds 10% by weight, it will cause development residue. [Examples] The present invention will be explained in more detail based on Examples below, but the present invention is not limited thereto. Unless otherwise specified, "parts" means [parts by weight J]
Quantify. Examples 1 to 18, Comparative Examples 1 to 18 The materials shown below were mixed to prepare a uniform solution. Methyl methacrylate/methacrylate 45 parts lithic acid/2
-35% by weight solution of ethylhexyl acrylate/pencil methacrylate copolymer (molar ratio = 55/28, 8/11.7/4, 5.weight average molecular weight = 90000) (solvent is methyl ethyl ketone/1-7 toxicity) 2-propyl=2/1 (weight ratio)) 9-) Luenesulfonamide FO, 5 parts 4.4-
Bis(noethylamine 0.04 part))benzo7eth/benzophenone 1.011 flS tribromomethylphenyls 0.15 part sulfone 3-morpholy/methyl-1-0,003 parts phenyl-1
, 3, 4-) Lyazole-2-thione leucocrystal violet 0.2 parts Malachite green 0.015 parts Monomers a and b represented by the general formula (1) of the present invention are added to the solution thus obtained. and/or C, respectively from Examples 1 to 1 in Table 1.
The amounts shown in Comparative Examples 1 to 18 were added. After further stirring and dissolving, each solution was applied to a 25μ polyethylene terephthalate film and dried at 100°C for 2 minutes. A photosensitive material having a thickness of approximately 40 μm was prepared. The photosensitive material thus obtained was evaluated as follows. "Evaluation of Developability" The above-mentioned sensitive material was laminated onto a clean copper-clad laminate whose surface had been polished and washed with water using an E7-heater at 120°C. After peeling off the polyethylene terephthalate film, the sensitive material was dissolved in a 1% aqueous sodium carbonate solution (30°C) sprayed from a spray nozzle at 2 kg/am. At this time, the time until the surface of the copper plate was exposed for the first time was measured. It was defined as ``development time''. The allowable range of "development time" is within 45 seconds. "Evaluation of peelability" In the same way as the evaluation of developability, after laminating the photosensitive material on a copper-clad laminate, it was laminated with a polyethylene terephthalate film using an ultra-high pressure mercury lamp (manufactured by Oak Manufacturing Co., Ltd., HMW-6N) for 10 minutes. Exposure for seconds. After 15 minutes, the polyethylene terephthalate film was peeled off and sprayed with a 1% aqueous sodium carbonate solution (30°C) for 1.5 times the "development time". Next, the substrate with renost obtained in this way was mixed with 3% 5
It was immersed in an aqueous sodium hydroxide solution at 0°C. At this time, measure the time until the resist peels off from the substrate,
It was referred to as "peeling time". Furthermore, after being peeled off, the peeled pieces floating in the peeling solution are
The sample was stirred in the stripping solution for 30 seconds. At this time, it was observed whether the peeled pieces were broken into small pieces or not, and this was defined as the "peeled piece shape." The allowable range of "peeling time" is within 90 seconds. In addition, the “peelable piece shape” must be made into small pieces. "Evaluation of tenting strength". After laminating a photosensitive material on both sides of a copper-clad laminate having a through hole of 2.5 mm φ, it was laminated as described above through a 7-otmask, which is transparent in the hole area and its surroundings, but is opaque elsewhere. exposed. After 15 minutes, peel off the polyethylene terephthalate film and add 1% sodium carbonate aqueous solution (30°C) for 1.5 of the "development time".
At the time of jg, 17+1 was sprayed, and the unexposed areas other than the through-hole areas were dissolved and removed to obtain 20 tents. 0.000 to the tent using an Instron device. [3+n+nφ
A needle was pressed against the tent, and the strain behavior under stress was measured until the tent was destroyed. From the response strain curve obtained in this way, the tent! Find the stress at the moment of m1j4 and find the "tenting strength"
And so. The allowable range of “tenting strength” is 250g/c-2
That's all. If it is less than 250 g/cm2, the tent may be destroyed in the etching process, or when laminated on a 7-lexiple substrate, the resist may be peeled off during transportation of the substrate. The results of these evaluations are shown in Table 1. From this, it can be seen that the photosensitive material using the photopolymerizable composition of the present invention has characteristics that simultaneously satisfy excellent developability, excellent peelability, and high tenting strength. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows the mixing molar ratio of components a, b and C used in the present invention represented by the general formula (1). The preferred mixing ratio is within the pentagon surrounded by points A, B, C, D, and E and on the boundary line, and more preferably within the quadrangle surrounded by points F, G, H, and and borderline range. FIG. 2 shows the preferred mixing ratio and the mixing ratio in the composition used in the comparative example. Patent applicant: Kushi Photo Film Co., Ltd. Figure C component 100% B component C component 100% 100% Written amendment (open) l. Display of the case 1999 Patent Application No. 91247 3゜Relationship with the case Patent applicant address 2-10 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo Film Co., Ltd. Telephone (406) 2537 Tokyo Head Office 4゜ Subject of the amendment [Detailed description of the invention, column 1 of the description, column 5 of "Brief description of the drawings" in the description, "Detailed description of the invention" and "Brief description of the drawings" of the description of the contents of the amendment The description in the section has been amended as follows. (1) On page 3, line 14, "in the monomer," is amended to "in the monomer," (2) Correct “9” in the 4th line of page 10 to “7”. (3) Replace pages 30 to 32 with separate sheets. A separate paper solution (30°C) was sprayed for a time 1.5 times the "development time" to dissolve and remove the unexposed areas other than the through-hole areas to obtain 20 tents. A needle of 0.6+amφ was pressed against the tent using an Instron device, and the stress strain behavior until the tent was destroyed was measured. From the stress strain curve obtained in this way, the stress between 111 and 111 at which the tent breaks was determined and defined as the "tenting strength". The allowable dryness of “tenting strength” is 250g/c
u'' or more. If it is less than 250 g/am2, the tent may be destroyed during the etching process, or when laminated on a flexible substrate, the resist may be peeled off during transportation of the substrate. Table 1 shows that the photosensitive material using the photopolymerizable composition of the present invention has characteristics that simultaneously satisfy excellent developability, excellent peelability, and high tenting strength. (Note) b ★1: Shin Nakamura Chemical Industry Co., Ltd.!! NK Ester 4G (
In formula (1), R,=CH,. R2 = H1 + 1 = 4) -1: Aloex M- manufactured by Toagosei Chemical Industry Co., Ltd.
245 (in formula (1), R1''H, R2=H,
(equivalent to n = 9) -2: N manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
K ester A-600 (corresponds to R, = H, R, = H, n = 14 in formula N) -1: NK ester APG-400 manufactured by Shin-Nakamura Chemical Co., Ltd.
(In formula (1) R+=H9R2=CH, n=7
) -2: Nippon Oil & Fats Co., Ltd.! J! Unior D-70
0 (polypropylene glycol) is treated with acrylic acid chloride to form diacrylate. (Formula (1)
(corresponds to R,"H,R,=CH1,n=12)

[Brief explanation of drawings]

FIG. 1 shows the mixing molar ratio of components a, b, and C represented by the general formula (1) used in the present invention. The preferred mixing ratio is within the pentagon surrounded by points A, B, C, D, and E and on the boundary line, and more preferably within the quadrangle surrounded by points F, G, H, and I. and borderline range. FIG. 2 shows the preferred mixing ratio and the mixing ratio in the composition used in the comparative example.

Claims (1)

[Scope of Claims] A photopolymerizable composition containing at least (1) to (3). (1) a carboxyl group-containing thermoplastic polymer binder, (2) a monomer represented by the following general formula (I) having two photopolymerizable ethylenically unsaturated double bonds in one molecule,
There are mixtures, ▲mathematical formulas, chemical formulas, tables, etc., consisting of the mixing ratio on and inside the pentagon represented by point ABCDEA in Figure 1.However, a component: n = 4, R_1 = CH_3, and R_2 = Hb
Component: n=9-14, R_1=H, and R_2=H c component: n=7-12, R_1=H, and R_2=CH
_3 (3) A photopolymerization initiator system capable of initiating photopolymerization of the monomer mixture in (2) with actinic light.