JPH0334056B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a photosensitive resin composition, more specifically, a photosensitive resin having particularly excellent adhesion, workability, and high sensitivity as an etching resist or plating resist used in the production of printed wiring boards, precision processing of metal, etc. Regarding the composition. In the fields of printed wiring board manufacturing, metal precision processing, etc., chemical processing of base materials such as etching and plating, etc.
It is known to use a photosensitive resin composition and a photosensitive element using the same as a resist material when using an electrical method. As a photosensitive element, one in which a photosensitive resin composition is laminated on a support is widely used. Such a photosensitive resin composition and a photosensitive element using the same are required to have sufficient chemical resistance and adhesion to a base material to be able to withstand use as an etching resist or a plating resist. The photosensitive resin composition and the photosensitive element using the same must have a practically sufficient photosensitive speed. Particularly in recent years, in the field of manufacturing printed wiring boards, the density of circuits has increased, and photosensitive resin compositions used for this purpose and photosensitive elements using the same have even better adhesion and workability. is required. Furthermore, from the viewpoint of shortening the process, a photosensitive resin composition with higher sensitivity and an element using the same are desired. As a method for obtaining a highly sensitive photosensitive resin composition,
Particularly in polymerization systems in which the composition consists of a free radical generating initiator and an unsaturated compound, it is common to increase the photosensitivity of the unsaturated compound used therein. Although various unsaturated compounds have been studied for such purposes, polyacrylates of polyhydric alcohols are widely used. Among these, acrylates having a polyether bond, particularly a polyethylene glycol structure, are particularly useful as highly sensitive acrylates. There are tetraethylene glycol diacrylate, nonaethylene glycol diacrylate, etc. that meet this purpose, and these are commercially available from Shin Nakamura Chemical Co., Ltd.
NK esters are available as A-4G and A-9G. In some cases, a polyethylene glycol structure may be introduced in addition to unsaturated compounds for the same purpose. Such an example is shown in Japanese Patent Publication No. 55-33801. However, although compounds such as acrylates having such a polyethylene glycol structure are useful for improving the sensitivity of photosensitive resin compositions and photosensitive elements using the same, they reduce the sticking resistance of the resulting resist. It has the following drawback. Therefore, for applications that require sticking resistance,
The amount of compounds such as acrylates having such a polyethylene glycol structure to be used is limited, leading to a corresponding decrease in photosensitivity. As a means to avoid this, the use of adhesion agents is known. Publication No. 50-9177 has 1,
2,3-benzotriazole, JP 55-65203
The publication describes indazole or its derivatives,
No. 55-65202 discloses phthalazone or its derivatives. The effect of such an adhesion agent is that the adhesion agent in the composition is oriented to form a monomolecular film on a substrate, such as a copper surface, that is in direct contact with the surface of the composition, usually by coating or laminating. ,
It is explained that this is to strengthen the adhesion between the substrate and the photosensitive resin composition or its cured product. However, such adhesion promoters may form a strong film on the surface, which may adversely affect subsequent steps. For example, in the case of benzotriazole, the photosensitive layer significantly discolors the surface of the substrate over time, so when the unexposed area is removed by means such as development, the surface of the substrate is difficult to be etched, or the plating precipitation is not likely to occur. It has the disadvantage that the adhesion of the deposited metal is poor. In addition, in the case of indazole or phthalazone, the compounds themselves are very expensive, and considering the manufacturing cost, it is difficult to say that they are industrially useful. On the other hand, these photosensitive resin compositions and photosensitive elements using the same must have excellent workability. This is usually applied to the surface of a substrate, especially a copper-clad laminate, by coating or laminating, and to a photosensitive element using the same, to prevent contamination of the mask during exposure. In order to prevent inhibition of polymerization by oxygen in the air, an organic polymer film is usually provided as an upper layer as a protective layer, and it is necessary to peel off these protective films prior to development. At this time, if the adhesion between the photosensitive resin layer and the base material, especially the copper-clad laminate, is insufficient, the photosensitive resin layer in the unexposed area will peel off from the base material together with the protective film when the protective film is peeled off. There are things to do. This not only adversely affects workability, but also causes chipping, lifting, etc. of the photosensitive resin layer in the exposed area, which may seriously affect the reliability of the printed circuit board. Particularly in the production of printed circuit boards, in order to avoid circuit shorts and disconnections due to the adhesion of minute pieces of hardened resist, artwork is printed on a negative mask so that the edges of the substrate are left unexposed during exposure. This issue is important because it is customary to design That is, in addition to the above-mentioned properties, the photosensitive resin composition and the element using the same have sufficient adhesion to the base material in the unexposed area, and when the protective film is removed, the photosensitive resin layer does not peel or lift. It is required that there be no. As a method for increasing the adhesion between a substrate and a photosensitive resin composition layer, a method is known in which a polar group is introduced into a side chain in a photosensitive resin composition layer, particularly in a film-imparting polymer. Hydroxyl groups, carboxyl groups, amide groups, imide groups, ester groups, ether groups, amino groups, etc. can be used as suitable for this purpose. It is thought that the polar groups of these side chains interact with the metal surface of the base material, usually copper, to promote adhesion between the photosensitive resin composition layer and the base material, for example, through chelate formation. However, although the adhesion promoting effect due to the introduction of such a polar group usually has almost the desired effect on the cured product after exposure, it does not necessarily have an effect on the unexposed photosensitive resin composition layer. . This is because the unexposed photosensitive resin composition layer usually has adhesiveness in order to maintain adhesion with the substrate, and the amount evaluated as the adhesion strength with the substrate at this time is the amount that can be peeled off. According to the theory of adhesion, this is given as the sum of the work of adhesion with the interface (static effect) and the work of deformation of the photosensitive resin composition layer (dynamic effect). In general, the latter is more effective in contributing to peel strength than the former. Since the effect of introducing a polar group is thought to mainly act on the adhesive work of the former, it is easily presumed that the introduction of a polar group does not necessarily lead to strengthening of the adhesive force with the base material in the unexposed area. In fact, 1 to 2% of monomers containing polar groups such as hydroxyl groups, amino groups, carboxyl groups, amide groups, etc., are added to the film properties imparting polymer in the photosensitive resin composition layer. When a polymerized vinyl copolymer is used, the effect of improving adhesion in the unexposed area is very small compared to a polymer whose polar groups are not copolymerized. In order to increase the effect of improving adhesion by these polar groups, it can only be achieved by copolymerizing more of these polar group-containing monomers. Although the carboxylic acid-containing monomer is relatively effective among the above-mentioned polar groups, it does not show much effect at a copolymerization weight ratio of several percent. On the other hand, sodium carbonate, sodium hydroxide,
Photosensitive resin compositions that use an aqueous solution of potassium hydroxide, sodium phosphate, etc. or an aqueous solution containing a small amount of an organic solvent as a developer (usually referred to as an alkali-developable type) are not soluble in an alkaline developer. Therefore, it is customary to include a relatively large amount (10% to 20%) of carboxylic acid side chains in the film-imparting polymer of the composition. In this case, the adhesive force due to the polar group effect increases, and the cured products of these alkali-developable resists exhibit good adhesion to the substrate.
However, in this case, the adhesive force is mainly based on the interfacial force between the base metal and the photosensitive resin composition layer, and is not based on the viscoelastic effect. The initial adhesive strength of the parts is poor, and there is a tendency for the adhesive strength to increase over time. Photosensitive elements having an alkali-developable photosensitive resin composition layer are known, but all of them have poor initial adhesion when laminated with a base material. The required initial adhesive strength is achieved by crimping with high pressure. On the other hand, as an attempt to strengthen the initial adhesive strength of such unexposed areas, a method can be considered to increase the tackiness by lowering the viscosity of the photosensitive resin composition layer. However, reducing the viscosity of the photosensitive resin composition layer is important, especially when the photosensitive resin composition layer is in the form of a photosensitive element comprising a support layer. There are limitations due to the additional problem of the layer flowing and sticking out of the support layer. The present invention has been made in view of the above problems. The present invention is based on the formula (A) (However, n is an integer of 0 to 3, R ₁ , R ₂ , R ₃ are hydrogen or methyl groups, R ₄ and R ₅ are alkyl groups having 1 to 4 carbon atoms, or 4 A monomer containing an aliphatic amino group represented by (forming a saturated alicyclic ring of 7 to 7 membered rings) is used as a copolymerization component to a polymer imparting film properties.
Film properties imparting polymer consisting of a vinyl copolymer compound obtained by using 0.1 to 10% by weight and a carboxyl group-containing monomer as a copolymerization component of 0.2 to 5% or 10 to 40% by weight based on the film properties imparting polymer. The present invention relates to a photosensitive resin composition comprising (B) an organic halogen compound, (C) an ethylenically unsaturated compound, and (D) a sensitizer and/or a sensitizer system capable of generating free radicals by actinic radiation. The film-imparting polymer in the present invention can be easily synthesized by ordinary vinyl polymerization using the above-mentioned aliphatic amino group-containing monomer and carboxyl group-containing monomer as copolymerization components. The aliphatic amino group-containing monomer used in the vinyl copolymer compound of the present invention is preferably one having a basic amine structure rather than a nucleophilic amine. This is because the aliphatic amino groups introduced into the side chains of the polymer that imparts film properties quickly combine with protons when irradiated with actinic radiation in the composition.
This is because it needs to become a grade ammonium salt.
Therefore, aliphatic alkylamines having appropriate steric hindrance are preferred. In the aliphatic amino group-containing monomer represented by the above formula, R ₁ , R ₂ and R ₃ are hydrogen or methyl groups, and R ₄ and R ₅ are alkyl groups having 1 to 4 carbon atoms. 4-membered ring to 7 including nitrogen atom
It forms a membered saturated alicyclic ring, and in the above formula, R ₄ and R ₅ are, for example, a methyl group,
Examples include ethyl group, propyl group, i-propyl group, n-butyl group, i-butyl group, and a piperidine ring which forms a saturated alicyclic ring together with a nitrogen atom, with methyl group and ethyl group being preferred. Further, when the alkylene chain is long, while it brings about an improvement in photosensitivity, the polyethylene glycol structure also becomes long, resulting in a decrease in sticking resistance. Therefore, a long alkylene chain is not necessary, and n in the above formula is an integer of 0 to 3. Particularly easily available and useful ones include dimethylaminoethyl methacrylate and dimethylaminoethyl acrylate. Carboxyl group-containing monomers include acrylic acid, methacrylic acid, α-bromoacrylic acid, α-
Examples include chloroacrylic acid, maleic anhydride, itaconic acid, and the like. Acrylic acid or methacrylic acid is preferred from the viewpoint of copolymerizability with monomers containing aliphatic amino groups. During vinyl polymerization, these functional group-containing monomers are mixed with other vinyl polymerization monomers and subjected to the polymerization reaction, or in some cases, they are mixed with aliphatic amino group-containing monomers and carboxyl group-containing monomers. The desired vinyl copolymer can be easily made into a film-imparting polymer by subjecting it to a polymerization reaction by shifting the timing of the addition of the vinyl copolymer. Other vinyl polymerizable monomers used in vinyl copolymer compounds include methyl methacrylate,
Butyl methacrylate, α-ethylhexyl methacrylate, lauryl methacrylate, ethyl acrylate, methyl acrylate, styrene, vinyltoluene, N-vinylpyrrolidone, α-methylstyrene, α-hydroxyethyl methacrylate, 2-
Hydroxyethyl acrylate, acrylamide, acrylonitrile, etc. are used. By using a copolymer of these aliphatic amino group-containing monomers and carboxyl group-containing monomers as a film-imparting polymer, it is possible to create photosensitive resin compositions that do not develop when these monomers are used alone. A significant improvement in the initial adhesion and adhesion between the material layer and the substrate is found in the unexposed and exposed areas. Moreover, these improvement effects are achieved by a polymer containing an extremely small amount of the above monomer as a copolymer component. The content of the aliphatic amino group-containing monomer is 0.1% to 10% by weight, preferably 0.2% to 5% by weight, based on the film-like polymer. on the other hand,
The content of the carboxyl group-containing monomer copolymerized with the aliphatic amino group-containing monomer is 0.2% by weight to 5% by weight or 10% by weight based on the film properties imparting polymer.
~40% by weight. 1 photosensitive resin composition layer,
When developing in an organic solvent such as 1,1-trichloroethane, the amount of carboxyl group-containing monomer present is sufficient at 0.2 to 5% by weight, preferably 0.5% by weight.
~3% by weight. When the photosensitive resin composition layer is of an alkali-developable type, the carboxyl group content used in conventional alkali-developable photosensitive resin compositions is used as is. The appropriate amount of the carboxyl group-containing monomer is 10% to 40% by weight, preferably 10% to 40% by weight, based on the film properties imparting polymer.
It is 15% to 30% by weight. The organic halogen compound is preferably one that easily releases halogen radicals by actinic light or one that easily releases halogen radicals by chain transfer. Examples of organic halogen compounds include carbon tetrachloride, chloroform, bromoform, 1,1,1-
Trichloroethane, methylene bromide, methylene iodide, methylene chloride, carbon tetrabromide, iodoform,
1,1,2,2-tetrabromoethane, pentabromoethane, tribromoacetophenone, bis-
Examples include (tribromomethyl)sulfone, tribromomethylphenylsulfone, vinyl chloride, and chlorinated olefin. Preferred are fatty acid halogen compounds with weak carbon-halogen bond strength, particularly compounds in which two or more halogen atoms are bonded to the same carbon, and especially organic bromine compounds. Organic halogen compounds having a tribromomethyl group give more favorable results. The amount of the organic halogen compound to be blended is not particularly limited, but is preferably 0.2 to 10 mol, more preferably 0.5 mol per mol of the above aliphatic amino group-containing monomer.
~3 moles. In the present invention, although the reaction that occurs inside the photosensitive resin composition is not clear, halogen radicals generated directly or indirectly from the organic halogen compound by irradiation with actinic radiation are present in the composition. Hydrogen is extracted from the hydrogen donor to produce hydrogen halide, which reacts with the alkylamino group present in the side chain of the film-imparting polymer to produce a quaternary ammonium salt, or at the same time to produce a vinyl copolymer compound. It is estimated that this process involves the quaternization of amino groups through intermolecular and intramolecular salt-forming reactions. Therefore, the actinic ray irradiation introduces a new polar group having an ionic structure into the side chain of the polymer imparting film properties, which is considered to be one of the reasons for the improvement in the adhesion of the photosensitive resin composition in the present invention. However, in general, the presence of polar groups in the side chains of film-imparting polymers provides physical adhesion between the substrate, the photosensitive composition, and its cured product, but the presence of polar groups in the side chains of the polymer imparting film properties provides physical adhesion between the substrate and the photosensitive composition and its cured product. It does not necessarily show the same effect on dripping liquid. This is particularly noticeable when plating is performed. For example, polymers with film properties that have carboxyl groups in their side chains exhibit sufficient resistance to acidic etching solutions, but they do not tolerate alkaline copper pyrophosphate plating baths. The resistance to these substances is significantly reduced. However, the photosensitive resin composition using the film-like polymer and the organic halogen compound and the photosensitive element using the same according to the present invention have good sticking resistance despite the fact that polar groups are expected to be formed in the cured product. It is surprising that no decrease was observed. Conventionally known ethylenically unsaturated compounds can be used as the ethylenically unsaturated compound in the photosensitive resin composition of the present invention, but from the viewpoint of high sensitivity, it is preferable to use acrylate monomers or methacrylate monomers. preferable. For example, trimethylolpropane triacrylate, pentaerythritol triacrylate, 1,6-hexanediol diacrylate, 2,2-bis(4-methacryloxyethoxyphenyl)propane, 2,2-bis(4-acryloxyethoxyphenyl) enyl) propane,
Polyacrylate or polymethacrylate of polyhydric alcohols such as dipentaerythritol pentaacrylate and trimethylolpropane trimethacrylate, adducts of trimethylpropane triglycidyl ether with acrylic acid or methacrylic acid, acrylic acid of bisphenol A epichlorohydrin-based epoxy resins Alternatively, epoxy acrylates such as methacrylic acid adducts, and low molecular weight unsaturated polyesters such as 1:1:2 condensates of phthalic anhydride-neopentyl glycol-acrylic acid may be mentioned. Polyethylene glycol acrylates or methacrylates such as diethylene glycol diacrylate, tetraethylene glycol diacrylate, nonaethylene glycol diacrylate, tetraethylene glycol dimethacrylate, and polyethylene glycol (molecular weight approximately 400) diacrylate are also used, but they are not durable when used. The amount to be added should be determined with consideration given to maintaining stickiness. In particular, it is desirable to use the above-mentioned polyhydric alcohol in combination with polyacrylate. Furthermore, there are no restrictions on the sensitizer and sensitizer system capable of generating free radicals by actinic rays in the present invention, and conventionally known ones can be used. For example, benzophenones such as benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 4,4'-dichlorobenzophenone, 2-ethylanthraquinone, t-butylanthraquinone, etc. anthraquinones, 2-chlorothioxanthone, benzoin ethyl ether, benzoin isopropyl ether, benzyl, 2,4,5-triarylimidazole dimer (lofin dimer), etc.
A species or two or more species may be used. In the photosensitive resin composition of the present invention, 30 to 80 parts by weight of the film-imparting polymer and 70 to 20 parts by weight of the ethylenically unsaturated compound are used so that the total amount is 100 parts by weight. It is preferable to use 0.5 to 10 parts by weight of a sensitizer and/or sensitizer system capable of generating free radicals by actinic radiation, and 0.2 to 10 parts by weight of an organic halogen compound, based on the weight part. There are no particular restrictions on the mixing order, mixing method, etc. of these materials. In addition, dyes, plasticizers, pigments, flame retardants, stabilizers, etc. can also be added to the photosensitive resin composition of the present invention, if necessary. It is also possible to use an adhesion imparting agent. Examples of the present invention will be described. Example 1 1-a A film-like polymer (hereinafter referred to as polymer) containing an aliphatic amino group-containing monomer and a carboxyl group-containing monomer as copolymerization components was synthesized by the procedure described below. Table 1 shows the monomer formulation.

[Table] The numbers are weight % and the total amount is 400g. 400 g of a monomer mixed solution was prepared according to the formulation shown in Table 1. Next, toluene was added to a 14-neck reaction flask connected to a condenser, thermometer, and dropping device.
250g of each monomer solution weighed according to Table 1, 150g of each were added, and the temperature was raised to 93°C through a nitrogen stream. Next, the remaining monomer 250g, toluene 150g
g and 0.50 g of azobisisobutyronitrile were mixed and the dissolved mixture was added dropwise over 3 hours. After completion of the dropwise addition, the mixture was kept warm for another 7 hours. During this time, the temperature of the flask was maintained at 93°C. Next, add 0.25g of azobisisobutyronitrile to 75g of toluene.
was added dropwise over 30 minutes. After the dropwise addition, the mixture was kept warm for 4 hours and diluted with 75 g of toluene and 75 g of methyl ethyl ketone to form polymers P-1 to P-6, respectively. Table 2 shows the properties of the obtained polymer. Of these, P-6
These are examples of the present invention, and the others are comparative examples.

[Table] 1-b The following photosensitive resin compositions were blended according to the formulations shown in Table 3.

[Table] V-6 in Table 3 is an example of the present invention,
The others are comparative examples. 1-c Using the apparatus shown in FIG. 1, the photosensitive composition solutions of V-1 to V-6 were applied to a polyethylene terephthalate film (Lumirror Film manufactured by Toray Industries, Inc.) having a thickness of 23 μm so that the film thickness after drying was 50 μm. The coating was dried and covered with a polyethylene film having a thickness of 35 μm to obtain a photosensitive element.
In Fig. 1, 1 is a polyethylene terephthalate film feed roll 2, 3, 4, 9, 1.
0 is a roll, 5 is a knife, 6 is a solution of photosensitive resin composition, 7 is a dryer (dried at 80°C for 5 minutes) 8
is a polyethylene film feed roll, 11
is the take-up roll of the photosensitive element. While peeling off the polyethylene film from the obtained photosensitive element, the photosensitive layer surface was polished and dried using a Scotch Bright buff roll, and a Hitachi high-temperature laminator was applied to the copper surface of a cleaned copper-clad laminate (100 mm x 200 mm). Sample pieces were obtained by sequentially stacking layers. The lamination conditions are shown in Table 4.

[Table] 1-d The sample piece obtained in 1-c was cut along the edge of the laminate, and the polyethylene terephthalate film was peeled off by hand without exposing it to light. The ease of peeling is summarized in Table 5. In addition, a polyethylene terephthalate film was separately peeled off (for comparative examples, only one end of the photosensitive film was exposed, and then the polyethylene terephthalate film was carefully peeled off from the exposed part), and a polyester adhesive tape (Hitachi Chemical Co., Ltd.) AYT-210-6) was applied, and the 180° peel strength was measured using an autograph as shown in FIG. 2, and the results are summarized in Table 5. In FIG. 2, 12 is a copper clad laminate, 13 is a photosensitive layer, and 14
1 is an adhesive layer, 15 is a polyethylene terephthalate film (14 and 15 constitute a polyester adhesive tape), and parts A and B are attached to a jig.

[Table] Table 5 shows that the photosensitive resin composition of the present invention has excellent adhesion strength between the photosensitive layer and the copper surface. Each sample obtained in 1-e and 1-c was passed through a 21-tone step-tablet negative film using an ultra-high pressure mercury lamp (Oak Co., Ltd. HMW-) equipped with a vacuum printing frame.
6-N type, 2KW) at 60 mJ/cm ² . After leaving it for 30 minutes, peel off the polyethylene terephthalate film and spray 1,1,1-trichloroethane as a developer for 60 seconds (18℃/, 1.5Kg/
cm ² ) After washing with water, the number of curing stages of the step tablet was continued. The larger the number, the higher the sensitivity. The results are summarized in Table 6.

[Table] Table 6 shows that the photosensitive resin composition of the present invention has excellent sensitivity. Example 2 Polymer P-7 was synthesized using the formulation shown in Table 7.

[Table] The mixture was placed in the same reaction vessel as in 1-a, and the temperature was raised to 90°C through a nitrogen stream. Next, the solution was added dropwise over 3 hours, and after the completion of the addition, the mixture was kept warm for an additional 7 hours. During this time, the temperature of the flask was maintained at 90°C. Next, it was added dropwise over 30 minutes, kept warm for 4 hours, and then further diluted. Table 8 shows the properties of the obtained polymer P-7.

[Table] Using Polymer P-7, a photosensitive resin composition was prepared with the following formulation. P-7 50 (dry weight) DPHA ^*1 35 A-14G ^*2 10 2-Ethylanthraquinone 3.5 ANTAGE W500 0.5 Leuco Crystal Violet 0.5 Tribromomethylphenylsulfone 1.0 Spiron Blue 2BNH 0.2 Methyl Ethyl Ketone 30 Toluene 10 (The numbers are weight *1 Dipentaerythritol pentaacrylate manufactured by Nippon Kayaku Co., Ltd. *2 Polyethylene glycol diacrylate manufactured by Shin Nakamura Chemical Co., Ltd. It was coated on a terephthalate film and dried to obtain a photosensitive element with a film thickness of 50 μm. This material was laminated on the entire surface of a 250 mm x 330 mm copper clad laminate that had been polished and cleaned in the same manner as in Examples 1 and 1-c, and was exposed to light through a tenting mask negative with no exposed areas in the peripheral area. Lamination and exposure were performed in the same manner as in Example 1 and 1-e. After leaving it for 30 minutes, the polyethylene terephthalate film was peeled off. At this time, the polyester film was easily peeled off. When developed with 1,1,1-trichloroethane, a defect-free circuit pattern resist was obtained. When this was etched with a copper chloride etching solution, a defect-free printed wiring board with copper circuits formed in the areas where the resist was exposed was obtained. Etching conditions were carried out under conditions known to the manufacturer. As a comparative example, polymer P- of the above photosensitive composition
In the case where Polymer P-1 shown in Example 1 was used instead of Polymer P-1 (Comparative Example 6), the adhesion between the photosensitive layer and copper was poor, and part of the photosensitive layer was peeled off when the polyester film was peeled off. This was developed and etched at the same time, but the circuit broke, making it impossible to put it to practical use. Example 3 Photosensitive resin compositions of Example 3 and Comparative Example 7 were obtained according to Table 9.

[Table] Using the same method as described in Example 1, a photosensitive element with a photosensitive layer thickness of 25 μm and a blank sample piece were prepared, and the adhesive strength between the unexposed photosensitive layer and the copper surface was shown in Example 1. It was measured over time using the same method.
The results are shown in Figure 3. C shows the curve for Example 3, and D shows the curve for Comparative Example 7. From FIG. 3, it can be seen that the adhesive strength of the photosensitive resin composition according to the present invention to the copper surface is stronger than that at the initial stage of lamination, and has good adhesion. The photosensitive element of Example 3 exposed through a circuit pattern negative mask (120 mJ/cm ² ) and spray developed for 40 seconds with a 2% aqueous sodium carbonate solution formed a good resist image; It showed good properties as an etching resist for diiron. The photosensitive resin composition of the present invention has excellent adhesion to laminated surfaces, especially initial adhesion, and has high sensitivity, and is suitable as an etching resist material, a plating resist material, etc. in the production of printed wiring boards, for example. It is something.

[Brief explanation of the drawing]

Fig. 1 is a schematic diagram showing an example of a photosensitive element manufacturing apparatus, Fig. 2 is a schematic diagram showing a method for measuring peel strength carried out in Examples, and Fig. 3 is a schematic diagram showing the measurement results of adhesive strength carried out in Examples. FIG. Explanation of symbols, 1...Polyethylene terephthalate film feed roll, 2, 3, 4, 9, 1
0... Roll, 5... Knife, 6... Solution of photosensitive resin composition, 7... Dryer, 8... Polyethylene film feed roll, 11... Photosensitive element winding roll, 12... Copper clad Laminated board, 1
3...Photosensitive layer, 14...Adhesive layer, 15...Polyethylene terephthalate film.

Claims (1)

[Claims] 1 Formula (A) (However, n is an integer of 0 to 3, R ₁ , R ₂ , R ₃ are hydrogen or methyl groups, R ₄ and R ₅ are alkyl groups having 1 to 4 carbon atoms, or 4 A monomer containing an aliphatic amino group represented by (forming a saturated alicyclic ring of 7 to 7 membered rings) is used as a copolymerization component to a polymer imparting film properties.
Film properties imparting polymer consisting of a vinyl copolymer compound obtained by using 0.1 to 10% by weight and a carboxyl group-containing monomer as a copolymerization component of 0.2 to 5% or 10 to 40% by weight based on the film properties imparting polymer. A photosensitive resin composition comprising (B) an organic halogen compound, (C) an ethylenically unsaturated compound, and (D) a sensitizer and/or a sensitizer system capable of generating free radicals by actinic radiation. 2 The film property-imparting polymer is composed of an aliphatic amino group-containing monomer as a copolymerization component of 0.2% to 5% by weight of the film property-imparting polymer and a carboxyl group-containing monomer as a copolymerization component. 0.5% to 3% by weight
The photosensitive resin composition according to claim 1, which is a film-forming polymer containing 15% to 30% by weight. 3. The photosensitive material according to claim 1 or 2, wherein the aliphatic amino group-containing monomer is dimethylaminoethyl acrylate or dimethylaminoethyl methacrylate, and the carboxyl group-containing monomer is acrylic acid or methacrylic acid. resin composition. 4. The photosensitive resin composition according to claim 1, 2, or 3, wherein the organic halogen compound is an organic halogen compound having a tribromomethyl group. 5. The photosensitive resin composition according to claim 1, 2, 3, or 4, wherein the ethylenically unsaturated compound is an acrylate monomer or a methacrylate monomer.