JP2011048270A - Photosensitive element, method for forming resist pattern using the same, and method for manufacturing printed wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive element having good balance of adhesion and resolution, and strippability. <P>SOLUTION: The photosensitive element includes a support film 10 and a photosensitive layer 20 formed on the support film 10 using a photosensitive resin composition, wherein the photosensitive resin composition includes: (A) a binder polymer; (B) a photopolymerizable compound having an ethylenically unsaturated bond; and (C) a photopolymerization initiator, wherein a carbonate bond-containing urethane (meth)acrylate compound having a weight average molecular weight of ≤3,300 is included as the photopolymerizable compound having an ethylenically unsaturated bond (B). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a photosensitive element, a resist pattern forming method using the same, and a printed wiring board manufacturing method.

  Conventionally, in the field of printed wiring board manufacturing and metal precision processing, as a resist material used for etching, plating, etc., a layer formed using a photosensitive resin composition (hereinafter referred to as “photosensitive layer”), Photosensitive elements composed of a support film and a protective film are widely used.

  A printed wiring board is manufactured as follows, for example. First, after peeling off the protective film of the photosensitive element from the photosensitive layer, the photosensitive layer is laminated on the conductive film of the circuit forming substrate. Next, after pattern exposure is performed on the photosensitive layer, an unexposed portion is removed with a developing solution to form a resist pattern. And a printed wiring board is formed by patterning a conductive film based on this resist pattern.

  Examples of the developer used for removing the unexposed portion mainly include an alkali developer such as a sodium hydrogen carbonate solution. The developer generally needs to have an ability to dissolve the photosensitive layer to some extent. At the time of development, the photosensitive layer is dissolved in the developer or dispersed in the developer.

  In recent years, the contact area between a circuit-forming substrate and a photosensitive layer that is a resist material has been reduced with the increase in the density of printed wiring boards. For this reason, the photosensitive layer is required to have excellent mechanical strength, chemical resistance, and flexibility in the etching or plating process, as well as excellent adhesion to the circuit forming substrate and excellent resolution in pattern formation. Yes. Recently, a material capable of forming a resist pattern having a line width and a space width of 10 μm or less is particularly desired for use as a package substrate.

  By the way, Patent Document 1 proposes a photosensitive resin composition containing a photopolymerizable compound having an ethylenically unsaturated bond polymerizable in a specific molecule. Patent Document 2 proposes a photopolymerizable composition containing a specific carboxyl group-containing binder polymer. Patent Document 3 proposes a photosensitive resin composition containing a specific photopolymerization initiator. Patent Document 4 and Patent Document 5 propose a photopolymer resin composition containing a specific carboxyl group-containing binder polymer and a photopolymerizable monomer.

  Moreover, when using a photosensitive element for formation of a resist, generally, after laminating a photosensitive layer on a substrate, exposure is performed without peeling the support film. In order to cope with such an exposure process, a light-transmitting material may be employed for the support film, and in order to obtain a high resolution in pattern formation, the support film needs to be made as thin as possible. However, in order to apply the photosensitive resin composition with a uniform thickness and good yield on the support film, the support film is required to have a certain thickness (generally 10 μm to 30 μm). Further, in order to improve the productivity of the support film, that is, for the purpose of improving the winding property of the support film, the support film generally contains inorganic or organic fine particles. For example, Patent Document 13 and Patent Document 14 propose that the outermost surface on one side of the support film contains inorganic or organic fine particles having an average particle diameter of about 0.01 to 5 μm.

  As a method for achieving high resolution, there is a method in which a support film provided on a photosensitive element is peeled off before exposure and exposed without using a support film. However, since the photosensitive layer usually has a certain degree of adhesiveness, it is difficult to remove the adhered phototool when the phototool is directly adhered to the photosensitive layer for exposure. Further, the phototool is contaminated by the photosensitive layer, or the photosensitive layer is exposed to oxygen in the atmosphere by peeling the support film, so that the photosensitivity is likely to be lowered.

  Patent Documents 6 to 7 disclose a method in which two or more photosensitive layers are formed, and a layer that is in direct contact with the phototool is made non-adhesive. Patent Documents 8 to 12 propose a material in which an intermediate layer is provided between the support film and the photosensitive layer, and a material in which a protective layer is provided on the surface of the photosensitive layer.

Japanese Patent Laid-Open No. 01-25147 Japanese Patent No. 2706858 Japanese Patent No. 3004595 Japanese Patent Application Laid-Open No. 2006-234995 WO2008 / 015983 pamphlet JP-A-01-221735 Japanese Patent Laid-Open No. 02-230149 Japanese Examined Patent Publication No. 56-040824 JP 55-501072 A JP 59-097138 A JP 59-216141 A JP-A 63-197942 Japanese Patent Application Laid-Open No. 07-333853 WO2000 / 079344 Pamphlet

  However, the resist pattern releasability significantly deteriorates as the ultrafine line portions of the resist pattern become highly adhered.

  Specifically, in order to obtain sufficient adhesion at the ultrafine line portion of the resist pattern, it is necessary to improve the developer resistance of the resist pattern after exposure. Usually, the amount of hydrophobic material contained in the resist is increased. Or the crosslink density of the resist is increased to improve the developer resistance. However, since a weak alkaline aqueous solution is usually used for the developer and a strong alkaline aqueous solution is used for the stripping solution, the stripping solution resistance is improved as the developer resistance is improved. For this reason, in particular, in a method of manufacturing a printed wiring board by a plating method, it tends to be difficult to remove the resist pattern at the ultrathin wire portion.

  As a result of the study by the present inventors, in the photosensitive resin compositions described in Patent Document 1 and Patent Document 2, the adhesiveness and resolution of the resist are sufficiently compatible with the recent thinning of the wiring of the printed wiring board. Absent. Moreover, in the photosensitive resin composition of patent document 3, there exists room for improvement in the peelability of the resist pattern after plating. Furthermore, in the photosensitive resin compositions described in Patent Document 4 and Patent Document 5, the resist pattern peeling time is long, and there is room for improvement in the composition from the viewpoint of productivity of the printed wiring board.

  Moreover, in the photosensitive element of the said patent documents 6-12, the coating process for providing an intermediate | middle layer, a protective layer, or providing a some photosensitive layer is needed, and the number of manufacturing processes increases that much. To do. In Patent Documents 6 to 7, since the photosensitive layer is exposed to oxygen in the atmosphere when placed on the substrate, it is difficult to maintain its photosensitivity high. Furthermore, according to the description of Patent Documents 8 to 12, since the thickness of the intermediate layer and the protective layer is thin, it is not easy to handle the photosensitive element composed of the photosensitive layer and the intermediate layer or the protective layer after removing the support. Absent.

  Further, according to Patent Documents 13 and 14, although the side surface burrs of the resist are improved, the adhesion and resolution are still insufficient.

  The present invention has been made in view of the above-described problems of the prior art, a photosensitive element having a good balance between adhesion and resolution, and peelability, a method for forming a resist pattern using the photosensitive element, and It aims at providing the manufacturing method of a printed wiring board.

  To achieve the above object, the present invention provides a photosensitive element comprising a support film and a photosensitive layer formed on the support film using a photosensitive resin composition, the photosensitive resin composition The product contains (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator, and (B) the ethylenically unsaturated bond. The photosensitive element which contains the carbonate bond containing urethane (meth) acrylate compound whose weight average molecular weight is 3,300 or less as a photopolymerizable compound which has this is provided.

  In the photosensitive element of the present invention, the photosensitive resin composition constituting the photosensitive layer is (B) a photopolymerizable compound having an ethylenically unsaturated bond, and a carbonate bond-containing urethane having a weight average molecular weight of 3,300 or less. By containing a (meth) acrylate compound, the balance between adhesion and resolution and peelability is improved. Therefore, it is possible to form a resist pattern of very fine lines, and it becomes possible to cope with the recent increase in the density of printed wiring boards and the reduction in the thickness of wiring.

  In the photosensitive element of the present invention of the present invention, the carbonate bond-containing urethane (meth) acrylate compound preferably has a plurality of carbonate bonds in one molecule. The molecular weight is preferably 900 or more.

  In the photosensitive element of the present invention, the carbonate bond-containing urethane (meth) acrylate compound reacts (a) a polycarbonate polyol compound, (b) a polyisocyanate compound, and (c) a hydroxyl group-containing (meth) acrylate compound. It is preferable that it is a urethane (meth) acrylate compound obtained by this. As a result, the photosensitive element has a better balance between adhesion, resolution, and peelability, and can form a very fine line resist pattern more reliably.

  In the photosensitive element of the present invention, the (a) polycarbonate polyol compound is preferably an aliphatic polycarbonate polyol compound and / or an alicyclic polycarbonate polyol compound. As a result, the flexibility of the resist is improved, and even when a thin plate substrate is used, it is possible to more reliably form a resist pattern of ultra fine wires.

  In the photosensitive element of the present invention, the (a) polycarbonate polyol compound is preferably a 1,6-hexanediol-based polycarbonate polyol compound. As a result, the balance between the flexibility and resolution of the resist is good, and even when a thin plate substrate is used, it is possible to more reliably form a resist pattern of ultrathin lines.

  Moreover, the photosensitive element of this invention WHEREIN: It is preferable that the said (B) photopolymerizable compound which has an ethylenically unsaturated bond contains 2-methoxyethyl (meth) acrylate. As a result, the balance between the adhesiveness and the peelability of the resist pattern is improved, and a very fine line resist pattern can be more reliably formed.

  In the photosensitive element of the present invention, the photopolymerizable compound (B) having an ethylenically unsaturated bond is a compound represented by the following general formula (I) and a compound represented by the following general formula (II). It is preferable to contain. As a result, the balance between the adhesion and resolution and the releasability of the resist pattern becomes better, and a very fine line resist pattern can be more reliably formed.

[Wherein, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, m ¹ , m ² , m ³ and m ⁴ each represent an integer of ^{0~40, m 1 + m 2 +} m 3 + m 4 is from 1 to 40. When m ¹ + m ² + m ³ + m ⁴ is 2 or more, a plurality of Xs may be the same or different from each other. ]

[Wherein, R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, Y represents an alkylene group having 2 to 6 carbon atoms, n ¹ and n ² each represents a positive integer, and n ¹ + n ² is 4-40. When n ¹ + n ² is 4 or more, a plurality of Y may be the same as or different from each other. ]

In the photosensitive element of the present invention, 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 aggregates having a diameter of 5 μm or more contained in the support film is 5%. It is preferable that the number per piece / mm ² or less.

According to the study by the present inventors, when a resist pattern is formed using a conventional photosensitive element, particularly a photosensitive element having a layer formed using a thin photosensitive resin composition, Small defects occur, and the production yield of high-density printed wiring boards tends to decrease. As a result of detailed investigations on the cause of minute defects in the resist pattern, the present inventors have found that a large number of particles having a diameter of 5 μm or more and less than 20 μm are present in the support film constituting the photosensitive element. . Then, due to the particles and aggregates having a diameter of 5 μm or more, light scattering of the actinic rays irradiated at the time of exposure occurs, and the actinic rays hardly reach the photosensitive layer, so that there are minute defects in the resist pattern after development. Found out that it would occur. On the other hand, according to the photosensitive element of the present invention, by setting the haze of the support film to 0.01 to 2.0%, the width of the wiring is extremely narrow, and the resist pattern in which the jaggedness on the resist side surface is suppressed. The total number of particles having a diameter of 5 μm or more and aggregates having a diameter of 5 μm or more contained in the support film is 5 / mm ² or less, thereby sufficiently reducing the number of minute defects in the resist. It becomes possible.

  In the photosensitive element of this invention, it is preferable that the film thickness of a photosensitive layer is 3-50 micrometers. This makes it possible to form a resist pattern that is further excellent in adhesion and resolution.

  Moreover, in the photosensitive element of this invention, it is preferable that the weight average molecular weights of the said (A) binder polymer are 30000-150,000. Thereby, it is easy to reduce the thickness of the layer formed using the photosensitive resin composition, and it is further excellent in adhesion, resolution, and peelability after plating, and an ultrafine resist pattern can be more reliably formed.

  In the photosensitive element of the present invention, the (A) binder polymer preferably has a structural unit represented by the following general formulas (III), (IV) and (V). Thereby, the balance of adhesiveness, resolution, and peelability becomes better, and it becomes possible to form a very fine line resist pattern more reliably.

[Wherein R ⁷ , R ⁸ and R ¹⁰ each independently represent a hydrogen atom or a methyl group, and R ⁹ 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. R ¹¹ represents an alkyl group having 1 to 12 carbon atoms, and p represents an integer of 0 to 5. When p is 2 or more, a plurality of R ⁹ may be the same as or different from each other. ]

  Here, the (A) binder polymer has a structural unit represented by the following general formula (VI) in addition to the structural units represented by the general formulas (III) to (V). preferable. This further improves the balance of adhesion, resolution, and peelability.

[Wherein R ¹² represents a hydrogen atom or a methyl group, R ¹³ 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 an integer of 0 to 5] When q is 2 or more, a plurality of R ¹³ may be the same or different from each other. ]

  Furthermore, in the photosensitive element of the present invention, the (C) photopolymerization initiator preferably contains a 2,4,5-triarylimidazole dimer. Thereby, it is possible to obtain better adhesion and resolution while maintaining photosensitivity, and to form an extremely fine-line resist pattern more reliably.

  The present invention also includes a laminating step of laminating the photosensitive element of the present invention on the circuit-forming substrate in the order of the photosensitive layer and the support film, and an actinic ray through the support film to a predetermined portion of the photosensitive layer. There is provided a resist pattern forming method including an exposure step of irradiating to form a photocured portion on the photosensitive layer and a developing step of removing the photosensitive layer other than the photocured portion.

  According to the method for forming a resist pattern of the present invention, since the photosensitive element of the present invention is used, a resist pattern of ultra fine wires can be obtained efficiently.

  The present invention further provides a method for manufacturing a printed wiring board, in which etching or plating is performed on a circuit forming substrate on which a resist pattern is formed by the method for forming a resist pattern of the present invention.

  According to the method for producing a printed wiring board of the present invention, since the resist pattern forming method using the photosensitive element of the present invention is employed, a high-density printed wiring board having an ultrafine wiring pattern is obtained. It is done.

  According to the present invention, it is possible to provide a photosensitive element having a good balance between adhesion and resolution and peelability, a method for forming a resist pattern using the photosensitive element, and a method for producing a printed wiring board.

It is a schematic cross section which shows suitable embodiment of the photosensitive element of this invention. It is the polarizing microscope photograph which observed the surface of the support film which has particle | grains etc. with a diameter of 5 micrometers or more. It is a scanning electron micrograph of the resist pattern formed using the photosensitive element provided with a photosensitive layer on the support film which has many particle | grains with a diameter of 5 micrometers or more.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

  In addition, “(meth) acrylate” in the present specification means “acrylate” and “methacrylate” corresponding thereto. Similarly, “(meth) acryl” means “acryl” and “methacryl” corresponding thereto, and “(meth) acryloyl” means “acryloyl” and corresponding “methacryloyl”.

(Photosensitive element)
FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the photosensitive element of the present invention. The photosensitive element 1 shown in FIG. 1 includes a support film 10 and a photosensitive layer 20. The photosensitive layer 20 is provided on the first main surface 12 of the support film 10. The support film 10 has a second main surface 14 on the side opposite to the first main surface 12.

  The support film 10 is not particularly limited as long as it can support the photosensitive layer 20, but a polymer film having heat resistance and solvent resistance is preferably used. Examples of the polymer film include a film containing at least one resin material selected from the group consisting of polyesters such as polyethylene terephthalate (hereinafter referred to as “PET”) and polyolefins such as polypropylene and polyethylene. .

In addition, the support film 10 of the present invention has a haze of 0.01 to 2.0% from the viewpoint of improving the adhesion and resolution, suppressing the side dents of the resist, and reducing the number of minute defects in the resist. The total number of particles having a diameter of 5 μm or more and aggregates having a diameter of 5 μm or more (hereinafter simply referred to as “particles”) contained in the support film 10 is preferably 5 / mm ² or less. Here, the side surface roughness of the resist pattern refers to a state in which the side surface shape of the resist pattern is not straight but has an unevenness (unevenness).

  Here, the haze of the support film 10 is preferably 0.01 to 2.0%, more preferably 0.01 to 1.5%, and still more preferably 0.01 to 1.0%. Especially preferably, it is 0.01 to 0.5%. If the haze is less than 0.01%, the production of the support film itself tends to be difficult, and if it exceeds 2.0%, the sensitivity and the resolution tend to decrease. Here, “haze” means haze. The haze in the present invention refers to a value measured using a commercially available haze meter (turbidimeter) in accordance with the method defined in JIS K 7105. Haze can be measured with a commercially available turbidimeter such as NDH-1001DP (trade name, manufactured by Nippon Denshoku Industries Co., Ltd.).

  Moreover, the particle | grains with a diameter of 5 micrometers or more contained in the support film 10 include what protrudes from the main surface of a support film, and what exists in a film inside. In addition, particles having a diameter of 5 μm or more include aggregates of primary particles having a diameter of 5 μm or more and primary particles having a diameter of less than 5 μm.

The number of particles having a diameter of 5 μm or more is preferably 5 / mm ² or less, more preferably 3 / mm ² or less, and even more preferably 1 / mm ² or less. If the number of particles and the like exceeds 5 per 1 mm ² , partial defects of the resist after exposure and development (resist micro defects) are likely to occur. If such a photosensitive element is used in the production of a printed wiring board, it may cause an open defect during etching or a short circuit defect during plating, which tends to reduce the production yield of the printed wiring board. is there.

  In addition, even if many particle | grains less than 5 micrometers in diameter protrude from the main surface of a support film, the influence with respect to light scattering is not large. The reason is that in the exposure process, when the photosensitive layer is irradiated with light, the photocuring reaction of the photosensitive layer is not only in the light irradiation part, but in a lateral direction where light is not directly irradiated (relative to the light irradiation direction). Since it also proceeds in the vertical direction), it is considered that when the particle diameter is small (when the diameter is less than 5 μm), the photocuring reaction immediately below the particle proceeds sufficiently. On the other hand, when the particle diameter is large (when the diameter is 5 μm or more), the photocuring reaction immediately below the particles does not proceed sufficiently, so that it is considered that a resist fine defect occurs.

Particles having a diameter of 5 μm or more included in the support film 10 are components constituting the support film, for example, a gel-like polymer, a monomer as a raw material, a catalyst used during production, and inorganic or organic fine particles included as necessary. Agglomerates formed during film production, swelling due to lubricants and adhesives generated when a lubricant-containing layer is applied on the film, and particles with a diameter of 5 μm or more contained in the film Things. In order to reduce the number of particles having a diameter of 5 μm or more to 5 particles / mm ² or less, a support film including a particle having a small particle diameter or excellent dispersibility among these particles may be selectively used. .

  The number of particles having a diameter of 5 μm or more can be measured using a polarizing microscope. In addition, the aggregate formed by aggregating primary particles having a diameter of 5 μm or more and primary particles having a diameter of less than 5 μm is counted as one. FIG. 2 is a polarization micrograph observing the surface of the support film having particles having a diameter of 5 μm or more. In FIG. 2, a portion surrounded by a circle indicates an example of a portion corresponding to a particle having a diameter of 5 μm or more. FIG. 3 is a scanning electron micrograph of a resist pattern formed using a photosensitive element having a photosensitive layer on a support film having a large number of particles having a diameter of 5 μm or more. As described above, when a large number of particles having a diameter of 5 μm or more are present on the surface of the support film, a minute defect of the resist occurs.

  The support film 10 may have a single layer structure or may have a multilayer structure in which films having a plurality of compositions are laminated. For example, when a two-layer support film consisting of two layers is used, a two-layer film obtained by laminating a resin layer containing fine particles on one surface of a biaxially oriented polyester film is used as the support film, and contains the fine particles. The photosensitive layer is preferably formed on the surface opposite to the surface on which the resin layer is formed. Moreover, a multilayer support film consisting of three layers (for example, a support film consisting of three layers of A layer / B layer / A layer) can also be used as the support film. The configuration of the multilayer support film is not particularly limited, but the outermost layer (A layer in the case of the above-mentioned three layers) is preferably a resin layer containing fine particles from the viewpoint of film slipperiness and the like.

  In the present invention, it is more preferable to use a multilayer support film consisting of three layers produced by injection-molding a resin layer containing fine particles on both sides of a biaxially oriented polyester film. In addition, since the conventional two-layer support film is manufactured by applying a resin layer having fine particles to a biaxially oriented polyester film, the resin layer containing fine particles is easily peeled off when the photosensitive element is laminated. The layer may adhere to the photosensitive layer and cause defects.

In the present invention, particles having a diameter of 5 μm or more contained in the support film 10 are adjusted to 5 particles / mm ² or less, and the haze is set to 0.01 to 2.0%. It is particularly preferable to provide a multilayer support film having a resin layer to be contained. As a result, the slipperiness of the surface of the support film is improved, and the suppression of light scattering during exposure can be achieved at a higher level in a balanced manner. The average particle diameter of the fine particles is preferably 0.1 to 10 times, more preferably 0.2 to 5 times the thickness of the resin layer containing the fine particles. If the average particle size is less than 0.1 times, the slipping property tends to be inferior, and if it exceeds 10 times, the photosensitive layer tends to be particularly uneven.

  The fine particles are preferably contained in an amount of 0.01 to 50% by mass in the resin layer containing the fine particles. Examples of the fine particles include fine particles generated during polymerization with various nucleating agents, aggregates, silicon dioxide fine particles (aggregated silica, etc.), inorganic fine particles such as calcium carbonate fine particles, alumina fine particles, titanium oxide fine particles, and barium sulfate fine particles, Organic fine particles such as crosslinked polystyrene fine particles, acrylic fine particles, and imide fine particles, and mixtures thereof can be used.

  In the multilayer support film of three or more layers, the one or more intermediate layers sandwiched between the outermost layers containing fine particles may or may not contain the fine particles, but from the viewpoint of resolution Preferably does not contain the fine particles. When the intermediate layer contains the fine particles, the content in the intermediate layer is preferably 1/3 or less of the content of the outermost layer, and more preferably 1/5 or less.

  From the viewpoint of resolution, the thickness of the resin layer containing the fine particles is preferably 0.01 to 5 μm, more preferably 0.05 to 3 μm, and 0.1 to 2 μm. More preferably. And it is preferable that the surface which does not oppose the intermediate | middle layer of outermost layer has a static friction coefficient of 1.2 or less. If the coefficient of static friction exceeds 1.2, wrinkles tend to occur during film production and photosensitive element production, and static electricity tends to be generated, so that dust tends to adhere. In the present invention, the static friction coefficient can be measured according to ASTM D1894.

In addition, in order to make the particles having a diameter of 5 μm or more contained in the support film 10 to 5 particles / mm ² or less, the particle size of the majority of the fine particles contained in the resin layer is less than 5 μm. It is preferable. In order to further reduce light scattering during exposure, it is preferable to appropriately adjust the thickness of the resin layer containing fine particles in accordance with the particle size of the fine particles.

  In addition, the support film 10 may contain an antistatic agent or the like as necessary as long as the photosensitive characteristics are not impaired.

  Moreover, it is preferable that the thickness of the support film 10 is 5-40 micrometers, It is more preferable that it is 8-35 micrometers, It is further more preferable that it is 10-30 micrometers, It is especially preferable that it is 12-25 micrometers. When the thickness is less than 5 μm, the support film 10 tends to be easily broken when the support film 10 is peeled from the photosensitive element 1. On the other hand, when the thickness exceeds 40 μm, the resolution tends to decrease and the cost is inferior.

  Moreover, as the support film 10, you may obtain what can be used as a support film of the photosensitive element 1 from commercially available general industrial films, and may process and use it suitably. As a commercially available general industrial film that can be used as the support film 10, for example, “QS-48” (trade name, manufactured by Toray Industries, Inc.), which is a biaxially oriented PET film having a three-layer structure in which the outermost layer contains fine particles. , “HTR-02” (trade name, manufactured by Teijin DuPont Films), biaxially oriented PET film “A-1517” (trade name, manufactured by Toyobo Co., Ltd.) having a layer containing fine particles on one side ) And the like.

  The photosensitive layer 20 is a layer formed using a photosensitive resin composition. In general, the photosensitive layer is formed by diluting the photosensitive resin composition in an organic solvent, coating and drying it on a support film, and volatilizing the organic solvent. Therefore, the photosensitive layer is usually composed of the photosensitive resin composition. The photosensitive resin composition constituting the photosensitive layer 20 includes (A) a binder polymer (hereinafter referred to as “component (A)” in some cases) and (B) a photopolymerizable compound having an ethylenically unsaturated bond (hereinafter, Optionally (referred to as “component (B)”) and (C) a photopolymerization initiator (hereinafter sometimes referred to as “component (C)”), and (B) the ethylenically unsaturated bond. As the photopolymerizable compound, a carbonate bond-containing urethane (meth) acrylate compound having a weight average molecular weight of 3,300 or less is contained. Hereinafter, each component will be described in detail.

  The binder polymer as component (A) is not particularly limited as long as it is used in conventional photosensitive resin compositions. For example, acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin , Alkyd resin, phenol resin and the like. Among these, an acrylic resin is preferable from the viewpoint of alkali developability. These are used singly or in combination of two or more.

  (A) The binder polymer can be produced by radical polymerization of a polymerizable monomer. Examples of the polymerizable monomer include styrene; polymerizable styrene derivatives such as vinyl toluene, p-methyl styrene, p-ethyl styrene, and p-chlorostyrene; α-methyl styrene; α-methyl styrene derivative; acrylamide; acrylonitrile; Esters of vinyl alcohol such as vinyl-n-butyl ether; (meth) acrylic acid alkyl ester, (meth) acrylic acid benzyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, ( (Meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic Acid, α- Lomo (meth) acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, substituted (meth) acrylic acid such as β-styryl (meth) acrylic acid; maleic acid; maleic anhydride; Examples thereof include maleic acid monoesters such as monomethyl maleate, monoethyl maleate and monoisopropyl maleate; fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid and the like. These can be used alone or in combination of two or more.

  (A) The binder polymer preferably contains a carboxyl group in the molecule from the viewpoint of alkali developability. The binder polymer having a carboxyl group can be produced, for example, by radical polymerization of a polymerizable monomer having a carboxyl group and another polymerizable monomer.

  (A) It is preferable that a binder polymer contains the structural unit represented by the following general formula (III), (IV), and (V) from the viewpoint of the balance of alkali developability, developing solution tolerance, and peelability. Note that the adhesion and resolution tend to be improved due to the improvement in developer resistance.

[Wherein R ⁷ , R ⁸ and R ¹⁰ each independently represent a hydrogen atom or a methyl group, and R ⁹ 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. R ¹¹ represents an alkyl group having 1 to 12 carbon atoms, and p represents an integer of 0 to 5. When p is 2 or more, a plurality of R ⁹ may be the same as or different from each other. ]

The structural unit represented by the general formula (III) is a structural unit based on (meth) acrylic acid, and is preferably a structural unit based on methacrylic acid (R ⁷ = methyl group).

  The content of the structural unit represented by the general formula (III) is preferably 10 to 50% by mass based on the total solid content of the (A) binder polymer that is a copolymer, and is preferably 15 to 40% by mass. % Is more preferable, and 20 to 35% by mass is even more preferable. If this ratio is less than 10% by mass, the resistance to an aqueous alkaline solution generally used in a developer and a stripper is improved, and development and stripping tend to be difficult. Tends to deteriorate and the adhesion and resolution tend to decrease.

The structural unit represented by the general formula (IV) is a structural unit based on styrene (R ⁸ = hydrogen atom), a styrene derivative, α-methylstyrene (R ⁸ = methyl group), and an α-methylstyrene derivative. is there. In the present invention, the term “styrene derivative” and “α-methylstyrene derivative” mean that the hydrogen atom in the benzene ring of styrene and α-methylstyrene is a substituent R ⁹ (an alkyl group having 1 to 4 carbon atoms, 1 to 1 carbon atoms). 3 alkoxy group, hydroxyl group, halogen atom). Examples of the styrene derivative include methyl styrene, ethyl styrene, tert-butyl styrene, methoxy styrene, ethoxy styrene, hydroxy styrene, chlorostyrene, and the like, and are structural units in which R ⁹ is substituted at the p-position. More preferred. Examples of the α-methylstyrene derivative include those in which the hydrogen atom at the α-position of the vinyl group is substituted with a methyl group in the styrene derivative.

  The content of the structural unit represented by the general formula (IV) is preferably 3 to 60% by mass based on the total solid content of the copolymer (A) binder polymer, and is preferably 10 to 55% by mass. % Is more preferable, 15 to 50% by mass is more preferable, and 20 to 45% by mass is particularly preferable. If this content is less than 3% by mass, the adhesion and resolution tend to decrease, and if it exceeds 60% by mass, the exfoliation piece tends to be large, the exfoliation time tends to be long, and the flexibility of the resist after curing is further increased. There is a tendency to decrease.

The structural unit represented by the general formula (V) is a structural unit based on (meth) acrylic acid alkyl ester. As the (meth) acrylic acid alkyl ester of the general formula (V), R ¹¹ can be mentioned those alkyl groups 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 epoxy group, or a halogen atom. Such (meth) acrylic acid alkyl esters include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, (meth) ) Tert-butyl acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate and 2-ethylhexyl (meth) acrylate, and structural isomers thereof Is mentioned. From the viewpoint of improving the resolution and shortening the peeling time, among these, R ¹¹ is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms having no substituent. Preferably, it is a methyl group.

  The content of the structural unit represented by the general formula (V) is preferably 1 to 40% by mass based on the total solid content of the (A) binder polymer that is a copolymer, and is preferably 2 to 35% by mass. % Is more preferable, 4 to 30% by mass is further preferable, and 5 to 25% by mass is particularly preferable. If this content is less than 1% by mass, the resist releasability tends to decrease, and if it exceeds 40% by mass, the resolution tends to decrease.

  In addition, (A) the binder polymer, in addition to the structural units represented by the above general formulas (III) to (V), in addition to the structural units represented by the general formulas (III) to (V), from the viewpoint of the balance between adhesion and resolution and peelability It is preferable that the structural unit represented by these is included.

[Wherein R ¹² represents a hydrogen atom or a methyl group, R ¹³ 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 an integer of 0 to 5] When q is 2 or more, a plurality of R ¹³ may be the same or different from each other. ]

  The structural unit represented by the general formula (VI) is a structural unit based on benzyl (meth) acrylate and benzyl (meth) acrylate derivatives. Examples of the benzyl (meth) acrylate derivative include 4-methylbenzyl (meth) acrylate, 4-ethylbenzyl (meth) acrylate, 4-tert-butylbenzyl (meth) acrylate, 4-methoxybenzyl (meth) acrylate, 4- Examples thereof include ethoxybenzyl (meth) acrylate, 4-hydroxybenzyl (meth) acrylate, 4-chlorobenzyl (meth) acrylate and the like. The structural unit represented by the general formula (VI) is based on benzyl (meth) acrylate (when q = 0) from the viewpoint of maintaining developability, etching resistance, plating resistance, and flexibility of the cured film. A structural unit is preferred.

  The content of the structural unit represented by the general formula (VI) is preferably 5 to 60% by mass based on the total solid content of the copolymer (A) binder polymer, and is preferably 10 to 55% by mass. % Is more preferable, 15 to 50% by mass is further preferable, and 20 to 45% by mass is particularly preferable. If this content is less than 5% by mass, the adhesion tends to decrease. If it exceeds 60% by mass, the peeling time tends to be long, and the flexibility of the resist after UV curing tends to decrease.

  In addition, in order to make the structural unit of each said general formula into the said content rate, it can usually carry out by mix | blending and copolymerizing the monomer which forms each structural unit in the ratio similar to the said content rate. .

  (A) The weight average molecular weight of the binder polymer is preferably 30,000 to 150,000, more preferably 35,000 to 100,000, and further preferably 40,000 to 80,000. preferable. If the weight average molecular weight is less than 30,000, the photosensitive layer tends to be brittle, and if it exceeds 150,000, a residual thread development occurs and the resolution tends to decrease. The weight average molecular weight is measured by gel permeation chromatography (hereinafter referred to as “GPC”), and a value converted to standard polystyrene is used.

  (A) It is preferable that the acid value of a binder polymer is 30-300 mgKOH / g, It is more preferable that it is 100-250 mgKOH / g, It is further more preferable that it is 130-200 mgKOH / g. When the acid value is less than 30 mgKOH / g, the development time tends to be long, and when it exceeds 300 mgKOH / g, the resistance of the photocured resist to the alkaline developer tends to be lowered.

  These binder polymers are used singly or in combination of two or more. Examples of combinations of binder polymers in the case of using two or more in combination include, for example, two or more binder polymers composed of different copolymerization components (including different repeating units as constituent components), and two or more types of different weight average molecular weights. And two or more types of binder polymers having different degrees of dispersion. In addition, a polymer having a multimode molecular weight distribution described in JP-A No. 11-327137 can also be used.

  In addition, when developing with an organic solvent in a development process, it is preferable to prepare the polymerizable monomer which has a carboxyl group in a small quantity. Moreover, the binder polymer may have a photosensitive group as needed.

  The photopolymerizable compound having an ethylenically unsaturated bond as component (B) contains a carbonate bond-containing urethane (meth) acrylate compound having a weight average molecular weight of 3,300 or less as an essential component.

  Although the weight average molecular weight of the said carbonate bond containing urethane (meth) acrylate compound needs to be 3,300 or less, it is preferable that it is 900 as a minimum, and it is 1,000-3,000. More preferably, it is 2,000 to 3,000, more preferably 2,500 to 3,000. When the weight average molecular weight exceeds 3,300, the resolution decreases. On the other hand, when the weight average molecular weight is less than 900, the adhesion tends to decrease.

  The carbonate bond-containing urethane (meth) acrylate compound having a weight average molecular weight of 3,300 or less is composed of (a) a polycarbonate polyol compound from the viewpoint of the balance between adhesion and peelability and the resist pattern formability of ultrafine wires. A carbonate bond-containing urethane (meth) acrylate compound obtained by reacting (b) a polyisocyanate compound and (c) a hydroxyl group-containing (meth) acrylate compound is preferred.

  Here, the (a) polycarbonate polyol compound is preferably an aliphatic polycarbonate polyol compound and / or an alicyclic polycarbonate polyol compound from the viewpoint of improving the flexibility of the resist.

  The (a) polycarbonate polyol compound is a polyol having a carbonate bond in the molecule and having two or more hydroxyl groups, and is a reaction product of a polyol and an organic carbonate compound or phosgene. Examples of the polyol include diols such as alkylene diol, alkylene glycol, and polyoxyalkylene glycol. Examples of the polycarbonate polyol compound (a) include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, neopentyl glycol, 1,3- Butanediol, 1,4-butanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,9- Nonanediol, 1,10-decanediol, cyclohexane dimethylol, 1,4-cyclohexanediol, aliphatic and / or alicyclic polycarbonate diols, etc. starting from polyoxyethylene glycol are listed. These are used singly or in combination of two or more. Among these, the 1,6-hexanediol-based polycarbonate polyol compound has a good balance between the flexibility and resolution of the resist, and even when a thin plate substrate is used, it is possible to more reliably form an ultrathin line resist pattern. Therefore, it is preferable.

  The number average molecular weight of the (a) polycarbonate polyol compound is not particularly limited, but is preferably in a range where the balance between resist flexibility and resolution is not impaired, and is in the range of 200 to 5,000. It is more preferable.

  The (b) polyisocyanate compound refers to a compound containing two or more isocyanate groups in the molecule, and examples thereof include aliphatic diisocyanate compounds, aromatic diisocyanate compounds, and trimers thereof.

  Examples of the aliphatic diisocyanate compound include 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3-diisocyanate cyclohexane, and 1,4-diisocyanate. Cyclohexane, dicyclohexylmethane-4,4′-diisocyanate, m-tetramethylxylene diisocyanate, p-tetramethylxylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,12-dodecamethylene diisocyanate, 2,2,4-trimethylcyclohexane Diisocyanate, 2,4,4-trimethylcyclohexane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate Sulfonate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornene diisocyanate.

  Examples of aromatic diisocyanate compounds include diisocyanate monomers such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, 1,6-phenylene diisocyanate, and 1,4-phenylene diisocyanate. Is mentioned.

  These are used singly or in combination of two or more. Among these, an aliphatic diisocyanate compound is preferable, and specifically, isophorone diisocyanate is preferable because chemical resistance is improved and a very fine resist pattern can be more reliably formed.

  (C) Examples of the hydroxyl group-containing (meth) acrylate compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and ε-caprolactone adducts thereof. Etc., trimethylolpropane di (meth) acrylate, trimethylolpropane (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, dipentaerythritol Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned, These are used individually by 1 type or in combination of 2 or more types. Among these, 2-hydroxyethyl acrylate is preferable because resist releasability is improved and a very fine resist pattern can be more reliably formed.

  In addition, the photopolymerizable compound (B) having an ethylenically unsaturated bond is a compound represented by the following general formula (I) and the following general formula from the viewpoint of the balance between adhesion and resolution and resist peelability. It is preferable that the compound represented by Formula (II) is included.

In the general formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and preferably a hydrogen atom. X independently represents an alkylene group having 2 to 6 carbon atoms, preferably an alkylene group having 2 to 4 carbon atoms, and more preferably an ethylene group or a propylene group. In the formula, a plurality of Xs may be the same or different. m ¹ , m ² , m ³ and m ⁴ each represent an integer of 0 to 40, and m ¹ + m ² + m ³ + m ⁴ is an integer of 1 to 40, preferably an integer of 2 to 30. It is more preferably an integer of ˜20, further preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 12.

When the value of m ¹ + m ² + m ³ + m ⁴ is 0, there is a tendency that fine line adhesion of the resist is not obtained, and when the value of m ¹ + m ² + m ³ + m ⁴ is an integer exceeding 40, per unit mass Since the concentration of the photoreactive site is low, the sensitivity is lowered, the adhesion of the resist is deteriorated, the resist shape tends to be deteriorated, and the resist stripping time is prolonged, and sludge is easily generated during development. Tend to be.

Examples of the compound represented by the general formula (I) include pentaerythritol (poly) alkoxytetra (meth) acrylate. “Pentaerythritol (poly) alkoxytetra (meth) acrylate” includes “pentaerythritol alkoxytetra (meth) acrylate” in which m ¹ + m ² + m ³ + m ⁴ = 1 and m ¹ + m ² + m ³ + m ^4. Both “pentaerythritol polyalkoxytetra (meth) acrylates” = 2 to 40 are included. Examples of the pentaerythritol (poly) alkoxytetra (meth) acrylate include pentaerythritol (poly) ethoxytetra (meth) acrylate, pentaerythritol (poly) propoxytetra (meth) acrylate, and pentaerythritol (poly) butoxytetra (meth). ) Acrylate, pentaerythritol (poly) ethoxypolypropoxytetra (meth) acrylate, and the like. These are used singly or in combination of two or more.

  Examples of the pentaerythritol (poly) ethoxytetra (meth) acrylate include pentaerythritol ethoxytetra (meth) acrylate, pentaerythritol diethoxytetra (meth) acrylate, pentaerythritol triethoxytetra (meth) acrylate, and pentaerythritol tetraethoxy. Tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, pentaerythritol pentaethoxytetra (meth) acrylate, pentaerythritol hexaethoxytetra (meth) acrylate, pentaerythritol heptaethoxytetra (meth) acrylate, pentaerythritol octaethoxytetra (Meth) acrylate, pentaerythritol nonaethoxytetra ) Acrylate, pentaerythritol deca ethoxy tetra (meth) acrylate. These are used singly or in combination of two or more.

  Examples of the pentaerythritol (poly) propoxytetra (meth) acrylate include pentaerythritol propoxytetra (meth) acrylate, pentaerythritol dipropoxytetra (meth) acrylate, pentaerythritol tripropoxytetra (meth) acrylate, and pentaerythritol tetrapropoxy. Tetra (meth) acrylate, pentaerythritol pentapropoxytetra (meth) acrylate, pentaerythritol hexapropoxytetra (meth) acrylate, pentaerythritol heptapropoxytetra (meth) acrylate, pentaerythritol octapropoxytetra (meth) acrylate, pentaerythritol nonapropoxy Tetra (meth) acrylate, pentaerythrito Deca propoxy tetra (meth) acrylate. These are used singly or in combination of two or more.

  Examples of the pentaerythritol (poly) butoxytetra (meth) acrylate include pentaerythritol butoxytetra (meth) acrylate, pentaerythritol dibutoxytetra (meth) acrylate, pentaerythritol tributoxytetra (meth) acrylate, and pentaerythritol tetrabutoxy. Tetra (meth) acrylate, pentaerythritol pentabutoxytetra (meth) acrylate, pentaerythritol hexabutoxytetra (meth) acrylate, pentaerythritol heptavoxytetra (meth) acrylate, pentaerythritol octabutoxytetra (meth) acrylate, pentaerythritol nonabutoxy Tetra (meth) acrylate, pentaerythritol decabutoxytetra Meth) acrylate. These are used singly or in combination of two or more.

  Examples of the pentaerythritol (poly) ethoxypolypropoxytetra (meth) acrylate include pentaerythritol ethoxypropoxytetra (meth) acrylate, pentaerythritol diethoxypropoxytetra (meth) acrylate, and pentaerythritol triethoxydipropoxytetra (meth). Examples thereof include acrylate, pentaerythritol diethoxytetrapropoxytetra (meth) acrylate, and pentaerythritol tetraethoxytetrapropoxytetra (meth) acrylate. These are used singly or in combination of two or more.

In the general formula (II), R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, and preferably a methyl group. Y represents an alkylene group having 2 to 6 carbon atoms. n ¹ and n ² each represent a positive integer, n ¹ + n ² is an integer of 4 to 40, preferably an integer of 6 to 34, more preferably an integer of 8 to 30, It is more preferably an integer of ˜28, particularly preferably an integer of 8-20, very preferably an integer of 8-16, and most preferably an integer of 8-12. When the value of n ¹ + n ² is less than 4, the compatibility with the binder polymer decreases, and when the photosensitive element is laminated on the circuit forming substrate, it tends to be peeled off. When the value of n ¹ + n ² exceeds 40, The hydrophilicity increases, the resist tends to peel off during development, and the plating resistance tends to decrease. A plurality of Y present in the molecule may be the same as or different from each other.

  Examples of the alkylene group having 2 to 6 carbon atoms include an ethylene group, a propylene group, an isopropylene group, a butylene group, a pentylene group, and a hexylene group. Among these, from the viewpoint of improving resolution and plating resistance, an ethylene group or an isopropylene group is preferable, and an ethylene group is more preferable.

  Moreover, the aromatic ring in the said general formula (II) may have a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, a phenacyl group, an amino group, and 1 to 10 carbon atoms. Alkylamino group, dialkylamino group having 2 to 20 carbon atoms, nitro group, cyano group, carbonyl group, mercapto group, alkylmercapto group having 1 to 10 carbon atoms, allyl group, hydroxyl group, hydroxyalkyl having 1 to 20 carbon atoms Group, carboxyl group, carboxyalkyl group having 1 to 10 carbon atoms in alkyl group, acyl group having 1 to 10 carbon atoms in alkyl group, alkoxy group having 1 to 20 carbon atoms, alkoxycarbonyl group having 1 to 20 carbon atoms , An alkylcarbonyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an N-alkylcarbamoyl group having 2 to 10 carbon atoms, or a complex Groups containing, or an aryl group substituted with these substituents include. The above substituents may form a condensed ring, and a hydrogen atom in these substituents may be substituted with the above substituent such as a halogen atom. When the number of substituents is 2 or more, the two or more substituents may be the same or different.

  Examples of the compound represented by the general formula (II) include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, 2,2-bis (4-((meth) acrylic). Loxypolypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) Examples thereof include bisphenol A-based (meth) acrylate compounds such as propane.

  Examples of 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2,2- Bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptaethoxy) phenyl) propane 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy nonaethoxy) ) Phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl) propane, 2, 2-bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl) propane, 2,2-bis (4- ( (Meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexa) Decaethoxy) phenyl) propane and the like. Of these, 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is more preferable, and is commercially available as BPE-500 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.). 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is commercially available as BPE-1300 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.). These are used singly or in combination of two or more.

  Examples of 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydipropoxy) phenyl) propane, 2,2- Bis (4-((meth) acryloxytripropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxypentapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptapropoxy) phenyl) propane 2,2-bis (4-((meth) acryloxyoctapropoxy) phenyl) propane, 2,2-bis (4-((meth) acrylic) Xinonapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecapropoxy) phenyl) propane 2,2-bis (4-((meth) acryloxydodecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecapropoxy) phenyl) propane, 2,2-bis ( 4-((meth) acryloxytetradecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecapropoxy) phenyl) propane, 2,2-bis (4-((meth)) And acryloxyhexadecapropoxy) phenyl) propane. These are used singly or in combination of two or more.

  Examples of 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxyoctapropoxy) phenyl) propane, Examples include 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane. These are used singly or in combination of two or more.

  In addition, the photopolymerizable compound having an ethylenically unsaturated bond as the component (B) has a good balance between the adhesion and the releasability of the resist, and from the standpoint that an ultrafine resist pattern can be more reliably formed. , 2-methoxyethyl (meth) acrylate may be contained.

  As the component (B), polyalkylene glycol di (meth) acrylate can also be preferably used. As the polyalkylene glycol di (meth) acrylate, for example, a compound represented by the following general formula (VII), (VIII) or (IX) is preferable.

[Wherein, R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or a methyl group, EO represents an oxyethylene group (—CH ₂ —CH ₂ —O—), and PO represents an oxypropylene group (—CH (CH ₃ ) —CH ₂ —O— or —CH ₂ —CH (CH ₃ ) —O—), s ¹ represents an integer of ¹ to 30, and r ¹ and r ² each represents an integer of 0 to 30. , R ¹ + r ² (average value) is an integer of 1-30. ]

[Wherein, R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or a methyl group. EO represents an oxyethylene group, PO represents an oxypropylene group, r ³ represents an integer of 1 to 30, s ² and s ³ each represent an integer of 0 to 30, and s ² + s ³ (average value) Is an integer from 1 to 30. ]

[Wherein, R ¹⁸ and R ¹⁹ each independently represent a hydrogen atom or a methyl group, and is preferably a methyl group. EO represents an oxyethylene group, and PO represents an oxypropylene group. r ⁴ represents an integer of 1 to 30, and s ⁴ represents an integer of 1 to 30. ]

  In the general formulas (VII), (VIII), and (IX), when a plurality of oxyethylene units (EO) and oxypropylene units (PO) are present, the plurality of oxyethylene units and oxypropylene units are each continuously blocked. May exist in a random manner or may exist randomly.

  Furthermore, when the oxypropylene unit is an oxyisopropylene unit, the secondary carbon of the propylene group may be bonded to an oxygen atom, or the primary carbon may be bonded to an oxygen atom.

The total number of repeating oxyethylene units (r ¹ + r ² , r ³ and r ⁴ ) in the general formulas (VII), (VIII) and (IX) is preferably an integer of 1 to 30, each independently. It is more preferably an integer of 1 to 10, more preferably an integer of 4 to 9, and particularly preferably an integer of 5 to 8. If the number of repetitions exceeds 30, the tent reliability and the resist shape tend to deteriorate.

The total number of repeating oxypropylene units (s ¹ , s ² + s ³ and s ⁴ ) in the above general formulas (VII), (VIII) and (IX) is preferably independently an integer of 1 to 30, More preferably, it is an integer of 5-20, more preferably an integer of 8-16, and particularly preferably an integer of 10-14. If the number of repetitions exceeds 30, the resolution decreases and sludge tends to be generated during development.

Specific examples of the compound represented by the general formula (VII) include, for example, vinyl in which R ¹⁴ and R ¹⁵ are a methyl group, r ¹ + r ² = 4 (average value), and s ¹ = 12 (average value). Compound (manufactured by Hitachi Chemical Co., Ltd., trade name: FA-023M) and the like.

Specific examples of the compound represented by the general formula (VIII) include, for example, vinyl in which R ¹⁶ and R ¹⁷ are methyl groups, r ³ = 6 (average value), s ² + s ³ = 12 (average value) Compound (manufactured by Hitachi Chemical Co., Ltd., trade name: FA-024M) and the like.

Specific examples of the compound represented by the general formula (IX) include, for example, a vinyl compound in which R ¹⁸ and R ¹⁹ are hydrogen atoms, r ⁴ = 1 (average value), and s ⁴ = 9 (average value) ( Shin-Nakamura Chemical Co., Ltd., sample name: NK ester HEMA-9P) and the like.

  In addition, these are used individually by 1 type or in combination of 2 or more types.

  The component (B) may further contain a photopolymerizable compound having one ethylenically unsaturated bond from the viewpoint of improving developability such as adhesion and resolution, and peelability. As a photopolymerizable compound having one ethylenically unsaturated bond, it is preferable to contain a compound represented by the following general formula (X).

[Wherein, R ²⁰ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom. Z is synonymous with X and Y in the general formulas (I) and (II) described above, and is preferably an ethylene group. k represents a positive integer of 4 to 20, and is preferably an integer of 5 to 18, more preferably an integer of 6 to 12, and an integer of 6 to 10 from the viewpoint of developability. Further preferred. ]

  Moreover, the aromatic ring in the said general formula (X) may have a substituent, and the substituent similar to the aromatic ring in the general formula (II) mentioned above is mentioned as these substituents.

  Specific examples of the compound represented by the general formula (X) include, for example, nonylphenoxypolyethyleneoxy (meth) acrylate, nonylphenoxypolypropyleneoxy (meth) acrylate, butylphenoxypolyethyleneoxy (meth) acrylate, butylphenoxypolypropyleneoxy (Meth) acrylate etc. are mentioned.

  Examples of the nonylphenoxypolyethyleneoxy (meth) acrylate include nonylphenoxytetraethyleneoxy (meth) acrylate, nonylphenoxypentaethyleneoxy (meth) acrylate, nonylphenoxyhexaethyleneoxy (meth) acrylate, nonylphenoxyheptaethyleneoxy ( (Meth) acrylate, nonylphenoxyoctaethyleneoxy (meth) acrylate, nonylphenoxynonaethyleneoxy (meth) acrylate, nonylphenoxydecaethyleneoxy (meth) acrylate, nonylphenoxyundecaethyleneoxy (meth) acrylate, nonylphenoxide decaethyleneoxy (Meth) acrylate etc. are mentioned.

  Examples of the butylphenoxypolyethyleneoxy (meth) acrylate include butylphenoxytetraethyleneoxy (meth) acrylate, butylphenoxypentaethyleneoxy (meth) acrylate, butylphenoxyhexaethyleneoxy (meth) acrylate, butylphenoxyheptaethyleneoxy ( Examples include meth) acrylate, butylphenoxyoctaethyleneoxy (meth) acrylate, butylphenoxynonaethyleneoxy (meth) acrylate, butylphenoxydecaethyleneoxy (meth) acrylate, and butylphenoxyundecaethyleneoxy (meth) acrylate. In addition, these are used individually by 1 type or in combination of 2 or more types.

  Component (B) may contain a urethane monomer such as a (meth) acrylate compound having a urethane bond from the viewpoint of improving tenting properties and the like.

  Examples of the urethane monomer include a (meth) acryl monomer having a hydroxyl group at the β-position and a diisocyanate compound such as isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate. Addition reaction product, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate, and the like. Note that EO represents ethylene oxide, and the EO-modified compound has a block structure of an ethylene oxide group. PO represents propylene oxide, and the PO-modified compound has a block structure of propylene oxide groups. Examples of the EO-modified urethane di (meth) acrylate include the product name “UA-11” manufactured by Shin-Nakamura Chemical Co., Ltd. Examples of the EO, PO-modified urethane di (meth) acrylate include a product name “UA-13” manufactured by Shin-Nakamura Chemical Co., Ltd. These are used individually by 1 type or in combination of 2 or more types.

  The component (B) may contain a photopolymerizable compound having an ethylenically unsaturated bond other than those described above. Other (B) photopolymerizable compounds include, for example, compounds obtained by reacting an α, β-unsaturated carboxylic acid with a polyhydric alcohol, and reacting an α, β-unsaturated carboxylic acid with a glycidyl group-containing compound. The compound obtained by this, a phthalic-acid type compound, (meth) acrylic-acid alkylester, etc. are mentioned. These are used individually by 1 type or in combination of 2 or more types.

  Examples of the compound obtained by reacting the polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri ( And (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO, PO-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. These are used individually by 1 type or in combination of 2 or more types.

  Examples of the phthalic acid compounds include γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyalkyl-β ′-(meth) acryloloxyalkyl-o-phthalate. Etc. These may be used alone or in any combination of two or more.

  The photopolymerization initiator as component (C) preferably contains a 2,4,5-triarylimidazole dimer. Examples of the 2,4,5-triarylimidazole dimer include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxy). Phenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p- Methoxyphenyl) -4,5-diphenylimidazole dimer, 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenylimidazole dimer, 2- (o-bromophenyl) ) -4,5-diphenylimidazole dimer, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p-chlorophenyl) imidazole 2- (o-chlorophenyl) -4,5-tetra (m-methoxyphenyl) imidazole dimer, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra ( p-fluorophenyl) imidazole dimer, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra (p-chloro-p-methoxyphenyl) imidazole dimer, 2 , 2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) imidazole dimer, 2,2′-bis (o-chlorophenyl) -4,4 ′ , 5,5′-tetra (o, p-dibromophenyl) imidazole dimer, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p-chloronaphthyl) imidazole Dimer, 2,2'-bis ( , M-dichlorophenyl) -4,4 ′, 5,5′-tetra (p-chloronaphthyl) imidazole dimer, 2,2′-bis (o, m-dichlorophenyl) -4,4 ′, 5,5 '-Tetraphenylimidazole dimer, 2,2'-bis (o, p-dichlorophenyl) -4,4', 5,5'-tetraphenylimidazole dimer, 2,2'-bis (o, p -Dichlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) imidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2 , 4-Dimethoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazole dimer, 2,2′-bis (p-bromophenyl)- 4, 4 ', 5,5'-tetraphenylimidazole dimer, 2,2'-bis (o-bromophenyl) -4,4', 5,5'-tetra (o, p-dichlorophenyl) imidazole dimer, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetra (p-iodophenyl) imidazole dimer, 2,2′-bis (m-bromophenyl) -4, 4 ′, 5,5′-tetraphenylimidazole dimer, 2,2′-bis (m, p-dibromophenyl) -4,4 ′, 5,5-tetraphenylimidazole dimer, 2,2 ′ -Bis (2,6-dichlorophenyl) -4-5-diphenylimidazole dimer, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-fluorophenyl) imidazole Dimer, 2,2'-bis (o-bu Mophenyl) -4,4 ′, 5,5′-tetra (p-iodophenyl) imidazole dimer, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p -Chloronaphthyl) imidazole dimer, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-chlorophenyl) imidazole dimer, 2,2'-bis (o -Bromophenyl) -4,4 ', 5,5'-tetra (p-chloro-p-methoxyphenyl) imidazole dimer, 2,2'-bis (o-chlorophenyl) -4,4', 5 5'-tetra (o, p-dichlorophenyl) imidazole dimer, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (o, p-dibromophenyl) imidazole dimer 2,2′-bis (o-bromo Enyl) -4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) imidazole dimer, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′- Examples include tetra (o, p-dichlorophenyl) imidazole dimer. Among these, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer is preferable from the viewpoint of further improving adhesion and sensitivity.

  In addition, in the 2,4,5-triarylimidazole dimer, the aryl group substituents of two 2,4,5-triarylimidazoles may give the same and symmetric compounds, or differently asymmetric Such compounds may be provided.

  The content ratio of the 2,4,5-triarylimidazole dimer when the (C) component contains 2,4,5-triarylimidazole dimer is based on the total amount of the (C) component. It is preferably 70 to 100% by mass, more preferably 85 to 100% by mass, still more preferably 90 to 100% by mass, and particularly preferably 93 to 100% by mass. By containing 2,4,5-triarylimidazole dimer in this proportion, the photosensitive element of the present invention has better adhesion and sensitivity.

  Moreover, as a photoinitiator which is (C) component, you may use another photoinitiator other than the said 2,4,5-triaryl imidazole dimer. Other photopolymerization initiators include, for example, aromatic ketones, p-aminophenyl ketones, quinones, benzoin ether compounds, benzoin compounds, benzyl derivatives, acridine derivatives, coumarin compounds, oxime esters, N-aryls. -Α-amino acid compounds, aliphatic polyfunctional thiol compounds, acylphosphine oxides, thioxanthones, tertiary amine compounds and the like may be used, and these compounds may be used in combination.

  Examples of the aromatic ketones include acetophenone, benzophenone, methylbenzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone. 4-methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2 -Morpholino-propanone-1,4,4'-dichlorobenzophenone and the like.

  Examples of the p-aminophenyl ketones include aminobenzophenone, butylaminoacetophenone, dimethylaminoacetophenone, α, α-dimethoxy-α-morpholino-methylthiophenylacetophenone, dimethylaminobenzophenone, 4,4′-bis (ethylamino). ) Benzophenone, 4,4′-bis (dibutylamino) benzophenone, 2,2-dimethoxy-2-phenylacetophenone, 4,4′-diaminobenzophenone, 2,2-diethoxy-2-phenylacetophenone, and the like.

  Examples of the quinones include 2-methylanthraquinone, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, and 2-phenylanthraquinone. 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 3-chloro-2-methylanthraquinone, 9,10-phenantharaquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, 2-methyl Examples include -1,4-naphthoquinone, 1,4-dimethylanthraquinone, 2,3-dimethylanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone.

  Examples of the benzoin ether compound include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin phenyl ether.

  Examples of the benzoin compound include benzoin, methylbenzoin, and ethylbenzoin.

  Examples of the benzyl derivative include benzyl methyl ketal, benzyl diethyl ketal, benzyl dipropyne ketal, benzyl diphenyl ketal and the like.

  Examples of the acridine derivative include 1,2-bis (9-acridinyl) ethane, 1,3-bis (9-acridinyl) propane, 1,4-bis (9-acridinyl) butane, and 1,5-bis ( 9-acridinyl) pentane, 1,6-bis (9-acridinyl) hexane, 1,7-bis (9-acridinyl) heptane, 1,8-bis (9-acridinyl) octane, 1,9-bis (9- Acridinyl) nonane, 1,10-bis (9-acridinyl) decane, 1,11-bis (9-acridinyl) undecane, bis (9-acridinyl) alkane such as 1,12-bis (9-acridinyl) dodecane, , 3-bis (9-acridinyl) -2-oxapropane, 1,3-bis (9-acridinyl) -2-thiapropane, 1,5-bis (9-acrylic) Nyl) -3-thiapentane, 9-pyridylacridine, 9-pyrazinylacridine, 9-monopentylaminoacridine, 9-phenylacridine, 9- (p-methylphenyl) acridine, 9- (p-ethylphenyl) acridine 9- (p-n-propylphenyl) acridine, 9- (p-iso-propylphenyl) acridine, 9- (pn-butylphenyl) acridine, 9- (p-tert-butylphenyl) acridine, 9 -(P-methoxyphenyl) acridine, 9- (p-ethoxyphenyl) acridine, 9- (p-acetylphenyl) acridine, 9- (p-dimethylaminophenyl) acridine, 9- (p-cyanophenyl) acridine, 9- (p-chlorophenyl) acridine, 9- (p-bromophenyl) acridine Gin, 9- (m-methylphenyl) acridine, 9- (mn-propylphenyl) acridine, 9- (m-iso-propylphenyl) acridine, 9- (mn-butylphenyl) acridine, 9- (M-tert-butylphenyl) acridine, 9- (m-methoxyphenyl) acridine, 9- (m-ethoxyphenyl) acridine, 9- (m-acetylphenyl) acridine, 9- (m-dimethylaminophenyl) acridine 9- (m-diethylaminophenyl) acridine, 9- (m-cyanophenyl) acridine, 9- (m-chlorophenyl) acridine, 9- (m-bromophenyl) acridine, 9-cyanoethylacridine, 9-hydroxyethylacridine , 9-chloroethylacridine, 9-n-propoxyacridi And 9-chloroethoxyacridine.

  Examples of the coumarin compound include 7-amino-4-methylcoumarin, 7-dimethylamino-4-methylcoumarin, 7-diethylamino-4-methylcoumarin, 7-methylamino-4-methylcoumarin, and 7-ethyl. Amino-4-methylcoumarin, 7-dimethylaminocyclopenta [c] coumarin, 7-aminocyclopenta [c] coumarin, 7-diethylaminocyclopenta [c] coumarin, 4,6-dimethyl-7-ethylaminocoumarin, 4,6-diethyl-7-ethylaminocoumarin, 4,6-dimethyl-7-diethylaminocoumarin, 4,6-dimethyl-7-dimethylaminocoumarin, 4,6-diethyl-7-ethylaminocoumarin, 4,6 -Diethyl-7-dimethylaminocoumarin, 2,3,6,7,10,11-hexanehydride -1H, 5H-cyclopenta [3,4] [1] benzopyrano- [6,7,8-ij] quinolizine 12 (9H) -one, 7-diethylamino-5 ', 7'-dimethoxy-3,3'- Examples thereof include carbonyl biscoumarin, 3,3′-carbonylbis [7- (diethylamino) coumarin], 7-diethylamino-3-thienoxysilk marine and the like.

  Examples of the oxime esters include 1-phenyl-1,2-propanedione-2-o-benzoyloxime, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, and the like. It is done.

  Examples of the N-aryl-α-amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, N- (n-propyl) -N-phenylglycine, N- (n-butyl) -N-phenylglycine, N- (methoxyethyl) -N-phenylglycine, N-methyl-N-phenylalanine, N-ethyl-N-phenylalanine, N- (n-propyl) -N -Phenylalanine, N- (n-butyl) -N-phenylalanine, N-methyl-N-phenylvaline, N-methyl-N-phenylleucine, N-methyl-N- (p-tolyl) glycine, N-ethyl- N- (p-tolyl) glycine, N- (n-propyl) -N- (p-tolyl) glycine, N- (n-butyl) -N- (p-tolyl) g Syn, N-methyl-N- (p-chlorophenyl) glycine, N-ethyl-N- (p-chlorophenyl) glycine, N- (n-propyl) -N- (p-chlorophenyl) glycine, N-methyl-N -(P-bromophenyl) glycine, N-ethyl-N- (p-bromophenyl) glycine, N- (n-butyl) -N- (p-bromophenyl) glycine, N, N'-diphenylglycine, N -Methyl-N- (p-iodophenyl) glycine, N- (p-bromophenyl) glycine, N- (p-chlorophenyl) glycine, N- (o-chlorophenyl) glycine and the like.

  Examples of the aliphatic polyfunctional thiol compound include hexanethiol, decanethiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol. Bisthioglycolate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, trishydroxyethyltristhiopropionate, and other Examples thereof include thioglycolates and thiopropionates of polyvalent hydroxy compounds.

  Examples of the acylphosphine oxides include (2,6-dimethoxybenzoyl) -2,4,4-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and 2,4,6. -Trimethyl benzoyl diphenyl phosphine oxide etc. are mentioned.

  Examples of the thioxanthones include thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2-fluorothioxanthone. 4-fluorothioxanthone, 2-chlorothioxanthone, 4-chlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.

  Other photopolymerization initiators include, for example, ethyl-2,4,6-trimethylbenzoylphenyl phosphinate, 2,2-dioxo-3-phenylpropionic acid ethyl-2- (o-benzoylcarbonyl) -oxime, Examples include p-nitrodiphenyl, m-nitroaniline, p-nitroaniline, 2,6-dinitroaniline. Moreover, you may combine a thioxanthone type compound and a tertiary amine compound like the combination of diethyl thioxanthone and dimethylaminobenzoic acid.

  Examples of the tertiary amine compound include dimethylaminobenzoic acid, diethylaminobenzoic acid, diisopropylaminobenzoic acid, and the like.

  The (C) photopolymerization initiator in the present invention preferably contains the above aromatic ketones in addition to the 2,4,5-triarylimidazole dimer, and among them, N, N′-tetraethyl-4 4,4′-diaminobenzophenone (Michler ketone) is preferably contained.

  In the photosensitive resin composition, the blending amount of the binder polymer as the component (A) is preferably 40 to 70 parts by mass based on 100 parts by mass of the total amount of the component (A) and the component (B). More preferably, it is -65 mass parts, and it is further more preferable that it is 50-60 mass parts. If the blending amount is less than 40 parts by mass, the photocured product tends to be brittle, and if it exceeds 70 parts by mass, the resolution and photosensitivity tend to be insufficient.

  In the photosensitive resin composition, the blending amount of the photopolymerizable compound having an ethylenically unsaturated bond as the component (B) is 30 to 60 based on 100 parts by mass of the total amount of the component (A) and the component (B). The mass is preferably 35 parts by mass, more preferably 35 to 55 parts by mass, and still more preferably 40 to 50 parts by mass. If the blending amount is less than 30 parts by mass, resolution and photosensitivity tend to be insufficient, and if it exceeds 60 parts by mass, the photocured product tends to be brittle.

  In the photosensitive resin composition, the compounding amount of the carbonate bond-containing urethane (meth) acrylate compound having a weight average molecular weight of 3,300 or less, which is an essential component of the component (B), is that of the components (A) and (B). It is preferably 0.1 to 10 parts by mass, more preferably 1 to 8 parts by mass, further preferably 1 to 5 parts by mass, based on 100 parts by mass of the total amount, and 2 to 4 parts by mass. It is particularly preferred that If the blending amount is less than 0.1 parts by mass, it tends to be difficult to achieve both adhesion and peelability, and if it exceeds 10 parts by mass, the resolution tends to deteriorate.

  In the photosensitive resin composition, the blending amount of the photopolymerization initiator as the component (C) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). Is more preferable, 0.2 to 10 parts by mass is more preferable, and 0.5 to 5 parts by mass is particularly preferable. If the blending amount is less than 0.1 parts by mass, the photosensitivity tends to be insufficient, and if it exceeds 20 parts by mass, the light absorption on the surface of the photosensitive resin composition increases during the exposure, and the internal Photocuring tends to be inadequate.

  In addition, the photosensitive resin composition may include a photopolymerizable compound (oxetane compound or the like) having at least one cationically polymerizable cyclic ether group in the molecule, a cationic polymerization initiator, a dye such as malachite green, if necessary. , Photochromic agents such as tribromophenylsulfone and leucocrystal violet, thermochromic inhibitors, plasticizers such as p-toluenesulfonamide, pigments, fillers, antifoaming agents, flame retardants, stabilizers, inhibitors, leveling agents Further, additives such as a peeling accelerator, an antioxidant, a fragrance, an imaging agent, and a thermal crosslinking agent may be contained. These are used singly or in combination of two or more. As long as the achievement of the object of the present invention is not hindered, these additives may be contained in an amount of about 0.0001 to 20 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B).

  The photosensitive resin composition is dissolved in a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide and propylene glycol monomethyl ether, or a mixed solvent thereof, as necessary. Thus, it can be prepared as a solution having a solid content (components other than the solvent) of about 30 to 60% by mass.

  The photosensitive layer 20 in the photosensitive element 1 of the present invention can be formed by applying the above-described photosensitive resin composition solution on the support film 10 and removing the solvent. Here, as a coating method, for example, a known method such as roll coating, comma coating, gravure coating, air knife coating, die coating, or bar coating can be employed. Moreover, the removal of a solvent can be performed by processing for about 5 to 30 minutes at the temperature of 70-150 degreeC, for example. The amount of the remaining organic solvent in the photosensitive layer 20 is preferably 2% by mass or less from the viewpoint of preventing the organic solvent from diffusing in a later step.

  The thickness of the photosensitive layer 20 thus formed is preferably 3 to 50 μm, more preferably 5 to 45 μm, and even more preferably 7 to 40 μm after drying. It is especially preferable that it is 10-30 micrometers. If this thickness is less than 3 μm, defects are likely to occur when the photosensitive layer is laminated on the circuit forming substrate, or the tenting property is inferior, the resist is damaged during the development and etching processes, and open defects are caused. There is a possibility that the manufacturing yield of the printed wiring board tends to decrease. On the other hand, if the thickness exceeds 50 μm, the resolution of the photosensitive layer 20 is deteriorated or the circumference of the etching solution is deteriorated, so that the influence of side etching is increased, and it becomes difficult to manufacture a high-density printed wiring board. Tend.

  The photosensitive element 1 may include a protective film (not shown) on the main surface of the photosensitive layer 20 opposite to the main surface in contact with the support film 10. As the protective film, it is preferable to use a film in which the adhesive force between the photosensitive layer 20 and the protective film is smaller than the adhesive force between the photosensitive layer 20 and the support film 10. It is preferable to use the film. Specific examples include inert polyolefin films such as polyethylene and polypropylene. From the viewpoint of peelability from the photosensitive layer 20, a polyethylene film is preferable. Although the thickness of a protective film changes with uses, it is preferable that it is about 1-100 micrometers.

  The photosensitive element 1 may further include an intermediate layer or a protective layer such as a cushion layer, an adhesive layer, a light absorption 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 may be stored, for example, as it is or in a state where a protective film further laminated on the photosensitive layer 20 is wound around a cylindrical core. At this time, the support film 10 is preferably wound into a roll shape so as to be the outermost layer. Moreover, it is preferable to install an end face separator on the end face of the photosensitive element 1 wound up in a roll shape from the viewpoint of end face protection, and it is preferable to install a moisture-proof end face separator from the viewpoint of edge fusion resistance. Further, as a packing method, it is preferable to wrap and package in a black sheet with low moisture permeability.

  Examples of the core material include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer).

(Method for forming resist pattern)
In the resist pattern forming method of the present embodiment, the photosensitive element 1 is laminated on the circuit forming substrate in the order of the photosensitive layer 20 and the support film 10, and the active light is passed through the support film 10 to the photosensitive layer. 20 is a method including an exposure step of irradiating a predetermined portion 20 to form a photocured portion on the photosensitive layer 20 and a developing step of removing a portion of the photosensitive layer 20 other than the photocured portion.

  In the laminating step, as a method of laminating the photosensitive layer 20 on the circuit forming substrate, when a protective film is present on the photosensitive layer 20, the photosensitive layer 20 is removed by 70 to 70 after removing the protective film. The method of laminating | stacking by crimping | bonding to a circuit formation board | substrate with the pressure of about 0.1-1 Mpa etc., heating at about 130 degreeC is mentioned. In this lamination step, lamination can also be performed under reduced pressure. The surface on which the circuit forming substrate is laminated is usually a metal surface, but is not particularly limited. Further, in order to further improve the stackability, a pre-heat treatment of the circuit forming substrate may be performed.

  Next, a photomask having a negative or positive mask pattern is aligned and brought into close contact with the second main surface 14 of the support film 10 with respect to the photosensitive layer 20 that has been laminated in the laminating step. Thereafter, in the exposure step, the photosensitive layer 20 is irradiated with an actinic ray in an image form through the support film 10 to form a photocured portion in the photosensitive layer 20.

  As the light source of the actinic light, a known light source such as a carbon arc lamp, a mercury vapor arc lamp, a high pressure mercury lamp, a xenon lamp, or the like that effectively emits ultraviolet rays or visible light is used. In addition, a photocuring part can also be formed in the photosensitive layer 20 using a laser direct drawing exposure method.

  Next, after the exposure step, the photomask is peeled off from the support film 10. Further, the support film 10 is peeled off from the photosensitive layer 20. Next, in the development step, the unexposed portion (photocured portion) of the photosensitive layer 20 is removed and developed by wet development, dry development or the like using a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent, and a resist pattern is developed. Can be manufactured.

  Examples of the alkaline aqueous solution include a dilute solution of 0.1 to 5% by mass sodium carbonate, a dilute solution of 0.1 to 5% by mass potassium carbonate, and a dilute solution of 0.1 to 5% by mass sodium hydroxide. The pH of the alkaline aqueous solution is preferably in the range of 9 to 11, and the temperature is adjusted according to 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. Examples of the development method include a dip method, a spray method, brushing, and slapping.

Moreover, as a process after a development process, you may further harden a resist pattern by performing exposure with the heating amount of about 60-250 degreeC, or the exposure amount of about 0.2-10 J / cm < ² > as needed. .

(Printed wiring board manufacturing method)
The printed wiring board manufacturing method of the present embodiment is performed by etching or plating the circuit forming substrate on which the resist pattern is formed by the resist pattern forming method.

  As an etching solution used for etching, for example, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, or the like can be used.

  Examples of plating include copper plating, solder plating, nickel plating, and gold plating.

  After etching or plating, the resist pattern can be peeled off with a stronger alkaline aqueous solution than the alkaline aqueous solution used for development, for example. As this strongly alkaline aqueous solution, for example, a 1 to 10% by mass sodium hydroxide aqueous solution, a 1 to 10% by mass potassium hydroxide aqueous solution and the like are used. Moreover, as a peeling system, an immersion system, a spray system, etc. are mentioned, for example. The printed wiring board on which the resist pattern is formed may be a multilayer printed wiring board or may have a small diameter through hole.

  In addition, when plating is performed on a circuit forming substrate including an insulating layer and a conductor layer formed on the insulating layer, it is necessary to remove the conductor layer other than the pattern. As this removal method, for example, a method of lightly etching after removing the resist pattern, or performing solder plating after the above plating, and then masking the wiring portion with solder by peeling off the resist pattern, and then conducting layer The method etc. which process using the etching liquid which can etch only are mentioned.

(Method for manufacturing semiconductor package substrate)
The photosensitive element 1 of the present invention can also be used for a package substrate including a rigid substrate and an insulating film formed on the rigid substrate. In this case, the photocured portion of the photosensitive layer may be used as the insulating film. When the photocured portion of the photosensitive layer is used as, for example, a solder resist for a semiconductor package, after the development in the above resist pattern forming method, a high pressure mercury lamp is used for the purpose of improving solder heat resistance, chemical resistance, etc. It is preferable to perform ultraviolet irradiation or heating. In the case of irradiating ultraviolet rays, the irradiation amount can be adjusted as necessary. For example, the irradiation can be performed at an irradiation amount of about 0.2 to 10 J / cm ² . Moreover, when heating a resist pattern, it is preferable to carry out for about 15 to 90 minutes in the temperature range of about 100-170 degreeC. Furthermore, ultraviolet irradiation and heating can be performed at the same time, and after either one is performed, the other can be performed. When performing ultraviolet irradiation and heating simultaneously, it is more preferable to heat to 60 to 150 ° C. from the viewpoint of effectively imparting solder heat resistance, chemical resistance and the like.

  This solder resist is effective as a permanent mask for semiconductor packages because it also serves as a protective film for wiring after soldering to the substrate and has excellent physical properties such as tensile strength and elongation and thermal shock resistance. .

  The package substrate provided with the resist pattern in this manner is then mounted with a semiconductor element or the like (for example, wire bonding or solder connection) and then mounted on an electronic device such as a personal computer.

  As mentioned above, although this invention was demonstrated in detail based on the embodiment, this invention is not limited to the said embodiment. The present invention can be modified in various ways without departing from the scope of the invention.

  Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

[Examples 1 to 5 and Comparative Examples 1 to 4]
First, binder polymers having the compositions shown in Table 1 were synthesized according to Synthesis Examples 1 and 2.

(Synthesis Example 1)
Into a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen gas introduction tube, 420 g of a mixed solvent of toluene and methyl cellosolve having a mass ratio of 6: 4 was added and stirred while blowing nitrogen gas, Heated to 80 ° C. On the other hand, a solution (hereinafter referred to as “solution a”) prepared by mixing 150 g of methacrylic acid, 175 g of methyl methacrylate and 175 g of butyl methacrylate and 4.5 g of azobisisobutyronitrile as a comonomer is prepared. The solution a was added dropwise to the above mixed solvent of toluene and methyl cellosolve having a mass ratio of 6: 4 heated to 80 ° C. over 4 hours. Thereafter, 40 g of a mixed solvent of toluene and methyl cellosolve having a mass ratio of 6: 4 was added to the flask while washing the dropping funnel with this. Next, the solution in the flask was kept warm at 80 ° C. for 2 hours. Furthermore, a solution prepared by dissolving 1.0 g of azobisisobutyronitrile in 40 g of a mixed solvent of methyl cellosolve and toluene having a mass ratio of 6: 4 was dropped into the flask over 30 minutes. Thereafter, 120 g of a mixed solvent of toluene and methyl cellosolve having a mass ratio of 6: 4 was added to the flask while washing the dropping funnel using this. The solution after dropping was kept at 80 ° C. for 3 hours with stirring, and then heated to 90 ° C. over 30 minutes. The mixture was kept at 90 ° C. for 2 hours and then cooled to obtain a binder polymer solution as component (A). To this binder polymer solution, a mixed solvent of toluene and methyl cellosolve was added to prepare a nonvolatile component concentration (solid content concentration) of 40% by mass. This is designated as a binder polymer solution (A-1). The weight average molecular weight of the binder polymer was 50,000. The weight average molecular weight was measured by a gel permeation chromatography (GPC) method and calculated by using a standard polystyrene calibration curve. The GPC conditions are shown below.

(GPC conditions)
Pump: Hitachi L-6000 type [manufactured by Hitachi, Ltd.]
Column: Gelpack GL-R420 + Gelpack GL-R430 + Gelpack GL-R440 (3 in total) [above, manufactured by Hitachi Chemical Co., Ltd., product name]
Eluent: Tetrahydrofuran Measurement temperature: 24 ° C
Flow rate: 1.75 mL / min Detector: Hitachi L-3300 type RI [manufactured by Hitachi, Ltd., product name]

(Synthesis Example 2)
To a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel and a nitrogen gas introduction tube, 420 g of a mixed solvent of toluene and methyl cellosolve having a mass ratio of 6: 4 is added, and stirred while blowing nitrogen gas. Heated to 80 ° C. On the other hand, a solution in which 150 g of methacrylic acid, 25 g of methyl methacrylate, 200 g of styrene, 125 g of benzyl methacrylate and 4.5 g of azobisisobutyronitrile are mixed as a comonomer (hereinafter referred to as “solution b”). Was prepared, and the solution b was added dropwise to the above mixed solvent of toluene and methyl cellosolve having a mass ratio of 6: 4 heated to 80 ° C. over 4 hours. Thereafter, 40 g of a mixed solvent of toluene and methyl cellosolve having a mass ratio of 6: 4 was added to the flask while washing the dropping funnel with this. Next, the mixture was kept at 80 ° C. with stirring for 2 hours. Furthermore, a solution prepared by dissolving 1.0 g of azobisisobutyronitrile in 40 g of a mixed solvent of methyl cellosolve and toluene having a mass ratio of 6: 4 was dropped into the flask over 30 minutes. 120 g of a mixed solvent of toluene and methyl cellosolve having a mass ratio of 6: 4 was added to the flask while washing the dropping funnel using this. The solution after dropping was kept at 80 ° C. for 3 hours with stirring, and then heated to 90 ° C. over 30 minutes. After heating at 90 ° C. for 2 hours, the mixture was cooled to obtain a binder polymer solution as component (A). To this binder polymer solution, a mixed solvent of toluene and methyl cellosolve was added to prepare a nonvolatile component concentration (solid content concentration) of 40% by mass. This is designated as a binder polymer solution (A-2). The weight average molecular weight of the binder polymer was 50,000.

  (A) component synthesize | combined in the synthesis examples 1 and 2 and each component shown in Table 1 were mix | blended, and the basic solution of the photosensitive resin composition shown in Table 1 was prepared.

  Next, as a photopolymerizable compound having (B) an ethylenically unsaturated bond, a carbonate bond-containing urethane (meth) acrylate compound (B-1) was synthesized according to Synthesis Example 3.

(Synthesis Example 3)
Into a flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas inlet tube, 349, 1,6-hexanediol-based polycarbonate diol (manufactured by Ube Industries, trade name: ETERRNACOLL UH-50, number average molecular weight 500) Charged in parts by mass, 311 parts by mass of isophorone diisocyanate were added, and the mixture was reacted at 80 ° C. for 4 hours while suppressing heat generation. After the NCO equivalent was 472, which was almost the same as the theoretical value and stabilized, the mixture was cooled to 40 ° C., 171 parts by mass of 2-hydroxyethyl acrylate was added, 0.033 parts by mass of tin catalyst was added as a reaction promoting catalyst, The reaction was carried out at 0 ° C. for 7 hours. Thereby, the content rate of NCO became 0.3 mass% or less, and the carbonate bond containing urethane (meth) acrylate compound was obtained. The resulting compound was designated as B-1.

  Next, as a photopolymerizable compound having (B) an ethylenically unsaturated bond, a carbonate bond-free urethane (meth) acrylate compound (B-2) was synthesized according to Synthesis Example 4.

(Synthesis Example 4)
A flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas introduction tube was charged with 420 parts by mass of polypropylene glycol (manufactured by Mitsui Chemicals Polyurethanes, Inc., trade name: Actol DIOL-700, number average molecular weight 700), isophorone 266 parts by mass of diisocyanate was added and reacted at 80 ° C. for 4 hours while suppressing heat generation. After the NCO equivalent became 570 which was almost the same as the theoretical value and stabilized, the mixture was cooled to 40 ° C., 146 parts by mass of 2-hydroxyethyl acrylate was added, 0.034 parts by mass of tin catalyst was added as a reaction promoting catalyst, and 90 ° C. in an air atmosphere. The reaction was carried out at 0 ° C. for 7 hours. Thereby, the content rate of NCO became 0.3 mass% or less, and the carbonate bond non-containing urethane (meth) acrylate compound was obtained. The obtained compound was set to B-2.

(Preparation of solution of photosensitive resin composition)
(B) component shown in Table 2 was added to the basic solution mentioned above with the compounding quantity (unit: g) shown in the table, and the solution of the photosensitive resin composition was prepared. In addition, the compounding quantity of (B) component in Table 2 shows the compounding quantity of solid content.

(Production of photosensitive element)
Polyethylene terephthalate (hereinafter referred to as “PET”) films (a) to (c) shown in Table 2 were prepared as support films for the photosensitive element. The kind of each PET film is as follows.
(A) QS-48 (trade name): manufactured by Toray Industries, Inc., a biaxially oriented polyethylene terephthalate film having a three-layer structure having fine-particle-containing layers on the front and back, thickness 16 μm
(B) A-1517 (trade name): manufactured by Toyobo Co., Ltd., biaxially oriented polyethylene terephthalate film having a layer containing fine particles on one surface, thickness 16 μm
(C) HTR-02 (trade name): manufactured by Teijin DuPont Films, a biaxially oriented polyethylene terephthalate film having a layer containing fine particles on the front and back sides, a thickness of 16 μm

Table 2 shows the results of measuring the number of particles having a diameter of 5 μm or more and the haze value (%) in each PET film. The number of particles and the like is obtained by measuring the number of particles and the like of 5 μm or more existing in 1 mm ² units using a polarizing microscope. In this case, the n number was 5. The n number is the number of repeated measurements, and the average value is the evaluation result. The haze value was measured according to JIS K7105.

  Next, the above photosensitive resin composition solution is applied on each PET film so as to have a uniform thickness, and dried with a hot air convection dryer at 100 ° C. for 2 minutes to remove the solvent and sensitize. A layer was formed. After drying, the photosensitive layer was covered with a protective film made of polyethylene (manufactured by Tamapoly, trade name “NF-15”, thickness 20 μm) to obtain a photosensitive element. The thickness of the photosensitive layer after drying was 25 μm in all cases.

In Table 2, the details of the component (B) are as follows.
(B-1): Carbonate bond-containing urethane (meth) acrylate compound obtained by synthesizing 1,6-hexanediol-based polycarbonate, isophorone diisocyanate and 2-hydroxyethyl acrylate (synthesized in Synthesis Example 3, weight average molecular weight: 3,000)
(B-2): Carbonate bond-free urethane (meth) acrylate compound obtained by synthesizing polypropylene glycol, isophorone diisocyanate and 2-hydroxyethyl acrylate (synthesized in Synthesis Example 4, weight average molecular weight: 3,200)
(B-3): 2-methoxyethyl acrylate (B-4): UF-8003M (trade name, manufactured by Kyoeisha Chemical Co., Ltd., 80% by mass methyl ethyl ketone solution, weight average molecular weight: 3,500, carbonate bond-containing urethane (meta Acrylate compound)
(B-5): 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane (B-6): propoxylated pentaerythritol tetraacrylate (propylene oxide: average 4 mol addition)
(B-7): Ethoxylated pentaerythritol tetraacrylate (ethylene oxide: average 4 mol addition)
(B-8): EO-modified trimethylolpropane triacrylate (ethylene oxide: average 3 mol addition)

[Production of laminate]
A copper-clad laminate (made by Hitachi Chemical Co., Ltd., trade name “MLC-E-679”), which is a glass epoxy material in which copper foil (thickness: 35 μm) is laminated on both sides, is subjected to surface roughening treatment liquid “MEC etch bond”. Surface treatment was performed using “CZ-8100” (trade name, manufactured by MEC Co., Ltd.), followed by water washing, pickling and water washing, followed by drying with an air stream. The surface roughness was measured using an ultra-deep shape measuring microscope “VK-8500” (trade name, manufactured by Keyence Corporation). The substrate surface roughness (Ra) was 0.66 μm. The obtained copper-clad laminate was heated to 80 ° C., and the photosensitive element was laminated so that the photosensitive layer was in contact with the copper surface while peeling off the protective film. Thus, a laminate was obtained in which the copper-clad laminate, the photosensitive layer, and the support film were laminated in this order. Lamination was performed using a 120 ° C. heat roll at a pressure of 0.4 MPa and a roll speed of 1.5 m / min. These laminates were used as test pieces in the following tests.

[Evaluation of light sensitivity]
On the support film of the test piece, a stove 21-step tablet was placed as a negative, and the exposure amount 100 mJ / cm using an exposure machine (trade name “EXM-1201” manufactured by Oak Co., Ltd.) having a high-pressure mercury lamp. ² exposed the photosensitive layer. Next, the support film is peeled off, and the photosensitive layer is spray-developed using a 1% by mass aqueous sodium carbonate solution at 30 ° C. in a time twice as long as the minimum development time (minimum time for removing the unexposed portion). Development was performed by removing the exposed portion. And the photosensitivity of the photosensitive resin composition was evaluated by measuring the number of steps of the step tablet of the photocured film formed on the copper clad laminate. The minimum development time was determined by measuring the time during which the unexposed resist was completely removed by the development process. The results are shown in Table 3. The photosensitivity is indicated by the number of steps of the step tablet, and the higher the number of steps of the step tablet, the higher the photosensitivity.

[Evaluation of adhesion]
In order to investigate the adhesion, a phototool having a 21-step stove tablet and a glass chrome type having a wiring width of 2/1000 to 30/1000 (unit: μm) as a negative for adhesion evaluation The photo tool of No. 1 was adhered to the support film of the test piece, and the remaining after development of the stove 21-step step tablet using an exposure machine (trade name “EXM-1201”, manufactured by Oak Co., Ltd.) having a high-pressure mercury lamp lamp. The exposure was performed with an exposure amount at which the step number was 5.0. Next, the support film was peeled off, and using a 1% by mass aqueous sodium carbonate solution at 30 ° C., the photosensitive layer was spray-developed in a time twice as long as the minimum development time, and the unexposed portion was removed for development. Adhesion can remove unexposed areas neatly by development processing. When the resist pattern is observed using an optical microscope after development processing, it is the most of the remaining line width (unit: μm) that remains without peeling. Evaluation was made by measuring a small width. In addition, evaluation of adhesiveness is a favorable value, so that a numerical value is small. The results are shown in Table 3.

[Resolution evaluation]
In order to examine the resolution, a photo tool having a stove 21-step tablet and a glass chrome type photo having a wiring pattern with a line width / space width of 2/2 to 30/30 (unit: μm) as a negative for resolution evaluation The number of remaining steps after development of a stove 21-step tablet using an exposure machine (trade name “EXM-1201” manufactured by Oak Co., Ltd.) having a high-pressure mercury lamp lamp in close contact with the tool on the support film of the test piece The exposure was performed with an irradiation energy amount of 5.0. Next, the support film was peeled off, and using a 1% by mass aqueous sodium carbonate solution at 30 ° C., the photosensitive layer was spray-developed in a time twice as long as the minimum development time, and the unexposed portion was removed for development. The resolution was evaluated by the smallest value (unit: μm) of the space width between the line widths where the unexposed portions were completely removed when the resist pattern was observed using an optical microscope after the development processing. Note that the smaller the numerical value, the better the evaluation of resolution. The results are shown in Table 3.

[Measurement of peeling time]
In order to examine the peeling time, a photo tool having a stove 21 step tablet and a film type photo tool having a pattern with an opening of 60 × 45 (unit: mm) as a peeling time measuring negative Using an exposure machine (trade name “EXM-1201”, manufactured by Oak Co., Ltd.) having a high-pressure mercury lamp lamp in close contact with the support film, the number of remaining steps after development of the stove 21-step tablet is 5.0. Exposure was performed with an irradiation energy amount. Next, the support film was peeled off, and using a 1% by mass aqueous sodium carbonate solution at 30 ° C., the photosensitive layer was spray-developed in a time twice as long as the minimum development time, and the unexposed portion was removed for development. Next, using a 3% by mass aqueous sodium hydroxide solution at 50 ° C., the time required for the exposed resist to completely peel off was measured. The results are shown in Table 3.

[Evaluation of resist pattern side roughness]
In order to examine the side-surface jaggedness of the resist pattern, a phototool having a stove 21-step tablet and a glass chrome type phototool having a wiring pattern with a line width / space width of 10/30 (unit: μm), The number of remaining steps after development of the stove 21-step tablet is 5. using an exposure machine (trade name “EXM-1201” manufactured by Oak Co., Ltd.) having a high-pressure mercury lamp lamp in close contact with the support film of the test piece. Exposure was performed with an irradiation energy amount of zero. Next, the support film was peeled off, and the photosensitive layer was spray-developed using a 1% by mass aqueous sodium carbonate solution at 30 ° C. in a time twice as long as the minimum development time to remove unexposed portions. Next, the obtained resist pattern was observed with a scanning electron microscope (trade name “S-2100A”, manufactured by Hitachi, Ltd.), and the side surface roughness of the resist pattern was evaluated according to the following criteria. The resist pattern side surface jaggedness refers to a state where the side surface shape of the resist pattern is not straight and is not preferred due to the presence of unevenness (unevenness), and the side surface unevenness of the resist pattern is preferably shallow and smooth. . The results are shown in Table 3.
A: Smooth shape (unevenness on side ridges is 1 μm or less) B: Slightly rough shape (unevenness on side ridges is more than 1 μm and 2 μm or less) C: Rough shape (unevenness on side ridges is over 2 μm) ) Confirmed

[Evaluation of resist micro-defects]
In order to investigate the occurrence of minute defects in the resist, the number of resist defects was counted using a polarizing microscope in the substrate used in the evaluation of the side surface roughness of the resist pattern. The average value when the line length is 1 mm, the number of lines is 10 observation units, and the n number is 5, is defined as the number of occurrences of resist minute defects. The results are shown in Table 3.

As shown in Table 3, the photosensitive elements of Examples 1 to 5, which are an embodiment of the present invention, were peeled from the photosensitive elements of Comparative Examples 1 to 4 without reducing adhesion and resolution. The result that time can be shortened was obtained. Moreover, since the photosensitive element of Examples 1-4 is equipped with the support film whose haze is 0.4%, it is excellent also in the side surface roughness (side surface shape) of a resist pattern. Furthermore, since the photosensitive elements of Examples 1 to 3 are provided with a support film in which the number of particles of 5 μm or more existing in 1 mm ² units is 5 or less, the number of occurrences of resist micro-defects is sufficiently increased. It was confirmed that it can be reduced.

  As described above, according to the photosensitive element of the present invention, since the resist peeling time is short and the adhesion and resolution are good, it is possible to efficiently form a resist pattern with very thin wiring, It becomes possible to improve the production efficiency of a printed wiring board having a high density.

DESCRIPTION OF SYMBOLS 1 ... Photosensitive element, 10 ... Support film, 12 ... 1st main surface, 14 ... 2nd main surface, 20 ... Photosensitive layer.

Claims (15)

A photosensitive element comprising: a support film; and a photosensitive layer formed using the photosensitive resin composition on the support film,
The photosensitive resin composition contains (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator, and (B) A photosensitive element containing a carbonate bond-containing urethane (meth) acrylate compound having a weight average molecular weight of 3,300 or less as a photopolymerizable compound having an ethylenically unsaturated bond.   The photosensitive element of Claim 1 whose said carbonate bond containing urethane (meth) acrylate compound is a compound whose weight average molecular weight is 900 or more.   The carbonate bond-containing urethane (meth) acrylate compound is a urethane (meth) acrylate compound obtained by reacting (a) a polycarbonate polyol compound, (b) a polyisocyanate compound, and (c) a hydroxyl group-containing (meth) acrylate compound. The photosensitive element according to claim 1 or 2, wherein   The photosensitive element of Claim 3 whose said (a) polycarbonate polyol compound is an aliphatic polycarbonate polyol compound and / or an alicyclic polycarbonate polyol compound.   The photosensitive element of Claim 3 or 4 whose said (a) polycarbonate polyol compound is a 1, 6- hexanediol type polycarbonate polyol compound.   The photosensitive element as described in any one of Claims 1-5 in which the photopolymerizable compound which has the said (B) ethylenically unsaturated bond contains 2-methoxyethyl (meth) acrylate. The photopolymerizable compound having the (B) ethylenically unsaturated bond includes a compound represented by the following general formula (I) and a compound represented by the following general formula (II). A photosensitive element according to claim 1.


[Wherein, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, m ¹ , m ² , m ³ and m ⁴ each represent an integer of ^{0~40, m 1 + m 2 +} m 3 + m 4 is from 1 to 40. When m ¹ + m ² + m ³ + m ⁴ is 2 or more, a plurality of Xs may be the same or different from each other. ]


[Wherein, R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, Y represents an alkylene group having 2 to 6 carbon atoms, n ¹ and n ² each represents a positive integer, and n ¹ + n ² is 4-40. When n ¹ + n ² is 4 or more, a plurality of Y may be the same as or different from each other. ] The haze of the support film is 0.01 to 2.0%, and the total number of particles having a diameter of 5 μm or more and aggregates having a diameter of 5 μm or more contained in the support film is 5 / mm ² or less. The photosensitive element as described in any one of 1-7.   The photosensitive element as described in any one of Claims 1-8 whose film thickness of the said photosensitive layer is 3-50 micrometers.   The photosensitive element as described in any one of Claims 1-9 whose weight average molecular weights of the said (A) binder polymer are 30000-150,000. The photosensitive element as described in any one of Claims 1-10 in which the said (A) binder polymer has a structural unit represented by the following general formula (III), (IV), and (V). .






[Wherein R ⁷ , R ⁸ and R ¹⁰ each independently represent a hydrogen atom or a methyl group, and R ⁹ 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. R ¹¹ represents an alkyl group having 1 to 12 carbon atoms, and p represents an integer of 0 to 5. When p is 2 or more, a plurality of R ⁹ may be the same as or different from each other. ] The photosensitive element according to claim 11, wherein the (A) binder polymer further has a structural unit represented by the following general formula (VI).


[Wherein R ¹² represents a hydrogen atom or a methyl group, R ¹³ 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 an integer of 0 to 5] When q is 2 or more, a plurality of R ¹³ may be the same or different from each other. ]   The photosensitive element as described in any one of Claims 1-12 in which the said (C) photoinitiator contains a 2,4,5- triaryl imidazole dimer. A laminating step of laminating the photosensitive element according to any one of claims 1 to 13 on a circuit forming substrate in the order of the photosensitive layer and the support film;
An exposure step of irradiating a predetermined part of the photosensitive layer through the support film with an actinic ray to form a photocured portion in the photosensitive layer;
A developing step for removing the photosensitive layer other than the photocured portion;
A method for forming a resist pattern, comprising: The manufacturing method of a printed wiring board which performs etching or plating with respect to the board | substrate for circuit formation in which the resist pattern was formed by the formation method of the resist pattern of Claim 14.