Photosensitive resin laminate, photosensitive element, and pattern forming method

Abstract

The present disclosure provides a photosensitive element, a method for forming a resist pattern, a method for producing a conductor pattern, and a photosensitive resin laminate capable of achieving both high adhesion and high resolution.　Provided is a photosensitive resin laminate having a temporary support and a photosensitive resin layer on the temporary support. The average thickness of the photosensitive resin layer is 20 μm or lower, and the photosensitive resin layer includes a photosensitive resin composition containing (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, and (D) a polymerization inhibitor. The content of (C) the photopolymerization initiator is 5.0 parts by mass or more with respect to 100 parts by mass of the total amount of (A) the binder polymer and (B) the photopolymerizable compound. (D) The polymerization inhibitor contains a polymerization inhibitor having two or more phenolic hydroxyl groups, and the content thereof is 0.025 parts by mass or more with respect to 100 parts by mass of the total amount of (A) the binder polymer and (B) the photopolymerizable compound.

Description

Photosensitive resin laminate, photosensitive element, and pattern forming method

[0001] This disclosure relates to a photosensitive resin laminate, a method for manufacturing the same, and a photosensitive element and pattern formation method using the same.

[0002] Fine wiring (conductor patterns) in electronic devices are manufactured, for example, using a photolithography process. A photolithography process includes, for example, the following steps: forming a resist pattern by laminating a photosensitive resin layer in a photosensitive resin laminate onto a substrate, and then exposing and developing it; forming a conductor pattern by etching or plating the substrate on which the resist pattern has been formed; and removing the resist pattern from the substrate.

[0003] Generally, photosensitive resin layers include a photosensitive resin composition, and both negative and positive types are known. In the case of the negative type, a resist pattern is formed by the exposed areas of the photosensitive resin layer by removing the unexposed areas through development.

[0004] The photosensitive resin layer can be provided as a photosensitive resin laminate laminated on a temporary support, or as a photosensitive film, and the composition of the photosensitive resin composition, the thickness of the photosensitive film, the cross-sectional shape or scratch resistance in the developing solution, and the line / space ratio or number of defects of the resist pattern have been investigated (see, for example, Patent Documents 1 to 4).

[0005] International Publication No. 2022 / 190208, International Publication No. 2022 / 191125, Japanese Patent Publication No. 2006-220860, International Publication No. 2023 / 127755

[0006] As electronic devices have become smaller and more densely packed in recent years, there is a growing demand for improved image quality in resist patterns. In particular, when the photosensitive resin layer is thin, there is a strong need to achieve good adhesion to the substrate and good resolution. However, conventional technology has room for improvement in achieving both high adhesion and high resolution.

[0007] Therefore, the object of this disclosure is to provide a photosensitive resin laminate, a photosensitive element, a method for forming a resist pattern, and a method for manufacturing a conductor pattern that can achieve both high adhesion and high resolution.

[0008] One aspect of the present disclosure is listed below: [1] A photosensitive resin laminate having a temporary support and a photosensitive resin layer on the temporary support, wherein the average thickness of the photosensitive resin layer is 20 μm or less, the photosensitive resin layer comprises a photosensitive resin composition containing (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, and (D) a polymerization inhibitor, the content of the (C) photopolymerization initiator is 5.0 parts by mass or more with respect to 100 parts by mass of the total amount of the (A) binder polymer and the (B) photopolymerizable compound having an ethylenically unsaturated bond, and the content of the (D) polymerization inhibitor comprises a polymerization inhibitor having two or more phenolic hydroxyl groups, and the content is 0.025 parts by mass or more with respect to 100 parts by mass of the total amount of the (A) binder polymer and the (B) photopolymerizable compound having an ethylenically unsaturated bond. [2] The photosensitive resin laminate according to item 1, wherein the absorbance for light at a wavelength of 365 nm and 402 nm per 1 μm thickness of the photosensitive resin layer is greater than 0.010 and less than or equal to 0.040. [3] The photosensitive resin laminate according to item 1 or 2, wherein the absorbance for light at a wavelength of 365 nm and 402 nm per 1 μm thickness of the photosensitive resin layer is greater than 0.014. [4] The photosensitive resin laminate according to any one of items 1 to 3, wherein the (C) photopolymerization initiator contains a biimidazole compound, and the content of the biimidazole compound is 5.0 parts by mass or more per 100 parts by mass of the total amount of the (A) binder polymer and the (B) photopolymerizable compound having an ethylenically unsaturated bond. [5] (E) A photosensitive resin laminate according to any one of items 1 to 4, further comprising, as a sensitizer, at least one selected from the group consisting of dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, and coumarin compounds.[6] The photosensitive resin laminate according to item 5, wherein the product of the total content of the (E) sensitizer per 100 parts by mass of the total amount of the (A) binder polymer and the (B) photopolymerizable compound having an ethylenically unsaturated bond and the total content of the (D) polymerization inhibitor per 100 parts by mass of the total amount of the (A) binder polymer and the (B) photopolymerizable compound having an ethylenically unsaturated bond is 0.007 or more. [7] The photosensitive resin laminate according to any one of items 1 to 6, wherein the polymerization inhibitor having two or more phenolic hydroxyl groups is a compound having an aromatic ring in which two or more hydrogen atoms are substituted with phenolic hydroxyl groups. [8] The photosensitive resin laminate according to any one of items 1 to 7, wherein the polymerization inhibitor having two or more phenolic hydroxyl groups is at least one of tert-butylcatechol and gallic acid. [9] The photosensitive resin laminate according to any one of items 1 to 8, wherein the (A) binder polymer has structural units derived from a polymerizable monomer containing a hydroxyalkyl group.

[10] The photosensitive resin laminate according to any one of items 1 to 9, wherein the photosensitive resin layer further contains (F) a hydrogen donor, and the mass ratio of the content of the (F) hydrogen donor to the content of the (C) photopolymerization initiator ((F) hydrogen donor content / (C) photopolymerization initiator content) is 0.07 or more.

[11] The photosensitive resin laminate according to any one of items 1 to 10, wherein the absolute value of the difference between the absorbance for light at a wavelength of 365 nm and the absorbance for light at 402 nm per 1 μm thickness of the photosensitive resin composition is 0.018 or less.

[12] In the photosensitive resin layer, the following formula 1: MA occupancy = Σ{W. ｉ ×R / (R ｅｑ ) ｉ} ｉ ... (Formula 1) {wherein W is the weight % of one component (B) relative to the total weight of the photopolymerizable compound having an ethylenically unsaturated bond (B), R is the molecular weight of the (meth)acryloyl group in the photopolymerizable compound having an ethylenically unsaturated bond (B), R ｅｑis the equivalent of the (meth)acryloyl group, and i is the total number of types of the photopolymerizable compound having an ethylenically unsaturated bond in the above (B). The photosensitive resin laminate according to any one of Items 1 to 11, wherein the MA occupancy ratio calculated by {} is 18.0% or more.

[13] The photosensitive resin laminate according to Item 12, wherein the MA occupancy ratio calculated by the above formula 1 is 23.0% or more.

[14] In the photosensitive resin layer, further, the following formula 2: AO occupancy ratio = Σ{W ｉ ×A / (A ｅｑ ) ｉ}... (Formula 2) {In the formula, W is the weight% occupied by one kind of component (B) with respect to the total weight of the photopolymerizable compound having an ethylenically unsaturated bond in the above (B), A is the following chemical formula 1 with respect to the total weight of the photopolymerizable compound having an ethylenically unsaturated bond in the above (B): -AO- (Chemical formula 1) (In the formula, A is an alkylene group.) is the molecular weight of the structure represented by, A ｅｑ is the equivalent of the structure represented by Chemical formula 1, and i is the total number of types of the photopolymerizable compound having an ethylenically unsaturated bond in the above (B). The photosensitive resin laminate according to Item 12 or 13, wherein the AO occupancy ratio calculated by {} is 40.0% or more.

[15] The photosensitive resin laminate according to any one of Items 12 to 14, wherein the content of the compound having 4 or more (meth)acryloyl groups in one molecule among the photopolymerizable compounds having an ethylenically unsaturated bond in the above (B) is 40% by mass or more.

[16] The photosensitive resin laminate according to any one of Items 12 to 15, wherein the photopolymerizable compound having an ethylenically unsaturated bond in the above (B) contains a compound having 5 or more (meth)acryloyl groups in one molecule.

[17] The photosensitive resin laminate according to any one of Items 12 to 16, wherein the photopolymerizable compound having an ethylenically unsaturated bond in the above (B) contains a compound having the structure represented by the following chemical formula 3. -C ３ H ６O- (Chemical formula 3)

[18] A photosensitive resin laminate according to any one of items 1 to 17, wherein the acid value of the (A) binder polymer is 155 mg KOH / g or less.

[19] A photosensitive resin laminate according to any one of items 1 to 18, wherein the (A) binder polymer has all of the following constituent units derived from (A-1) to (A-3): (A-1) methacrylic acid and / or acrylic acid; (A-2) styrene and / or styrene derivatives; (A-3) compounds that do not fall under (A-1) and (A-2);

[20] A photosensitive resin laminate according to item 19, wherein the proportions of the constituent units derived from (A-1), (A-2), and (A-3) to the total mass of the (A) binder polymer are 10 to 30% by mass, 20 to 60% by mass, and 20 to 60% by mass, respectively.

[21] The photosensitive resin laminate according to any one of items 1 to 20, wherein the photosensitive resin layer further contains (F) a hydrogen donor, and the mass ratio of the content of the (F) hydrogen donor to the content of the (C) photopolymerization initiator ((F) hydrogen donor content / (C) photopolymerization initiator content) is 0.13 or more.

[22] The photosensitive resin laminate according to any one of items 1 to 21, wherein the photosensitive resin layer further contains (F) a hydrogen donor, and the mass ratio of the content of the (F) hydrogen donor to the content of the (C) photopolymerization initiator ((F) hydrogen donor content / (C) photopolymerization initiator content) is 0.25 or more.

[23] A photosensitive element having a laminated structure in which a support film, an intermediate layer, and the photosensitive resin layer of the photosensitive resin laminate according to any one of items 1 to 22 are sequentially laminated.

[24] The intermediate layer is a water-soluble resin layer, and the water-soluble resin layer is the following general formula (I): {In the formula, R １ and R ２ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and A is -CH ２ CH ２ O-unit and / or -CH ２ CH (CH ３

[25] A photosensitive element according to item 24, comprising a compound represented by {} which represents one or more single or repeating structures including an O-unit.

[26] A photosensitive element according to any one of items 23 to 25, wherein the water-soluble resin layer comprises polyvinyl alcohol.

[27] A photosensitive element according to any one of items 23 to 26, wherein the support film is a biaxially oriented polyester film comprising a resin layer containing fine particles on at least the side opposite to the side on which the intermediate layer is laminated.

[28] A photosensitive element according to any one of items 24 to 25, wherein the surface roughness (Rz1) of the side on which the intermediate layer is laminated of the support film is smaller than the surface roughness (Rz2) of the side opposite to the side on which the intermediate layer is laminated.

[29] A photosensitive element according to any one of items 23 to 26, wherein the water-soluble resin layer comprises 50% to 100% by mass of polyvinyl alcohol based on the mass of the water-soluble resin layer.

[29] A photosensitive element according to any one of items 24, 25, or 28, wherein the thickness of the water-soluble resin layer is 1 μm to 8 μm.

[30] A method for forming a resist pattern, comprising laminating the photosensitive element according to any one of items 23 to 29 onto the surface of a metal plate or a metal-coated insulator, peeling off the support film, exposing it to ultraviolet light, and then removing the unexposed areas by developing.

[31] A method for manufacturing a conductor pattern, comprising etching or plating a substrate on which a resist pattern has been formed by the method described in item 30.

[32] A photosensitive resin laminate according to any one of items 1 to 22, wherein the photosensitive resin laminate further comprises a protective film, and the protective film is a polyester film with a release layer.

[33] A photosensitive resin laminate according to any one of items 1 to 22 or 32, wherein the photosensitive resin laminate further comprises a protective film, and the protective film is a biaxially oriented polypropylene film.

[0009] Another aspect of the present disclosure is listed below: [1] A photosensitive resin laminate having a temporary support and a photosensitive resin layer on the temporary support, wherein the average thickness of the photosensitive resin layer is 20 μm or less, the photosensitive resin layer comprises a photosensitive resin composition containing (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator, the (A) binder polymer is composed of three or more repeating units, the content of the (C) photopolymerization initiator is 5.0 parts by mass or more per 100 parts by mass of the total amount of the (A) binder polymer and the (B) photopolymerizable compound having an ethylenically unsaturated bond, and the following formulas 1 and 2: MA occupancy = Σ{W ｉ ×R ｉ / (R ｅq ) ｉ}...(Formula 1) AO occupancy rate=Σ{W ｉ ×A ｉ / ( A ｅq ) ｉ}...(Formula 2) {In the formula, W is the weight % of one component (B) relative to the total weight of the photopolymerizable compound having an ethylenically unsaturated bond (B), R is the molecular weight of the (meth)acryloyl group in the photopolymerizable compound having an ethylenically unsaturated bond (B), R ｅq A is the equivalent amount of the (meth)acryloyl group, and A is the molecular weight of the structure represented by the following chemical formula 1 in (B) a photopolymerizable compound having an ethylenically unsaturated bond: -AO- (Chemical formula 1) (wherein A is an alkylene group), and A ｅq [2] A photosensitive resin laminate in which the MA occupancy rate calculated by formula 1 is 18.0% or more and the AO occupancy rate is 40.0% or more, and the MA occupancy rate calculated by formula 1 is 23.0% or more, and the AO occupancy rate is 40.0% or more. [2] A photosensitive resin laminate in which the MA occupancy rate calculated by formula 1 is 23.0% or more, and the EO occupancy rate ｉ {E ｉ / (E ｅq ) ｉ +P ｉ / (P ｅq ) ｉ}]...(Formula 3) {In the formula, E is the following chemical formula 2 in the photopolymerizable compound having an ethylenically unsaturated bond (B): -C ２ H ４ O- (Chemical formula 2) is the molecular weight of the structure, and E ｅq P is the equivalent weight of the structure represented by chemical formula 2, and P is the following chemical formula 3 in the photopolymerizable compound having an ethylenically unsaturated bond (B): -C ３ H ６ O- (Chemical formula 3) is the molecular weight of the structure, and P ｅq[3] The photosensitive resin laminate according to item 1, wherein the EOPO occupancy calculated by {where is the equivalent weight of the structure represented by chemical formula 3, and W and i are as defined in formulas 1 and 2 above} is 40.0% or more. [4] The photosensitive resin laminate according to item 1 or 2, wherein the content of a compound having four or more (meth)acryloyl groups in one molecule among the (B) photopolymerizable compounds having ethylenically unsaturated bonds is 40% by mass or more. [5] The photosensitive resin laminate according to any one of items 1 to 3, wherein the (B) photopolymerizable compound having ethylenically unsaturated bonds contains a compound having five or more (meth)acryloyl groups in one molecule. [6] The photosensitive resin laminate according to item 2, wherein the (B) photopolymerizable compound having ethylenically unsaturated bonds contains a compound having the structure represented by chemical formula 3 above. [6] The photosensitive resin laminate according to any one of items 1 to 5, wherein the acid value of the (A) binder polymer is 155 mg KOH / g or less. [7] The photosensitive resin laminate according to any one of items 1 to 6, wherein the (A) binder polymer has all of the following constituent units derived from (A-1) to (A-3): (A-1) methacrylic acid or acrylic acid; (A-2) styrene or styrene derivative; (A-3) compounds that do not fall under (A-1) or (A-2). [8] The photosensitive resin laminate according to item 7, wherein the proportions of the constituent units derived from (A-1), (A-2), and (A-3) to the total mass of the (A) binder polymer are 10 to 30% by mass, 20 to 60% by mass, and 20 to 60% by mass, respectively. [9] The photosensitive resin laminate according to any one of items 1 to 8, wherein the photosensitive resin layer further contains (D) a polymerization inhibitor, the (D) polymerization inhibitor comprises a compound having two or more phenolic hydroxyl groups, and the content of the (D) polymerization inhibitor is 0.025 parts by mass or more per 100 parts by mass of the total amount of the (A) binder polymer and the (B) photopolymerizable compound having an ethylenically unsaturated bond.

[10] The photosensitive resin laminate according to any one of items 1 to 9, wherein the photosensitive resin layer further contains (E) a hydrogen donor, and the mass ratio of the content of the (E) hydrogen donor to the content of the (C) photopolymerization initiator ((E) hydrogen donor content / (C) photopolymerization initiator content) is 0.07 or more.

[11] The photosensitive resin laminate according to any one of items 1 to 10, wherein the photosensitive resin layer further contains (E) a hydrogen donor, and the mass ratio of the content of the (E) hydrogen donor to the content of the (C) photopolymerization initiator ((E) hydrogen donor content / (C) photopolymerization initiator content) is 0.13 or more.

[12] A photosensitive element having a laminated structure in which a support film, an intermediate layer, and the photosensitive resin layer of the photosensitive resin laminate according to any one of items 1 to 11 are sequentially laminated.

[13] The intermediate layer is a water-soluble resin layer, and the water-soluble resin layer is the following general formula (I): {In the formula, R １ and R ２ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and A is -CH ２ CH ２ O-unit and / or -CH ２ CH (CH ３

[14] A photosensitive element according to item 13, comprising a compound represented by {} which represents one or more single or repeating structures including an O-unit.

[15] A photosensitive element according to any one of items 12 to 14, wherein the water-soluble resin layer comprises polyvinyl alcohol.

[16] A photosensitive element according to any one of items 12 to 15, wherein the support film is a biaxially oriented polyester film comprising a resin layer containing fine particles on at least the side opposite to the side on which the intermediate layer is laminated.

[17] A photosensitive element according to any one of items 13 to 14, wherein the surface roughness (Rz1) of the side on which the intermediate layer is laminated of the support film is smaller than the surface roughness (Rz2) of the side opposite to the side on which the intermediate layer is laminated.

[18] A photosensitive element according to item 13 or 17, wherein the water-soluble resin layer comprises 50% to 100% by mass of polyvinyl alcohol based on the mass of the water-soluble resin layer.

[19] A photosensitive element according to item 13 or 17, wherein the thickness of the water-soluble resin layer is 1 μm to 8 μm.

[19] A method for forming a resist pattern, comprising laminating a photosensitive element according to any one of items 12 to 18 onto the surface of a metal plate or a metal-coated insulator, peeling off the support film, exposing it to ultraviolet light, and then removing the unexposed areas by developing.

[20] A method for manufacturing a conductor pattern, comprising etching or plating a substrate on which a resist pattern has been formed by the method described in item 19.

[21] A photosensitive resin laminate according to any one of items 1 to 11, wherein the photosensitive resin laminate further comprises a protective film, and the protective film is a polyester film with a release layer.

[22] A photosensitive resin laminate according to any one of items 1 to 11, wherein the photosensitive resin laminate further comprises a protective film, and the protective film is a biaxially oriented polypropylene film.

[23] A photosensitive element according to any one of items 12 to 18, wherein the photosensitive element further comprises a protective film, and the protective film is a polyester film with a release layer.

[24] The photosensitive element according to any one of items 12 to 18, wherein the element further includes a protective film, and the protective film is a biaxially oriented polypropylene film.

[0010] According to this disclosure, it is possible to provide a photosensitive resin laminate, a photosensitive element, a method for forming a resist pattern, and a method for manufacturing a conductor pattern that can achieve both high adhesion and high resolution.

[0011] A plan view showing the configuration of the drawing pattern related to this embodiment. A plan view showing the configuration of the drawing pattern related to this embodiment. A plan view showing the configuration of the drawing pattern related to this embodiment.

[0012] Examples of embodiments of this disclosure are described below. This disclosure is not limited to the embodiments described below, and can be implemented in various ways within the scope of its gist.

[0013] In this specification, if there are multiple structures represented by the same reference numeral in the same formula, unless otherwise specified, each structure may be selected independently and may be identical or different from one another. Similarly, if there are multiple structures represented by the same reference numeral in different formulas, unless otherwise specified, each structure may be selected independently and may be identical or different from one another.

[0014] Furthermore, in this specification, the upper or lower limits in the stepped numerical ranges may be replaced with the upper or lower limits in the corresponding other stepped numerical ranges, and may also be replaced with the corresponding values ​​described in the examples.

[0015] Furthermore, in this specification, "(meth)acrylic" means "acrylic" and / or "methacrylic," "(meth)acrylate" means "acrylate" and / or "methacrylate," and "(meth)acryloyl" means "acryloyl" and / or "methacryloyl." A "(meth)acryloyl group compound" is referred to, for example, as a "(meth)acrylate compound."

[0016] Furthermore, within this specification, the term "process" is included not only in the case of an independent process, but also in cases where it cannot be clearly distinguished from other processes, as long as the function of that process is achieved. In the drawings, the scale, shape, and length may be exaggerated for the sake of clarity.

[0017] Furthermore, in this specification, "solid content" of a photosensitive resin composition refers to the components of the photosensitive resin composition other than the solvent. The measurement methods for the physical properties and parameters described herein refer to the methods described in the examples.

[0018] Furthermore, unless otherwise specified in this specification, "adhesion" refers to the adhesion performance of the resist pattern to the substrate; "resolution" refers to the resolution performance of the resist pattern; "developability" also refers to the developability of the photosensitive resin layer (resist); and "sensitivity" refers to the exposure sensitivity of the photosensitive resin layer (resist).

[0019] [First Embodiment] [Photosensitive Resin Laminate] A photosensitive resin laminate according to one embodiment of the present disclosure comprises a temporary support layer and a photosensitive resin layer containing a photosensitive resin composition, wherein the photosensitive resin composition comprises the following components: (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, and (D) a polymerization inhibitor.

[0020] In the photosensitive resin laminate according to the present disclosure, the average thickness of the photosensitive resin layer is 20 μm or less, (C) the content of the photopolymerization initiator is 5.0 parts by mass or more per 100 parts by mass of the total amount of the binder polymer (A) and the photopolymerizable compound (B), and (D) the polymerization inhibitor includes a polymerization inhibitor having two or more phenolic hydroxyl groups, and the content is 0.025 parts by mass or more per 100 parts by mass of the total amount of the binder polymer (A) and the photopolymerizable compound (B).

[0021] The photosensitive resin laminate according to this disclosure tends to achieve both high adhesion and high resolution by specifying the average thickness of the photosensitive resin layer, (C) the content of the photopolymerization initiator, and (D) the structure and content of the polymerization inhibitor as described above. This tendency is particularly pronounced when the average thickness of the photosensitive resin layer is 20 μm or less.

[0022] By setting the average thickness of the photosensitive resin layer to 20 μm or less, the aspect ratio is relaxed compared to when the thickness is 25 μm, making it possible to form finer patterns.

[0023] (C) By setting the content of the photopolymerization initiator to 5.0 parts by mass or more per 100 parts by mass of the total amount of (A) binder polymer and the above (B) photopolymerizable compound, the concentration of active radicals generated by exposure increases, improving the initial rate of monomer polymerization, and as a result, improving the monomer reaction rate at the end. Such high initial reaction rate and monomer reaction rate contribute to the formation of more uniform and high-density crosslinks, and are therefore thought to be effective not only in increasing sensitivity but also in improving image formation.

[0024] (D) By including a polymerization inhibitor having two or more phenolic hydroxyl groups, the polymerization inhibition ability is enhanced, and hardening of unexposed areas can be efficiently suppressed. In particular, in thin-film photosensitive resin layers, hardening of unexposed areas due to reflection of light from the substrate surface is significant, and as a result, it was difficult to achieve higher resolution than in 25 μm thick layers.

[0025] In contrast, by increasing the content of (D) polymerization inhibitor to 0.025 parts by mass or more per 100 parts by mass of the total amount of (A) binder polymer and (B) photopolymerizable compound, hardening of unexposed areas can be efficiently suppressed, resulting in higher resolution. By specifying the types and contents of (C) photopolymerization initiator and (D) polymerization inhibitor as described above, it is possible to achieve both high adhesion and high resolution by simultaneously improving the reactivity of exposed areas and suppressing unexpected hardening of unexposed areas.

[0026] Furthermore, in one embodiment, the photosensitive resin laminate relating to this disclosure is composed of three or more repeating units of (A) binder polymer.

[0027] Furthermore, in one embodiment, the photosensitive resin laminate relating to this disclosure is given by the following formula 1: MA occupancy = Σ{W} ｉ ×R ｉ / (R ｅｑ ) ｉ}...(Formula 1) {In the formula, W is the weight % of one component (B) relative to the total weight of the photopolymerizable compound having an ethylenically unsaturated bond (B), R is the molecular weight of the (meth)acryloyl group in the photopolymerizable compound having an ethylenically unsaturated bond (B), Rｅｑ is the equivalent amount of (meth)acryloyl groups, and i is the number assigned to each type of photopolymerizable compound having an ethylenically unsaturated bond. The MA occupancy calculated by} is 18.0% or more.

[0028] Furthermore, in one embodiment, the photosensitive resin laminate relating to this disclosure is given by the following formula 2: AO occupancy = Σ{W} ｉ ×A ｉ / ( A ｅｑ ) ｉ}...(Formula 2) {In the formula, W is the weight % of one component (B) relative to the total weight of the photopolymerizable compound having an ethylenically unsaturated bond (B), and A is the molecular weight of the structure represented by the following chemical formula 1: -AO- (Chemical formula 1) (In the formula, A is an alkylene group) in the photopolymerizable compound having an ethylenically unsaturated bond (B), A ｅｑ is the equivalent weight of the structure represented by chemical formula 1, and i is the number assigned to each type of photopolymerizable compound having an ethylenically unsaturated bond. The AO occupancy calculated by} is 40.0% or more.

[0029] In one embodiment, the photosensitive resin laminate according to this disclosure tends to achieve both high adhesion and high resolution by specifying the average thickness of the photosensitive resin layer, the repeating units constituting the binder polymer (A), the MA occupancy rate, the AO occupancy rate, etc., as described above. This tendency is particularly pronounced when the average thickness of the photosensitive resin layer is 20 μm or less.

[0030] While this disclosure does not wish to be bound by theory, the MA occupancy calculated by Equation 1 above can be correlated with the occupancy of (meth)acryloyl groups in the photopolymerizable compound having an ethylenically unsaturated bond (B). It is conceivable that increasing the MA occupancy in component (B) to 18.0% or more will increase the crosslinking density and improve adhesion. From this viewpoint, the MA occupancy calculated by Equation 1 above is preferably 23.0% or more in order to further improve crosslinking density and adhesion. The upper limit of the MA occupancy is not particularly limited, but may be, for example, less than 60.0% or less than 50.0%.

[0031] In equation 2 above, A ｉ (B) The total weight of the photopolymerizable compound having an ethylenically unsaturated bond is used as the basis for R in formula 1 above. ｉ This can be calculated by subtracting the weight percentage of other main components.

[0032] While this disclosure does not wish to be bound by theory, the AO occupancy calculated by Equation 2 above can be correlated with the occupancy of alkylene oxides such as ethylene oxide and propylene oxide in the photopolymerizable compound having an ethylenically unsaturated bond (B). It is conceivable that increasing the AO occupancy in component (B) to 40.0% or more will improve the penetration of the developer into the photosensitive resin layer and enhance resolution. The upper limit of the AO occupancy is not particularly limited, but may be, for example, less than 100.0%, less than 90.0%, less than 85.0%, etc.

[0033] From the viewpoint of further improving the permeability of the developer into the photosensitive resin layer and the resolution of the photosensitive resin laminate, the MA occupancy rate calculated by formula 1 above should be 23.0% or higher, or the following formula 3: EOPO occupancy rate = Σ[{W ｉ {E ｉ / (E ｅｑ ) ｉ +P ｉ / (P ｅｑ ) ｉ}]...(Equation 3) {In the formula, E is (B) a photopolymerizable compound having an ethylenically unsaturated bond, with the following chemical formula 2: -C ２ H ４ O- (Chemical formula 2) is the molecular weight of the structure, and E ｅｑ P is the equivalent weight of the structure represented by chemical formula 2, and P is the following chemical formula 3 in a photopolymerizable compound having an ethylenically unsaturated bond: -C ３ H ６ O- (Chemical formula 3) is the molecular weight of the structure, and P ｅｑis the equivalent weight of the structure represented by chemical formula 3, and W and i are as defined in formulas 1 and 2 above. The EOPO occupancy calculated by} is preferably 40.0% or more, and from the viewpoint of further improving adhesion and resolution, it is more preferable that the MA occupancy calculated by formula 1 above is 23.0% or more, and the EOPO occupancy calculated by formula 3 above is 40.0% or more. The upper limit of the EOPO occupancy is not particularly limited, but may be, for example, less than 100.0%, less than 90.0%, less than 85.0%, etc.

[0034] The photosensitive resin laminates of this disclosure are suitably used in the manufacture of conductor patterns. For example, the photosensitive resin laminates of this disclosure can be suitably used in the manufacture of printed circuit boards; wiring for semiconductor packages; lead frames for mounting IC chips; metal foils such as metal masks; packages such as ball grid arrays (BGAs) and chip-size packages (CSPs); tape substrates such as chip-on-film (COF) and tape automated bonding (TAB); semiconductor bumps; and partitions for flat panel displays such as ITO electrodes, address electrodes, and electromagnetic shields.

[0035] If desired, the photosensitive resin laminate may consist only of a temporary support and a photosensitive resin layer, or it may include a protective layer such as a protective film in addition to the temporary support and the photosensitive resin layer. The photosensitive resin laminate may have a protective layer on the side of the temporary support layer opposite to the photosensitive resin layer. In this case, a photosensitive resin laminate having a temporary support layer, a photosensitive resin layer, and a protective layer is provided.

[0036] A photosensitive resin laminate may have layers other than the temporary support layer, the photosensitive resin layer, and the protective layer (other layers). Examples of other layers include an "intermediate layer" placed between the temporary support layer and the photosensitive resin layer, and / or between the photosensitive resin layer and the protective layer. For example, a photosensitive resin laminate having an intermediate layer between the temporary support layer and the photosensitive resin layer is manufactured by applying a coating liquid to the intermediate layer on the temporary support layer to form a coating film, and then drying the coating film to obtain the photosensitive resin layer. Another example of other layers is a "release layer" placed on the side of the protective layer opposite to the photosensitive resin layer.

[0037] The temporary support layer, the photosensitive resin layer, and / or protective layer may each consist of a single layer or multiple layers. If they consist of multiple layers, their total thickness may be treated as the thickness of that layer.

[0038] The components of the photosensitive resin laminate relating to this disclosure are described below.

[0039] [Temporary Support] The temporary support is a substrate for supporting the photosensitive resin layer and is also called a "support film." The temporary support may be in the form of a layer for supporting the photosensitive resin layer, and it is preferable that it is transparent to the extent that it can transmit exposure light (active light) emitted from the exposure light source. The temporary support is peeled off from the photosensitive resin layer before the exposure process in which the photosensitive resin layer is exposed, or before the development process in which the photosensitive resin layer is developed.

[0040] Suitable substrates for use as temporary supports, particularly transparent substrates, include synthetic resins such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. Of these, polyethylene terephthalate (PET) is preferred as a temporary support because it possesses moderate flexibility and strength. The temporary support may be stretched as needed.

[0041] The absorbance of the temporary support at a wavelength of 365 nm is preferably 0.3 or less, more preferably 0.2 or less, even more preferably 0.1 or less, and most preferably 0.08 (e.g., 0.080) or less. The above absorbance may be 0 or greater.

[0042] It is preferable to use a film with few internal foreign matter, such as a high-quality film, as a temporary support. Examples of high-quality films include PET films synthesized using a Ti-based catalyst, PET films with small lubricant diameters and low lubricant content, PET films containing lubricant on only one side, thin-film PET films, PET films with smoothing treatment on at least one side, and PET films with roughening treatment such as plasma treatment on at least one side. By using a high-quality film as a temporary support, exposure light is less likely to be blocked by internal foreign matter in the temporary support, making it easier to irradiate the photosensitive resin layer with exposure light, and as a result, resolution tends to improve.

[0043] When the temporary support is in the form of a temporary support layer, the thickness of the temporary support layer is preferably 5 to 25 μm, and more preferably 6 to 20 μm. By adjusting the thickness of the temporary support layer within this range, it is easier to reduce the number of internal foreign matter, and therefore easier to prevent a decrease in resolution. In addition, it is easier to ensure the strength of the temporary support layer, and therefore easier to prevent wrinkles from forming in the photosensitive resin layer during the manufacturing process of the photosensitive resin laminate and / or when laminating the photosensitive resin laminate onto the substrate.

[0044] The haze of the temporary support is preferably 0.01 to 1.5%, more preferably 0.01 to 1.2%, and even more preferably 0.01 to 0.95%, from the viewpoint of improving the parallelism of the exposure light irradiated onto the photosensitive resin layer and obtaining good resolution.

[0045] [Protective Layer] The protective layer is a layer for protecting the photosensitive resin layer, and is often in the form of a film, also called a "protective film." The protective layer has appropriate adhesion to the photosensitive resin layer. When the adhesion between the photosensitive resin layer and the protective layer is sufficiently smaller than the adhesion between the photosensitive resin layer and the temporary support, the protective layer can be easily peeled off the photosensitive resin layer. The photosensitive resin layer exposed by peeling off the protective layer is laminated onto the substrate in the lamination process described later.

[0046] Examples of protective layers include polyethylene film, polypropylene film, oriented polypropylene film, biaxially oriented polypropylene film, and polyester film. Specifically, examples of protective layers include Alphan® EM-501, E-200, E-200C3, E-201F, FG-201, MA-411 (all manufactured by Oji F-Tex Co., Ltd.), Trefan® KW37, 2578, 2548, 2500, YM17S, Therapiel® PJ271, PJ111, HP2, PJ101, WZ, MDA, MFA, TK07, BKE, BX8A, SY (all manufactured by Toray Industries, Inc.), GF-18, GF-818, GF-858 (all manufactured by Tamapoly Co., Ltd.).

[0047] The thickness of the protective layer is preferably 10 to 100 μm, and more preferably 15 to 50 μm. This makes it easier to ensure the marketability and handling of the photosensitive resin laminate, and also makes it easier to realize a photosensitive resin laminate roll by winding (rolling) the photosensitive resin laminate of this disclosure.

[0048] The protective layer may have a release layer on its surface, in which case the protective layer is easily peeled off from the photosensitive resin layer. The compounds constituting this type of release layer are classified, for example, into silicone compounds and non-silicone compounds.

[0049] Examples of silicone compounds include: condensation reaction type silicone resins obtained by reacting terminally silanol polydimethylsiloxane with polymethylhydrogen siloxane or polymethylmethoxysiloxane; addition reaction type silicone resins obtained by reacting dimethylsiloxane-methylvinylsiloxane copolymer or dimethylsiloxane-methylhexenylsiloxane copolymer with polymethylhydrogen siloxane; UV-curable or electron-beam-curable silicone resins obtained by curing acrylic silicone and epoxy group-containing silicone with ultraviolet light or electron beams; modified silicone resins such as epoxy-modified silicone resin (silicone epoxy), polyester-modified silicone resin (silicone polyester), acrylic-modified silicone resin (silicone acrylic), phenol-modified silicone resin (silicone phenol), alkyd-modified silicone resin (silicone alkyd), and melamine-modified silicone resin (silicone melamine); and the like.

[0050] Examples of non-silicone compounds include alkyd resins, long-chain alkyl resins, acrylic resins, and polyolefin resins.

[0051] Examples of protective layers with a release layer include polyester films with a release layer, specifically the "X2NY" release film manufactured by Toyobo Film Solutions Co., Ltd.

[0052] The thickness of the release layer is preferably 0.001 to 2 μm, more preferably 0.005 to 1 μm, and even more preferably 0.01 to 0.5 μm. This may result in advantages such as a good appearance of the coating film, easier curing of the coating film, and easier securing of sufficient release properties.

[0053] [Photosensitive resin layer] The photosensitive resin layer constitutes the photosensitive resin laminate of the present disclosure. The photosensitive resin layer comprises a photosensitive resin composition comprising the following components: (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, and (D) a polymerization inhibitor. In this specification, these components are described as "component (A)," etc. Optionally, the photosensitive resin composition may further contain components other than components (A) to (D), such as (E) a sensitizer, (F) a hydrogen donor, an antioxidant, a stabilizer, a base dye, a solvent, etc. Each component and / or the raw material for each component may be used alone or in combination of two or more.

[0054] (Content of various components) From the viewpoint of easily achieving the effects of this disclosure, or from the viewpoint of suitability for forming a conductive pattern, the total content of component (A) and component (B) in the photosensitive resin composition is preferably 80% by mass or more, and more preferably 90% by mass or more, based on the solid content of the photosensitive resin composition.

[0055] (Thickness) The average thickness of the photosensitive resin layer is 20 μm or less. From the viewpoint of achieving both high adhesion and high resolution, a smaller thickness is preferable, and it may be 19 μm or less, 15 μm or less, or 10 μm or less. The lower limit of the average thickness of the photosensitive resin layer is not limited, but for example, it may be greater than 0 μm, or 1 μm or more.

[0056] A photosensitive resin layer with an average thickness of 20 μm or less is suitably used in providing a photosensitive element having a laminated structure in which a support film, an intermediate layer, and the photosensitive resin layer are sequentially laminated, as described later.

[0057] <Component (A): Binder Polymer> Component (A) is a binder polymer, and from the viewpoint of forming a resist pattern, it may be a polymer soluble in an alkaline aqueous solution.

[0058] (A) Component (A) preferably has a carboxyl group from the viewpoint of exhibiting suitable alkali solubility.

[0059] (A) The acid value of component (A) is preferably 155 mg KOH / g or less, from the viewpoint of suppressing swelling during the development process of the photosensitive resin laminate and photosensitive element and further improving adhesion.

[0060] The acid value can be calculated by accurately weighing approximately 1 g of the sample, dissolving it in 100 mL of acetone, and then performing a neutralization titration with a 1 mol / L potassium hydroxide solution. The acid value (mgKOH / g) is then calculated based on the volume of potassium hydroxide solution added using the following formula: Acid value (mgKOH / g) = 56.1 × {Volume of 1 mol / L potassium hydroxide solution added (mL)} / {Mass of accurately weighed sample (g)}. The neutralization titration can be performed, for example, using a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd.

[0061] The lower limit of the acid value of component (A) is not limited, but based on the calculation method described above, it may exceed 0 mg KOH / g, or it may be 50 mg KOH / g or more, 60 mg KOH / g or more, 80 mg KOH / g or more, etc. The acid value of component (A) is controlled by the content of compounds having an acid group among the compounds (A-1), (A-2), and (A-3) described below.

[0062] Component (A) is preferably composed of multiple types of repeating units, more preferably of three or more types of repeating units, and is even more preferably composed of all of the following (A-1) to (A-3): (A-1) methacrylic acid and / or acrylic acid; (A-2) styrene and / or styrene derivatives; (A-3) compounds that do not fall under (A-1) and (A-2);

[0063] Regarding the content ratio of the constituent units derived from (A-1) to (A-3) above, from the viewpoint of achieving both high adhesion and high resolution, it is preferable that the proportions of the constituent units derived from (A-1), (A-2), and (A-3) relative to the total mass of component (A) be 10 to 30% by mass, 20 to 60% by mass, and 20 to 60% by mass, respectively. The proportion of each constituent unit means the weighted average value of the copolymerization ratio of each constituent unit, with the content ratio of each binder polymer as the weight. Similarly, each value described for component (A) (for example, weight-average molecular weight and polydispersity, etc.) also means the weighted average value with the content ratio of each binder polymer as the weight.

[0064] Component (A) is preferably formed from a monomer providing a constituent unit derived from (A-1) above, a monomer providing a constituent unit derived from (A-2) above, and a monomer providing a constituent unit derived from (A-3) above.

[0065] The monomers that provide the constituent units derived from (A-1) above are methacrylic acid and / or acrylic acid.

[0066] The monomer providing the constituent unit derived from (A-2) above is styrene and / or a styrene derivative. Examples of styrene derivatives include methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer. Among these, the (A-2) compound is preferably styrene, from the viewpoint of easily achieving the effects of this disclosure or from the viewpoint of being suitable for forming a conductive pattern.

[0067] As monomers providing the constituent units derived from (A-3) above, any monomer may be used as long as it is a compound that does not fall under (A-1) and (A-2) above, for example, acrylic acid, fumaric acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid semi-ester, benzyl (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, phenoxyethyl (meth)acrylate, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl] Ethyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth) Examples include acrylates, glycerin mono(meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, pentamethylpiperidyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethyl carbitol (meth)acrylate, methoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, poly(ethylene glycol) methyl ether (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, vinyl alcohol esters (e.g., vinyl acetate), (meth)acrylonitrile, etc.

[0068] Furthermore, among the above compounds, from the viewpoint of easily achieving the effects of this disclosure or being suitable for forming a conductive pattern, the (A-3) compound preferably includes benzyl (meth)acrylate and alkyl (meth)acrylate.

[0069] (A-3) When the compound contains alkyl (meth)acrylate, the alkyl (meth)acrylate content is preferably 20 to 60% by mass from the viewpoint of the flexibility of the binder polymer.

[0070] In particular, it is preferable that the (A) binder polymer has structural units derived from a polymerizable monomer containing a hydroxyalkyl group. The inclusion of a hydroxyalkyl group in the (A) binder polymer increases the development speed, thereby expanding the range of use for other high-performance raw materials with slower development speeds, and as a result, improving developability and image formation.

[0071] The weight-average molecular weight (Mw) of component (A) is preferably 5,000 to 600,000, more preferably 10,000 to 200,000, even more preferably 10,000 to 100,000, and particularly preferably 15,000 to 55,000. A weight-average molecular weight (Mw) of component (A) of 5,000 or more makes it easier to maintain a uniform thickness of the photosensitive resin laminate and to ensure resistance to developing solutions. A weight-average molecular weight (Mw) of component (A) of 600,000 or less makes it easier to ensure flexibility and developability of the photosensitive resin laminate. Furthermore, from the viewpoint of improving resolution, the weight-average molecular weight (Mw) of component (A) is preferably 10,000 to 35,000, and more preferably 15,000 to 25,000.

[0072] The polydispersity of component (A) {weight-average molecular weight of component (A) (Mw) / number-average molecular weight of component (A) (Mn)} is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and particularly preferably 1.0 to 3.0.

[0073] (A) The content of component (A) is preferably 1 to 80% by mass, more preferably 1 to 70% by mass, and even more preferably 5 to 60% by mass, relative to the solid content of the photosensitive resin composition. When the content of component (A) is 1% by mass or more, excellent adhesion and fine line strength are easily achieved. When the content of component (A) is 80% by mass or less, resistance to developing solutions is easily ensured.

[0074] 《Synthesis of Component (A)》 Component (A) can be synthesized by diluting one or more monomers described above with a solvent such as acetone, methyl ethyl ketone, and isopropanol, mixing appropriate amounts of benzoyl peroxide and a radical polymerization initiator such as azobisisobutyronitrile into the solution, and then heating and stirring. In some cases, component (A) can be synthesized by adding a portion of the mixture dropwise to the reaction solution. After the reaction is complete, the solvent may be further added to adjust to the desired concentration. In addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may also be used as synthesis methods. Furthermore, synthesis may be carried out by living radical polymerization.

[0075] <Component (B): Photopolymerizable compound having an ethylenically unsaturated bond> Component (B) is a photopolymerizable compound having an ethylenically unsaturated bond, for example, a compound having one or more ethylenically unsaturated bonds in one molecule. Component (B) may contain multiple such compounds that are different from each other.

[0076] The ethylenically unsaturated bond in component (B) functions as a photopolymerizable bond. The compound having such an ethylenically unsaturated bond may be a compound containing a photopolymerizable functional group, for example, a compound containing a (meth)acryloyl group.

[0077] Regarding component (B), having "n" photopolymerizable functional groups in one molecule is sometimes referred to as "n-functional." For example, a compound having n (meth)acryloyl groups is sometimes referred to as an n-functional (meth)acrylate compound. For example, with respect to component (B), having one, two, three, four, five, or six photopolymerizable functional groups in one molecule is sometimes referred to as "monofunctional (or monofunctional)," "difunctional," "trifunctional," "tetrafunctional," "pentafunctional," or "hexafunctional," respectively.

[0078] Examples of bifunctional (meth)acrylate compounds include alkyl di(meth)acrylates, 1,3-bis(meth)acryloyloxy-2-propanol, polyalkylene glycol di(meth)acrylates, tricyclodecanol di(meth)acrylates, ethoxylated (hydrogenated) bisphenol A di(meth)acrylates, propoxylated (hydrogenated) bisphenol A di(meth)acrylates, and tetramethylene oxide-modified (hydrogenated) bisphenol A di(meth)acrylates.

[0079] Examples of polyalkylene glycol di(meth)acrylates include polyethylene glycol di(meth)acrylate, polypropylene di(meth)acrylate, and polytetramethylene glycol di(meth)acrylate. Furthermore, the polyalkylene glycol di(meth)acrylate may be a compound having multiple alkylene groups, consisting of ethylene groups, propylene groups, and tetramethylene groups. Examples of such compounds include a polyalkylene glycol di(meth)acrylate obtained by adding an average of 3 ethylene oxides to each end of a polypropylene glycol containing an average of 12 propion oxides; and a di(meth)acrylate obtained by adding an average of 6 moles of propylene oxide to each end of 6 moles of ethylene oxide.

[0080] In this specification, the average number of alkylene oxides such as ethylene oxide and propylene oxide can be understood to be determined by number averaging, and for reference, catalog values ​​can be referred to within a range that does not deviate from the above values.

[0081] Furthermore, as a bifunctional (meth)acrylate compound, the following general formula (2I) is used: (In the formula, R ２ Each is independently a hydrogen atom or a methyl group, and X ２ O and Y ２Bisphenol A type di(meth)acrylates can also be found, represented as follows: O is independently an oxyethylene group or an oxypropylene group, m3, m4, n2, and n3 are independently integers from 0 to 40, m3 + m4 is from 1 to 40, and n2 + n3 is from 0 to 20.

[0082] Furthermore, examples of bifunctional (meth)acrylate compounds include: di(meth)acrylates of polyalkylene glycols obtained by adding an average of 2 moles of propylene oxide to each end of bisphenol A, which has an average of 6 moles of ethylene oxide added to each end; di(meth)acrylates of polyalkylene glycols obtained by adding an average of 4 moles of propylene oxide to each end of bisphenol A, which has an average of 2 moles of ethylene oxide added to each end; di(meth)acrylates of polyalkylene glycols obtained by adding an average of 2 moles of propylene oxide to each end of bisphenol A, which has an average of 4 moles of ethylene oxide added to each end; di(meth)acrylates of polyethylene glycols obtained by adding an average of 5 moles of ethylene oxide to each end of bisphenol A; and di(meth)acrylates of polyethylene glycols obtained by adding an average of 5 moles of ethylene oxide to each end of 9,9-bis(4-hydroxyphenyl)fluorene. Examples include polyethylene glycol di(meth)acrylate obtained by adding an average of 2 moles of ethylene oxide to each end of bisphenol A; polyethylene glycol di(meth)acrylate obtained by adding an average of 1 mole of ethylene oxide to each end of bisphenol A; and so on.

[0083] Examples of trifunctional or more (meth)acrylate compounds include trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, pentaerythritol (tri / tetra)(meth)acrylate, diglycerin tetra(meth)acrylate, triglycerin penta(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, tetraglycerin hexa(meth)acrylate, and dipentaerythritol (tetra / penta / hexa)(meth)acrylate.

[0084] Furthermore, examples of trifunctional or more (meth)acrylate compounds include compounds obtained by forming a (meth)acrylate from an alcohol having three or more groups in which alkylene oxide groups can be added to the molecule as a central skeleton, to which alkylene oxide groups such as ethylene oxide groups, propylene oxide groups, butylene oxide groups, triethylene oxide groups, or tetraethylene oxide groups are added, and (meth)acrylic acid. Examples of such compounds include trimethylolpropane alkylene oxide-modified tri(meth)acrylate, glycerin alkylene oxide-modified tri(meth)acrylate, alkylene oxide-modified pentaerythritol (tri / tetra)(meth)acrylate, alkylene oxide-modified diglycerin tetra(meth)acrylate, alkylene oxide-modified triglycerin penta(meth)acrylate, alkylene oxide-modified ditrimethylolpropane tetra(meth)acrylate, alkylene oxide-modified tetraglycerin hexa(meth)acrylate, alkylene oxide-modified dipentaerythritol (tetra / penta / hexa)(meth)acrylate, and alkylene oxide-modified isocyanuric acid tri(meth)acrylate. The alkylene oxide group is preferably an ethylene oxide group, a propylene oxide group, or a butylene oxide group.

[0085] As the trifunctional or higher (meth)acrylate compound, from the viewpoint of excellent developability, it may contain alkylene oxide-modified pentaerythritol (tri / tetra)(meth)acrylate and / or alkylene oxide-modified dipentaerythritol (tetra / penta / hexa)(meth)acrylate.

[0086] As an example of the trifunctional (meth)acrylate compound, there is a compound represented by the following general formula (II) having trimethylolpropane as a skeleton: {In the formula, n １ , n ２ , and n ３ are each independently an integer of 1 to 25, provided that n １ + n ２ + n ３ is an integer of 3 to 75, and R １ , R ２ , and R ３ are each independently a methyl group or a hydrogen atom.}

[0087] Further, as an example of the trifunctional (meth)acrylate compound, there is a compound represented by the following general formula (III) having glycerin as a skeleton: {In the formula, Y each independently represents an alkylene group, R each independently represents a methyl group or a hydrogen atom, and n each independently represents an integer of 0 to 200.}

[0088] As an example of the tetrafunctional (meth)acrylate compound, there is a compound represented by the following general formula (IV) having pentaerythritol as a skeleton: {In the formula, n １ , n ２ , n ３ , and n ４ each independently represent an integer of 1 to 25, n １ + n ２ + n ３ + n ４ is an integer of 4 to 100, and R １ , R ２ , R ３ , and R ４ each independently represent a methyl group or a hydrogen atom, and R ５ , R ６, R ７ , and R ８ Each of these independently represents an alkylene group, R ５ , R ６ , R ７ , and R ８ If there are multiple instances of each, then the multiple R ５ , R ６ , R ７ , and R ８ Compounds represented by} may be identical or different from each other.

[0089] An example of a hexafunctional (meth)acrylate compound is the following general formula (V), which has dipentaerythritol as its backbone: Examples of compounds represented by {wherein R independently represents a methyl group or a hydrogen atom, and n independently represents an integer from 0 to 30} include compounds represented by the formula (V). In general formula (V), n may be 0, that is, the ethylene oxide moiety may not be present.

[0090] Furthermore, an example of a (meth)acrylate compound with four or more functions is the following general formula (VI), which has polyglycerin as its backbone: [In the formula, n is between 2 and 20, each i is a natural number between 1 and n, k, each li, and m are each an integer between 0 and 30, and R １ , R ２ｉ , and R ３ Each of these independently represents either a hydrogen atom or a methyl group, and R ４ , R ５ｉ , and R ６ Each of these is an alkylene group having 1 to 10 carbon atoms. Examples of compounds represented by the above general formula (VI) include alkylene oxide-modified diglycerin tetra(meth)acrylate, alkylene oxide-modified triglycerin penta(meth)acrylate, alkylene oxide-modified tetraglycerin hexa(meth)acrylate, etc.

[0091] Examples of (B) components with three or more functionalities that can be specifically used include: tri(meth)acrylate obtained by adding an average of 21 moles of ethylene oxide to trimethylolpropane; tetra(meth)acrylate obtained by adding an average of 9 moles of ethylene oxide to pentaerythritol; tetra(meth)acrylate obtained by adding an average of 9 moles of ethylene oxide to diglycerin; polyethylene glycol hexa(meth)acrylate obtained by adding 13 moles of ethylene oxide to dipentaerythritol; hexa(meth)acrylate obtained by adding an average of 21 moles of ethylene oxide to tetraglycerin; and so on. The abbreviations "EO" and "PO" mean ethylene oxide and propionate oxide, respectively.

[0092] From the viewpoint of achieving both adhesion and resolution, and from the viewpoint of improving crosslinking density or developer penetration, it is preferable that in the photosensitive resin laminate or photosensitive resin layer described above, as well as in component (B), the MA occupancy rate calculated by formulas 1 and 2 above is 18.0% or more and / or the AO occupancy rate is 40.0% or more, more preferably the MA occupancy rate calculated by formula 1 above is 23.0% or more, and even more preferably the EOPO occupancy rate calculated by formula 3 above is 40.0% or more.

[0093] In the MA occupancy rate calculated by formula 1 above, the AO occupancy rate calculated by formula 2 above, and the EOPO occupancy rate calculated by formula 3 above, W ｉ This may be measured by assigning the chemical structure using gel permeation chromatography (GPC) and / or mass spectrometry, R ｉ A ｉ , E ｉ and P ｉ These values ​​can be calculated based on known atomic weights, and R ｅｑ This value may be obtained by calculating (total mass of a specific monomer) / (total number of moles of (meth)acryloyl groups in a specific monomer) based on the chemical structure assigned by gel permeation chromatography (GPC) and / or mass spectrometry, and A ｅｑ , E ｅｑ , and P ｅｑThese values ​​may be obtained by calculating (total mass of the specific monomer) / (number of moles of chemical formula 1, chemical formula 2, or chemical formula 3 in the specific monomer) based on the assigned chemical structure obtained by gel permeation chromatography (GPC) and / or mass spectrometry, respectively.

[0094] From the viewpoint of further improving adhesion, it is preferable that the content of a compound having four or more (meth)acryloyl groups in one molecule of component (B) is 40% by mass or more; it is preferable that component (B) contains a compound having five or more (meth)acryloyl groups in one molecule; and / or it is preferable that component (B) contains a compound having the structure represented by the above chemical formula 3.

[0095] (B) The content of component (B) is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 80% by mass or less, and more preferably 70% by mass or less, relative to the solid content of the photosensitive resin composition, from the viewpoint of excellent sensitivity and conformability.

[0096] <Component (C): Photopolymerization Initiator> Component (C) is a photopolymerization initiator. The photopolymerization initiator generates radicals in response to active light emitted from the exposure light source, thereby promoting the polymerization of compounds having ethylenically unsaturated bonds.

[0097] The content of component (C) is 5.0 parts by mass or more per 100 parts by mass of the total amount of components (A) and (B). This makes it easier to obtain sufficient sensitivity, allowing light to penetrate sufficiently to the bottom of the photosensitive resin layer even with a small exposure, and consequently making it easier to achieve good resolution and adhesion. From a similar viewpoint, the content of component (C) is preferably 5.0% by mass or more, and more preferably 5.5% by mass or more, relative to the solid content of the photosensitive resin composition. The content of component (C) may be 30% by mass or less, and may be 20% by mass or less, relative to the solid content of the photosensitive resin composition.

[0098] Examples of component (C) include biimidazole compounds, N-aryl-α-amino acid compounds, quinone compounds, aromatic ketone compounds, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, benzoin ether compounds, dialkylketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, and acridine compounds, as well as pyrazoline derivatives, and ester compounds of N-aryl amino acids, and halogen compounds.

[0099] Examples of biimidazole compounds include compounds having a biimidazole structure, such as rophine dimers, i.e., dimers of 2,4,5-triarylimidazole.

[0100] Dimers of 2,4,5-triarylimidazole include the dimer of 2-(o-chlorophenyl)-4,5-diphenylbiimidazole (also known as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole), the dimer of 2-(o-chlorophenyl)-4,5-bis-(m-methoxyphenyl)imidazole, the dimer of 2-(p-methoxyphenyl)-4,5-diphenylimidazole, and 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl Nylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, 2,4,5-tris-(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis-(3-methylphenyl) Toxyphenyl)-biimidazole, 2,2'-bis-(2,4-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetrakis-(3 -Methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,Examples include 5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, and 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole.

[0101] From the viewpoint of high sensitivity, resolution, and adhesion, it is preferable that component (C) contains a rofin dimer, and more preferably a dimer of 2-(o-chlorophenyl)-4,5-diphenylimidazole.

[0102] When component (C) contains a biimidazole compound, the content of the biimidazole compound may be 4.5% by mass or more, preferably 5.0% by mass or more, more preferably 5.3% by mass or more, and even more preferably 5.5% by mass or more, relative to the solid content of the photosensitive resin composition. As an upper limit for component (C) relative to the solid content of the photosensitive resin composition, which can be optionally combined with the preferred lower limit for the solid content of the photosensitive resin composition, when a biimidazole compound is included, the content of the biimidazole compound may be, for example, 15.0% by mass or less, 12.0% by mass or less, or 10.0% by mass or less. Furthermore, when component (C) contains a biimidazole compound, the content of the biimidazole compound is preferably 5.0 parts by mass or more, more preferably 5.5 parts by mass or more, and even more preferably 6.0 parts by mass or more, relative to 100 parts by mass of the total amount of components (A) and (B). As a preferred lower limit for component (A) and component (B) relative to 100 parts by mass of the total amount, and as an upper limit for component (C) relative to 100 parts by mass of the total amount of components (A) and (B), if a biimidazole compound is included, the content of the biimidazole compound may be, for example, 15.0 parts by mass or less, 12.0 parts by mass or less, or 10.0 parts by mass or less.

[0103] Examples of N-aryl-α-amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Among these, N-phenylglycine is preferred due to its high sensitizing effect.

[0104] Examples of quinone compounds include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthaquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.

[0105] Examples of aromatic ketone compounds include benzophenone.

[0106] Examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1. Examples of commercially available acetophenone compounds include the Irgacure series (manufactured by Ciba Specialty Chemicals: Irgacure-907, Irgacure-369, and Irgacure-379, etc.).

[0107] Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide. Examples of commercially available acylphosphine oxide compounds include Lucilin TPO (manufactured by BASF) and Irgacure-819 (manufactured by Ciba Specialty Chemicals).

[0108] Examples of benzoin compounds and benzoin ether compounds include benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, and ethylbenzoin.

[0109] Examples of dialkylketal compounds include benzyldimethylketal and benzyldiethylketal. Examples of thioxanthone compounds include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorthioxanthone. Examples of dialkylaminobenzoic acid ester compounds include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, and 2-ethylhexyl-4-(dimethylamino)benzoate.

[0110] Examples of oxime ester compounds include 1-phenyl-1,2-propanedione-2-O-benzoyl oxime and 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl) oxime. Examples of commercially available oxime ester compounds include CGI-325, Irgacure-OXE01, and Irgacure-OXE02 (all manufactured by Ciba Specialty Chemicals).

[0111] As for the acridine compound, 1,7-bis(9,9'-acridinyl)heptane or 9-phenylacridine are preferred in terms of sensitivity, resolution, and availability.

[0112] Examples of ester compounds of N-aryl amino acids include methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, n-propyl ester of N-phenylglycine, isopropyl ester of N-phenylglycine, 1-butyl ester of N-phenylglycine, 2-butyl ester of N-phenylglycine, tert-butyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, and octyl ester of N-phenylglycine.

[0113] Examples of halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, chlorinated triazine compounds, and diallylodonium compounds. Among these, tribromomethylphenylsulfone is preferred.

[0114] <Component (D): Polymerization Inhibitor> The photosensitive resin composition or photosensitive resin layer may optionally contain a polymerization inhibitor as component (D). In this disclosure, the inclusion of a polymerization inhibitor tends to improve the transparency and resolution between resist patterns, as the polymerization inhibitor present near the exposed and unexposed areas suppresses the reaction in the unexposed areas.

[0115] Examples of component (D) include phenothiazine, p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, gallic acid, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], nitrosophenylhydroxyamine aluminum salt (for example, an aluminum salt to which 3 moles of nitrosophenylhydroxylamine have been added), and diphenylnitrosamine. Among these, phenothiazine, tert-butylcatechol, gallic acid, or nitrosophenylhydroxyamine aluminum salt are preferred from the viewpoint of further improving transparency and resolution, and compounds having two or more phenolic hydroxyl groups are more preferred. These can be used individually or in combination of two or more types.

[0116] Compounds having two or more phenolic hydroxyl groups are more preferably compounds having an aromatic ring in which two or more hydrogen atoms are substituted with phenolic hydroxyl groups. Compounds having an aromatic ring in which two or more hydrogen atoms are substituted with phenolic hydroxyl groups include those with the following general formula (VII): (VII) [wherein, R ５ Compounds represented by ] include: where is a group selected from the group consisting of a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a carboxyl group, a carboxyalkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms, m is an integer of 2 or more selected such that m + n is 6 or less, and n is an integer of 0 or more selected such that m + n is 6 or less. It is preferable that m is an integer between 2 and 4, and that n is an integer between 0 and 2. Also, when n is an integer of 2 or more, R ５ These may be the same or different. ５The hydrocarbon group having 1 to 20 carbon atoms is preferably a carboxyl group, and the hydrocarbon group having 1 to 20 carbon atoms is more preferably a non-aromatic ring group such as an alkyl group or a cycloalkyl group. Among these, tert-butylcatechol or gallic acid are the most preferred compounds having two or more phenolic hydroxyl groups.

[0117] The content of component (D) is 0.025 parts by mass or more per 100 parts by mass of the total amount of components (A) and (B). Increasing the content of component (D) to 0.025 parts by mass or more per 100 parts by mass of the total amount of components (A) and (B) tends to improve clarity and resolution, and this tendency is particularly pronounced when component (D) is a compound having two or more phenolic hydroxyl groups. The content of component (D) is more preferably 0.035 parts by mass or more, more preferably 0.050 parts by mass or more, and particularly preferably 0.075 parts by mass or more. There is no particular upper limit to the content of component (D), but for example, it may be 0.150 parts by mass or less, 0.120 parts by mass or less, or 0.090 parts by mass or less per 100 parts by mass of the total amount of components (A) and (B). The preferred content of component (D) is the same when a compound having two or more phenolic hydroxyl groups is used.

[0118] The mass ratio of the content of (D) polymerization inhibitor to (C) photopolymerization initiator (i.e., mass of (D) polymerization inhibitor / mass of (C) photopolymerization initiator) is preferably 0.002 or higher, and more preferably 0.004 or higher. When the above mass ratio is 0.002 or higher, the polymerization inhibitor present near the boundary between the exposed and unexposed areas can more effectively suppress the reaction in the unexposed areas. Furthermore, when the above mass ratio of the content of (D) polymerization inhibitor to (C) photopolymerization initiator is preferably 0.020 or lower, and more preferably 0.015 or lower. When the above mass ratio is 0.020 or lower, both the photosensitivity of the photosensitive resin composition and the suppression of the reaction in the unexposed areas can be achieved. The preferred mass ratio of the content of (D) polymerization inhibitor to (C) photopolymerization initiator is the same when a compound having two or more phenolic hydroxyl groups is used.

[0119] <Component (E): Sensitizer> As the sensitizer, sensitizing compounds other than component (C) above may be used, for example, pyrazoline compounds, anthracene compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, dialkylaminobenzophenone compounds, and coumarin derivatives. In particular, it is preferable to include at least one selected from the group consisting of dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, and coumarin derivatives. Furthermore, as the sensitizer, from the viewpoint of increasing the sensitization efficiency for light in the range of 350 to 410 nm, compounds having an absorbance maximum at 350 to 410 nm are preferred, and the molar extinction coefficient at the absorbance maximum wavelength is 1000 L·mol. －１ ・cm －１ It is preferable to include the above-mentioned compounds. Furthermore, by including a compound having an absorbance maximum at 350-410 nm, it is easier to control either the absorbance for light at wavelengths of 365 nm or 402 nm to a desired range. By using such a highly efficient sensitizer, sensitivity is increased, and as a result the required amount of light decreases, which suppresses hardening of unexposed areas caused by light reflection on the substrate surface, improving transparency and resolution.

[0120] Examples of dialkylaminobenzophenone compounds include Michla's ketone [4,4'-bis(dimethylamino)benzophenone] and 4-methoxy-4'-dimethylaminobenzophenone. As for aromatic ketone compounds, 4,4'-bis(diethylamino)benzophenone can also be mentioned from the viewpoint of sensitizing effect and adhesion.

[0121] As pyrazoline compounds, 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline, and 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline are preferred from the viewpoint of adhesion and rectangularity of the resist pattern.

[0122] Examples of anthracene compounds include anthracene and anthracene derivatives, of which anthracene derivatives include, for example, 9,10-dialkoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, and 10-phenyl-9-anthraceneboronic acid. Among these, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, and 10-phenyl-9-anthraceneboronic acid are preferred from the viewpoint of sensitizing effect.

[0123] The coumarin derivative can be any compound having a coumarin skeleton, such as 2,3,6,7-tetrahydro-9-methyl-1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinoridine-11-one (also known as "coumarin 102").

[0124] From the viewpoint of sensitivity, the sensitizer content is preferably 0.1 to 0.6% by mass (for example, 0.10 to 0.60% by mass) relative to the solid content of the photosensitive resin composition, and more preferably 0.1 to 0.4% by mass (for example, 0.10 to 0.40% by mass).

[0125] Furthermore, the product of the total content of components (A) and (B) of the sensitizer (E) relative to 100 parts by mass and the content of components (A) and (B) of the polymerization inhibitor (D) relative to 100 parts by mass is preferably 0.007 or more, more preferably 0.015 or more, even more preferably 0.05 or more, and particularly preferably 0.10 or more. In order to suppress hardening of unexposed areas, by increasing the absorbance of the photosensitive resin composition to reduce the amount of light reaching the substrate surface, and by increasing the amount of the highly sensitive sensitizer as described above, a synergistic effect is expected to increase sensitivity and further improve clarity and resolution. In addition, by increasing the amount of the inhibitor in line with the increased sensitivity due to the increase in the sensitizer, hardening of unexposed areas can be efficiently suppressed while maintaining the same level of sensitivity, thereby further improving clarity and resolution.

[0126] <Component (F): Hydrogen Donor> The photosensitive resin composition or photosensitive resin layer may optionally contain a hydrogen donor as component (F). While this disclosure does not wish to be bound by theory, it has been found that the combined use of component (C) and component (F) is involved in the hydrogen abstraction reaction from the hydrogen donor by the radical of the photopolymerization initiator, and that improvements in sensitivity and crosslinking density can be expected by controlling the reaction rate.

[0127] Component (F) is not particularly limited, but for example, leucocrystal violet may be used.

[0128] The mass ratio of the content of component (F) to the content of component (C) (i.e., mass of hydrogen donor (F) / mass of photopolymerization initiator (C)) is preferably 0.07 or higher, more preferably 0.09 or higher, even more preferably 0.13 or higher, and particularly preferably 0.25 or higher, from the viewpoint of improving sensitivity and crosslinking density. The effect of the photosensitive resin laminate of this disclosure is not intended to be constrained by theory, but as described above, it is thought to be due to increasing the rate of hydrogen abstraction reaction from the hydrogen donor by the radicals of the photopolymerization initiator. Therefore, increasing the amount of hydrogen donor increases the initial concentration of the reaction, improves reactivity, and consequently improves sensitivity and crosslinking density. Accordingly, it was found that the degree of improvement in sensitivity and crosslinking density correlates more with controlling the above mass ratio (mass of hydrogen donor (F) / mass of photopolymerization initiator (C)) than with controlling the content of component (F) alone.

[0129] <Other Ingredients> The photosensitive resin composition may optionally contain other ingredients (base dyes, antioxidants, stabilizers, plasticizers, etc.).

[0130] Examples of base dyes include Basic Green 1 [CAS number (same below): 633-03-4] (e.g., Aizen Diamond Green GH, product name, manufactured by Hodogaya Chemical Co., Ltd.), Malachite Green [CAS number 569-64-2], Tris(4-dimethylamino-2-methylphenyl)methane [Leucomalachite Green], Fuchsine [632-99-5], Methyl Violet [603-47-4], Methyl Green [82-94-0], Victoria Blue B [2580-56-5], Basic Blue 7 [2390-60-5] (e.g., Aizen Victoria Pure Blue) Examples include BOH (trade name, manufactured by Hodogaya Chemical Co., Ltd.), Rhodamine B [81-88-9], Rhodamine 6G [989-38-8], Basic Yellow 2 [2465-27-2], etc. Among these, Basic Green 1 is preferred from the viewpoint of improving colorability, hue stability, and exposure contrast. These can be used individually or in combination of two or more.

[0131] The base dye content is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 0.5% by mass, and even more preferably 0.01 to 0.1% by mass. From the viewpoint of obtaining good colorability, the base dye content is preferably above the lower limit, while from the viewpoint of maintaining the sensitivity of the photosensitive layer, it is preferably below the upper limit.

[0132] Examples of antioxidants include triphenyl phosphite (e.g., manufactured by ADEKA, trade name: TPP), tris(2,4-di-tert-butylphenyl) phosphite (e.g., manufactured by ADEKA, trade name: 2112), tris(mononylphenyl) phosphite (e.g., manufactured by ADEKA, trade name: 1178), and bis(mononylphenyl)-dinonylphenyl phosphite (e.g., manufactured by ADEKA, trade name: 329K). These can be used individually or in combination of two or more.

[0133] The antioxidant content is preferably 0.01 to 0.8% by mass, and more preferably 0.01 to 0.3% by mass, relative to the total solid content mass of the photosensitive resin composition. From the viewpoint of exhibiting good hue stability of the resist pattern and improving the sensitivity of the photosensitive layer, the antioxidant content is preferably above the lower limit. On the other hand, from the viewpoint of exhibiting good hue stability while suppressing the color development of the resist pattern and improving adhesion, it is preferably below the upper limit.

[0134] Stabilizers can be used to improve the thermal stability of the photosensitive resin composition. Examples of stabilizers include at least one alkylene oxide compound having a glycidyl group and a benzotriazole compound. These can be used individually or in combination of two or more.

[0135] Examples of plasticizers include glycol esters such as polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxyethylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether; phthalate esters of diethyl phthalate; o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, triethyl acetyl citrate, tri-n-propyl acetyl citrate, tri-n-butyl acetyl citrate, etc.

[0136] The plasticizer content is preferably 1 to 50% by mass, and more preferably 1 to 30% by mass, relative to the solid content of the photosensitive resin composition. When this percentage is 1% by mass or more, it is easier to suppress delays in development time and to impart flexibility to the cured film. When this percentage is 50% by mass or less, it tends to suppress insufficient curing and edge fusing.

[0137] Preferably, the absorbance for light with a wavelength of 365 nm and the absorbance for light with a wavelength of 402 nm per 1 μm thickness of the photosensitive resin layer are greater than 0.010 and 0.040 or less, more preferably greater than 0.010 and 0.030 or less, and particularly preferably greater than 0.010 and 0.025 or less.

[0138] Furthermore, it is preferable that the absorbance for light with a wavelength of 365 nm and the absorbance for light with a wavelength of 402 nm per 1 μm of thickness of the photosensitive resin layer be greater than 0.014, and more preferably greater than 0.017.

[0139] In thin-film photosensitive resin layers, the light transmittance during exposure increases, resulting in a greater amount of light reaching the substrate surface. Therefore, light that is not absorbed as it passes through the photosensitive resin layer is reflected from the substrate surface, leading to hardening of the resist in unexposed areas. By increasing the absorbance of the photosensitive resin layer, the amount of light reaching the substrate surface is reduced, suppressing hardening in unexposed areas. As a result, transparency and resolution are further improved.

[0140] When the absorbance of the photosensitive resin composition per 1 μm thickness for light with a wavelength of 365 nm is greater than 0.010 and less than or equal to 0.040, the photosensitive resin laminate is preferably used in applications where it is exposed to light at 355 to 375 nm, and in particular, it is preferably used in applications where it is exposed to i-line (365 nm) light.

[0141] When the absorbance of the photosensitive resin composition per 1 μm thickness for light with a wavelength of 402 nm is greater than 0.010 and less than or equal to 0.040, the photosensitive resin laminate is preferably used in applications where it is exposed to light with a wavelength of 395 to 410 nm, and is particularly preferably used in applications where it is exposed to h-rays, or to light having a maximum wavelength of 395 to 410 nm, such as an InGaN semiconductor laser.

[0142] The absolute value of the difference between the absorbance for light at a wavelength of 365 nm and the absorbance for light at 402 nm per 1 μm thickness of the photosensitive resin composition is preferably 0.018 or less, more preferably 0.010 or less, and particularly preferably 0.005 or less.

[0143] Because the difference in absorbance between the i-line and h-line wavelength bands is small, even when using an exposure machine with both i-line and h-line sources, the sensitizer can transfer energy from either source to the initiator, enabling efficient curing with either i-line or h-line. In other words, both i-line and h-line radiation can be used during exposure.

[0144] Here, if the absorbance of the photosensitive resin composition per 1 μm thickness for light at a wavelength of 365 nm or for light at a wavelength of 402 nm is greater than 0.010, it is preferable to increase the content of the compound having two or more phenolic hydroxyl groups as the absorbance value increases. Specifically, the value of the content of the compound having two or more phenolic hydroxyl groups per 1 μm thickness of the photosensitive resin composition relative to the absorbance of light at a wavelength of 365 nm or for light at a wavelength of 402 nm, i.e., (mass of the compound having two or more phenolic hydroxyl groups) / (absorbance of the photosensitive resin composition per 1 μm thickness for light at a wavelength of 365 nm or for light at a wavelength of 402 nm), is preferably 1.0 or higher, and more preferably 1.5 or higher. This makes it easier to suppress excessive reaction in the unexposed area near the boundary between the exposed and unexposed areas, and tends to improve the transparency and resolution between resist patterns.

[0145] Furthermore, the content of a compound having two or more phenolic hydroxyl groups per 1 μm thickness of the photosensitive resin composition, with respect to the absorbance for light at a wavelength of 365 nm or light at a wavelength of 402 nm, i.e., (mass of compound having two or more phenolic hydroxyl groups) / (absorbance for light at a wavelength of 365 nm or light at a wavelength of 402 nm per 1 μm thickness of the photosensitive resin composition), may be 4 or less, and preferably 3 or less. This allows the photosensitivity of the photosensitive resin composition to be within a better range.

[0146] The sensitivity of the photosensitive resin layer to exposure light is 30 mJ / cm². ２ More than 200mJ / cm ２ Preferably, it is 40 mJ / cm ２ More than 100mJ / cm ２The following is more preferable. Here, the exposure light can be, for example, light having a peak wavelength of 365 nm or light having a peak wavelength of 402 nm. When the sensitivity of the photosensitive resin layer to the exposure light is within the above range, excessive reaction in the unexposed area near the boundary between the exposed and unexposed areas is suppressed, and the exposure time can be easily set within an appropriate range, which tends to improve the transparency and resolution between resist patterns.

[0147] The sensitivity of the photosensitive resin layer to exposure light can be controlled to the above range by appropriately adjusting the type and content of (C) photopolymerization initiator, (D) polymerization inhibitor, (E) sensitizer, and (F) hydrogen donor. The methods for controlling the sensitivity of the photosensitive resin layer to exposure light are shown in the examples described below.

[0148] (Solvent) The photosensitive resin layer is formed by applying a coating solution, in which the photosensitive resin composition is dispersed in a solvent, to a temporary support or to any intermediate layer applied to the temporary support, and then drying it. The resulting photosensitive resin layer may contain residual solvent.

[0149] Examples of solvents include ketones, such as methyl ethyl ketone; alcohols, such as methanol, ethanol, and isopropanol; and toluene. Acetone is also an example of a solvent. The solvent content remaining in the photosensitive resin layer is preferably 5.0% by mass or less, and more preferably 3.0% by mass or less, relative to the solid content of the photosensitive resin composition.

[0150] [Second Embodiment] [Photosensitive Resin Laminate] A photosensitive resin laminate according to one embodiment of the present disclosure comprises a temporary support layer and a photosensitive resin layer containing a photosensitive resin composition, wherein the photosensitive resin composition comprises the following components: (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator. The photosensitive resin composition may further contain components other than components (A) to (C), such as (D) a polymerization inhibitor, (E) a hydrogen donor, antioxidant, stabilizer, base dye, solvent, etc., and each component and / or the raw material of each component may be used alone or two or more may be used in combination.

[0151] In the photosensitive resin laminate according to this disclosure, the average thickness of the photosensitive resin layer is 20 μm or less, (A) the binder polymer is composed of three or more repeating units, (C) the content of the photopolymerization initiator is 5.0 parts by mass or more per 100 parts by mass of the total amount of (A) the binder polymer and (B) the photopolymerizable compound, and the following formulas 1 and 2: MA occupancy = Σ{W ｉ ×R ｉ / (R ｅq ) ｉ}...(Formula 1) AO occupancy rate=Σ{W ｉ ×A ｉ / ( A ｅq ) ｉ}...(Formula 2) {In the formula, W is the weight % of one component (B) relative to the total weight of the photopolymerizable compound having an ethylenically unsaturated bond (B), R is the molecular weight of the (meth)acryloyl group in the photopolymerizable compound having an ethylenically unsaturated bond (B), R ｅｑ A is the equivalent amount of the (meth)acryloyl group, and A is the molecular weight of the structure represented by the following chemical formula 1 in a photopolymerizable compound having an ethylenically unsaturated bond: -AO- (Chemical formula 1) (wherein A is an alkylene group), and A ｅｑ The MA occupancy is 18.0% or more and the AO occupancy is 40.0% or more, calculated by (B) = the equivalent weight of the structure represented by chemical formula 1, and i is a number assigned to each type of photopolymerizable compound having an ethylenically unsaturated bond.

[0152] While this disclosure does not wish to be bound by theory, the MA occupancy calculated by Equation 1 above can be correlated with the occupancy of (meth)acryloyl groups in the photopolymerizable compound having an ethylenically unsaturated bond (B), and it is conceivable that increasing the MA occupancy in component (B) to 18.0% or more will increase the crosslinking density and improve adhesion. From this viewpoint, it is preferable that the MA occupancy calculated by Equation 1 above be 23.0% or more in order to further improve crosslinking density and adhesion. The upper limit of the MA occupancy is not particularly limited, but for example, it may be less than 60.0% or less than 50.0%. Furthermore, the AO occupancy calculated by Equation 2 above can be correlated with the occupancy of alkylene oxides such as ethylene oxide and propylene oxide in the photopolymerizable compound having an ethylenically unsaturated bond (B), and it is conceivable that increasing the AO occupancy in component (B) to 40.0% or more will improve the developability and developer penetration into the unexposed areas of the photosensitive resin layer, thereby improving resolution. There is no particular upper limit to the AO occupancy rate, but it may be, for example, less than 100.0%, less than 90.0%, less than 85.0%, etc.

[0153] A preferred embodiment of the photosensitive resin laminate in the second embodiment is as described in the first embodiment of the photosensitive resin laminate.

[0154] [Method for producing a photosensitive resin laminate] A further aspect of the present disclosure is a method for producing a photosensitive resin laminate. Such a method may include, for example, the following steps: applying a photosensitive resin composition containing the above-mentioned components and adjusted so that the content of component (C) is 5.0 parts by mass or more per 100 parts by mass of the total amount of components (A) and (B) onto a temporary support to form a coating film; and drying the coating film to obtain a photosensitive resin layer.

[0155] The process of forming a coating film may include the following steps: a step of obtaining a coating solution by dissolving a photosensitive resin composition in a solvent, and a step of applying the coating solution to a temporary support. The coating solution can be prepared by mixing a photosensitive resin composition with a solvent that dissolves the composition. Examples of solvents include ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol, and isopropyl alcohol; and so on. The photosensitive resin composition and solvent may be mixed so that the viscosity of the coating solution is 500 to 4000 mPa·sec at 25°C.

[0156] A known method can be used to apply the coating liquid to the temporary support, for example, by using a bar coater or a roll coater. A coating film is obtained by applying the coating liquid to the temporary support. Drying of the coating film can be carried out using a known dryer and under known conditions (drying temperature and drying time).

[0157] Furthermore, the preferred details (composition, content, various ratios, etc.) described in the section on photosensitive resin laminates above may also be applied to the method for manufacturing photosensitive resin laminates.

[0158] <Photosensitive Element> The photosensitive element of this disclosure has a laminated structure in which a support film, an intermediate layer, and the photosensitive resin layer described above are sequentially laminated. The photosensitive resin layer may be the photosensitive resin layer of the first embodiment and / or the second embodiment. The photosensitive element may optionally be provided with a protective film.

[0159] The photosensitive element, having an intermediate layer in its laminated structure, allows for exposure after the support film has been removed, and also reduces rattle of the resist pattern's sidewalls caused by scratches or foreign matter on the support film. Furthermore, by having an intermediate layer, the photosensitive element can impart any desired functionality, such as oxygen barrier properties, to the intermediate layer, and consequently, these functionalities can be maintained even after the support film has been removed.

[0160] The laminated structure of the photosensitive element can be formed by placing an intermediate layer between a temporary support and a photosensitive resin layer in the photosensitive resin laminate described above; or by peeling the temporary support from the photosensitive resin laminate described above to remove the photosensitive resin layer, and then sequentially laminating the support film, the intermediate layer, and the photosensitive resin layer. The placement or lamination of the intermediate layer can be carried out by coating the resin composition constituting the intermediate layer onto the support or film.

[0161] As described above, the intermediate layer is preferably an oxygen barrier layer and / or a water-soluble resin layer, and more preferably a water-soluble resin layer, from the viewpoint of ensuring exposure performance and functionality even after the support film has been peeled off from the photosensitive element.

[0162] The water-soluble resin layer as an intermediate layer is given by the following general formula (I): {In the formula, R １ and R ２ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and A is -CH ２ CH ２ O-unit and / or -CH ２ CH (CH ３ It is preferable to include a compound represented by the formula (I) which contains one or more single or repeating structures including an O-unit. By including the compound represented by the above general formula (I) in the water-soluble resin, the tackiness of the intermediate layer can be reduced and the bleeding of the compound itself can be suppressed.

[0163] The water-soluble resin layer, which serves as an intermediate layer, preferably contains polyvinyl alcohol (PVA). Including PVA in the water-soluble resin constituting the water-soluble resin layer can improve oxygen barrier properties. It is more preferable that the water-soluble resin layer contains 50% to 100% by mass of PVA, based on the mass of the water-soluble resin layer. Including 50% or more by mass of PVA in the water-soluble resin layer can further improve oxygen barrier properties.

[0164] The thickness of the water-soluble resin layer as an intermediate layer is preferably 1 μm to 8 μm. By making the thickness of the water-soluble resin layer 1 μm or more, the stability of the water-soluble resin layer can be ensured after peeling off the support film such as PET film. On the other hand, by making the thickness of the water-soluble resin layer 8 μm or less, developability can be ensured.

[0165] Furthermore, the photosensitive element may be in the form of a long length, or it may be in the form of a roll in which a long length of photosensitive element is wound around a core.

[0166] The support film for the photosensitive element may have the same configuration as the temporary support for the photosensitive resin laminate described above, and / or the protective film for the photosensitive element may have the same configuration as the protective layer for the photosensitive resin laminate described above. Therefore, the preferred details (composition, content, various ratios, etc.) described in the section on the photosensitive resin laminate may also be applied to the photosensitive element and its roll.

[0167] The support film for the photosensitive element is preferably a biaxially oriented polyester film containing a fine particle-containing resin layer on at least the side opposite to the side where the intermediate layer is laminated, and it is also preferable that fine particles are present on both sides. The fine particles in the fine particle-containing resin layer may be, for example, a lubricant. Among support films such as PET, it is preferable to have a lubricant on the uncoated surface where the intermediate layer is not arranged, as this ensures the transportability of the photosensitive element.

[0168] It is preferable that the surface roughness (Rz1) of the surface on which the intermediate layer of the support film is laminated of the photosensitive element is smaller than the surface roughness (Rz2) of the surface on the opposite side of the support film from which the intermediate layer is laminated. It is preferable to make the surface roughness (Rz) of the coated surface of the support film on which the intermediate layer is arranged by coating relatively smaller, as this smooths the contact surface between the intermediate layer, which is made of PVA or the like, and the support film (e.g., PET film), thereby reducing patterning defects.

[0169] 《Method for Forming a Resist Pattern》 A further aspect of the present disclosure is a method for forming a resist pattern using the above-mentioned photosensitive resin laminate or photosensitive element. Such a method includes the following steps: a step of laminating the photosensitive resin layer of the above-mentioned photosensitive resin laminate or photosensitive element onto a substrate (lamination step); a step of exposing the photosensitive resin layer laminated on the substrate (exposure step); and a step of removing the unexposed portion of the photosensitive resin layer using an alkaline aqueous solution (development step). A resist pattern is formed by going through these steps.

[0170] [Lamination Process] In the lamination process, the photosensitive resin layer of the photosensitive resin laminate is laminated onto the substrate. Specifically, the lamination process includes: a step of exposing the photosensitive resin laminate by peeling off the protective layer from the photosensitive resin laminate or peeling off the protective film from the photosensitive element; and a step of laminating the photosensitive resin layer onto the substrate so that the exposed photosensitive resin laminate is in contact with the substrate. In the lamination process, a predetermined laminator device may be used, in which case the photosensitive resin layer may be heat-pressed onto the surface of the substrate.

[0171] Examples of substrate materials include metals and / or insulators, such as copper, stainless steel (SUS), glass, and indium tin oxide (ITO). The heating temperature during lamination is, for example, 40°C to 160°C. Heat bonding can be performed by using a laminator device equipped with rolls, or by repeatedly passing the laminate of the substrate and photosensitive resin layer through the rolls several times. Heat bonding may be performed under reduced pressure if desired. When laminating the photosensitive resin laminate onto the substrate, the laminated surface on the substrate may be smoothed as needed. From the viewpoint of optimizing the exposure process after peeling off the temporary support or support film, the substrate is preferably a metal plate or a metal-coated insulator.

[0172] [Exposure Process] In the exposure process, the photosensitive resin layer laminated on the substrate is exposed. Specifically, in the exposure process, the photosensitive resin layer is exposed using an exposure machine. Exposure can be performed before peeling off the temporary support from the photosensitive resin laminate or before peeling off the support film from the photosensitive element, or it can be performed after peeling off the temporary support or support film. In the exposure process, when exposure is performed via a photomask, the exposure amount may be determined by the illuminance of the light source and the exposure time, or it may be measured using a light meter.

[0173] In the exposure process, direct imaging exposure may be performed. In direct imaging exposure, the photosensitive resin layer is exposed by a direct writing device without using a photomask. As the light source at this time, a semiconductor laser or an ultra-high pressure mercury lamp with a wavelength of 350 to 410 nm is used. If the writing pattern is controlled by a computer, the exposure amount may be determined by the illuminance of the exposure light source and the moving speed of the substrate.

[0174] In the exposure process, the method of irradiating with exposure light is preferably at least one method selected from projection exposure, proximity exposure, contact exposure, direct imaging exposure, and electron beam direct writing, with projection exposure or direct imaging exposure being more preferred.

[0175] The exposure process may include a step of heating the substrate and the photosensitive resin layer after exposure (post-exposure heating step) after the exposure and before the development step. In this heating step, the heating temperature is preferably about 30 to about 200°C, more preferably 30 to 150°C, and even more preferably 35 to 120°C. Performing the heating step makes it easier to achieve excellent resolution and adhesion. Heating may be performed using an infrared or far-infrared heating furnace, hot air, a constant temperature bath, a hot plate, a hot air dryer, an infrared dryer, and a hot roll, etc.

[0176] The elapsed time from the exposure process to the heating process, or more precisely, the time from when exposure is completed (i.e., when exposure is stopped) to when heating begins, is preferably 10 to 600 seconds, and more preferably 20 to 300 seconds. The time from when heating begins to when heating is stopped is preferably 1 to 120 seconds, and more preferably 5 to 60 seconds.

[0177] [Development Process] In the development process, the unexposed areas of the photosensitive resin layer are removed using an alkaline aqueous solution. This yields a resist pattern. If a temporary support layer or support film is laminated on the photosensitive resin layer, the development process may be performed after removing the temporary support layer or support film.

[0178] As for alkaline aqueous solutions in developing solutions, Na ２ CO ３ _K ２ CO ３ Aqueous solutions of , and tetramethylammonium hydroxide are preferred. The alkaline aqueous solution is selected according to the properties of the photosensitive resin layer, for example, a concentration of 0.2 to 2% by mass of Na ２ CO ３ An aqueous solution is used. The developer may contain a surfactant and / or an antifoaming agent, and may also contain a small amount of organic solvent to accelerate development. In the development process, it is preferable to keep the temperature of the developer constant within the range of 20°C to 40°C.

[0179] The development process preferably includes a step of washing the substrate and resist pattern with water after development (water washing step). The water washing step makes it easier to remove any developer remaining on the substrate and resist pattern. Examples of water used for washing in the water washing step include pure water and industrial water. From the viewpoint of excellent resolution and ease of forming a highly rectangular resist pattern, a polyvalent metal salt at a concentration of 0.001 to 1% by mass may be mixed into the water for washing, according to the characteristics of the photosensitive resin layer. Examples of polyvalent metal salts include MgSO4. ４ These are some examples. In the washing process, it is preferable to keep the temperature of the washing water constant within the range of 20°C to 40°C.

[0180] The developing process may include a step of heating the substrate and the formed resist pattern (post-developing heating step) after the above-mentioned developing, or after the above-mentioned developing and washing with water. In this heating step, the heating temperature is preferably 60°C to 300°C. Performing this heating step makes it easier to improve the chemical resistance of the resist pattern. Heating may be carried out using an infrared or far-infrared heating furnace, or by hot air, etc.

[0181] Regarding the order of the steps described above, it is preferable from the viewpoint of optimizing the exposure process after peeling off the support film to perform the following steps: laminating the photosensitive element onto the surface of a metal plate or metal-coated insulator, peeling off the support film from the photosensitive element, exposing it to ultraviolet light, and then removing the unexposed areas by developing.

[0182] 《Method for Manufacturing Conductor Patterns》 A further aspect of the present disclosure is a method for manufacturing a conductor pattern using the above-mentioned photosensitive resin laminate or photosensitive element. Such a method includes, for example, the following steps: a step of obtaining a substrate on which a resist pattern is formed (a step of manufacturing a substrate with a resist pattern); a step of performing an etching or plating treatment on the substrate on which the resist pattern is formed and forming a conductor pattern (a step of forming a conductor pattern); and a step of peeling the resist pattern from the substrate on which the conductor pattern is formed (a peeling step).

[0183] [Process for manufacturing a substrate with a resist pattern] In the process for manufacturing a substrate with a resist pattern, a substrate on which a resist pattern has been formed is obtained. In this process, the section on "Method for forming a resist pattern" above can be referred to, thereby obtaining a substrate with a resist pattern.

[0184] [Conductor Pattern Formation Process] In the conductor pattern formation process, an etching or plating process is performed on the substrate on which the resist pattern has been formed, and then a conductor pattern is formed. Specifically, in the conductor pattern formation process, a conductor pattern is formed on the surface (e.g., copper surface) of the substrate (as described above, for example, a metal plate and a metal film insulating plate) exposed by development, using a known etching method or plating method.

[0185] Etching is performed, for example, by spraying an etching solution onto the resist pattern and the substrate surface. Examples of etching methods include acid etching and alkaline etching. Examples of etching solutions include aqueous hydrochloric acid solution, aqueous ferric chloride solution, or mixtures thereof.

[0186] Plating is performed by developing (removing) the exposed substrate portion according to a known plating method, and then applying metal plating (for example, metal plating with copper sulfate plating solution) or solder plating to that portion.

[0187] [Peeling process] In the peeling process, the resist pattern is peeled off from the substrate on which the conductor pattern is formed. By removing the resist pattern from the substrate, a wiring board (e.g., a printed circuit board) having the desired conductor pattern is obtained.

[0188] In the stripping process, the resist pattern is removed from the substrate using an aqueous solution (stripping solution) that is more alkaline than the developer. Examples of the stripping solution include an aqueous solution of NaOH or KOH with a concentration of 2 to 5% by mass, and an aqueous solution of an organic amine. The stripping solution may contain a small amount of water-soluble solvent. Examples of water-soluble solvents include alcohol. The temperature of the stripping solution in the stripping process is preferably in the range of 40°C to 70°C. The stripping time may be set as appropriate.

[0189] This disclosure is not limited to the embodiments described above, and can be implemented in various ways within the scope of its gist.

[0190] The embodiments of this disclosure will be described below with reference to examples and comparative examples. However, this disclosure is not limited to the following examples. With respect to the examples and comparative examples, various manufacturing, measurement, and evaluation methods were carried out as follows.

[0191] [Preparation of photosensitive resin composition solutions: Compositions 1-94, Compositions B1-2, Compositions C1-5] [Synthesis of component (A)] The monomers (copolymer components) in component A shown in Table 1 were mixed with 3.0 parts by mass of azobisisobutyronitrile in the amounts (unit: parts by mass) shown in Table 1 to obtain solution (a). A mixture of 200 g of methyl ethyl ketone and 100 g of ethanol was placed in a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel, and nitrogen gas inlet tube. The mixture was stirred while blowing nitrogen gas into the flask, and the temperature of the mixture in the flask was raised to 80°C. 300 g of solution (a) was added to the mixture in the flask dropwise over 4 hours at a constant dropping rate, and then stirred at 80°C for 2 hours.

[0192] Next, solution (b) was obtained by dissolving 0.5 parts by mass of azobisisobutyronitrile in 50 parts by mass of a mixture of 30 parts by mass of methyl ethyl ketone and 20 parts by mass of ethanol. 50 g of solution (b) was added dropwise to the mixture in the flask over 10 minutes at a constant dropping rate, and then stirred at 80°C for 3 hours. The mixture in the flask was then further heated to 90°C over 30 minutes, and then kept at 90°C for 2 hours. After that, stirring was stopped, and the mixture in the flask was cooled to room temperature (25°C). This yielded solutions containing components (A-1) to (A-8) as alkali-soluble polymers, respectively.

[0193] [Weight-Average Molecular Weight] For each solution, the weight-average molecular weight of component (A) was derived by using gel permeation chromatography (GPC) and converting it using a calibration curve for standard polystyrene. The GPC conditions are as follows: (GPC conditions) Pump: JASCO PU-980 Columns: A total of four columns as follows: Shodex KF-807 x 1, KF-806M x 2, KF-802.5 x 1 Eluent: Tetrahydrofuran Measurement temperature: 40°C Flow rate: 2.05 mL / min Detector: JASCO RI-1530

[0194] A coating solution (a prepared solution for a photosensitive resin composition) was obtained by stirring and mixing the components shown in the table below (the numbers for each component indicate the amount of solids (parts by mass)) with ethanol measured to a solid content concentration of 60%, so that the amount of each component as solids matches the values ​​shown in the table below.

[0195] [Preparation of Photosensitive Resin Laminates: Examples 1-94, Reference Examples 1-2, Comparative Examples 1-5] A 16 μm thick polyethylene terephthalate film (Toray Industries, Ltd., "16FS30") was used as the support film. The above coating solution was applied to its surface using a bar coater according to the coating conditions described in Tables 2 and 3, and then dried in a 95°C dryer for 1.5 minutes. This formed a photosensitive resin layer on the support film, obtaining a photosensitive resin laminate. In this example, a 33 μm thick polyethylene film (Tamapoly Co., Ltd., product name "GF-858"), a 22 μm thick polyester film with a release layer (Toyobo Film Solutions Co., Ltd., product name "X2NY"), or an 18 μm thick biaxially oriented polypropylene film (Oji F-Tex Co., Ltd., product name "E-200C3") was laminated on the side opposite the support film of the photosensitive resin layer as a protective film, and this was treated as the photosensitive resin laminate.

[0196] Here, Example Group 1 consists of Examples 1 to 31, Example Group 2 consists of Examples 32 to 58, and Example Group 3 consists of Examples 59 to 94. Example Group 1 is a group of examples that mainly evaluate the effects of (A) alkali-soluble polymers and (B) compounds having ethylenically unsaturated bonds. Example Groups 2 and 3 are groups of examples that mainly evaluate the effects of (C) photopolymerization initiators, (D) polymerization inhibitors, (E) sensitizers, and related optical properties. For Example Groups 1 and 2, as well as the reference examples and comparative examples, the image quality evaluation described below was performed. For Example Group 3, in addition to the image quality evaluation described below, the photosensitivity evaluation described below was performed.

[0197] [Formation of resist pattern] <Surface preparation of substrate> A copper-clad laminate with a total thickness of 0.4 mm was prepared by laminating rolled copper foil with a thickness of 18 μm. Then, this surface was treated with 10 mass% H ２ SO ４The copper-clad laminate was washed with an aqueous solution, and then with pure water. After washing, the copper-clad laminate was preheated to 50°C.

[0198] <Lamination> While peeling off the protective film from the photosensitive resin laminate, the copper-clad laminate, preheated to 50°C, was laminated using a hot roll laminator (Taisei Laminator Co., Ltd., VA-700SH) at a roll temperature of 105°C so that the photosensitive resin layer was in contact with the surface of the copper-clad laminate. This obtained an evaluation substrate. The air pressure during lamination was set to 0.35 MPa and the lamination speed was set to 1.5 m / min.

[0199] <Exposure> After lamination, the substrate was exposed directly using a direct imaging (DI) exposure machine (FDi-3, manufactured by Oak Manufacturing Co., Ltd.) with a predetermined drawing pattern for direct imaging exposure. Exposure was performed at the optimal exposure level (the exposure level at which the maximum number of remaining film layers after exposure using a 41-step step tablet as a mask and subsequent development was 15 layers).

[0200] <Heating> Two minutes after exposure, the substrate was heated for 30 seconds in a forced-air constant-temperature incubator (Yamato Scientific Co., Ltd., DKM600) set to 70°C.

[0201] <Developing> The support film was peeled off the substrate. Then, using an alkaline developer (Fuji Kiko Co., Ltd., dry film developer), 1% by mass of Na was used at 30°C. ２ CO ３ An aqueous solution was sprayed onto the photosensitive resin layer for a predetermined period of time, thereby performing development. The spraying time was set to twice the minimum development time, and the washing time after development (water rinsing by spraying) was also set to twice the minimum development time. In this case, the shortest time required for the unexposed portion of the photosensitive resin layer to completely dissolve was treated as the minimum development time. From the above, a substrate with a resist pattern (evaluation substrate) was obtained.

[0202] [Fabrication of Conductor Patterns] Using the evaluation substrate obtained above, a conductor pattern was fabricated by a conventional method.

[0203] [Other Examples B1-B23, C1-C23, D1-D23] Except for changing the items listed in Tables 2 and 3 as shown in Table 4, a photosensitive resin laminate and a photosensitive resin laminate roll were manufactured based on the same method as in Example 1, and then a resist pattern was formed and a conductor pattern was manufactured (Examples B1-B23, C1-C23, D1-D23).

[0204] [Preparation of photosensitive resin laminates with water-soluble resin layer: Examples 95-118] The water-soluble resin compositions for forming the water-soluble resin layer shown in Table 5 were added to water heated to 90°C, stirred and mixed well, and cooled to room temperature. Then, the mixture was uniformly applied to the side with the finer surface roughness of a 16 μm thick polyethylene terephthalate film (film 1, "16FS30" manufactured by Toray Industries, Inc., or film 2, "A-1517" manufactured by Toyobo Industries Ltd.) using a blade coater, and dried in a 95°C dryer for 10 minutes to form a uniform water-soluble resin layer on the support film. The thickness of the water-soluble resin layer was adjusted to 1 μm, 3 μm, 5 μm, or 8 μm by adjusting the blade gap during application. The photosensitive resin compositions for forming the photosensitive resin layer shown in Table 5 were uniformly applied to the water-soluble resin layer laminated on the support film using a blade coater, and dried at 95°C for 1.5 minutes to form a uniform photosensitive resin layer on the water-soluble resin layer. Next, a photosensitive element was obtained by laminating a 33 μm thick polyethylene film (Tamapoly Co., Ltd., GF-858), a 22 μm thick polyester film with a release layer (Toyobo Film Solutions Co., Ltd., product name "X2NY"), or an 18 μm thick biaxially oriented polypropylene film (Oji F-Tex Co., Ltd., product name "E-200C3") as a protective film onto the surface of the photosensitive resin layer. In some examples, a laminate was obtained in the same manner as above, except that film 3 (Toray Industries, Inc., "16FB40") was used instead of film 1 and film 2, or the photosensitive resin layer was laminated on a support film without using a water-soluble resin layer.

[0205] The configuration having a water-soluble resin layer (intermediate layer) as described in Table 5 was also tested not only for composition 1 described in Table 5, but also for compositions 2-8 and 28-34, and similar results were obtained.

[0206] [Evaluation and Measurement] [Absorbance at 365 nm / μm, Absorbance at 402 nm / μm] After peeling off the protective film of the photosensitive resin laminate, the absorbance of the photosensitive resin layer at wavelengths of 365 nm and 402 nm was measured using a U-3010 spectrophotometer (manufactured by Hitachi High-Technologies Corporation) with a 16 μm thick polyethylene terephthalate film (support film, Toray Industries, Inc. "16FS30") as a reference. The absorbance at 365 nm / μm and the absorbance at 402 nm / μm were derived by dividing the measured absorbance by the thickness of the photosensitive resin layer. The measurement was performed with a slit of 4 nm and a scan speed of 600 nm / min.

[0207] [Mn (Number-Average Molecular Weight)] For each solution, the number-average molecular weight of component (B) was derived by using gel permeation chromatography (GPC) and converting it using a calibration curve for standard polystyrene. The GPC conditions are as follows: (GPC conditions) Pump: JASCO PU-1580 Columns: Two columns in total, Shodex KF-401HQ / KF-402HQ Eluent: Tetrahydrofuran Measurement temperature: 40°C Flow rate: 1.05 mL / min Detector: JASCO RI-1530

[0208] [MA occupancy rate] R ｅｑ The MA occupancy is calculated using the mass and number-average molecular weight of the sample as follows: (Total mass parts of monomers used in synthesis) / (Number of moles of methacrylate or acrylic acid ester used in synthesis) Using these values, MA occupancy = Σ{W ｉ ×R ｉ / (R ｅｑ ) ｉ We sought}.

[0209] [AO occupancy rate, EOPO occupancy rate] A ｅｑ This is calculated using the mass and number-average molecular weight of the sample as follows: (Total mass parts of monomers used in synthesis) / (Number of moles of chemical formula 1 in monomers used in synthesis) If only ethylene oxide (chemical formula 2) and propylene oxide (chemical formula 3) are present in A, then A is E and P, A ｅｑ is E ｅｑ and Pｅｑ This corresponds to: Using these values, AO occupancy = Σ{W} ｉ ×A ｉ / ( A ｅｑ ) ｉ}, and EOPO occupancy rate = Σ[{W ｉ {E ｉ / (E ｅｑ ) ｉ +P ｉ / (P ｅｑ ) ｉ We sought}].

[0210] [Light Sensitivity] When directly exposed using a direct imaging (DI) exposure machine (FDi-3, manufactured by Oak Manufacturing Co., Ltd.) with a predetermined drawing pattern for direct imaging exposure, the optimal exposure amount was defined as the amount at which the maximum number of remaining film stages after exposure using a 41-step step tablet as a mask and subsequent development was 15 stages. This optimal exposure amount was defined as the value of the light sensitivity.

[0211] [Image Quality (including Resolution)] Evaluation was performed using a drawing pattern where the line width (L) / space width (S) is x / x {x = 1 to 20 (varying at 1 μm intervals)} (unit: μm). That is, a resist pattern was formed by exposure with the optimal exposure amount, followed by the heating and developing processes described above.

[0212] Figure 1 is a plan view showing an example of a drawing pattern configuration. In the figure, in the drawing area 100, the exposed area is indicated by reference numeral 10, and the unexposed area (shaded area) is indicated by reference numeral 1. The unexposed area 1 has a predetermined width and extends in the X direction, and multiple such unexposed areas 1 are arranged in the width direction (Y direction) at predetermined intervals. Theoretically, by exposing the photosensitive resin layer based on the drawing pattern in Figure 1, it is expected that a resist pattern with L / S corresponding to the width of the unexposed area 1 (S: space) and the width of the exposed area 10 (L: line) will be formed.

[0213] When the obtained resist pattern was observed with an optical microscope at a magnification of 100x, the minimum line width at which the line portions (exposed areas) did not meander or break, and the space portions (unexposed areas) were removed without residue, was determined as the "resolution line width (unit: μm)". A smaller value indicates better resolution.

[0214] [Image Quality (including Adhesion)] Evaluation was performed using a drawing pattern where the line width (L) / space width (S) is x / 3x {x = 1 to 20 (varying at 1 μm intervals)} (unit: μm). That is, a resist pattern was formed by exposure with the optimal exposure amount, followed by the heating and developing processes described above.

[0215] Figure 2 is a plan view showing an example of a drawing pattern configuration. In the figure, in the drawing area 100A, the exposed area is indicated by reference numeral 10, and the unexposed area (shaded area) is indicated by reference numeral 1. In the area 100A shown in Figure 2, the L / S value is different from that of the area 100 shown in Figure 1. Based on the drawing pattern in Figure 2, it is theoretically expected that a resist pattern with an L / S value corresponding to the width of the unexposed area 1 (S: space) and the width of the exposed area 10 (L: line) will be formed.

[0216] When the obtained resist pattern was observed with an optical microscope at 100x magnification, the minimum line width at which the line portions (exposed areas) were formed without meandering or chipping was determined as the "adhesion line width (unit: μm)". A smaller value indicates better adhesion.

[0217] [Image Quality (particularly, transparency)] Evaluation was performed using a drawing pattern where the line width (L) / space width (S) is 3x / x {x = 1 to 20 (varying at 1 μm intervals)} (unit: μm). That is, a resist pattern was formed by exposure with the optimal exposure amount, followed by the heating and developing processes described above.

[0218] Figure 3 is a plan view showing an example of a drawing pattern configuration. In the figure, in the drawing area 100B, the exposed area is indicated by reference numeral 10, and the unexposed area (shaded area) is indicated by reference numeral 1. The unexposed area 1 has a predetermined width and extends in the x direction, and multiple such unexposed areas 1 are arranged in the width direction (y direction) at predetermined intervals. Theoretically, by exposing the photosensitive resin layer based on the drawing pattern in Figure 3, it is expected that a resist pattern with L / S corresponding to the width of the unexposed area 1 (S: space) and the width of the exposed area 10 (L: line) will be formed.

[0219] When the obtained resist pattern was observed under an optical microscope at 100x magnification, the minimum line width at which the empty areas (unexposed areas) were completely removed was defined as the "penetration line width (unit: μm)". A smaller value indicates better penetration.

[0220] [Image Quality] Based on the evaluation results of image quality related to resolution, adhesion, and permeability, rankings were made according to the following criteria: Pass: The resolution line width and adhesion line width are 7 μm or less, and the permeability line width is 4 μm or less, OR the resolution line width and adhesion line width are 8 μm or less, and the permeability line width is 3 μm or less. Fail: The above pass conditions are not met.

[0221] [Compatibility of Water-Soluble Resin Layer] After thoroughly stirring the aqueous solution of the water-soluble resin composition for forming the water-soluble resin layer, the uniform compatibility of the water-soluble resin composition was observed and ranked as follows: ○: The water-soluble resin composition is uniformly compatible and colorless and transparent. △: The water-soluble resin composition is cloudy. ×: The water-soluble resin composition has separated into two layers.

[0222] [Laminated Air] A copper alloy substrate with a thickness of 1.6 mm was prepared. Then, this surface was treated with 10 mass% H ２ SO ４The copper-clad laminate was washed with an aqueous solution, and then with pure water. After washing, the copper-clad laminate was preheated to 50°C. Next, the photosensitive resin laminate was exposed from the support film side using a scattered light exposure machine (Oak Co., Ltd., HMW-801KB). The exposure dose was 10 mJ / cm². ２ The protective film was peeled off the photosensitive resin laminate after exposure, and the photosensitive resin layer was laminated to a copper-clad laminate preheated to 50°C using a hot roll laminator (Taisei Laminator Co., Ltd., VA-700SH) at a roll temperature of 105°C, so that the photosensitive resin layer was in contact with the surface of the copper-clad laminate. This obtained an evaluation substrate. The air pressure during lamination was set to 0.35 MPa, and the lamination speed was set to 3.0 m / min. Next, the laminated substrate was exposed again with a scattered light exposure machine. The exposure amount was 60 mJ / cm². ２ The above procedure was followed to obtain a substrate for evaluating Lamia. The above substrate was 40 cm². ２ The area was observed using an optical microscope, and the number of laminated air particles with a diameter of 5 μm or larger was ranked as follows: ○: 2 or fewer laminated air particles; △: 3 or more laminated air particles.

[0223] [Developability] A copper-clad laminate with a total thickness of 0.4 mm was prepared by laminating rolled copper foil with a thickness of 18 μm. Then, this surface was subjected to 10 mass% H ２ SO ４ The copper-clad laminate was washed with an aqueous solution, and then with pure water. After washing, the copper-clad laminate was preheated to 50°C.

[0224] Next, while peeling the protective film from the photosensitive resin laminate, the copper-clad laminate, preheated to 50°C, was laminated using a hot roll laminator (Taisei Laminator Co., Ltd., VA-700SH) at a roll temperature of 105°C, so that the photosensitive resin layer was in contact with the surface of the copper-clad laminate. The air pressure during lamination was set to 0.35 MPa and the lamination speed was set to 1.5 m / min.

[0225] After removing the support film from the laminated substrate, it was directly exposed using a direct imaging (DI) exposure machine (FDi-3, manufactured by Oak Manufacturing Co., Ltd.) with a predetermined drawing pattern for direct imaging exposure. Exposure was performed at the optimal exposure level (the exposure level at which the maximum number of remaining film layers after exposure using a 41-step step tablet as a mask and subsequent development was 15 layers). However, in some cases, exposure was performed without removing the support film.

[0226] Two minutes after exposure, the substrate was heated for 30 seconds in a forced-air constant-temperature incubator (Yamato Scientific Co., Ltd., DKM600) set to 70°C.

[0227] Subsequently, using an alkaline developing machine (manufactured by Fuji Kiko Co., Ltd., for dry film), 1% by mass of Na at 30°C was used. ２ CO ３ An aqueous solution was sprayed onto the photosensitive resin layer for a predetermined time, thereby performing development. The spraying time was set to twice the minimum development time, and the washing time after development (water rinsing by spraying) was also set to twice the minimum development time. In this case, the shortest time required for the unexposed portion of the photosensitive resin layer to completely dissolve was treated as the minimum development time. From the above, a substrate with a resist pattern (evaluation substrate) was obtained. Based on the minimum development time, the substrates were ranked as follows: ○: Minimum development time delay is less than +5 seconds compared to the case without an intermediate layer △: Minimum development time delay is +5 seconds or more but less than +10 seconds compared to the case without an intermediate layer ×: Minimum development time delay is +10 seconds or more compared to the case without an intermediate layer

[0228] [Resist Shape] The shape of the 10 μm line of the cured resist pattern obtained by the developability evaluation procedure was ranked as follows: ○: The formed cured resist pattern is rectangular. △: The formed cured resist pattern is not rectangular. ×: The formed cured resist pattern is not rectangular and also shows film thinning.

[0229] [Resist Sidewall Irregularity] The resist sidewall shape of the 10 μm line of the cured resist pattern obtained by the developability evaluation procedure was ranked as follows: ◎: There is almost no irregularity in the formed resist sidewall. ○: There is slight irregularity in the formed resist sidewall. △: There is irregularity in some parts of the formed resist sidewall. ×: There is irregularity everywhere in the formed resist sidewall.

[0230] [Exposure Defects] The 10 μm line of the cured resist pattern obtained by the developability evaluation procedure was observed and ranked as follows: ○: The formed resist pattern has almost no defects due to exposure defects. △: The formed resist pattern has a few defects due to exposure defects. ×: The formed resist pattern has defects due to exposure defects in some places.

[0231] [Water-soluble resin layer stability] The polyethylene terephthalate film, which is the support film for the photosensitive element laminated to the substrate, was peeled off, exposed using a chromium glass photomask after 30 minutes, and developed. The depressions on the resist surface of the 10 μm line of the obtained cured resist pattern were ranked as follows: ○: There are almost no depressions on the formed resist surface. △: There are slight depressions on the formed resist surface. ×: There are depressions in some places on the formed resist surface.

[0232] [Post-Storage Support Film Peelability] A photosensitive element was laminated to a substrate and left for 72 hours in an environment of 23°C and 50% humidity. The peeling behavior of the polyethylene terephthalate film, which served as the support film, was then ranked as follows: ○: Only the polyethylene terephthalate film peeled off. △: Some of the water-soluble resin layer adhered to the polyethylene terephthalate film and peeled off together. ×: The polyethylene terephthalate film and the water-soluble resin layer peeled off together (peeling occurred between the water-soluble resin layer and the photosensitive resin layer).

[0233] The results regarding the above are shown in the table below.

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246]

[0247]

[0248]

[0249]

[0250]

[0251]

[0252]

[0253]

[0254]

[0255]

[0256]

[0257]

[0258] As can be seen from the table above, it was confirmed that good image quality can be achieved in Examples 1 to 94. Furthermore, Examples 95 to 118 show that by using the photosensitive resin laminate with a water-soluble resin layer of this disclosure, a resist pattern with reduced rattle of the resist sidewall can be formed. Moreover, it is found that by including the compound represented by the above general formula (I) in the water-soluble resin layer, the peelability of the support film after storage can be improved, and the compatibility of the water-soluble resin layer can be improved. It was also confirmed that similar effects can be achieved in photosensitive resin laminates with a water-soluble resin layer to which compositions 2 to 88 other than composition 1 used in Examples 95 to 118 are applied.

[0259] According to this disclosure, it is possible to provide a photosensitive resin laminate capable of realizing a resist pattern with good image quality. Furthermore, it is possible to provide a photosensitive resin laminate with a water-soluble resin layer capable of forming a resist pattern with reduced rattle of the resist sidewalls. Such photosensitive resin laminates, and photosensitive resin laminates with a water-soluble resin layer, can be suitably used in precision metal foil processing such as the manufacture of printed circuit boards, flexible printed circuit boards, lead frames, or metal masks; the manufacture of semiconductor packages such as ball grid arrays (BGAs) or chip-size packages (CSPs); the manufacture of tape substrates such as TABs or COFs; the manufacture of semiconductor bumps; and the manufacture of indium tin oxide (ITO) electrodes or address electrodes, electromagnetic shields, and the like.

[0260] 1: Light-blocking area 10: Transmitting area 100, 100A, 100B: Areas L: Line S: Space

Claims

1. A photosensitive resin laminate having a temporary support and a photosensitive resin layer on the temporary support, wherein the average thickness of the photosensitive resin layer is 20 μm or less, the photosensitive resin layer comprises a photosensitive resin composition containing (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, and (D) a polymerization inhibitor, the content of the (C) photopolymerization initiator is 5.0 parts by mass or more per 100 parts by mass of the total amount of the (A) binder polymer and the (B) photopolymerizable compound having an ethylenically unsaturated bond, and the content of the (D) polymerization inhibitor comprises a polymerization inhibitor having two or more phenolic hydroxyl groups, and the content is 0.025 parts by mass or more per 100 parts by mass of the total amount of the (A) binder polymer and the (B) photopolymerizable compound having an ethylenically unsaturated bond.

2. The photosensitive resin laminate according to claim 1, wherein the absorbance of either 365 nm or 402 nm light per 1 μm thickness of the photosensitive resin layer is greater than 0.010 and less than or equal to 0.

040.

3. The photosensitive resin laminate according to claim 1, wherein the absorbance for light at wavelengths of 365 nm and 402 nm per 1 μm thickness of the photosensitive resin layer is greater than 0.

014.

4. The photosensitive resin laminate according to claim 1, wherein the (C) photopolymerization initiator contains a biimidazole compound, and the content of the biimidazole compound is 5.0 parts by mass or more with respect to 100 parts by mass of the total amount of the (A) binder polymer and the (B) photopolymerizable compound having an ethylenically unsaturated bond.

5. (E) The photosensitive resin laminate according to claim 1, further comprising at least one selected from the group consisting of dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, and coumarin compounds as a sensitizer.

6. The photosensitive resin laminate according to claim 5, wherein the product of the total content of the (E) sensitizer per 100 parts by mass of the total amount of the (A) binder polymer and the (B) photopolymerizable compound having an ethylenically unsaturated bond and the total content of the (D) polymerization inhibitor per 100 parts by mass of the total amount of the (A) binder polymer and the (B) photopolymerizable compound having an ethylenically unsaturated bond is 0.007 or more.

7. The photosensitive resin laminate according to claim 1, wherein the polymerization inhibitor having two or more phenolic hydroxyl groups is a compound having an aromatic ring in which two or more hydrogen atoms are substituted with phenolic hydroxyl groups.

8. The photosensitive resin laminate according to claim 1, wherein the polymerization inhibitor having two or more phenolic hydroxyl groups is at least one of tert-butylcatechol and gallic acid.

9. The photosensitive resin laminate according to claim 1, wherein the (A) binder polymer has structural units derived from a polymerizable monomer containing a hydroxyalkyl group.

10. The photosensitive resin laminate according to claim 1, wherein the photosensitive resin layer further contains (F) a hydrogen donor, and the mass ratio of the content of (F) the hydrogen donor to the content of (C) the photopolymerization initiator (content of (F) the hydrogen donor / content of (C) the photopolymerization initiator) is 0.07 or more.

11. The photosensitive resin laminate according to claim 1, wherein the absolute value of the difference between the absorbance of light at a wavelength of 365 nm and the absorbance of light at a wavelength of 402 nm per 1 μm of thickness of the photosensitive resin composition is 0.018 or less.

12. In the photosensitive resin layer, the following formula 1: MA occupancy = Σ{W} ｉ ×R / (R ｅｑ ) ｉ } ｉ ... (Formula 1) {wherein W is the weight % of one component (B) relative to the total weight of the photopolymerizable compound having an ethylenically unsaturated bond (B), R is the molecular weight of the (meth)acryloyl group in the photopolymerizable compound having an ethylenically unsaturated bond (B), R ｅｑ The photosensitive resin laminate according to claim 1, wherein the MA occupancy calculated by} is 18.0% or more, where i is the equivalent amount of (meth)acryloyl groups, and i is the total number of types of photopolymerizable compounds having ethylenically unsaturated bonds.

13. The photosensitive resin laminate according to claim 12, wherein the MA occupancy rate calculated by formula 1 is 23.0% or more.

14. In the photosensitive resin layer, further, the following formula 2: AO occupancy = Σ{W ｉ ×A / (A ｅｑ ) ｉ}... (Formula 2) {In the formula, W is the weight percentage occupied by one kind of component (B) with respect to the total weight of the photopolymerizable compound having an ethylenically unsaturated bond, A is the following chemical formula 1 with respect to the total weight of the photopolymerizable compound having an ethylenically unsaturated bond: -AO- (Chemical formula 1) (wherein A is an alkylene group), and it is the molecular weight of the structure represented by A ｅｑ is the equivalent of the structure represented by Chemical formula 1, and i is the total number of types of the photopolymerizable compound having an ethylenically unsaturated bond.}, the photosensitive resin laminate according to claim 12, wherein the AO occupancy calculated by this formula is 40.0% or more.

15. The photosensitive resin laminate according to claim 12, wherein the content of the photopolymerizable compound having an ethylenically unsaturated bond (B) is 40% by mass or more, wherein the compound having four or more (meth)acryloyl groups in one molecule is 40% by mass or more.

16. The photosensitive resin laminate according to claim 12, wherein the (B) photopolymerizable compound having an ethylenically unsaturated bond contains a compound having five or more (meth)acryloyl groups in one molecule.

17. The photosensitive resin laminate according to claim 12, wherein the (B) photopolymerizable compound having an ethylenically unsaturated bond contains a compound having a structure represented by the following chemical formula 3. -C ３ H ６ O- (chemical formula 3) 18. The photosensitive resin laminate according to claim 1, wherein the acid value of the binder polymer (A) is 155 mg KOH / g or less.

19. The photosensitive resin laminate according to claim 1, wherein the (A) binder polymer has all of the following constituent units derived from (A-1) to (A-3): (A-1) methacrylic acid and / or acrylic acid; (A-2) styrene and / or styrene derivatives; (A-3) compounds that do not fall under (A-1) and (A-2); 20. The photosensitive resin laminate according to claim 19, wherein the proportions of the constituent units derived from (A-1), (A-2), and (A-3) to the total mass of the binder polymer (A) are 10 to 30% by mass, 20 to 60% by mass, and 20 to 60% by mass, respectively.

21. The photosensitive resin laminate according to claim 1, wherein the photosensitive resin layer further contains (F) a hydrogen donor, and the mass ratio of the content of (F) the hydrogen donor to the content of (C) the photopolymerization initiator (content of (F) the hydrogen donor / content of (C) the photopolymerization initiator) is 0.13 or more.

22. The photosensitive resin laminate according to claim 1, wherein the photosensitive resin layer further contains (F) a hydrogen donor, and the mass ratio of the content of (F) the hydrogen donor to the content of (C) the photopolymerization initiator (content of (F) the hydrogen donor / content of (C) the photopolymerization initiator) is 0.25 or more.

23. A photosensitive element having a laminated structure in which a support film, an intermediate layer, and the photosensitive resin layer of the photosensitive resin laminate according to any one of claims 1 to 22 are sequentially laminated.

24. The intermediate layer is a water-soluble resin layer, and the water-soluble resin layer is the following general formula (I): {In the formula, R １ and R ２ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and A is -CH ２ CH ２ O-unit and / or -CH ２ CH (CH ３ The photosensitive element according to claim 23, comprising a compound represented by {} which represents one or more individual or repeating structures including an O-unit.

25. The photosensitive element according to claim 24, wherein the water-soluble resin layer contains polyvinyl alcohol.

26. The photosensitive element according to claim 23, wherein the support film is a biaxially oriented polyester film containing a resin layer containing fine particles on at least the side opposite to the side on which the intermediate layer is laminated.

27. The photosensitive element according to claim 23, wherein the surface roughness (Rz1) of the surface on which the intermediate layer of the support film is laminated is smaller than the surface roughness (Rz2) of the surface opposite to the surface on which the intermediate layer is laminated.

28. The photosensitive element according to claim 24, wherein the water-soluble resin layer contains 50% to 100% by mass of polyvinyl alcohol based on the mass of the water-soluble resin layer.

29. The photosensitive element according to claim 24, wherein the thickness of the water-soluble resin layer is 1 μm to 8 μm.

30. A method for forming a resist pattern, comprising laminating the photosensitive element described in claim 24 onto the surface of a metal plate or a metal-coated insulator, peeling off the support film, exposing it to ultraviolet light, and then removing the unexposed areas by development.

31. A method for manufacturing a conductive pattern, comprising etching or plating a substrate on which a resist pattern is formed by the method described in claim 30.

32. The photosensitive resin laminate according to claim 1, wherein the photosensitive resin laminate further includes a protective film, and the protective film is a polyester film with a release layer.

33. The photosensitive resin laminate according to claim 1, wherein the photosensitive resin laminate further includes a protective film, and the protective film is a biaxially oriented polypropylene film.

Images