TW201217905A - in which the Haze of the support film is 0.01-2.0%, and the total particles with diameter greater than 5 μm and agglutinate with diameter greater than 5 μm in the support film are less than 5 per mm<SP>2</SP> - Google Patents

Abstract

The photosensitive device of the present invention includes a support film where a photosensitive device for forming a photosensitive resin composition layer is thereon, in which the Haze of the support film is 0.01-2.0%, and the total particles with diameter greater than 5 μm and agglutinate with diameter greater than 5 μm in the support film are less than 5 per mm<SP>2</SP>. The photosensitive resin composition layer includes: adhesive polymer, photo-polymerization compounds having an ethylenic unsaturated link and photopolymerization initiator, where the adhesive polymer having an acid value x being 60-130mgKOH/g, with a weight average molecular weight Mw satisfying the relation defined by Formula (I), 10000 ≤ Mw < 4000e0.02x.

Description

201217905 SUMMARY OF THE INVENTION [Technical Field] The present invention relates to a photosensitive element, a method of forming a photoresist pattern using the same, a method of manufacturing a printed circuit board, and a printed circuit board. [Prior Art] Conventionally, in the field of manufacturing of printed circuit boards and the field of precision metal processing, photoresist materials for etching, plating, etc. are widely used for a layer composed of a photosensitive resin (hereinafter referred to as "photosensitive layer". </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. The printed circuit board is manufactured as follows. First, after the protective film of the photosensitive element is peeled off from the photosensitive layer, the photosensitive layer is laminated on the conductive film of the substrate for circuit formation. Next, after the pattern exposure is applied to the photosensitive layer, the unexposed portion of the photosensitive layer is removed by the developing liquid to form a photoresist pattern. Then, according to the photoresist pattern, the conductive film is patterned to form a printed circuit board. In recent years, with the increase in density of printed circuit boards, the contact area between the circuit-forming substrate and the photosensitive layer of the photoresist material has become small. Therefore, the photosensitive resin composition forming the photosensitive layer is required to have excellent mechanical strength, chemical resistance, and flexibility in the etching or plating step. At the same time, excellent adhesion to the substrate for forming a circuit and excellent resolution at the time of pattern formation are required. Example -5 - 201217905 A photosensitive resin composition containing a binder polymer having a specific structure for the purpose of excellent plating resistance is disclosed (see JP-A-2006-234995, JP-A-2008-03 9978). When a photosensitive element is usually used to form a photoresist, the photosensitive layer is laminated on a substrate, and then placed on a support film to expose the photosensitive layer. Therefore, in order to obtain a high resolution in the formation of a pattern, not only a photosensitive resin composition but also the properties of the supporting film to be used are considered. In order to obtain a high resolution, for example, it is proposed to contain inorganic or organic fine particles having an average particle diameter of about 〜1 to 5 μηι on the outermost surface of one of the supporting films to reduce the haze of the supporting film even if the supporting film is used for the photosensitive layer. The exposure can also be a method of high resolution (for example, refer to Japanese Patent No. 401 4872, International Publication No. 08/093643, Japanese Patent Publication No. Hei 07-3 3 3 8 53, and International Publication No. 00/079344). SUMMARY OF THE INVENTION However, in the conventional method, it is possible to suppress a decrease in the resolution of the photosensitive layer due to the influence of the supporting film and to suppress the photoresist shape defect (photoresist defect) after the curing is suppressed to some extent, but in order to satisfy the characteristics required for the photosensitive element in recent years. , need further improvement. Only the conventional photosensitive resin composition is described in Japanese Patent Publication No. 40 1 48 72, International Publication No. 08/093643, Japanese Patent Application Laid-Open No. Hei No. Hei. When supporting film combination, there is still room for further improvement when there is a limit to the 'requirement for resolution and resolution required in recent years. -6 - 201217905 The present invention has been made in view of the above, and an object of the present invention is to provide a photosensitive element which can sufficiently reduce a photoresist defect and which has excellent developability and resolution at the time of pattern formation. The present invention provides a photosensitive element comprising a photosensitive member having a support film and a photosensitive resin composition layer formed on the support film, wherein the support film has a haze of 0.01 to 2.0%, and the support film is provided The total number of particles having a diameter of 5 μm or more and agglomerates having a diameter of 5 μm or more is 5 pieces/mm 2 or less, and the photosensitive resin composition layer contains a binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, and light. In the polymerization initiator, the binder polymer has an acid value X of 60 to 130 mgKOH/g, and the weight average molecular weight Mw satisfies the relationship represented by the following formula (I). 10000 ^ Mw &lt; 4000e ° 02x (I) [In the formula (I), x represents the acid value of the binder polymer, and Mw represents the weight average molecular weight of the binder polymer]. The photosensitive element of the present invention is provided with a support film having the above configuration, and the photoresist defect can be sufficiently reduced. Further, since the photosensitive element of the present invention has the photosensitive resin composition layer having the above-described configuration, the photoresist defect can be sufficiently reduced, and the image forming property and the resolution at the time of pattern formation are excellent. The photopolymerizable compound having an ethylenically unsaturated bond may contain a compound represented by the following general formula (II).

(H)

201217905 In the general formula (Π), 'R1 and R are independent of each other, Y is an alkylene group having 2 to 6 carbon atoms, η1 and η2 are integers, and rikn2 is 4 to 40. The polar type can be formed because the compound represented by the above general formula (Π) has a good balance of resolution and chemical resistance. Further, the photosensitive element of the present invention has a good balance between the valence, resolution and releasability represented by the general formula (ΠΙ), (IV) and (V) of the binder, and can form a pattern. &lt;πι&gt; indicates that a hydrogen atom or a radical is represented by the same or different. Therefore, the photoresist pattern of the adhesive fine line has the following groups, and thus the photoresist of the dense fine line

(IV) &quot;CH2#e*C*—

&lt;V) OR7 In the general formula (III) (IV) and (V), R3, R4 and R6 each of 201217905 independently represent a hydrogen atom or a methyl group, and R5 represents an alkyl group having a carbon number of 1 to 4 and a carbon number. 1 to 3 of the alkoxy group, a hydroxyl group or a halogen atom, and R7 means an alkyl group having a carbon number of 10'. The P group represents an integer of 0 to 5, and when p is 2 or more, the plural R5 may be the same or different. In the photosensitive element of the present invention, since the binder polymer further has a divalent group represented by the following general formula (VI), the balance of adhesion, resolution and releasability is further improved. R15 I - CH2-C— (VI)

0 into. In the general formula (VI), R15 represents a hydrogen atom or a methyl group, and Ri6 represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a hydroxyl group or a halogen atom, and q represents 0 to 5 When the integer 'q is 2 or more, the plural R16s may be the same or different from each other. Further, in the photosensitive element of the present invention, the photopolymerization initiator may contain a 2,4,5-triarylimidazole dimer. Thereby, the light sensitivity can be maintained, so that the adhesion and the resolution are more excellent, and a photoresist pattern of an extremely thin line can be formed. Further, the present invention provides a method for forming a photoresist pattern, comprising: laminating the photosensitive element on a circuit-forming substrate in the order of the photosensitive resin composition layer and the -9 - 201217905 support film; a laminating step of exposing the active light to the predetermined portion of the photosensitive resin composition layer through the support film, and forming a photocured portion on the photosensitive resin composition layer: removing the photocuring portion a developing step of the photosensitive resin composition layer. According to the method for forming a photoresist pattern of the present invention, since the photosensitive element of the present invention described above is used, a photoresist pattern of an extremely fine line can be obtained efficiently. The present invention provides a method of manufacturing a printed circuit board, which is a method of manufacturing a printed circuit board having a step of performing etching or plating on a circuit for forming a circuit pattern having a photoresist pattern, and a method of manufacturing the same by the above-described manufacturing method Printed circuit board. According to the method for producing a printed wiring board of the present invention, a pattern of forming a photoresist pattern using the photosensitive element of the present invention is used, whereby a high-density printed circuit board having a wiring pattern of an extremely thin line can be obtained. According to the photosensitive element of the present invention, the photoresist defect can be sufficiently reduced, and a photosensitive element having excellent developability and resolution at the time of pattern formation can be provided. DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In the drawing, the positional relationship of up, down, left, and right, etc., is based on the positional relationship shown in the drawing when there is no special statement. Further, the dimensional ratio of the drawings is not limited to the ratio shown. In addition, in this specification, "(meth)acrylate-10-201217905" means "acrylate" and the corresponding "methacrylate", and "(meth)acryloyl group" means "acryloyl group" And the corresponding "methacryl oxime". BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a preferred embodiment of a photosensitive member of the present invention. The photosensitive element 1 shown in Fig. 1 is composed of a support film 10 and a photosensitive layer (photosensitive resin composition layer) 20. The photosensitive layer 20 is provided on the first main surface 12 of the support film 10. Further, the support film 10 has a second main surface 14 on the side opposite to the first main surface 12. (Support film) The film 10 has a haze of 0.01 to 2.0%, and the total number of particles having a diameter of 5 μm or more and agglomerates having a diameter of 5 μm or more (hereinafter simply referred to as "particles" or the like) contained in the film 10 is 5 pieces. /mm2 or less. Here, the particles having a diameter of 5 μm or more contained in the support film 10 include both the first main surface 12 and the second main surface 14 of the support film 1 and those existing inside the film 10. Further, particles having a diameter of 5 μm or more include agglomerates of primary particles having a diameter of 5 μm or more and primary particles having a diameter of 5 μm or less. The total number of particles having a diameter of 5 μm or more is preferably 5 pieces/mm 2 or less, more preferably 3 pieces/mm 2 or less, and more preferably 1 part, from the viewpoint of reducing partial defects of light resistance after exposure and development. /mm2 or less. When a photosensitive element having a total number of particles or the like of more than 5/mm 2 is used in the production of a printed circuit board, it causes a baking failure during etching or a short-circuit defect during plating, and the manufacturing yield of the printed circuit board is lowered. tendency. Even if the support film 10 contains a large number of particles which are not in diameter, etc., the effect of 'preferential -11 - 201217905 on light scattering is small" is mainly due to the light hardening of the photosensitive layer 20 when light is irradiated onto the photosensitive layer 20 in the exposure step described later. The reaction is not only a part of the light-irradiating portion, but also reacts in the lateral direction (the vertical direction with respect to the light irradiation direction) in which the light is not directly irradiated. Therefore, when the particle diameter is small, the photohardening reaction in the lower portion of the particle proceeds sufficiently. However, as the particle diameter increases, the photohardening reaction in the lower portion of the particle does not sufficiently proceed, and a photoresist defect (photoresist defect) may occur. Particles having a diameter of 5 μm or more contained in the support film 10 constitute a component of the support film 10, and examples thereof include a gel of a polymer, a monomer of a raw material, a catalyst used in the production, and an inorganic or organic material if necessary. When the microparticles are formed in a film, agglomerates formed by agglutination, swelling caused by a slip agent and an adhesive generated when a lubricant layer is applied to the film, and particles having a diameter of 5 μm or more contained in the film are generated. . When the particles having a diameter of 5 μm or more are set to 5 pieces/mm 2 or less, those having a small particle diameter or excellent dispersibility can be selected among these particles and the like. The total number of particles having a diameter of 5 μm or more can be measured using a polarizing microscope. The aggregate formed by the primary particles having a diameter of 5 μm or more and the primary particles having a diameter of less than 5 μm is regarded as one calculation. Fig. 2 is a photograph of a polarizing microscope for observing the surface of a supporting film having particles having a diameter of 5 μm or more. In Fig. 2, a portion surrounded by a circle is an example of a portion corresponding to a particle having a diameter of 5 μm or more. Fig. 3 is a scanning-type micrograph of a resist pattern formed by a photosensitive member having a photosensitive layer on a support film having a plurality of particles having a diameter of 5 μm or more. The portion surrounded by the frame indicates the photoresist defect. Thus, when a large number of particles having a diameter of 5 μm or more and -12 to 201217905 are formed on the surface of the support film, a photoresist defect occurs. The material of the support film 10 is not particularly limited as long as the total number of particles having a diameter of 5 μm or more is 5 pieces/mm 2 or less. The support film 10 is, for example, a film containing one or more kinds of resin materials selected from the group consisting of polyesters such as polyethylene terephthalate (hereinafter referred to as "PET") and polyolefins such as polypropylene and polyethylene. . The support film 10 may be a single layer or a plurality of layers. For example, when a two-layer support film composed of two layers is used, a two-layer film formed by laminating a resin layer containing fine particles on one surface of a biaxially oriented polyester film is used as a support film, and a resin layer containing the above-mentioned fine particles is formed. It is preferable that the photosensitive layer 20 is formed on the surface on the opposite side. The support film 10 can also use a multilayer support film composed of three layers (e.g., layer A/layer B/layer A). The configuration of the multilayer support film is not particularly limited. However, from the viewpoint of the smoothness of the film and the like, the outermost layer (the layer A when the three layers are formed) is preferably a resin layer containing fine particles. In the conventional two-layer support film, a resin layer having fine particles is applied to a biaxially oriented polyester film, and thus, when the photosensitive layer is laminated, the resin layer containing fine particles is easily peeled off, and the resin layer after peeling adheres to the photosensitive layer. Layers may cause undesirable causes. Therefore, in the present embodiment, it is preferred to use a multilayer support film composed of three layers of a resin layer containing fine particles and a biaxially oriented polyester film. In the present embodiment, it is particularly preferable to adjust the total number of particles or the like of the support film 1 5 to 5 μm or less, and to provide a multilayer support film containing the resin layer of such fine particles. Therefore, the smoothness of the film is improved, and at the same time, the balance of light scattering at the time of exposure is suppressed, and a higher water level can be achieved -13 - 201217905. The average particle diameter of the fine particles is preferably from 0" to 10 times, more preferably from 2 to 5 times, the layer thickness of the resin layer containing the fine particles. When the average particle diameter is less than 0.1, the slip property tends to be deteriorated. When the average particle diameter is less than 10 times, the photosensitive layer tends to have irregularities. The fine particles are preferably contained in the resin layer containing fine particles in an amount of 0.01 to 50% by mass based on the mass of the resin. For the fine particles, for example, fine particles such as fine particles, aggregates, cerium oxide fine particles (such as aggregated cerium oxide) generated by various nucleating agents, calcium carbonate fine particles, alumina fine particles, titanium oxide fine particles, and barium sulfate fine particles can be used. Organic fine particles such as crosslinked polystyrene fine particles, acrylic resin fine particles, and yttrium imide fine particles, and the like. In the multilayer support film of three or more layers, the intermediate layer containing one or more of the outermost layers containing the fine particles may be one containing or not containing the fine particles, and it is preferable that the fine particles are not contained from the viewpoint of resolution. . When the intermediate layer contains the above fine particles, the content of the intermediate layer is preferably 1/3 or less, more preferably 1/5 or less, of the content of the outermost layer. Further, from the viewpoint of the resolution, the thickness of the resin layer containing the fine particles is preferably from 〇1 to 5 μm, more preferably from 〇5 to 3 μη, particularly preferably from 0.1 to 2 μηη. The surface which is not opposed to the intermediate layer of the outermost layer preferably has a static friction coefficient of 1.2 or less. When the static friction coefficient exceeds 1.2, ruthenium tends to occur during film production and photosensitive element production, and static electricity tends to occur, and there is a tendency for easy adhesion of garbage. In the present embodiment, the static friction coefficient can be measured in accordance with ASTM D 1894. When the total number of-14-201217905 such as particles having a diameter of 5 μη or more contained in the support film 10 is set to 5/mm 2 or less, the particle diameter of the fine particles contained in the resin layer containing fine particles is preferably not reached. 5 μιη. In order to further reduce the light scattering at the time of exposure, it is preferable to appropriately adjust the layer thickness of the resin layer containing the fine particles in accordance with the particle diameter of the fine particles. The support film 10 may contain an antistatic agent or the like when necessary in a range that does not affect the photosensitivity of the photosensitive layer 20. The haze of the support film 10 is preferably 2.0% or less, more preferably 1.5% or less, still more preferably 1.0% or less, and particularly preferably 0.5% or less from the viewpoint of excellent light sensitivity and resolution. Here, "haze" means turbidity. The haze of the support film 10 in the present embodiment is measured by a commercially available turbidity measurement in accordance with the method specified in JIS Κ 71 05. The haze can be measured using, for example, a commercially available turbidity meter such as NDH-1 00 1DP (manufactured by Nippon Denshoku Industries Co., Ltd.). The lower limit of the haze is preferably close to zero from the viewpoint of excellent light sensitivity and resolution, and the haze is preferably 0.01 or more from the viewpoint of the winding property at the time of production of the support film 10. When the haze is less than 0.01, the support film does not contain fine particles or the like, which causes problems in the winding of the support film, and tends to cause creases and the like. The thickness of the support film 10 is preferably 5 to 40 μm, more preferably 8 to 35 μm, still more preferably 10 to 30 μm, and particularly preferably 12 to 25 μm. When the thickness is less than 5 μm, the support film tends to be easily broken when the support film is peeled off from the photosensitive element. Further, when the thickness exceeds 40 μm, the resolution tends to decrease, and at the same time, the price tends to be inferior. The support film 10 can be obtained from a commercially available general industrial film as a support film 10 for the photosensitive element 1, or can be suitably processed to be used for -15-201217905. A commercially available general-purpose film which can be used as the support film 10, for example, a PET film "QS-48" (manufactured by Toray Industries, Inc.) having a three-layer structure containing fine particles in the outermost layer (photosensitive layer) photosensitive layer 20 A layer composed of a photosensitive resin composition. The photosensitive resin composition constituting the photosensitive layer 20 contains (a) a binder polymer (hereinafter referred to as "(A) component"), (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) light. A polymerization initiator (hereinafter referred to as "(C) component"). Each component will be described in detail below. (Binder Polymer) The binder polymer of the component (A) is not particularly limited as long as it has an acid value x of 60 to 130 mg KOH/g and a weight average molecular weight Mw satisfying the relationship represented by the following formula (I). use. 10000^Mw&lt;4000e°°2x (I) The relationship between the acid value X of the binder polymer and the weight average molecular weight Mw satisfies the relationship of the above formula, and provides properties after hardening (developability, adhesion, resolution) Excellent photosensitive resin composition for the shape of the photoresist, the shape of the photoresist side, and the photoresist defect. The acid value X of the binder polymer is 60 to 130 mgKOH/g, but is preferably 65 to 130 mgKOH/g, more preferably 90 to 130 mgKOH/g, still more preferably 110 to 130 mgKOH/g, from the viewpoint of balance and satisfying the above characteristics. g. The same index as the acid value (mg of potassium hydroxide (KOH) required for neutralizing the sample lg-16 - 201217905), for example, an acid equivalent (g number of a polymer having 1 equivalent of a carboxylic acid), etc. Can be converted to each other. The weight average molecular weight of the binder polymer satisfies the relationship expressed by the above formula (I). The lower limit of the Mw of the binder polymer is 10,000 or more, and from the viewpoint of excellent toughness of the photosensitive layer, it is preferably 150,000 or more, more preferably 20,000 or more, still more preferably 25,000 or more. Further, the upper limit of the Mw of the binder polymer is less than or equal to WOOe^x, and from the viewpoint of balance and satisfying the properties after hardening, it is preferably 90 °/ of WOOjMx. Hereinafter, the better one is 80% or less, and more preferably 70% or less. The weight average molecular weight is measured by gel permeation chromatography (hereinafter referred to as "GPC") and converted to standard polystyrene. The measurement conditions are the same as those described in the examples below. The binder polymer is, for example, an acrylic resin, a styrene resin, an epoxy resin, a guanamine resin, a guanamine epoxy resin, an alkyd resin, and a phenol resin. Among these, an acrylic resin is preferred from the viewpoint of alkali developability. These may be used alone or in combination of two or more. The binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer. The polymerizable monomer is, for example, a polymerizable styrene derivative such as styrene, vinyl toluene, p-methylstyrene, P-chlorostyrene, α-methylstyrene or α-methylstyrene derivative, Ethyl alcohol esters such as acrylamide, acrylonitrile and vinyl-η-butyl ester, alkyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, Methyl) dimethylaminoethyl acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate And (2,2,3,3-tetrafluoropropyl (meth) acrylate (A-17-201217905) acrylate, (meth)acrylic acid, α-bromo (meth)acrylic acid, α-chloride (Meth)acrylic acid, β-furyl (meth)acrylic acid, and (meth)acrylic acid derivatives such as β-styryl (meth)acrylic acid, maleic acid, maleic anhydride, monomethyl maleate Maleic acid derivatives such as maleic acid monoethyl ester and maleic acid monoisopropyl ester, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, and bar Acid, propiolic acid and the like. These may be used alone or in combination of two or more.

The binder polymer preferably has a structure represented by the following general formulas (111), (IV), and (V) from the viewpoint of the balance between the resistance (development + liquid resistance) and the peelability of the developing solution. unit. Further, since the development liquid resistance is improved, there is a tendency that the adhesion and the resolution are improved. &lt;ΙΠ)

〇 OH

In the general formulae (III), (IV) and (V), 'R3, R4 and R6 are each -18-201217905 from independently representing a hydrogen atom or a methyl group, and R5 is an alkyl group having a carbon number of 1 to 4' carbon number 1. An alkoxy group of ~3, a hydroxyl group or a halogen atom, R7 represents an alkyl group having a carbon number, P represents an integer of 0 to 5, and when p is 2 or more, R5 which is present in plural plural may be the same or different. The structural unit represented by the above general formula (III) is based on the structural unit of (meth)acrylic acid, and is preferably a structural unit based on methacrylic acid (R3 = methyl group). (A) When the binder polymer contains the structural unit represented by the above general formula (III), the content ratio is based on the total solid content of the (A) binder polymer of the copolymer, and the development and releasability are based on Further, the viewpoint is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more. In addition, from the viewpoint of excellent adhesion and resolution, it is preferably 50% by mass or less, more preferably 4% by mass or less, and still more preferably 35% by mass or less. The structural unit represented by the above general formula (IV) is based on styrene (R4 = hydrogen atom, ρ = 〇), styrene derivative, α-methylstyrene methyl group, ρ = 0) and α-methyl styrene. The structural unit of the derivative. In the present embodiment, the "styrene derivative" and the "α-methylstyrene derivative" mean that the hydrogen atom of the benzene ring of styrene and α-methylstyrene is substituted with a substituent R5 (carbon number 1 to 4). The alkyl group, the alkylene group having a carbon number of 1 to 3, a hydroxyl group, and a halogen atom are substituted. The above styrene derivatives are, for example, methyl styrene, ethyl styrene, tert-butyl styrene, methoxy styrene, ethoxy styrene, hydroxystyrene and chlorostyrene, preferably P-. A structural unit with a substitution of R5. The α-styrene styrene derivative is, for example, one in which the hydrogen atom at the α-position of the vinyl group is substituted with a methyl group in the above styrene derivative. -19- 201217905 (A) When the binder polymer contains the structural unit represented by the above general formula (IV), the ratio is based on the total solid content of the (A) binder polymer of the copolymer, and the adhesion is based on the adhesion. The viewpoint of excellent resolution is preferably 3% by mass or more, more preferably 丨〇% by mass or more, still more preferably 15% by mass or more, and particularly preferably 20% by mass or more. Further, from the viewpoint of the flexibility of the peeling property and the photoresist after curing, it is preferably 60% by mass or less, more preferably 55% by mass or less, still more preferably 50% by mass or less, and still more preferably 45% by mass or less. The structural unit represented by the above general formula (V) is based on the structural unit of the alkyl (meth) acrylate. The above alkyl (meth)acrylate is, for example, a compound of the formula (V) wherein R7 is an alkyl group having 1 to 12 carbon atoms. The alkyl group having 1 to 12 carbon atoms may be linear or branched, and may have a substituent such as a hydroxyl group, an ethoxy group or a halogen atom. The alkyl (meth)acrylate may, for example, be methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate or butyl (meth)acrylate. Tert-butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl hexyl ester and structural isomers thereof. From the viewpoint of improving the resolution and shortening the peeling time, R7 is preferably an alkyl group having 1 to 6 carbon atoms. More preferably, it is an alkyl group having 1 to 6 carbon atoms which does not have a substituent, and more preferably a methyl group. (A) When the binder polymer contains the structural unit represented by the above general formula (V), the content ratio is based on the total solid content of the (A) binder polymer of the copolymer, and is superior from the viewpoint of excellent releasability. It is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 1% by mass or more, and particularly preferably 15% by mass or more. Further, from the viewpoint of excellent resolution, it is preferably from 5 to 20, and from 2012 to 175%, more preferably 50% by mass or less, more preferably 45% by mass or less, and still more preferably 40% by mass or less. Further, the (A) binder polymer is preferably a structural unit represented by the following general formula (VI) from the viewpoint of balance between adhesion, resolution and releasability. —ch9-c

(VI)

In the general formula (VI), R15 represents a hydrogen atom or a methyl group, and R16 represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a hydroxyl group or a halogen atom. The q system represents an integer of 〇~5, and when q is 2 or more, the R16 in which the plural number exists may be the same or different from each other. The structural unit represented by the above general formula (VI) is a structural unit based on a benzyl (meth) acrylate and a benzyl (meth) acrylate derivative. The above benzyl (meth) acrylate derivative is, for example, 4-methylbenzyl (meth) acrylate, 4-ethylbenzyl (meth) acrylate, 4 tert-butyl benzyl (meth) acrylate , 4-methoxybenzyl (meth) acrylate, 4-ethoxybenzyl (meth) acrylate, 4-hydroxybenzyl (meth) acrylate, 4-chlorobenzyl (methyl) Acrylate. The structural unit represented by the above general formula (-21 - 201217905 VI) is based on developmental properties, etching resistance, plating resistance, and flexibility of maintaining a cured film, and preferably based on benzyl (meth) acrylate ( The structural unit of q = 〇). (A) The binder polymer contains the content ratio of the structural unit represented by the above formula (VI) based on the total solid content of the (A) binder polymer of the copolymer, and is excellent in adhesion. It is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more. Further, from the viewpoint of the flexibility of the peeling property and the photoresist after curing, it is preferably 60% by mass or less, more preferably 55% by mass or less, still more preferably 50% by mass or less, and still more preferably 45% by mass or less. . These binder polymers may be used alone or in combination of two or more. When a combination of two or more kinds of binder polymers is used, for example, there are two types of binder polymers composed of different copolymerization components (including different repeating units as constituent components), and two different weight average molecular weights. The above binder polymer, two or more types of binder polymers having different degrees of dispersion, and the like. Further, as the binder polymer, a polymer having various morphological molecular weight distributions described in JP-A-H11-327137 may be used. In the development step described later, when the image is developed in an organic solvent, the polymerizable monomer having a shutdown is prepared in a smaller amount. If necessary, the bonded polymer can have a photosensitive functional group. The amount of the binder polymer of the component (A) is preferably from 40 to 70 parts by mass, based on the total amount of the component (a) and the component (B) described later, preferably from 40 to 70 parts by mass. 65. Parts by mass, more preferably 5〇~60质量份-22- 201217905. When the amount is less than 40 parts by mass, the photosensitive layer after exposure curing tends to become brittle, and when it exceeds 70 parts by mass, the resolution and the light sensitivity tend to be insufficient. (Photopolymerizable compound having an ethylenically unsaturated bond) The photopolymerizable compound having an ethylenically unsaturated bond of the component (B) contains a compound represented by the following general formula (II)

R1 H2C=C-C-^Y-〇 0 In the above general formula (π), R1 and R2 each independently represent a hydrogen atom or a methyl group, preferably a methyl group. The Y system represents an alkylene group having 2 to 6 carbon atoms. Η1 and η2 each independently represent a positive integer, and t^+n2 is an integer of 4 to 40, preferably an integer of 6 to 34, more preferably an integer of 8 to 30, more preferably an integer of 8 to 28, particularly preferably It is an integer of 8 to 20, and is preferably an integer of 8 to 16, and is preferably an integer of 8 to 12. When the nkri2 is less than 4, the compatibility with the binder polymer is lowered, and when the photosensitive element is laminated on the substrate for forming a shop, the film tends to be easily peeled off. When the η 1+n2 is more than 40, the hydrophilic layer is hydrophilic. When the image is increased, the photoresist is easily peeled off, and the plating resistance is lowered. The Y in the intramolecular plural may be the same or different. The above alkylene group having 2 to 6 carbon atoms is, for example, an exoethyl group, a propyl group, an exopropyl group, a butyl group, a pentyl group and a hexyl group. Among these, from the viewpoint of improving the resolution and the electroplating resistance, it is preferred to extend the ethyl group and extend the isopropyl group, and more preferably to extend the -23-201217905 ethyl group. The aromatic ring in the above general formula (II) may have a substituent. These substituents are, for example, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a ring-membered group having a carbon number of 3 to 1 fluorene, an aryl group having 6 to 18 carbon atoms, an phenylhydrazine methyl group, an amine group, and an alkyl group having a carbon number. Amino group, dialkylamino group having 2 to 20 carbon atoms, nitro group, cyano group, carbonyl group, thiol group, alkyl thio group having 1 to 1 carbon number, allyl group, hydroxyl group, carbon number The hydroxyalkyl group, the carboxyl group, the alkyl group has a carbon number of carboxyalkyl group, the alkyl group has a carbon number of 1 to 10, an alkoxy group having a carbon number of 1 to 2, and a carbon number of 1 to 2 0. An alkoxycarbonyl group, an alkylcarbonyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an N-alkylaminocarbamyl group having 2 to 10 carbon atoms, a group having a hetero ring, and the like Substituent substituted aryl. The above substituent may also form a condensed ring, or the hydrogen atom in the substituent may be substituted with the above substituent or the like of a halogen atom or the like. Further, when the number of substitution bases is 2 or more, respectively. The substituents of 2 or more may be the same or different. The compound represented by the above general formula (Π) is, for example, 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis(4-((methyl) Propyleneoxypolypropoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolybutoxy)phenyl)propane and 2,2-bis(4-((A) A bisphenol A-based (meth) acrylate compound such as a propylene-polyoxypolyethoxypolypropoxy)phenyl) propyl compound. Specific examples of the compound represented by the above general formula (II) include, for example, E〇-modified bisphenol A diacrylate wherein Ri and R2 are a hydrogen atom, Y is an ethylidene group, and i^+nL10 (average 値) (Hitachi Chemical Co., Ltd.) Industrial Co., Ltd., trade name: FA-32 1 Μ ). -24- 201217905 The balance of the hydrophilic component and the hydrophobic component in the component (B) affects the resolution, adhesion, and peeling properties after hardening. From this point of view, in order to obtain a photosensitive element excellent in resolution, adhesion, and peeling property after curing, the component (B) preferably contains a polyalkylene glycol bis(meth)acrylate. The polyalkylene glycol di(meth)acrylate is preferably, for example, a compound represented by the following general formula (VII), (VIII) or (IX). Ο 0 CH2=C—丛一〇—^EQ-^-^-PO-) ( EO^—I—e==CH2 (10) R8 Γ δ1 χ2 R9 In general (VII), the R8 and R9 systems are independently represented. A hydrogen atom or a methyl group, EO represents an oxyethylene group, P〇 represents an oxypropylene group, s1 represents an integer of 1 to 30, and r1 and r2 each represent an integer of 0 to 30, and J+r2 (average 値) An integer from 1 to 30. 0II CHo^C_C* 2 I R10 •Ο— r3 fp〇-)~ s3 ΟII c- •C ΌΗ2 (VI)

R 11 is a compound of the formula (VIII) wherein R 1 R and R 11 represent a hydrogen atom or a methyl group, respectively. The EO system represents an oxyethylene group. PO represents an oxypropylene group, r3 represents an integer of 1 to 30, s2 and s3 each represent an integer of 0 to 30, and s2 + s3 (average 値) is an integer of 1 to 30. -25- 201217905 ο II ch2=9-c 一〇 R12

\ II ^c-c=ch2 s R13 (E) In the general formula (IX), R12 and R13 each independently represent a hydrogen atom or a methyl group, preferably a methyl group. EO represents an oxyethylene group, and PO represents an oxypropylene group. R4 represents an integer from 1 to 30, and S4 represents an integer from 1 to 30. In the above general formulas (VII), (VIII) and (IX), when the structural unit (EO, oxyethylene unit) of the oxyethylene group and the structural unit (PO, oxypropylene unit) of the oxypropylene group are present in plural, the plural oxygen The ethylene unit and the oxypropylene unit may be present in a continuous block manner or irregularly, respectively. When the oxypropylene unit is a structural unit of oxyisopropenyl group, the propylene-based secondary carbon may be bonded to the oxygen atom, and the first-order carbon may be bonded to the oxygen atom. The total number of oxyethylene units (rUr2, r3 and r4) in the above general formulas (VII), (VIII) and (IX) are each independently an integer of from 1 to 30, preferably an integer of 4 or more, more preferably 5 The above integer. From the viewpoint of excellent masking reliability and photoresist shape, it is preferably an integer of 1 〇 or less, more preferably an integer of 9 or less, and still more preferably an integer of 8 or less. The total number of oxypropylene units (S1, s2 + s3 and S4) in the above general formulas (VII), (VIII) and (IX) are each independently an integer of from 1 to 30, but from the resolution and low sludge The viewpoint is preferably an integer of 5 or more, more preferably an integer of 8 or more, and more preferably an integer of 1 or more. From the viewpoint of resolution and low sludge, it is preferably an integer of 20 or less, more preferably an integer of 16 or less, and still more preferably an integer of 14 or less. Specific examples of the compound represented by the above general formula (VII), for example, a vinyl compound having -26 to 201217905 R8 and R9 being a methyl group, 1^ + ^ = 6 (average 値) 'skuC average () (Hitachi Chemical Industry Co., Ltd.) Company system, product name: FA_ 023M). Specific examples of the compound represented by the above general formula (VIII) include, for example, a vinyl compound in which R1 () and R11 are a methyl group, γ3 = 6 (average 値), and s2 + s3 = 12 (average 値) (Hitachi Chemical Industry Co., Ltd. Company system, trade name: FA-024M). Specific examples of the compound represented by the above formula (IX) include, for example, a vinyl compound in which R12 and R13 are a hydrogen atom, r4 = 1 (average 値), and s4 = 9 (average 値) (manufactured by Shin-Nakamura Chemical Co., Ltd., Product Name: NK ester HEMA-9P ). These may be used alone or in combination of two or more. The component (B) is preferably an amine urethane monomer containing a (meth) acrylate compound having a urethane bond, from the viewpoint of improving the masking property. The above-mentioned ethyl urethane monomer is, for example, a (meth)acrylic monomer having a hydroxyl group at the β-position, isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6. An addition reaction product of a diisocyanate compound such as hexamethylene diisocyanate, tris((meth)acryloxytetraethyleneethylene glycol isocyanate) hexamethylene terephthalate, or hydrazine-modified urethane di(methyl) Acrylate, and hydrazine, hydrazine-modified urethane di(meth) acrylate. The ruthenium-modified compound has a block structure of an oxirane group. In addition, the 'ruthenium-modified compound has a propylene oxide-based block structure. Ε0-modified urethane di(meth)acrylate-27-201217905, for example, is manufactured by Shin-Nakamura Chemical Industry Co., Ltd. Product name "UA-ll" and so on. Further, ytterbium, yttrium modified urethane di(meth) acrylate is, for example, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., product name "UA-13", and the like. These may be used alone or in combination of two or more. The (Β) component is preferably a compound obtained by reacting a polyol with an α,β-unsaturated carboxylic acid from the viewpoint of excellent adhesion, resolution and releasability. Such compounds are, for example, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, hydrazine-modified trimethylolpropane tri(meth)acrylate, hydrazine-modified Trimethylolpropane tri(meth)acrylate, hydrazine, hydrazine modified trimethylolpropane tri(meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa(meth) acrylate . The hydrazine-modified trimethylolpropane tri(meth)acrylate is, for example, a product of the company Sartomer, trade name "SR-454". These may be used alone or in combination of two or more. The component (B) is excellent in adhesion, resolution and releasability, and preferably contains a photopolymerizable compound having one ethylenically unsaturated bond. The photopolymerizable compound having one ethylenically unsaturated bond preferably contains a compound represented by the following general formula (X).

In the general formula (X), R14 is a hydrogen atom or a methyl group, preferably a hydrogen atom. B is synonymous with Y in the above general formula (II). Preferably, exoethyl*k-28-201217905 represents an integer of 4 to 2, and is preferably an integer of 5 to 18 from the viewpoint of development. More preferably, it is an integer of 6 to 12, and more preferably an integer of 6 to 10. Further, the aromatic ring in the above formula (X) may have a substituent, and the substituents thereof have, for example, the same substituents as the aromatic ring in the above general formula (II). The compound represented by the above general formula (X), specifically exemplified by polyethylenoxy (meth) acrylate, nonyl phenoxy polyoxypropylene (meth) acrylate, butyl phenoxy Polyoxyethylene (meth) acrylate, butyl phenoxy polyoxypropylene (meth) acrylate. The above nonylphenoxy polyoxyethylene (meth) acrylate is, for example, a nonyl phenoxy tetraoxyethylene (meth) acrylate, a nonyl phenoxy pentoxide (meth) acrylate, a nonyl benzene Oxyhexaoxyethylene (meth) acrylate, nonyl phenoxy hexaoxyethylene (meth) acrylate, nonyl phenoxy oxyethylene (meth) acrylate, nonyl phenoxy hexaoxyethylene (Meth) acrylate, nonylphenoxy oxyethylene (meth) acrylate, nonyl phenoxy undecoxy ethylene (meth) acrylate, nonyl phenoxy oxydooxyethylene (methyl) )Acrylate. The above butylphenoxypolyoxyethylene (meth) acrylate, for example, butyl phenoxytetraoxyethylene (meth) acrylate, butyl phenoxy pentoxide (meth) acrylate, butyl Phenoxyhexaoxyethylene (meth) acrylate, butyl phenoxy heptaoxyethylene (meth) acrylate, butyl phenoxy ethoxy oxy (meth) acrylate, butyl phenoxy hexaoxy Ethylene (meth) acrylate, butyl phenoxy oxyethylene (meth) acrylate, and butyl phenoxy unoxyethylene (meth) acrylate. These can be used alone or in combination of -29- 201217905. (B) The component may contain a photopolymerizable compound having an ethylenically unsaturated bond other than the above. The other (B) photopolymerizable compound is, for example, a compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid, a phthalic acid compound, and an alkyl (meth)acrylate. The above phthalic acid-based compound is, for example, γ-chloro-β-hydroxypropyl_β, _(meth)acryloxyethyl-terpene-phthalate and β-hydroxyalkyl-β'- (Methyl) acryloxyalkyl-indole-phthalate. These may be used alone or in combination of two or more. The amount of the photopolymerizable compound having an ethylenically unsaturated bond of the (Β) component is preferably from 30 to 60 parts by mass based on 100 parts by mass of the total of the components (A) and (Β). Preferably, it is 35 to 55 parts by mass, more preferably 40 to 50 parts by mass. When the amount is less than 30 parts by mass, the resolution and the photosensitivity tend to be insufficient. When the amount is more than 60 parts by mass, the photosensitive layer after exposure curing tends to become brittle. (Photopolymerization initiator) The photopolymerization initiator of the component (C) preferably contains a 2,4,5-triarylimidazole dimer from the viewpoint of excellent photosensitivity and adhesion. The 2,4,5-triaryl imidazole dimer is, for example, 2-( 〇-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(〇-bromophenyl)-4,5 - Diphenylimidazole dimer, 2-(anthracene-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(anthracene-methoxyphenyl)-4,5-diphenylimidazolium Polymer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(〇-chlorophenyl)-4,5-bis(methoxyphenyl)imidazole Dimer-30- 201217905, 2-(〇-chlorophenyl)-4,5-di(?-fluorophenyl)imidazole dimer, 2_(_ 2,6-dichlorophenyl)_4,5 -diphenylimidazole dimer, 2_(0-chlorophenyl) 4,5-di(P-fluorophenyl)imidazole dimer, 2_(〇_bromophenyl)_4,5-one (p- Iodophenyl)imidazole dimer, 2-( 〇-chlorophenyl)-4,5-bis(polynaphthyl)imidazole dimer, 2-(〇-chlorophenyl)_4,5-one (P_ Chloroquinone imidazole dimer, 2-(〇-bromophenyl)-4,5-bis(0-chloromethoxyindole) imidazole dimer, 2-(〇-chlorophenyl)-4,5-二(〇,Ρ-一气察基. 咏imidazole dimer, 2-(〇-chlorophenyl)-4,5-di(〇,Ρ--bromophenyl hydrazine one ( 备兹| )咪# 嗤二Polymer, 2-(0,m _: chlorophenyl)-4,5--(Ρ-氛蔡基; 一ΑΛΛ, 2-polymer 2-(甘, (o,p-dichlorophenyl)_4,5_二(m-甲Oxyphenyl)imidine dimer, —* 2,4-di(p-methoxyphenyl)-5-phenylimidazole dimer, 2-(2, cardiomethoxyphenyl )_4,5_diphenylimidazole dimer, 2_(P-methylyithiophenyl)-4,5-diphenylimidazolium dimer, 2·(Ρ-bromophenyl)_4,5 -monoimidazole dimer, 2_(〇-bromophenyl)-4,5-di(indole, fluorene-dichlorophenyl) imidazole dimer, 2-(m-bromophenyl)-4,5 -diphenylimidazole dimer, 2_(m,p.dibromophenyl)_4,5-diphenylimidazole dimer, 2,2'-bis-diphenyl)-4,4',5, 5,-tetrakis (p-gas-p-methoxyphenyl) oxime polymer 2-(anthracene-chlorophenyl)-4,5-di(anthracene, p-dichlorophenyl)imidazole dimerization , 2_(〇-chlorophenyl)-4,5-di(indole, P-dibromophenyl)imidazole dimer, 2_(〇-bromophenyl)-4,5-di(〇,p- Dichlorophenyl)imidazole dimer and 2,4,5-di(o,p-dichlorophenyl)imidazole dimer. Among these, 'from the viewpoint of improving adhesion and light sensitivity, it is preferred 2- ( 〇-chloride — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — To be identical, symmetric compounds may be provided, or may be different, providing asymmetric compounds. When the component (C) contains a 2,4,5-triaryl imidazole dimer, the ratio is based on the total amount of the component (C), preferably 70 to 10,000% by mass, more preferably 85 to 100%. The mass %, more preferably 90 to 100% by mass, particularly preferably 93 to 100% by mass. The 2,4,5-triarylimidazole dimer is contained in this ratio, and the photosensitive element of the present embodiment has more excellent adhesion and light sensitivity. Photopolymerization initiator of component (C) In addition to the above 2,4,5-triarylimidazole dimer, other photopolymerization initiators can be used. Other photopolymerization initiators include, for example, aromatic ketones, P-aminophenyl ketones, anthraquinones, benzoin ether compounds, benzoin compounds, benzyl derivatives, acridine derivatives, and peas a compound, an oxime ester, an N-aryl-α-amino acid compound, an aliphatic polyfunctional thiol compound, a fluorenyl phosphine oxide, a thioxanthone, a tertiary amine compound, and these compounds can be combined use. The photopolymerization initiator (C) of the present embodiment preferably contains the above aromatic ketones in addition to the 2,4,5-triarylimidazole dimer, and preferably contains ruthenium, Ν'-tetrazine. Base-4,4'-diaminobenzophenone (milaxone). The amount of the photopolymerization initiator of the component (C) is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10, based on 1 part by mass of the total of the components (A) and (B). The mass fraction is particularly preferably 0.5 to 5 parts by mass. When the amount is less than 5% by mass, the light sensitivity tends to be insufficient, and when it exceeds 20 parts by mass, the light absorption on the surface of the photosensitive resin composition increases during exposure.

-32- 201217905 There is a tendency for light hardening to be insufficient. When necessary, the photosensitive resin composition may contain a photopolymerizable compound (oxycyclobutane compound or the like) having at least one cationically polymerizable cyclic ether group in the molecule, a cationic polymerization initiator, malachite green (Malachite) Green), such as dyes, tribromophenyl maple, colorless crystal violet, etc., photochromic agent, thermal hair color preventive agent, p-toluenesulfonamide and other plasticizers' pigments, enamels, defoamers, flame retardants Additives such as a stabilizer, an inhibitor, a flattening agent, a peeling accelerator, an antioxidant, a fragrance, an imaging agent, and a thermal crosslinking agent such as 4-t-butyl catechol. These may be used alone or in combination of two or more. These additives may contain ~·〇〇〇1 to 2 parts by mass based on 100 parts by mass of the total of the components (A) and (B), within the range which does not affect the object of the present embodiment. The photosensitive resin composition is dissolved in methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, hydrazine, hydrazine-dimethylformamide, and propylene glycol alone. A solvent such as ether or a mixed solvent of these is prepared by preparing a solution having a solid content of about 30 to 60% by mass. The photosensitive layer 20 in the photosensitive element 1 of the present embodiment is formed by applying the above-mentioned photosensitive resin composition onto a support film 1 and removing the solvent. Among the coating methods, for example, a conventional method such as roll coating, comma coat, gravure coating, air knife coating, die coating, and bar coating can be used. Further, the solvent may be removed by, for example, treating at a temperature of 70 to 150 ° C for 5 to 30 minutes. Further, the amount of the residual organic solvent in the photosensitive layer 20 is preferably 2% by mass or less from the viewpoint of preventing the diffusion of the organic solvent in the subsequent step. The thickness of the photosensitive layer 20 thus formed is preferably from 3 to 25 μm, more preferably from 5 to 25 μm, even more preferably from 7 to 20 μm, particularly preferably from 10 to 15 μm. When the thickness is less than 3 μm, when the photosensitive layer is laminated on the substrate for circuit formation, defects may occur easily or the tenting property may be insufficient. In the development and etching steps, the photoresist may be damaged, which may cause an exit. (OPEN) One of the causes of defects is that the manufacturing yield of printed circuit boards tends to decrease. On the other hand, when the thickness exceeds 25 μm, the resolution of the photosensitive layer 20 is insufficient, and the liquid movement of the etching liquid tends to be insufficient. Further, the influence of the side etching may become large, and it is difficult to manufacture a high-density printed circuit board. Further, the photosensitive element 1 may be provided with a protective film (not shown) on the main surface opposite to the first main surface 12 which is in contact with the support film 10 of the photosensitive layer 20. The protective film preferably uses a film having a smaller adhesion between the photosensitive layer 20 and the protective film than the adhesion between the photosensitive layer 20 and the support film 10, and a fish eye can be used. Film. Specifically, for example, an inert polyolefin film such as polyethylene or polypropylene is used. From the viewpoint of the releasability from the photosensitive layer 20, a polyethylene film is preferred. The thickness of the protective film varies depending on the application, and is preferably about 1 to 100 μm. The photosensitive element 1 may further have an intermediate layer or a protective layer such as a buffer layer, an adhesive layer, a light absorbing layer, and a gas barrier layer in addition to the support film 10, the photosensitive layer 20, and the protective film. The photosensitive element 1 of the present embodiment can be stored in a state in which, for example, a photosensitive element state or a layer in which a protective film is laminated on a photosensitive layer 20 and wound into a roll-shaped winding core. At this time, the support film 10 is in the state of the outermost layer, and it is preferable to wind it into a roll shape. The end surface of the photosensitive element 1 wound in a roll shape is -34 to 201217905. From the viewpoint of end face protection, it is preferable to provide an end face spacer, and it is preferable to provide a moisture-proof end face spacer from the viewpoint of resistance to melting. The bag method is preferably packaged in a black sheet having a low moisture permeability. The core material is, for example, a plastic such as a polyethylene resin, a polypropylene resin, a polystyrene resin, a polyvinyl chloride resin, or an ABS (acrylonitrile-butadiene-styrene copolymer). (Formation Method of Photoresist Pattern) The method for forming a photoresist pattern according to the present embodiment includes a method of laminating the photosensitive element 1 in the order of the photosensitive layer 20 and the support film 10 in the circuit formation. a step of laminating on the substrate; an active light is passed through the support film 10, irradiated to a predetermined portion of the photosensitive layer 20, and an exposure step of forming a photocured portion on the photosensitive layer 20; and removing the photosensitive layer 20 other than the photocured portion Part of the imaging steps. In the laminating step, a method of laminating the photosensitive layer 20 on a substrate for forming a circuit, for example, when a protective film is present on the photosensitive layer 20, 'after removing the protective film, the photosensitive layer 20 is heated to about 7 〇 to 13 ° C. 'At the same time, a method of laminating the substrate for circuit formation with a pressure of about 0.1 to 1 MPa, and laminating. In this lamination step, it is also possible to laminate under reduced pressure. The laminated surface of the circuit-forming substrate is usually a metal surface, but is not particularly limited. In order to further improve the high-level compatibility, the substrate for circuit formation can be pre-heat treated. Next, the photosensitive layer 20' laminated for the lamination step is aligned with the mask having the negative or positive mask pattern at the second main surface of the support film 10 to be adhered. Then, in the exposure step, the photosensitive layer 20 is irradiated with active light rays in the form of an image by the photomask and the support film 10, and a photocured portion is formed on the photosensitive layer 2. The light source of the above-mentioned active light is a known light source, and for example, a carbon arc lamp, a mercury vapor arc lamp, a high pressure mercury lamp, and a xenon lamp are effective for emitting ultraviolet rays or visible light. Further, a photohardening portion can be formed on the photosensitive layer 20 by laser direct drawing. Next, after the above exposure step, the photomask is peeled off from the support film 10. Next, the support film 10 is peeled off from the photosensitive layer 20. In the development step, the unexposed portion (photocured portion) of the photosensitive layer 20 is removed by wet development or dry development of a developing solution such as an aqueous alkaline solution, a water-based developing solution, or an organic solvent. Imaging can produce a resist pattern. The alkaline aqueous solution is, for example, a thin solution of 0.1 to 5% by mass of sodium carbonate, a dilute solution of 0.1 to 5% by mass of potassium carbonate, and a dilute solution of 5% to 5% by mass of sodium hydroxide. The pH of the above aqueous alkaline solution is preferably in the range of 9 to 1 1 and the temperature thereof can be adjusted in accordance with the developability of the photosensitive layer 20. Further, a surfactant, an antifoaming agent, an organic solvent or the like may be mixed in the alkaline aqueous solution. The methods of development include, for example, dipping, spraying, rinsing, and washing. Further, the treatment after the development step may be performed by, for example, heating at a temperature of about 60 to 250 ° C or an exposure of 2 2 to 10 J/cm 2 to re-harden the photoresist pattern. (Manufacturing Method of Printed Circuit Board) The method of manufacturing a printed circuit board according to the present embodiment is formed by etching the pattern of the circuit-forming substrate-36 201217905 formed by the resist pattern. Electroplating is carried out. The photosensitive element of the present embodiment is particularly suitable for producing a printed circuit board by a method including a plating step, and is suitably used in a semi-additive process (SAP). The inventors of the present invention have reason to be suitable for use in SAP as described below. The line width of printed circuit boards produced by SAP has a very fine tendency compared to printed circuit boards produced by subtractive methods. Further, in the case of SAP, the photoresist shape is directly transferred into a plating line shape. When a printed circuit board having an extremely thin line pattern produced by SAP has a slight photoresist defect, the production yield tends to decrease. Therefore, the photosensitive element of the present embodiment is particularly suitable for use in SAP. The etching liquid for etching includes, for example, a copper chloride solution, a ferric chloride solution, and an alkali etching solution. Electroplating is, for example, copper plating, welding shovel, nickel ore and gold plating. After etching or electroplating, the photoresist pattern can be peeled off, for example, using an aqueous solution which is more alkaline than the alkaline aqueous solution used for development. As the strongly alkaline aqueous solution, for example, a 1 to 1% by mass aqueous sodium hydroxide solution and a 1 to 10% by mass aqueous potassium hydroxide solution can be used. The peeling method includes, for example, a dipping method and a spraying method. The printed circuit board forming the photoresist pattern may be a multilayer printed circuit board or have a small diameter through hole. Further, when plating a circuit board for forming a circuit layer having an insulating layer and a conductor layer formed on the insulating layer, it is necessary to remove the conductor layer other than the pattern. For the removal method, for example, after the photoresist pattern is peeled off, a method of etching is slightly performed or after the plating, followed by solder plating or the like, and then the photoresist pattern is peeled off, and the wiring portion is masked by soldering, and secondly, only the conductor can be etched. Layer etch - 37 - 201217905 Method for processing etchant, etc. As described above, the photosensitive element of the present embodiment can be used for a printed circuit board. (Manufacturing Method of Semiconductor Package Substrate) The photosensitive element 1 of the present embodiment can be used for a package substrate including a hard substrate and an insulating film formed on the hard substrate. At this time, the light-cured portion of the photosensitive layer 20 may be used as an insulating film. When the photocured portion of the photosensitive layer 20 is used as a solder resist for a semiconductor package, for example, after the development of the photoresist pattern is completed, it is preferable to improve solder heat resistance, chemical resistance, and the like. Ultraviolet irradiation or heating of a high pressure mercury lamp. When irradiating ultraviolet rays, the amount of irradiation can be adjusted as necessary, and for example, irradiation can be performed at an irradiation amount of about 0 to 10 J/cm2. When the photoresist pattern is heated, it is preferably in the range of about 10 to 170 ° C for about 15 to 90 minutes. UV irradiation and heating can be performed at the same time, or one of them can be carried out before another. At the same time, when ultraviolet light is irradiated and heated, it is more preferably heated to 604 50 ° C from the viewpoint of effectively imparting heat resistance to soldering, chemical resistance, and the like. The solder resist formed of the photosensitive element of the present embodiment has a protective film for wiring after soldering to the substrate, and is excellent in physical properties such as tensile strength and elongation, and heat-resistant punchability, and thus can be used as a semiconductor package. The permanent reticle is used. As described above, the package substrate having the resist pattern is used, and then assembly of semiconductor elements or the like (for example, wire bonding or soldering connection) is performed, and then mounted on an electronic device such as a computer. -38 - 201217905 The present invention will be described in detail based on the embodiments thereof, but the present invention is not limited to the above embodiments. The present invention can be variously modified without departing from the spirit of the invention. [Embodiment] [Embodiment] Hereinafter, the present invention will be described in detail based on the embodiments thereof, but the present invention is not limited to the embodiments. (Examples 1 to 9 and Comparative Examples 1 to 10) (A) A binder polymer having a composition shown in the following Table 1 or 2 was synthesized. The weight average molecular weight of the binder polymer is determined by gel permeation chromatography (GPC) and is derived using a calibration curve of standard polystyrene. The GPC conditions and the acid value measurement procedure are as follows, and the measurement results are shown in Table 1 or 2. (GPC condition) Pump: Hitachi L-6000 (manufactured by Hitachi, Ltd., trade name) Pipe column: Gelpack GL-R420, Gelpack GL-R430, Gelpack GL-R440 (3 in total) (The above is Hitachi Chemical Industry (share) system, product name)

Isolation liquid: tetrahydrofuran measurement temperature: 40 ° C -39 - 201217905 Flow rate: 2.05 mL / min Detector: Hitachi L-3 3 00 type RI (manufactured by Hitachi, Ltd., trade name) (acid value measurement method) The medium scale takes about 1 g of the synthesized binder polymer, and after adding the mixed solution (mass ratio: toluene/methanol=70/30), the appropriate amount of the indicator phenolphthalein solution is added, and the 1N potassium hydroxide aqueous solution is used. For titration, the acid value was determined by the following formula (α). χ = 1 〇χ Vfx56. l/(WpxI) (a) In the formula (a), x represents the acid value (mgKOH/g), and Vf represents the titer of the KOH aqueous solution of 0. IN (mL) Wp is the mass (g) of the resin solution after the measurement, and I is the ratio (% by mass) of the nonvolatile content in the resin solution after the measurement. The measurement results are shown in Tables 1 and 2. [Table 1] Adhesive Polymer Example 1 2 3 4 5 6 7 8 9 Input amount during synthesis (g) Methacrylic acid 100 100 100 100 85 75 70 60 50 Methyl methacrylate 150 150 150 150 165 175 180 190 200 Styrene 200 — 200 200 200 200 200 200 200 Benzyl methacrylate-200 — Weight average molecular weight 30000 30000 40000 50000 30000 25000 24000 18000 13000 Acid value (mmgKOH) 130 130 130 130 110 100 90 80 65 -40 - 201217905 [Table 2] Adhesives Comparative Example 1 2 3 4 5 6 7 8 9 10 Input amount during synthesis (g) Methyl acrylic acid 100 100 85 70 60 60 50 100 100 100 Methyl methacrylate 150 150 190 180 180 180 200 150 150 150 Styrene 200 200 200 200 200 200 200 200 200 - Benzyl methacrylate - 200 Weight average molecular weight 60000 54000 60000 30000 25000 22000 16000 8000 30000 30000 Acid price (paid gKOH) 130 130 110 90 80 80 65 130 130 130 The components shown in Table 3 below were prepared to prepare a photosensitive resin composition [Table 3] Composition amount u) (A) Composition 150 shown in Table 1 or 2 (solid content) -· 60) (B) into FA-321 M·1 20 FA-023M12 5 UA-1 1 13 10 SR-454·4 5 (C) Component EAB15 0. 1 B-CIM16 3 Other components UCV17 0. 3 MKG18 0. 03 TBC19 0. 03 Solvent Methanol 5 Acetone 9 Toluene 5 -41 - 1 1 : EO modified bisphenol A dimethacrylate (manufactured by Hitachi Chemical Co., Ltd.) * 2: ΕΟ, ΡΟ modified dimethacrylate (Hitachi Chemical Co., Ltd.) Industrial Co., Ltd., product name) * 3: Ε0 modified g-based ethyl ester dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name) » 4: E0 modified dimethylol propyl hydride Methyl acrylate (manufactured by Sartomer Co., Ltd.) * 5: Ν, Ν'-tetramethyl-4,-diaminobenzophenone* 6: 2-(anthracene-chlorophenyl)-4 ,5-diphenylimidazole dimer*7: colorless crystal violet*8: malachite green* 9 : 4-t-butyl phthalic phenol 201217905 (production of photosensitive element) Preparation of Table 4 or Table 5 The "PET" film shown is used as a support film for a photosensitive element. Table 4 and Table 5 show the total number of haze and the like of the particles of 5 μΐη or more contained in each PET film. The total number of the above-mentioned particles and the like is measured by a polarizing microscope to measure the number of particles or the like present in 5 μm or more of 1 mm 2 unit. The number of η (measurement number) at this time was 5. Further, the haze of the supporting film is 値 measured in accordance with JIS Κ 7105. The thickness of these support films is 16 μm. Next, a solution of the above photosensitive resin composition was applied to each PET film in a uniform thickness. Then, it was dried by a hot air convection dryer at 100 ° C for 2 minutes to remove the solvent to form a photosensitive layer. After drying, the photosensitive layer was coated with a polyethylene protective film (manufactured by TAMAPOLY Co., Ltd., trade name "NF-15", thickness 20 μm) to obtain a photosensitive element. The thickness of the photosensitive layer after drying was 15 μm. (Production of Laminated Fabric) The copper surface of a copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd., trade name "MLC-E-679") of a glass epoxy material having a copper foil (thickness: 35 μm) was laminated on both sides. The surface was roughened using MEC etch BOND CZ-8100 (manufactured by MEC Co., Ltd.), and after pickling and washing with water, it was dried by air flow. The obtained copper clad laminate was heated to 80 ° C, and the protective film was peeled off while the photosensitive layer was in contact with the copper surface to laminate the photosensitive member. Thus, a laminate in which a copper clad laminate, a photosensitive layer, and a support film were laminated in this order was obtained. The laminating system was carried out by using a heating roller of 120 ° C at a pressure of 〇 4 MPa and a roller speed of 1.5 m / min. These laminate systems were used as test pieces of the test shown below. (Measurement of minimum development time) The photosensitive layer laminated on a substrate of 125 mm x 200 mm square was subjected to spray development, and the time for completely removing the unexposed portion was measured as the minimum development time. The measurement results are shown in Tables 4 and 5. (Measurement of Photosensitivity Test) The support film of the test piece was placed on a Stauffer 21-segment exposure tablet (Step Tablets) as a negative image, and an exposure machine having a high-pressure mercury lamp (manufactured by OAK Co., Ltd., trade name "EXM-1201" was used. ”), the photosensitive layer was exposed to light at an irradiation energy of 100 mJ/cm 2 . Next, the support film was peeled off, and a 1% by mass aqueous sodium carbonate solution at 30 ° C was spray-developed at twice the minimum development time to remove the unexposed portion, followed by development. The photosensitivity of the photosensitive resin composition was evaluated by measuring the number of stages of the exposed patches of the photocured film formed on the copper-clad laminate. The results are shown in Tables 4 and 5. The light sensitivity is expressed by the number of segments of the exposure grid, and the higher the number of segments of the exposure grid, the higher the light sensitivity. (Measurement test of resolution) In order to solve the resolution, the image tool having the Stauffer 2-segment exposure cell and the negative image for the resolution evaluation have a line width/space width of -23 - 201217905 of 2/2 to 3 0 /3 0 (The unit of the gas layer type image of the wiring pattern of μη〇 is attached to the support film of the test piece, and the exposure machine with a high-pressure mercury lamp (manufactured by the company) is used. ΕΧΜ-1201"), the exposure energy of the SUuffer 21-segment exposure image is exposed to an irradiation energy of 5.0. Secondly, the support film is peeled off, using a 1% by mass aqueous sodium carbonate solution at 30 ° C to minimize The development was carried out four times as long as the development time, and the unexposed portion was removed for development, wherein the resolution was completely removed by the development process to completely remove the space width between the line widths of the unexposed portions (unit: μηι The evaluation was performed. The smaller the evaluation coefficient 解 of the resolution, the better the enthalpy. The results are shown in Tables 4 and 5. (Evaluation of the side shape of the photoresist line) The substrate evaluated by the measurement test of the above resolution The side shape of the photoresist line was observed by a scanning electron microscope (manufactured by Hitachi High-Tech Co., Ltd., trade name SU- 1 500), and the results of the following evaluations are shown in Tables 4 and 5: A: smooth shape B: slightly rough shape C: rough shape (measurement test of adhesion) In order to investigate the adhesion, the image tool having the Stauffer 21-segment exposure grid and the negative image for the adhesion evaluation have a line The width/space width is 2/1000-3 0/1 0 00 (unit: μιη). The wiring pattern of the gas color layer type -44- 201217905 The image tool is attached to the test piece of the support film. The exposure lamp of the mercury lamp (manufactured by the company), the product name "ΕΧΜ-12〇1", is exposed by the irradiation energy of 8.0 after the image of the Stauffer 21-segment exposure image is displayed. The support film was peeled off using a 1% by mass aqueous sodium carbonate solution at 30 ° C for 4 times of the minimum development time, and the unexposed portion was removed for development. The adhesion was developed by imaging. Can completely remove the unexposed part of the line width is the most The small width (unit: μηι) was used to evaluate the adhesion. The evaluation coefficient of the adhesion was as small as possible, and the results were as shown in Tables 4 and 5. (Measurement test of the number of occurrences of photoresist defects) The number of occurrences of photoresist defects, and an image tool with a StaUffer 21-segment exposure grid image and a gas color layer type image tool having a wiring pattern with a line width/space width of 10/30 (unit: μηι) On the support film of the test piece, an exposure machine having a high-pressure mercury lamp was used, and exposure was performed with an irradiation energy of 5.0 after the development of the StaUffer 21-segment cell. Next, the support film was peeled off, and a 1% by mass aqueous sodium carbonate solution at 30 ° C was used for spraying at twice the minimum development time to remove the unexposed portion. Next, the number of photoresist defects was counted using a microscope. The average 値 of the line length is 1 mm ′ and the number of lines is 1 〇 as the observation unit η number is 5 as the number of occurrences of the photoresist defect. The results are shown in Tables 4 and 5 * -45- 201217905 [Table 4] Item Example 1 2 3 4 5 6 7 8 9 Support film trade name QS-48*1 QS-48*' QS-48*' QS- 48·1 QS-48*' QS-48*1 QS-48*' QS-48*1 QS-48*' Film thickness Wm) 16 16 16 16 16 16 16 16 16 Number of particles etc. 1 1 1 1 1 1 1 1 Haze 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Minimum development time (seconds) 12 12 13 16 13 18 13 14 14 Light sensitivity 5 5 5 5 5 5 5 5 5 Adhesion (//m) 5 4 4 4 4 5 5 5 6 Resolution (//m) 6 6 7 7 6 5 5 5 5 Shape of the photoresist side AAAAAAAAA Photorefractive defect occurrence 0 0 0 0 0 0 0 0 0 * 1: The table has Biaxial alignment PET film of three-layer structure containing microparticles, manufactured by Toray Co., Ltd. [Table 5] Item Comparative Example 1 2 3 4 5 6 7 8 9 10 Support film trade name QS-48., QS-48· , QS-48*' QS-48*' QS-48*' QS-48*' QS-48*, QS-48*1 HTF-01 *2 HTR-02 *3 Film thickness ((4)) 16 16 16 16 16 16 16 16 16 16 Number of particles etc. 1 1 1 1 1 1 1 1 28 318 Haze 0,4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.2 2 Minimum development time (seconds) &gt;40 23 &gt;40 &gt ;40 &gt;40 20 18 7 12 12 Light sensitivity — 5 — — — 5 5 5 5 5 Adhesion (&quot;m) — 4 — — — 5 5 12 5 5 Resolution (Um) — 9 — — — 8 12 5 6 7 Shape of the photoresist side— A — — — AACBC Photorefractive defect occurrence — 0 — — A 0 0 42 13 213 * 1: Two-axis alignment PET film with a three-layer structure with microparticle-containing layers in the table, Toray Co., Ltd.*2: Microparticles The two-axis alignment PET film of the two-layer structure, which is different in the table, and the three-axis alignment PET film of the three-layer structure with the microparticle-containing layer in the watch, made by Teijin DuPon Co., Ltd.

As shown in Tables 4 and 5, the haze of the PET-46 - 201217905 film used in Examples 1 to 9 and Comparative Example 9 was substantially the same, but the PET film used in Examples 1 to 9 was present in 5 μm of 1 mm 2 unit. The total number of the above particles and the like was one, and the PET film used in Comparative Example 9 (the total number of particles and the like was 28) was extremely small. Therefore, in the number of occurrences of the photoresist defect, the number of occurrences of the photoresist defect in Examples 1 to 9 was 0, which was extremely inferior to that of Comparative Example 9. Further, when a total of 318 support films of the particles of Comparative Example 1 and the like were used, the number of occurrences of photoresist defects increased to 213. The shape of the photoresist side after the development of the examples 1 to 9 was smooth, and a good photoresist pattern was formed. As shown in Table 4, the acid value and the weight average molecular weight of the component (A) used in Examples 1 to 9 were within an appropriate range, so that the minimum development time was extremely short, and the productivity of the printed circuit board was not lowered. The range of the weight average molecular weight determined by the above formula (I) is from 1 to 539,000 at an acid value of 130 mgKOH/g, from 1 to 30,000,000 at an acid value of 110 mgKOH/g, and an acid value of 90 mgKOH. When it is /g, it is 1 to 24,000, and when the acid value is 8 OmgKOH/g, it is 1 to 2,000,000. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a preferred embodiment of a photosensitive element of the present invention, and Fig. 2 is a view showing a polarizing microscope photograph of a surface of a supporting film having particles having a diameter of 5 μm or more, and Fig. 3 is used. A scanning-type micrograph of a resist pattern formed of a photosensitive element having a photosensitive layer on a support film having a plurality of particles having a diameter of 5 μm or more. [Main component symbol description] 1 : Photosensitive element -47- 201217905 ι〇 : Support film 12 : 1st main surface 14 : 2nd main surface 20 : Photosensitive layer (photosensitive resin composition layer) -48-

Claims (1)

201217905 VII. Patent Application Range: 1. A photosensitive element comprising a photosensitive element supporting a film and a photosensitive resin composition layer formed on the support film, wherein the support film has a haze of 0.01 to 2.0%. And the total number of particles having a diameter of 5 μm or more and agglomerates having a diameter of 5 μm or more contained in the support film is 5 pieces/mm 2 or less, and the photosensitive resin composition layer contains a binder polymer and has an ethylenic unsaturated bond. The photopolymerizable compound and the photopolymerization initiator have an acid value X of 60 to 130 mgKOH/g, and the weight average molecular weight Mw satisfies the relationship expressed by the following formula (I): 1 0000 ^ Mw &lt; 4000 e ° ° 2x (I) [In the formula (I), X represents the acid value of the binder polymer, and Mw represents the weight average molecular weight of the binder polymer]. 2. The photosensitive member of claim 1, wherein the photopolymerizable compound contains a compound represented by the following general formula (II), R2 o-4y-o^-cc=ch2 &lt;π&gt; ο [In the formula (II), R1 and R2 each independently represent a hydrogen atom or a methyl group, and Y represents an alkylene group having a carbon number of 2 to 6, Π1 And η2 are each independently represented by a positive integer, n kn2 is 4 to 40, and the plurals may be the same or different from each other]. 3. The photosensitive member according to claim 1 or 2, wherein the above-mentioned binder polymer has a divalent group represented by the following general formula (III), (IV) or (V) -49 - 201217905, (ΐπ&gt; (V) In the formulae (III), (IV) and (V), R represents a hydrogen atom or a methyl group, R5 represents an alkoxy group having 1 carbon atom, a hydroxyl group or a halogen atom, and R7 represents a P system representing 〇~5. An integer, when p is 2 or more, complex _ is the same or different]. 4. The photosensitive binder polymer according to item 3 of the patent application scope further contains the following general formula (VI) R15 I -CH2-C- (VI), R4 and R6 are each independently 4, the carbon number 1 to 3, the number of carbon atoms 1 to 10, the presence of R5, which are mutually comparable elements, wherein the aforementioned sticky group represents a divalent group, -50- 201217905 [In the formula (VI), "R15 represents a hydrogen atom or a methyl group", an alkyl group having an R16 coefficient of 1 to 4, an alkoxy group having a carbon number of 1 to 3, a hydroxyl group or a dentinogen, and a 0 to 5 An integer, when q is 2 or more, R16 exists in a plural or different]. 5. The photosensitive property according to any one of claims 1 to 4, wherein the photopolymerization initiator contains a 2,4,5-triarylimidazole dimer, and a method for forming a photoresist pattern, And the laminating step of laminating the photosensitive element according to any one of the above-mentioned resin composition layer and the support film in the order of the support film; and passing the active light through the aforementioned support film Irradiation of a predetermined portion of the photosensitive composition layer, exposure step of the photosensitive resin composition layer photocured portion, and removal of the photosensitive resin composition development step other than the photocured portion. 7. A method of manufacturing a printed circuit board, comprising: forming a circuit for forming a circuit having a photoresist pattern by forming a photoresist pattern according to claim 6 of the patent application, performing etching or plating? 8. A printed circuit board characterized by being manufactured by the manufacturing method of claim 7. 9. Photosensitive according to any one of claims 1 to 5, which is used for a printed circuit board. It is indicated that the carbon 1 * q system can be the same component, and I ° will form a layer on the base resin as a photosensitive resin: for the shape of the step range element, -51 -