Photosensitive resin laminate, and producing method thereof

Abstract

To provide a photosensitive resin laminate capable of realizing a resist pattern satisfying characteristics required particularly recently in a resist pattern and capable of securing quality stability in time.SOLUTION: A photosensitive resin laminate comprises a temporary support layer, a photosensitive resin layer containing a photosensitive resin composition, and a protective layer, wherein the photosensitive resin composition comprises the following components: (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator; the component (B) includes (b1) a compound having a weight-average molecular weight of 540 or less and having two or more ethylenically unsaturated bonds; the thickness tr (μm) of the photosensitive resin layer and the thickness tp (μm) of the protective layer satisfy both of the following equations: tp≥25 (1) and 1≤tp / tr≤3 (2).SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a photosensitive resin laminate and a method for producing the same. [Background technology]

[0002] Micro wiring (conductor patterns) in electronic devices are manufactured using, for example, a photolithography process. The photolithography process includes, for example, the following steps: a step of laminating a photosensitive resin layer of the photosensitive resin laminate on a substrate, and then exposing and developing the photosensitive resin layer to form a resist pattern; forming a conductive pattern by etching or plating the substrate on which the resist pattern has been formed; and removing the resist pattern on the substrate; It has.

[0003] Here, the photosensitive resin layer contains a photosensitive resin composition. Known photosensitive resin compositions include, for example, those containing an alkali-soluble polymer, a compound having an ethylenically unsaturated bond, and a photopolymerization initiator (see, for example, Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2019-133143 [Patent Document 2] International Publication No. 2018 / 105532 Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, electronic devices have become smaller and denser, and therefore resist patterns are required to have good resolution and good adhesion to the substrate. Therefore, there is room for improvement in the prior art in terms of improving these types of properties.

[0006] Furthermore, since photosensitive resin layers are used after being stored for a certain period of time (including transportation), a solution to the problem of how to ensure quality stability over time has been awaited.

[0007] An object of the present invention is to provide a photosensitive resin laminate that can realize a resist pattern that satisfies the characteristics that have recently been particularly required of resist patterns, and that can ensure quality stability over time. Another object of the present invention is to provide a photosensitive resin laminate roll obtained by using such a photosensitive resin laminate, and a method for producing such a photosensitive resin laminate. [Means for solving the problem]

[0008] One aspect of the present invention is as follows. [1] A photosensitive resin laminate comprising a temporary support layer, a photosensitive resin layer containing a photosensitive resin composition, and a protective layer, The photosensitive resin composition comprises the following components: (A) alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator, Including, The component (B) is (b1) a compound having a molecular weight of 540 or less and having two or more ethylenically unsaturated bonds; Including, The thickness tr (μm) of the photosensitive resin layer and the thickness tp (μm) of the protective layer are expressed by the following formula: tp≧25 (1) 1≦tp / tr≦3 (2) The photosensitive resin laminate satisfies both of the above requirements. [2] The photosensitive resin composition further comprises the following components: (D) Polymerization inhibitor 2. The photosensitive resin laminate according to item 1, wherein the component (D) comprises a compound having a boiling point of 280° C. or higher. [3] 3. The photosensitive resin laminate according to item 2, wherein the compound having a boiling point of 280° C. or higher includes at least one selected from the group consisting of phenothiazine, phenothiazine derivatives, and catechol derivatives. [4] 4. The photosensitive resin laminate according to any one of items 1 to 3, wherein the compound (b1) is a compound having two ethylenically unsaturated bonds. [5] 5. The photosensitive resin laminate according to any one of items 1 to 4, wherein the content of the (b1) compound is 1.5 to 5.0 mass % based on the solid content of the photosensitive resin composition. [6] 6. The photosensitive resin laminate according to any one of items 1 to 5, wherein the thickness tp (μm) of the protective layer is 2.0 times or more the content (mass%) of the (b1) compound relative to the solid content of the photosensitive resin composition. [7] The component (B) further comprises (b2) a compound having a molecular weight of 900 or more and having 3 to 6 ethylenically unsaturated bonds; 7. The photosensitive resin laminate according to any one of items 1 to 6, comprising: [8] 8. The photosensitive resin laminate according to item 7, wherein the ratio of the content of the (b1) compound to the content of the (b2) compound {(b1) compound / (b2) compound} is 0.1 to 1.0. [9] 9. The photosensitive resin laminate according to any one of items 1 to 8, wherein the ratio of the content of the component (A) to the content of the component (B) {component (A) / component (B)} is 1.30 or more.

[10] 10. The photosensitive resin laminate according to any one of items 1 to 9, wherein the ratio of the content of the component (A) to the content of the component (B) {component (A) / component (B)} is 1.50 or more.

[11] 11. The photosensitive resin laminate according to any one of items 1 to 10, wherein the ratio of the content of the component (A) to the content of the component (B) {component (A) / component (B)} is 1.69 or less.

[12] Contains: (A) alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator, a step of applying a photosensitive resin composition containing the above compound onto a temporary support layer to form a coating film; a step of drying the coating film to obtain a photosensitive resin layer; a step of laminating a protective layer on the photosensitive resin layer on the side opposite to the temporary support layer; Including, The component (B) is (b1) a compound having a molecular weight of 540 or less and having two or more ethylenically unsaturated bonds; Including, The thickness tr (μm) of the photosensitive resin layer and the thickness tp (μm) of the protective layer are expressed by the following formula: tp≧25 (1) 1≦tp / tr≦3 (2) The method for producing a photosensitive resin laminate satisfies both of the above.

[13] The step of forming the coating film includes: a step of dissolving the photosensitive resin composition in a solvent to obtain a coating liquid; A step of applying the coating liquid onto a temporary support layer; Item 13. The method for producing a photosensitive resin laminate according to Item 12, comprising:

[14] The photosensitive resin composition further comprises the following components: (D) Polymerization inhibitor Including, The component (D) contains a compound having a boiling point of 280°C or higher, The boiling point of the solvent is Ts (°C) and the boiling point of the compound having a boiling point of 280°C or higher is Td (°C), which satisfies the following formula: Td-Ts≧150 (3) Item 14. The method for producing a photosensitive resin laminate according to Item 12 or 13, wherein

[15] A photosensitive resin laminate roll including a temporary support layer, a photosensitive resin layer containing a photosensitive resin composition, and a protective layer, The photosensitive resin composition comprises the following components: (A) alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator, Including, The component (B) is (b1) a compound having a molecular weight of 540 or less and having two or more ethylenically unsaturated bonds; Including, The thickness tr (μm) of the photosensitive resin layer and the thickness tp (μm) of the protective layer are expressed by the following formula: tp≧25 (1) 1≦tp / tr≦3 (2) The photosensitive resin laminate roll satisfies both of the above requirements. [Effects of the Invention]

[0009] In recent years, the properties particularly required of resist patterns are resolution and adhesion, and when focusing on this, the term "imaging property" is used in combination, the present invention can provide a photosensitive resin laminate that can realize a resist pattern with good imaging property and ensure quality stability over time. Furthermore, according to the present invention, it is possible to provide a photosensitive resin laminate roll obtained using the photosensitive resin laminate, and a method for producing the photosensitive resin laminate. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 2 is a plan view showing the configuration of a mask pattern related to this embodiment. [Figure 2] FIG. 2 is a plan view showing the configuration of a mask pattern related to this embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0011] An embodiment of the present invention (hereinafter also referred to as "the present embodiment") will be described below. The present invention is not limited to the present embodiment, and various modifications can be made within the scope of the gist thereof.

[0012] In the present specification, when a plurality of structures represented by the same symbol exist in the same formula, the structures may be independently selected and may be the same or different from each other, unless otherwise specified. When a plurality of structures represented by the same symbol exist in different formulas, the structures may be independently selected and may be the same or different from each other, unless otherwise specified.

[0013] Furthermore, in this specification, the upper or lower limit value of a numerical range described in stages may be replaced with the corresponding upper or lower limit value of another numerical range described in stages, and may also be replaced with the corresponding value described in the examples.

[0014] In addition, 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 "compound containing a (meth)acryloyl group" is referred to as, for example, a "(meth)acrylate compound".

[0015] Furthermore, in this specification, the term "step" includes not only an independent step but also a step that cannot be clearly distinguished from other steps, as long as the function of the step is achieved. In the contents shown in the drawings, the scale, shape, and length may be exaggerated for clarity.

[0016] In this specification, the "solid content" of a photosensitive resin composition means the components of the photosensitive resin composition other than the solvent. Regarding the physical properties and parameters described in this specification, the methods for measuring them are those described in the Examples.

[0017] In addition, unless otherwise specified in this specification, "Adhesion" refers to the ability of the resist pattern to adhere to the substrate; "Resolution" refers to the resolution performance of the resist pattern; "Developability" refers to the development performance of the photosensitive resin layer (resist); "Sensitivity" refers to the exposure sensitivity of the photosensitive resin layer (resist); Each means:

[0018] [First embodiment] [Photosensitive resin laminate] The photosensitive resin laminate of the present disclosure includes a temporary support layer, a photosensitive resin layer containing a photosensitive resin composition, and a protective layer. The photosensitive resin composition includes the following components: (A) alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator, Includes:

[0019] In the photosensitive resin laminate of the present disclosure, Component (B) is (b1) A compound having a molecular weight of 540 or less and having two or more ethylenically unsaturated bonds; The thickness tr (μm) of the photosensitive resin layer and the thickness tp (μm) of the protective layer are determined by the following formula: tp≧25 (1) 1≦tp / tr≦3 (2) Both are satisfied.

[0020] As electronic devices become smaller and denser, the required resist pattern is required to have good resolution, and the required pattern width tends to become smaller, i.e., the contact width between the required pattern and the substrate tends to become smaller. A smaller contact width between the resist pattern and the substrate is often disadvantageous to adhesion. On the other hand, the photosensitive resin laminate of the present disclosure can achieve good adhesion while also achieving good resolution. Focusing on the fact that resolution and adhesion, which are properties particularly required of resist patterns in recent years, are collectively referred to as "imageability," the present disclosure provides a photosensitive resin laminate that can realize a resist pattern with good imageability.

[0021] According to the photosensitive resin laminate of the present disclosure, the component (B) contains a specific compound (b1) (a compound having a relatively low molecular weight and excellent reactivity). This can improve various reactivities in the photosensitive resin layer. Therefore, the present disclosure provides a photosensitive resin laminate capable of forming a resist pattern with good imaging properties.

[0022] In addition to the above, the photosensitive resin laminate of the present disclosure has a sufficiently thick protective layer relative to the photosensitive resin layer. This prevents the photosensitive resin component from bleeding (emerging) onto the surface of the protective layer, even if the photosensitive resin component penetrates into the protective layer, or even if the photosensitive resin component is obtained using compound (b1), which is a compound that tends to improve the image quality of the resist pattern (as described above, compound (b1) has a relatively low molecular weight). Therefore, the present disclosure provides a photosensitive resin laminate that can ensure stable quality over time.

[0023] In one embodiment, the laminate may be stored in a state in which the temporary support layer and the protective layer are in contact with each other (for example, in a state in which the laminate is wound so that the temporary support layer and the protective layer are in contact with each other, forming a photosensitive resin laminate roll). In this case, the bleeding can be prevented, thereby avoiding transfer of the photosensitive resin component to the temporary support layer through the protective layer. This prevents the transfer from adversely affecting various properties of the temporary support layer and, ultimately, the subsequent photolithography process.

[0024] In a preferred embodiment of the photosensitive resin laminate, the ratio of the protective layer to the photosensitive resin layer is suitably ensured, which makes it easy to ensure the low cost and ease of handling of the photosensitive resin laminate and also makes it easy to realize a photosensitive resin laminate roll by winding (rolling) the photosensitive resin laminate of the present disclosure.

[0025] The photosensitive resin laminate of the present disclosure is suitable for use in producing conductor patterns. For example, the photosensitive resin laminate of the present disclosure can be suitable for use in producing printed wiring boards, 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 partition walls of flat panel displays such as ITO electrodes, address electrodes, and electromagnetic wave shields.

[0026] The photosensitive resin laminate of the present disclosure may consist only of a temporary support layer, a photosensitive resin layer, and a protective layer. As described above, the photosensitive resin laminate of the present disclosure can ensure quality stability over time without providing a specific functional layer for ensuring quality stability over time, particularly without providing a functional layer as the outermost layer of the photosensitive resin laminate. On the other hand, the photosensitive resin laminate of the present disclosure may have layers (other layers) other than the temporary support layer, the photosensitive resin layer, and the protective layer.

[0027] [Temporary support layer] The temporary support layer is a film substrate for supporting the photosensitive resin layer, and is also called a "support film." The temporary support layer preferably has transparency to the extent that it can transmit exposure light (actinic rays) emitted from an exposure light source. The temporary support layer is peeled off from the photosensitive resin layer before an exposure step in which the photosensitive resin layer is exposed to light or before a development step in which the photosensitive resin layer is developed.

[0028] Substrates that can be used as the temporary support layer, particularly transparent substrates, include synthetic resins such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. Among these, polyethylene terephthalate (PET) is preferred as the temporary support layer because it has moderate flexibility and strength. The temporary support layer may be stretched as necessary.

[0029] As described above, according to the photosensitive resin laminate of the present disclosure, even if it is stored in an embodiment in which the temporary support layer and the protective layer are in contact with each other, for example, in the form of a photosensitive resin laminate roll, it is possible to avoid transfer of the photosensitive resin component to the temporary support layer via the protective layer. Therefore, even when the photosensitive resin laminate after storage is used and the photosensitive resin layer is exposed via the temporary support layer, no adverse effects due to such transfer occur.

[0030] The absorbance of the temporary support layer 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 (for example, 0.080) or less. The absorbance may be 0 or more.

[0031] It is preferable to use a film with few internal foreign matters, for example, a high-quality film, as the temporary support layer. Examples of high-quality films include PET films synthesized using a Ti-based catalyst, PET films with small lubricant diameters and low content, PET films containing lubricant on only one side of the film, thin 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 the temporary support layer, the exposure light is less likely to be blocked by internal foreign matters in the temporary support layer, and in this case, the exposure light can be easily irradiated onto the photosensitive resin layer, which results in improved resolution.

[0032] The thickness of the temporary support layer is preferably 5 to 25 μm, more preferably 6 to 20 μm. By adjusting the thickness of the temporary support layer within this range, the number of internal foreign matter can be easily reduced, thereby making it easier to prevent a decrease in resolution. In addition, the strength of the temporary support layer can be easily ensured, thereby making it easier to prevent wrinkles from occurring in the photosensitive resin layer during the manufacturing process of the photosensitive resin laminate and / or when the photosensitive resin laminate is laminated onto a substrate.

[0033] The haze of the temporary support layer 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 from the viewpoint of obtaining good resolution.

[0034] [Protective layer] The protective layer is a film for protecting the photosensitive resin layer, and is also called a "protective film." The protective layer has an appropriate adhesive strength to the photosensitive resin layer. When the adhesive strength between the photosensitive resin layer and the protective layer is sufficiently weaker than the adhesive strength between the photosensitive resin layer and the temporary support layer, the protective layer can be easily peeled off from the photosensitive resin layer. The photosensitive resin layer exposed by peeling off the protective layer is laminated on a substrate in the lamination process described below.

[0035] Examples of the protective layer include polyethylene film, polypropylene film, stretched polypropylene film, polyester film, etc. Specific examples of the protective layer include Alphan (registered trademark), Alphan E-201F, Alphan FG-201 (all manufactured by Oji F-Tex Co., Ltd.), Torayfan KW37, 2578, 2548, 2500, YM17S, Therapeel PJ271, PJ111, HP2, PJ101, WZ, MDA, MFA, TK07, BKE, BX8A, SY (all manufactured by Toray Industries, Inc.), GF-18, GF-858 (all manufactured by Tamapoly Co., Ltd.), etc.

[0036] The thickness (tp) of the protective layer is 25 μm or more. By ensuring such a thickness, even if the photosensitive resin component penetrates into the protective layer, or even if the photosensitive resin component is obtained using the compound (b1) having a relatively low molecular weight, the photosensitive resin component can be prevented from bleeding (lifting out) onto the surface of the protective layer.

[0037] From the viewpoint of suitably preventing bleeding (protrusion) of the photosensitive resin component onto the surface of the protective layer, the thickness tp (μm) of the protective layer is preferably 2.0 times or more, more preferably 4.0 times or more, even more preferably 5.0 times or more, and particularly preferably 6.0 times or more, the content (mass%) of the (b1) compound relative to the solid content of the photosensitive resin composition.

[0038] The thickness (tp) of the protective layer is preferably 25 to 100 μm, more preferably 30 to 50 μm, which makes it easy to ensure the merchantability and handleability of the photosensitive resin laminate and also makes it easy to realize a photosensitive resin laminate roll by winding (rolling) the photosensitive resin laminate of the present disclosure.

[0039] The protective layer may have a release layer on its surface, in which case the protective layer can be easily peeled off from the photosensitive resin layer. Compounds constituting this type of release layer are classified into, for example, silicone compounds and non-silicone compounds.

[0040] Examples of silicone compounds include condensation reaction type silicone resins obtained by reacting polydimethylsiloxane containing silanol groups at both ends with polymethylhydrogensiloxane or polymethylmethoxysiloxane; addition reaction type silicone resins obtained by reacting a dimethylsiloxane-methylvinylsiloxane copolymer or a dimethylsiloxane-methylhexenylsiloxane copolymer with polymethylhydrogensiloxane; ultraviolet-curable or electron-beam-curable silicone resins obtained by curing acrylic silicones and epoxy group-containing silicones with ultraviolet light or electron beams; and modified silicone resins such as epoxy-modified silicone resins (silicone epoxy), polyester-modified silicone resins (silicone polyester), acrylic-modified silicone resins (silicone acrylic), phenol-modified silicone resins (silicone phenol), alkyd-modified silicone resins (silicone alkyd), and melamine-modified silicone resins (silicone melamine).

[0041] Examples of non-silicone compounds include alkyd resins, long-chain alkyl resins, acrylic resins, and polyolefin resins.

[0042] 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, which may provide advantages such as the coating film having a good appearance, the coating film being easily cured sufficiently, and sufficient releasability being easily ensured.

[0043] [Photosensitive resin layer] The photosensitive resin layer constitutes the photosensitive resin laminate of the present disclosure. The photosensitive resin layer contains a photosensitive resin composition, and the photosensitive resin composition contains the following components: (A) alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator. In the present specification, these components are referred to as "component (A)" and the like. The photosensitive resin composition may contain components other than components (A) to (C). Each component and / or the raw materials for each component may be used alone or in combination of two or more.

[0044] (Various contents) From the viewpoint of easily achieving the effects of this embodiment and being suitable for forming a conductive pattern, the total content of the component (A), the component (B), and the component (C) in the photosensitive resin composition is preferably 90 mass % or more, and more preferably 95 mass % or more, based on the solid content of the photosensitive resin composition.

[0045] From the viewpoint of easily achieving the effects of this embodiment and being suitable for forming a conductive pattern, the ratio of the content of component (A) to the content of component (B) in the photosensitive resin composition {(A) component / (B) component} is preferably 1.30 or more, and more preferably 1.50 or more. The ratio {(A) component / (B) component} may be 2.50 or less, preferably 2.20 or less, more preferably 2.00 or less, and particularly preferably 1.69 or less.

[0046] (Thickness) The smaller the thickness (tr) of the photosensitive resin layer, the easier it is to improve resolution, and the greater the thickness, the easier it is to ensure the strength of the photosensitive resin layer. Therefore, the thickness of the photosensitive resin layer is preferably 3 to 100 μm, for example, 7 μm or more, or 15 μm or more, and may be 60 μm or less, or 50 μm or less.

[0047] In the photosensitive resin laminate of the present disclosure, the thickness (tr) of the photosensitive resin layer and the thickness (tp) of the protective layer are expressed by the following formula: 1≦tp / tr≦3 Meet. By satisfying 1≦tp / tr (e.g., 1.00≦tp / tr), that is, by making the protective layer sufficiently thick relative to the photosensitive resin layer, even if the photosensitive resin component penetrates into the protective layer, or even if the photosensitive resin component is obtained using the above-mentioned (b1) compound having a relatively low molecular weight, it is possible to prevent the photosensitive resin component from bleeding (lifting out) onto the surface of the protective layer. Furthermore, satisfying tp / tr≦3 (e.g., tp / tr≦3.00), that is, the protective layer in the photosensitive resin laminate is not too thick, makes it easier to ensure the marketability and handleability 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 the present disclosure.

[0048] The thickness of the photosensitive resin layer may be selected depending on the configuration and use of the photosensitive resin laminate, the configuration and use of the resist pattern obtained using the photosensitive resin laminate, and the configuration and use of the conductor pattern or electronic device produced using the photosensitive resin laminate. The thickness of the photosensitive resin layer may also be selected depending on the thickness of the protective layer. When plating is performed on a substrate on which a resist pattern has been formed, the thickness of the photosensitive resin layer is preferably 10 to 30 μm.

[0049] <Component (A): Alkali-soluble polymer> Component (A) is a polymer that is soluble in an alkaline aqueous solution. From the viewpoint of favorably exhibiting alkali solubility, component (A) preferably has a carboxyl group, and from the same viewpoint, it preferably has an acid value of 50 to 500 mgKOH / g. The acid value of component (A) may be 60 mgKOH / g or more, 80 mgKOH / g or more, 400 mgKOH / g or less, or 200 mgKOH / g or less.

[0050] The acid value was determined by accurately weighing approximately 1 g of a sample, dissolving it in 100 mL of acetone, and then neutralizing it with a 1 mol / L aqueous potassium hydroxide solution. The acid value was calculated based on the amount of potassium hydroxide solution added dropwise using the following formula: Acid value (mgKOH / g) = 56.1 × {amount of 1 mol / L potassium hydroxide solution dropped (mL)} / {mass of precisely weighed sample (g)} It can be calculated as follows. Neutralization titration can be carried out using, for example, Hiranuma Automatic Titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd.

[0051] The component (A) preferably has a repeating unit containing at least one type selected from the "first monomers" described below. In this case, the "proportion of the monomer component in the component (A)" refers to the copolymerization ratio when the component (A) contains only one type of alkali-soluble polymer.

[0052] It is more preferable that component (A) has a repeating unit containing at least one monomer selected from the "first monomers" described below and at least one monomer selected from the "second monomers" described below. In this case, the "proportion of the monomer components in component (A)" refers to a weighted average of the copolymerization ratios, with the content ratio of each alkali-soluble polymer used as a weight. Similarly, the values ​​described for component (A) (e.g., weight-average molecular weight, polydispersity index, etc.) refer to weighted averages, with the content ratio of each alkali-soluble polymer used as a weight.

[0053] 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 20,000 to 100,000, and particularly preferably 23,000 to 60,000. When the weight-average molecular weight (Mw) of component (A) is 5,000 or more, it becomes easier to maintain a uniform thickness of the photosensitive resin laminate and to ensure resistance to a developing solution. When the weight-average molecular weight (Mw) of component (A) is 600,000 or less, it becomes easier to ensure the flexibility and developability of the photosensitive resin laminate.

[0054] The polydispersity of component (A) {weight average molecular weight (Mw) of component (A) / number average molecular weight (Mn) of component (A)} 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.

[0055] The content of component (A) is preferably 40 to 80 mass%, more preferably 45 to 75 mass%, even more preferably 50 to 70 mass%, and particularly preferably 55 to 65 mass%, based on the solid content of the photosensitive resin composition. When the content of component (A) is 40% or more, excellent adhesion and fine line strength are likely to be achieved. When the content of component (A) is 80% or less, resistance to the developer is likely to be ensured.

[0056] (First Monomer) The first monomer is a compound having a carboxyl group and at least one ethylenically unsaturated bond in the molecule.

[0057] Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, maleic acid half ester, etc. Among these, from the viewpoint of realizing good adhesion and good resolution, (meth)acrylic acid is preferred, and methacrylic acid is more preferred.

[0058] Regarding (meth)acrylic acid, "methacrylic acid" means a compound represented by the chemical formula C4H6O2, and "acrylic acid" means a compound represented by the chemical formula C3H4O2.

[0059] In the component (A), the content of the structural unit derived from the first monomer is preferably from 10 to 55% by mass, more preferably from 15 to 35% by mass, and even more preferably from 18 to 30% by mass, from the viewpoint of realizing good developability and good resolution.

[0060] (Second Monomer) The second monomer is a non-acidic compound having at least one radically polymerizable ethylenically unsaturated bond in the molecule.

[0061] Examples of the second monomer include 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)acrylate, glycerin mono(meth)acrylate, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, and nonylphenoxy polyethylene. (meth)acrylates such as glycol (meth)acrylate, pentamethylpiperidyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenoxyethyl (meth)acrylate, ethyl carbitol (meth)acrylate, methoxyethyl (meth)acrylate, methoxytriethylene glycol (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, 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl (meth)acrylate; Styrene, styrene derivatives (methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, styrene dimer, styrene trimer, etc.); Esters of vinyl alcohol, such as vinyl acetate; and (Meth)acrylonitrile; etc.

[0062] In the component (A), the content of the structural unit derived from the second monomer is preferably from 45 to 90% by mass, more preferably from 65 to 85% by mass, and even more preferably from 70 to 82% by mass, from the viewpoint of realizing good developability and good resolution.

[0063] The second monomer preferably includes a compound having an aromatic ring. The content of structural units derived from this compound in component (A) is preferably 45 to 90% by mass. From the viewpoint of realizing good adhesion and good resolution, the content is preferably 45% by mass or more, more preferably 50% by mass or more, even more preferably 55% by mass or more, even more preferably 60% by mass or more, and particularly preferably 65% ​​by mass or more. From the viewpoint of realizing good developability, the content is preferably 90% by mass or less, more preferably 80% by mass or less.

[0064] Examples of compounds having an aromatic ring include styrene, styrene derivatives, benzyl (meth)acrylate, 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl (meth)acrylate, etc. Among these, styrene and benzyl (meth)acrylate are preferred, and styrene is more preferred.

[0065] The second monomer may include a compound having an alicyclic ring, and the content of structural units derived from this compound in the component (A) may be 10 to 40 mass %.

[0066] Examples of the compound having an alicyclic ring include (meth)acrylic acid esters having a group having one cyclic hydrocarbon group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, or a cycloheptyl group, or a group consisting of a derivative thereof, and also include (meth)acrylic acid esters having a group having two or more cyclic hydrocarbon groups such as a dicyclopentanyl group, a dicyclopentenyl group, an adamantyl group, or an isobornyl group, or a group consisting of a derivative thereof.

[0067] The second monomer may include a compound having a hydroxy group. In component (A), the content of structural units derived from such a compound is preferably 1.0 to 25% by mass, more preferably 1 to 10% by mass, and even more preferably 1 to 6% by mass. Controlling this proportion within the above range is preferred from the viewpoint of achieving good adhesion and good resolution.

[0068] Examples of compounds having a hydroxy group include hydroxyalkyl (meth)acrylates, specifically 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and glycerin-based (meth)acrylates (e.g., glycerin mono(meth)acrylate). These compounds are relatively easy to obtain. Furthermore, the developability and adhesion are easy to control, and therefore, resist patterns with excellent properties can be easily realized.

[0069] The second monomer may be a monomer other than those mentioned above, for example, It may optionally contain (meth)acrylic acid alkyl esters (chain alkyl esters and cyclic alkyl esters) other than those mentioned above, conjugated diene compounds other than those mentioned above, polar monomers (amino group-containing monomers, amide group-containing monomers, cyano group-containing monomers, epoxy group-containing monomers, etc.) other than those mentioned above, crosslinkable monomers other than those mentioned above, acid anhydrides other than those mentioned above, etc.

[0070] From the viewpoint of developability and resolution, the component (A) may be a copolymer consisting of only a monomer containing one polymerizable unsaturated group, i.e., the component (A) does not need to contain a polymerizable unsaturated group.

[0071] Component (A) may contain a copolymer containing a polymerizable unsaturated group. The copolymer containing a polymerizable unsaturated group can be obtained, for example, by adding glycidyl (meth)acrylate to a copolymer having a carboxyl group. When the photosensitive resin composition contains a copolymer containing a polymerizable unsaturated group, whether it is component (A) or component (B) may be determined, for example, by the following method. A copolymer containing a monomer having a carboxyl group in the molecule and at least one polymerizable unsaturated group in the molecule as a copolymerization component may be classified as component (A). A compound that is not a copolymer and a copolymer that does not contain a monomer having a carboxyl group in the molecule and at least one polymerizable unsaturated group in the molecule as a copolymerization component may be classified as component (B).

[0072] <<Synthesis of component (A)>> Component (A) can be synthesized by mixing an appropriate amount of a radical polymerization initiator such as benzoyl peroxide and azobisisobutyronitrile into a solution obtained by diluting one or more of the monomers described above with a solvent such as acetone, methyl ethyl ketone, or isopropanol, and then heating and stirring the mixture. Component (A) may also be synthesized by adding a portion of the mixture dropwise to a reaction solution. After the reaction is complete, additional solvent may be added to adjust the concentration to the desired level. In addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may also be used as a synthesis method. Synthesis may also be performed by living radical polymerization.

[0073] <Component (B): Compound Having an Ethylenically Unsaturated Bond> The component (B) is a compound having an ethylenically unsaturated bond, for example, a compound having one or more ethylenically unsaturated bonds in one molecule. The component (B) may contain a plurality of compounds different from each other.

[0074] 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. Note that component (B) having a (meth)acryloyl group will be referred to as a (meth)acrylate compound in the following description.

[0075] With respect to component (B), the presence of "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. With respect to component (B), the presence of 1, 2, 3, 4, 5, or 6 photopolymerizable functional groups in one molecule is sometimes referred to as "monofunctional (or monofunctional)," "bifunctional," "trifunctional," "tetrafunctional," "pentafunctional," or "hexafunctional," respectively.

[0076] Examples of bifunctional (meth)acrylate compounds include alkyl di(meth)acrylate, 1,3-bis(meth)acryloyloxy-2-propanol, polyalkylene glycol di(meth)acrylate, tricyclodecanol di(meth)acrylate, ethoxylated (hydrogenated) bisphenol A di(meth)acrylate, propoxylated (hydrogenated) bisphenol A di(meth)acrylate, and tetramethylene glycosylated (hydrogenated) bisphenol A di(meth)acrylate.

[0077] Examples of polyalkylene glycol di(meth)acrylates include polyethylene glycol di(meth)acrylate, polypropylene di(meth)acrylate, and polytetramethylene glycol di(meth)acrylate. The polyalkylene glycol di(meth)acrylate may also be a compound having multiple alkylene groups, such as ethylene, propylene, and tetramethylene. Examples of such compounds include polyalkylene glycol dimethacrylates, which are obtained by adding an average of three ethylene oxide units to each end of polypropylene glycol containing an average of 12 propionoxide units.

[0078] In this specification, the average number of alkylene oxides such as ethylene oxide and propylene oxide may be understood to be determined by number average.

[0079] Furthermore, the bifunctional (meth)acrylate compound may be a compound represented by the following general formula (I): General formula (I) [ka] (In the formula, R 2 are each independently a hydrogen atom or a methyl group, and X 2 O and Y 2 Each O is independently an oxyethylene group or an oxypropylene group, m3, m4, n2, and n3 are independently an integer of 0 to 40, m3+m4 is 1 to 40, and n2+n3 is 0 to 20. Also included are bisphenol A di(meth)acrylates represented by the following formula:

[0080] Further, examples of the bifunctional (meth)acrylate compound include: Dimethacrylate of polyalkylene glycol, in which an average of 12 propionoxide units are added to both ends of polypropylene glycol, and an average of 3 ethylene oxide units are added to each end of the polypropylene glycol. Dimethacrylate of polyethylene glycol, in which an average of two ethylene oxide units are added to each end of bisphenol A. Dimethacrylate of polyethylene glycol, in which an average of five ethylene oxide units are added to each end of bisphenol A. etc.

[0081] Commercially available bifunctional (meth)acrylate compounds include NK Ester (registered trademark) A-HD-N, A-NOD-N, A-DOD-N, A-NPG, 701A, A-200, A-400, A-600, A-1000, APG-200, APG-400, APG-700, A-PTMG65, A-DCP, ABE-300, A-BPE-4, A-BPE-10, A-BPE-20, HD-N, NOD-N, DOD-N, NPG, 701, 2G, 3G, 4G, 9G, and 14G. 23G, 9PG, DCP, BPE-80N, BPE-100, BPE-200, BPE-500, BPE-900, BPE-1300N, NK Oligo (registered trademark) UA-4200, UA-160™, UA-290™, UA-W2A, UA-4400, UA-122P, U-200PA (all manufactured by Shin-Nakamura Chemical Co., Ltd.), Light Acrylate (registered trademark) 3EG-A, 4EG-A, 9EG-A, 14EG-A, PTMGA-250, NP-A, MPD-A, 1.6HX-A, and 1.9ND-A, DCP-A, BP-4EAL, BP-4PA, HPP-A, Light Ester G-201P (all manufactured by Kyoeisha Chemical Co., Ltd.), Fancryl (registered trademark) FA-124AS, FA-023M, FA-121M, FA-124M, FA-125M, FA-129AS, FA-137M, FA-220M, FA-222A, and FA-240 A, FA-240M, FA-320M, FA-3218M, FA-321A, FA-321M, FA-324A, FA-731A, FA-P240A, FA-P270A, FA-PTG9A, FA-PTG9M, FA-PTG28A, FA-PTG49A (all manufactured by Resonac), DPGDA, HDDA, TPGDA, EBECRYL 145, EBECRYL 150, PEG400DA, EBECRYL 11, IRR 214-K, EBECRYL 130, EBECRYL PEG200DMA (all manufactured by Daicel-Allnex Co., Ltd.), SR212, SR213, SR230, SR238F, SR259, SR268, SR272, SR306H, SR344, SR349, SR508, CD560, CD561, CD564, SR601, SR602, SR610, SR833S, SR9003, SR9045, SR9209, SR205, SR206, SR209, SR210, SR214, SR231, SR239, SR248, SR252, SR297, SR348, SR480, CD540, CD541, CD542, SR603, SR644, SR9036 (all manufactured by Arkema), KAYARAD (registered trademark) Examples include NPGDA, PEG400DA, FM-400, R-167, HX-220, HX-620, R-551, R-712, R-604, and R-684 (all manufactured by Nippon Kayaku Co., Ltd.).

[0082] Examples of tri- or higher functional (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, tetraglycerin hexa(meth)acrylate, ditrimethylolpropane (tetra / penta / hexa)(meth)acrylate, and dipentaerythritol (tetra / penta / hexa)(meth)acrylate.

[0083] Examples of tri- or higher functional (meth)acrylate compounds include compounds that have, as a central skeleton, three or more groups to which alkylene oxide groups can be added within the molecule, and are obtained by forming a (meth)acrylate from an alcohol to which an alkylene oxide group such as an ethylene oxide group, a propylene oxide group, or a butylene oxide group has been added, and (meth)acrylic acid. Examples of such compounds include alkylene oxide-modified tri(meth)acrylate of trimethylolpropane, alkylene oxide-modified tri(meth)acrylate of glycerin, 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 / penta / hexa)(meth)acrylate, alkylene oxide-modified dipentaerythritol (tetra / penta / hexa)(meth)acrylate, and alkylene oxide-modified isocyanuric acid tri(meth)acrylate. Preferred alkylene oxide groups include ethylene oxide, propylene oxide, and butylene oxide.

[0084] The tri- or higher functional (meth)acrylate compound may contain alkylene oxide-modified pentaerythritol (tri / tetra)(meth)acrylate and / or alkylene oxide-modified dipentaerythritol (tetra / penta / hexa)(meth)acrylate, from the viewpoint of realizing good developability.

[0085] Commercially available tri- or higher functional (meth)acrylate compounds include NK Ester (registered trademark) A-TMPT, A-TMPT-9EO, AT-20E, A-GLY-3E, A-GLY-9E, A-GLY-20E, A-9300, A-9200YN, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMMT, ATM-35E, AD-TMP, A-DPH, A-9550, and A- DPH-12E, TPOA-50, NK Oligo (registered trademark) UA-7100, UA-1100H, U-6LPA, UA-33H, U-10HA, U-10PA, and U-15HA (all manufactured by Shin-Nakamura Chemical Co., Ltd.), Light Acrylate (registered trademark) TMP-A, cPE-3A, PE-4A, and DPE-6A (all manufactured by Kyoeisha Chemical Co., Ltd.), FA-731A (manufactured by Resonac Co., Ltd.), TMPTA, and EBECRYL (registered trademark). 160S, OTA 480, PETIA, PETRA, EBECRYL 40, PETA, EBECRYL 140, EBECRYL 1140, EBECRYL 1142, DPHA, EBECRYL 895, EBECRYL 896, EBECRYL TMPTMA (all manufactured by Daicel-Allnex Co., Ltd.), SR351S, SR368, SR415, SR444, SR454, SR492, SR499, CD501, SR502, SR9020, D9021, SR9035, SR295, SR355, SR399, SR494, SR9041 (all manufactured by Arkema), KAYARAD (registered trademark) Examples include GPO-303, TMPTA, THE-330, TPA-330, PET-30, T-1420(T), RP-1040, DPHA, DPEA-12, D-310, and DPCA-20 (all manufactured by Nippon Kayaku Co., Ltd.).

[0086] An example of the trifunctional (meth)acrylate compound is a compound represented by the following general formula (II) having a trimethylolpropane skeleton: [ka] {In the formula, n1, n2, and n3 each independently represent an integer of 1 to 25, provided that n1+n2+n3 represents an integer of 3 to 75, and R1, R2, and R3 each independently represent a methyl group or a hydrogen atom.} Examples of the compound include compounds represented by the following formula:

[0087] An example of the tetrafunctional (meth)acrylate compound is a compound having a pentaerythritol skeleton represented by the following general formula (III): [ka] {In the formula, n1, n2, n3, and n4 each independently represent an integer of 1 to 25, n1 + n2 + n3 + n4 is an integer of 4 to 100, R1, R2, R3, and R4 each independently represent a methyl group or a hydrogen atom, R5, R6, R7, and R8 each independently represent an alkylene group, and when there are multiple R5, R6, R7, and R8, the multiple R5, R6, R7, and R8 may be the same or different from one another.} Examples of the compound include compounds represented by the following formula:

[0088] An example of the hexafunctional (meth)acrylate compound is a compound having a dipentaerythritol skeleton represented by the following general formula (IV): [ka] {In the formula, each R independently represents a methyl group or a hydrogen atom, and each n independently represents an integer of 0 to 30.} In general formula (V), n may be 0, that is, the ethylene oxide moiety may not be present.

[0089] The content of component (B) relative to the solid content of the photosensitive resin composition is preferably 30% by mass or more, more preferably 35% by mass or more, from the viewpoint of excellent sensitivity, tackiness, and followability, and is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 42% by mass or less.

[0090] ((b1) compound) Here, the component (B) includes the compound (b1). The compound (b1) is a compound having a molecular weight of 540 or less and two or more ethylenically unsaturated bonds. In one embodiment, the compound (b1) is a (meth)acrylate compound having a molecular weight of 540 or less and two or more (meth)acryloyl groups.

[0091] Examples of the (b1) compound include those having a molecular weight of 540 or less among the above-listed "difunctional or higher (meth)acrylate compounds." For example, the (b1) compound is so that the molecular weight of the photosensitive resin composition is 540 or less. In the above general formula (I), R 2 , X 2 O, Y 2 A compound in which O, m3, m4, n2, and n3 are selected; In the above general formula (II), a compound in which n1 to n3 and R1 to R3 are selected, and A compound in which n1 to n4 and R1 to R8 are selected in the above general formula (III), Examples include:

[0092] Here, the (b1) compound is preferably a compound having two ethylenically unsaturated bonds, which makes it easier to adjust the molecular weight of the (b1) compound to 540 or less.

[0093] An example of the (b1) compound is: Dimethacrylate of polyethylene glycol, in which 1 to 2 ethylene oxide units are added to each end of bisphenol A. etc. The above compound is included in, for example, polyethylene glycol dimethacrylate (product name: BLEMMER (registered trademark) PDBE-200A) in which an average of two ethylene oxide units are added to each end of bisphenol A.

[0094] As described above, according to the photosensitive resin laminate of the present disclosure, the component (B) contains a specific (b1) compound (a compound with a relatively low molecular weight and excellent reactivity). This can improve various reactivities in the photosensitive resin layer. Therefore, the present disclosure provides a photosensitive resin laminate that can realize a resist pattern having both good resolution and good adhesion. For this purpose, the molecular weight of the (b1) compound may be 150 or more, or may be 250 or more.

[0095] The content of the (b1) compound is preferably 1.5 to 5.0 mass% based on the solid content of the photosensitive resin composition. This makes it easier to achieve the effects of this embodiment. In particular, by appropriately specifying the upper limit of the content of the (b1) compound, it is easier to ensure the flexibility of the resulting photosensitive resin layer, and in this case, it is easier to prevent the entrapment of air bubbles (laminated air) when the photosensitive resin layer is laminated on a substrate. From the same perspective, the content of the (b1) compound is more preferably 2.0 to 4.5 mass% based on the solid content of the photosensitive resin composition.

[0096] ((b2) compound) The component (B) may contain the compound (b2) in addition to the compound (b1). The compound (b2) has a molecular weight of 900 or more and has 3 to 6 ethylenically unsaturated bonds. In one embodiment, the compound (b2) is a (meth)acrylate compound having a molecular weight of 900 or more and having 3 to 6 or more (meth)acryloyl groups.

[0097] Examples of the (b1) compound include those having a molecular weight of 900 or more among the "tri- to hexa-functional (meth)acrylate compounds" exemplified above. For example, the (b2) compound is so that the molecular weight of the photosensitive resin composition is 900 or more, A compound in which n1 to n3 and R1 to R3 are selected in the above general formula (II), A compound in which n1 to n4 and R1 to R8 are selected in the above general formula (III), and A compound in which n and R are selected in the above general formula (IV), Examples include:

[0098] Examples of the (b2) compound include those having a molecular weight of 900 or more among the "tri- or higher functional (meth)acrylate compounds" exemplified above. (b2) An example of the compound is: Ethylene oxide-modified pentaerythritol tetramethacrylate with 15 ethylene oxide units added, etc. The above compound is included in, for example, ethylene oxide-modified pentaerythritol tetramethacrylate to which an average of 15 ethylene oxide units have been added.

[0099] The content of the (b2) compound is preferably 1.5 to 20.0 mass% and more preferably 2.5 to 10.0 mass% based on the solid content of the photosensitive resin composition. This makes it easier to achieve the effects of this embodiment. From the same viewpoint, the content of the (b2) compound is more preferably 5.0 to 20.0 mass% based on the solid content of the photosensitive resin composition. However, as described above, the inclusion of the (b2) compound is optional; that is, the content of the (b2) compound in the (B) component may be 0 mass%.

[0100] (Ratio {(b1) compound / (b2) compound}) The ratio of the content of the (b1) compound to the content of the (b2) compound {(b1) compound / (b2) compound} is preferably 0.1 to 1.0. This makes it easier to achieve the effects of this embodiment. From the same viewpoint, this ratio is more preferably 0.15 to 0.5.

[0101] The molecular weights of the (b1) compound and the (b2) compound can generally be measured by advanced polymer chromatography (APC), which allows for more accurate quantification of the molecular weight distribution based on the number of alkylene oxides than conventional gel permeation chromatography (GPC). That is, the "molecular weight and content of the (b1) compound and the (b2) compound" in this embodiment may be values ​​measured by advanced polymer chromatography (APC).

[0102] The above-mentioned "value measured by advanced polymer chromatography" can be measured, for example, using an ACQUITY (registered trademark) Advanced Polymer Chromatography (APC) system (manufactured by Waters) under the following conditions. Solvent used: Tetrahydrofuran Flow rate: 0.5mL / min Column: XT45 x 3 Detector: Differential refractometer or UV-visible absorption spectrometer

[0103] <Component (C): Photopolymerization initiator> Component (C) is a photopolymerization initiator. The photopolymerization initiator generates radicals when exposed to actinic rays emitted from an exposure light source, thereby promoting the polymerization of a compound having an ethylenically unsaturated bond.

[0104] The content of component (C) is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, based on the solid content of the photosensitive resin composition. By adjusting the content of component (C) within the above range, sufficient sensitivity can be easily obtained, making it easier to transmit light sufficiently to the bottom of the photosensitive resin layer even with a small exposure dose, and ultimately making it easier to achieve good resolution.

[0105] Examples of component (C) include biimidazole compounds, N-aryl-α-amino acid compounds, quinone compounds, aromatic ketone compounds, anthracene or anthracene derivatives, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, benzoin ether compounds, dialkyl ketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, acridine compounds, and pyrazoline derivatives, as well as N-arylamino acid ester compounds and halogen compounds.

[0106] Examples of biimidazole compounds include compounds having a biimidazole structure, such as lophine dimer, that is, a dimer of 2,4,5-triarylimidazole.

[0107] 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), 2-(o-chlorophenyl)-4,5-bis-(m-methoxyphenyl)biimidazole, 2-(p-methoxyphenyl)-4,5-diphenylbiimidazole, and 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole. Bis-(o-chlorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 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-methoxyphenyl)-biimidazole phenyl)-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- 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.

[0108] From the viewpoints of good sensitivity, good resolution, and good adhesion, it is preferable that the component (C) contains a lophine dimer, and in particular, it is more preferable that the component (C) contains a dimer of 2-(o-chlorophenyl)-4,5-diphenylimidazole.

[0109] 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 because of its high sensitizing effect.

[0110] 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-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.

[0111] Examples of aromatic ketone compounds include benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], and 4-methoxy-4'-dimethylaminobenzophenone. From the viewpoints of sensitization effect and adhesion, examples of aromatic ketone compounds include 4,4'-bis(diethylamino)benzophenone.

[0112] Examples of anthracene derivatives include 9,10-dialkoxyanthracenes, 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. Examples of 9,10-dialkoxyanthracenes include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 9,10-dibutoxyanthracene. From the viewpoints of sensitization effect and adhesion, 9,10-dibutoxyanthracene and 9,10-diphenylanthracene are preferred, and 9,10-diphenylanthracene is particularly preferred.

[0113] 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. Commercially available acetophenone compounds include the Irgacure series (manufactured by Ciba Specialty Chemicals: Irgacure-907, Irgacure-369, and Irgacure-379, etc.).

[0114] 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-trimethylpentylphosphine oxide. Commercially available acylphosphine oxide compounds include Lucirin TPO (manufactured by BASF) and Irgacure-819 (manufactured by Ciba Specialty Chemicals).

[0115] Examples of the benzoin compound and benzoin ether compound include benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, and ethylbenzoin.

[0116] Examples of the dialkyl ketal compound include benzyl dimethyl ketal and benzyl diethyl ketal. Examples of thioxanthone compounds include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone. Examples of dialkylaminobenzoate compounds include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, and 2-ethylhexyl-4-(dimethylamino)benzoate.

[0117] Examples of oxime ester compounds include 1-phenyl-1,2-propanedione-2-O-benzoyloxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, etc. Commercially available oxime ester compounds include CGI-325, Irgacure-OXE01, and Irgacure-OXE02 (all manufactured by Ciba Specialty Chemicals).

[0118] As the acridine compound, 1,7-bis(9,9'-acridinyl)heptane or 9-phenylacridine is preferred in terms of sensitivity, resolution, availability, and the like.

[0119] From the viewpoints of adhesion and rectangularity of the resist pattern, the pyrazoline derivatives are preferably 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, or 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline.

[0120] Examples of the ester compound of N-arylamino acid 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.

[0121] 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 diaryliodonium compounds. Among these, tribromomethylphenylsulfone is preferred.

[0122] <Component (D): Polymerization inhibitor> In the photosensitive resin laminate of the present disclosure, the photosensitive resin composition further contains the following component(s) in addition to the components (A) to (C): (D) a polymerization inhibitor, may include:

[0123] Examples of component (D) include p-methoxyphenol, methoquinone, hydroquinone, pyrogallol, naphthylamine, phenothiazine, 2,6-dibutylhydroxytoluene, tert-butylcatechol, 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], N-nitroso-N-phenylhydroxylamine aluminum salt (for example, aluminum salt with 3 moles of N-nitroso-N-phenylhydroxylamine added), and diphenylnitrosamine.

[0124] The content of the component (D) is preferably 0.01 to 0.8 mass %, and more preferably 0.01 to 0.3 mass %, based on the solid content of the photosensitive resin composition.

[0125] Here, the component (D) preferably contains a compound having a boiling point of 280°C or higher as a polymerization inhibitor. The boiling point Td (°C) of such a compound is often sufficiently higher than the boiling point Ts (°C) of the solvent contained in the photosensitive resin composition (for example, the boiling point Td is 150°C or higher than the boiling point Ts). The component (D), which has a boiling point sufficiently higher than that of the solvent, is less likely to form an azeotrope when the solvent is heated and dried in the process of producing the photosensitive resin laminate, and therefore is more likely to function as the component (D) in the final photosensitive resin laminate.

[0126] An example of a preferred compound having a boiling point of 280°C or higher is: Phenothiazine (boiling point: approximately 371°C) tert-Butylcatechol (boiling point: approximately 285°C) The boiling point of component (D) can be measured using a differential scanning calorimeter, and the values ​​listed in the catalog may be used as a reference. The boiling point of component (D) may be, for example, 500°C or lower.

[0127] The compounds having a boiling point of 280° C. or higher as component (D) are not limited to those mentioned above. In particular, compounds having a skeleton derived from catechol can often be suitably used as component (D), which is a compound having a boiling point of 280° C. or higher.

[0128] That is, examples of compounds with a boiling point of 280°C or higher include: phenothiazines, Compounds having a skeleton derived from phenothiazine, and a compound having a skeleton derived from catechol, That is, the compound having a boiling point of 280° C. or higher preferably includes at least one selected from the group consisting of phenothiazine, a phenothiazine derivative, and a catechol derivative. Here, "a compound having a skeleton derived from phenothiazine" means a phenothiazine derivative in which an arbitrary substituent has been added to phenothiazine, and "a compound having a skeleton derived from catechol" means a catechol derivative in which an arbitrary substituent has been added to catechol. Catechol alone does not have a boiling point of 280°C or higher, but by adding an arbitrary substituent to catechol, the boiling point can be easily controlled to 280°C or higher. An example of a compound having a skeleton derived from catechol and a boiling point of 280°C or higher is tert-butylcatechol.

[0129] The content of the compound having a boiling point of 280° C. or higher as component (D) is preferably 0.01 to 0.8 mass %, more preferably 0.01 to 0.3 mass %, based on the solid content of the photosensitive resin composition.

[0130] As described above, in the photosensitive resin laminate of the present disclosure, the effects of this embodiment can be easily achieved by appropriately controlling the type and content of the component (D).

[0131] <Other ingredients> In the photosensitive resin laminate of the present disclosure, the photosensitive resin composition may optionally contain components (other components) other than the above components (A) to (D), if desired. Examples of other components include dyes, antioxidants, stabilizers, halogen compounds, plasticizers, hindered amine compounds, and solvents.

[0132] (dye) Examples of the dye include leuco dyes, base dyes, etc. When the photosensitive resin composition contains these dyes, the resulting photosensitive resin laminate tends to have excellent color development properties in the unexposed areas and excellent peeling properties of the resist pattern.

[0133] Examples of leuco dyes include leuco crystal violet (tris[4-(dimethylamino)phenyl]methane) and 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide. Among these, leuco crystal violet is preferred as the leuco dye.

[0134] The content of the leuco dye is preferably 0.01 to 2 mass %, more preferably 0.1 to 1.5 mass %, based on the solid content of the photosensitive resin composition. By adjusting the content of the leuco dye within this range, it is easy to achieve good color development and good sensitivity of the photosensitive resin layer.

[0135] Examples of base dyes include Diamond Green [CAS number (hereinafter the same): 633-03-4] (e.g., Aizen Diamond Green GH, manufactured by Hodogaya Chemical Co., Ltd.), Fuchsin [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 BOH, manufactured by Hodogaya Chemical Co., Ltd.), Rhodamine B [81-88-9], Rhodamine 6G [989-38-8], and Basic Yellow 2 [2465-27-2]. Among these, Diamond Green is preferred as the base dye from the viewpoints of excellent coloring properties, hue stability, and exposure contrast.

[0136] The content of the base dye is preferably 0.001 to 3 mass %, more preferably 0.01 to 2 mass %, and even more preferably 0.04 to 1 mass %, based on the solid content of the photosensitive resin composition. By adjusting the content of the base dye within this range, good color development and good sensitivity of the photosensitive resin layer can be easily achieved.

[0137] (antioxidant) Examples of antioxidants include triphenyl phosphite (e.g., manufactured by ADEKA under the trade name: TPP), tris(2,4-di-tert-butylphenyl) phosphite (e.g., manufactured by ADEKA under the trade name: 2112), tris(mononylphenyl) phosphite (e.g., manufactured by ADEKA under the trade name: 1178), and bis(mononylphenyl)-dinonylphenyl phosphite (e.g., manufactured by ADEKA under the trade name: 329K).

[0138] The content of the antioxidant is preferably 0.01 to 0.8% by mass, more preferably 0.01 to 0.3% by mass, based on the solid content of the photosensitive resin composition. By adjusting the content of the antioxidant within this range, advantages such as favorable hue stability of the resist pattern and improved sensitivity of the photosensitive resin layer can be obtained.

[0139] (stabilizer) The stabilizer can be used to improve the thermal stability and / or storage stability of the photosensitive resin composition. Examples of the stabilizer include at least one of benzotriazoles and alkylene oxide compounds having a glycidyl group.

[0140] Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.

[0141] The benzotriazoles are preferably compounds having a carboxy group, and examples thereof include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole, and a 1:1 mixture of 1-(2-di-n-butylaminomethyl)-5-carboxylbenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxylbenzotriazole. Among these, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and a 1:1 mixture of 1-(2-di-n-butylaminomethyl)-5-carboxylbenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxylbenzotriazole are preferred.

[0142] Examples of alkylene oxide compounds having a glycidyl group include neopentyl glycol diglycidyl ether (e.g., Epolite 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (e.g., Epolite 400E manufactured by Kyoeisha Chemical Co., Ltd.), bisphenol A-propylene oxide 2-mol adduct diglycidyl ether (e.g., Epolite 3002 manufactured by Kyoeisha Chemical Co., Ltd.), and 1,6-hexanediol diglycidyl ether (e.g., Epolite 1600 manufactured by Kyoeisha Chemical Co., Ltd.).

[0143] The total content of the stabilizers is preferably 0.001 to 3 mass %, more preferably 0.05 to 1 mass %, based on the solid content of the photosensitive resin composition. The total content is preferably equal to or greater than the above lower limit from the viewpoint of imparting good storage stability to the photosensitive resin composition, and is preferably equal to or less than the above upper limit from the viewpoint of maintaining the sensitivity of the photosensitive resin layer.

[0144] (halogen compounds) The photosensitive resin composition may further contain a halogen compound, or may contain a halogen compound together with the leuco dye. When the photosensitive resin composition contains both a leuco dye and a halogen compound, adhesion and contrast tend to be improved.

[0145] 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, and chlorinated triazine compounds. Among these, tribromomethylphenylsulfone is preferred. Halogen compounds such as tribromomethylphenylsulfone are highly effective when used in combination with an acridine-based compound (B3), and are preferred in this case from the viewpoints of improving resolution, adhesion, sensitivity, contrast, tent film penetration resistance, suppressing resist footing, and / or etching resistance.

[0146] From the above viewpoints, the content of the halogen compound is preferably 0.01% by mass or more relative to the solid content of the photosensitive resin composition. This proportion is more preferably 0.1% by mass or more, even more preferably 0.3% by mass or more, and particularly preferably 0.5% by mass or more. Furthermore, it is preferable that this proportion be 3% by mass or less from the viewpoints of maintaining the storage stability of the hue in the photosensitive resin layer and suppressing the generation of aggregates in the photosensitive resin layer during development. This proportion is more preferably 2% by mass or less, even more preferably 1.5% by mass or less.

[0147] (plasticizer) Examples of the plasticizer 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, polyoxypropylene monoethyl ether, and polyoxyethylene polyoxypropylene monoethyl ether; Phthalate esters of diethyl phthalate; o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, triethyl acetylcitrate, tri-n-propyl acetylcitrate, tri-n-butyl acetylcitrate, etc.; Propylene glycol, which is propylene oxide added to both ends of bisphenol A, ethylene glycol, which is ethylene oxide added to both ends of bisphenol A, etc.; Aluminum salts to which 1 to 3 moles of nitrosophenylhydroxylamine have been added; Examples include:

[0148] The content of the plasticizer is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, based on the solid content of the photosensitive resin composition. When this proportion is 1% by mass or more, delays in development time are easily suppressed and flexibility is easily imparted to the cured film. When this proportion is 50% by mass or less, insufficient curing and edge fuse tend to be suppressed.

[0149] (Hindered amine compounds) Examples of the hindered amine compound include 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethyl-1-hydroxypiperidine, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethyl-1-oxypiperidine, 2,2,6,6-tetramethylpiperidyl methacrylate, and 1,2,2,6,6-pentamethylpiperidyl methacrylate.

[0150] From the viewpoint of improving the flexibility of the cured film after the crosslinking reaction and improving the releasability, the hindered amine compound preferably has a monofunctional polymerizable group, and 2,2,6,6-tetramethylpiperidyl methacrylate and 1,2,2,6,6-pentamethylpiperidyl methacrylate are particularly preferred.

[0151] The content of the hindered amine compound is preferably 0.001 to 10% by mass relative to the solid content of the photosensitive resin composition. From the viewpoint of excellent releasability, this proportion is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, even more preferably 0.1% by mass or more, and particularly preferably 0.3% by mass or more. On the other hand, from the viewpoint of achieving good resolution, this proportion is preferably 5% by mass or less, more preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less. The hindered amine compound may be used as a repeating unit in component (A).

[0152] (solvent) The photosensitive resin layer is formed by applying a coating liquid in which a photosensitive resin composition is dispersed in a solvent to the temporary support layer or to an optional intermediate layer to be applied to the temporary support layer, and then drying the coating liquid. The resulting photosensitive resin layer may contain residual solvent. Examples of the solvent include ketones such as methyl ethyl ketone; alcohols such as methanol, ethanol, and isopropanol; and toluene. Another example of the solvent is acetone. The content of the solvent remaining in the photosensitive resin layer is preferably 5% by mass or less, and more preferably 3% by mass or less, based on the solid content of the photosensitive resin composition.

[0153] [Method for producing photosensitive resin laminate] Another aspect of the present embodiment is a method for producing a photosensitive resin laminate. Such methods include, for example, combining the following ingredients: (A) alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator, a step of applying a photosensitive resin composition containing the above compound onto a temporary support layer to form a coating film; a step of drying the coating film to obtain a photosensitive resin layer; a step of laminating a protective layer on the photosensitive resin layer on the side opposite to the temporary support layer; Includes:

[0154] In particular, in the method of the present disclosure for producing the photosensitive resin laminate of the present disclosure, The component (B) is (b1) a compound having a molecular weight of 540 or less and having two or more ethylenically unsaturated bonds; Including, The thickness tr (μm) of the photosensitive resin layer and the thickness tp (μm) of the protective layer are determined by the following formula: tp≧25 (1) 1≦tp / tr≦3 (2) Both are satisfied.

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

[0156] The coating liquid can be applied to the temporary support layer by a known method, for example, by using a bar coater, a roll coater, or the like. A coating film is obtained by applying the coating liquid to the temporary support layer. The coating film can be dried using a known dryer under known conditions (drying temperature and drying time).

[0157] Here, in the method for producing a photosensitive resin laminate, The photosensitive resin composition further comprises the following components: (D) Polymerization inhibitor Including, Component (D) contains a compound with a boiling point of 280°C or higher, The boiling point of the solvent, Ts (°C), and the boiling point of the compound having a boiling point of 280°C or higher, Td (°C), are expressed by the following formula: Td-Ts≧150 (3) This makes it easy to avoid loss of component (D) due to azeotropy with the solvent when the solvent is heated and dried in the process of producing the photosensitive resin laminate. The solvent used here may be any of the solvents exemplified above. The boiling point Ts (°C) of a typical solvent is, for example, Ethanol (boiling point: approximately 78°C), Methyl ethyl ketone (boiling point: approximately 80°C), Toluene (boiling point: approximately 111°C), The boiling point Ts (°C) of the solvent can be measured by a known method, or a catalog value may be used as a reference.

[0158] [Photosensitive resin laminate roll] The photosensitive resin laminate roll of the present disclosure is obtained by winding (rolling) the photosensitive resin laminate of the present disclosure. In the laminate, when the temporary support layer and the photosensitive resin layer are in contact with each other and the photosensitive resin layer and the protective layer are in contact with each other, the temporary support layer and the photosensitive resin layer are also in contact with each other in the roll obtained by winding such a laminate.

[0159] Furthermore, in the laminate, when one outermost layer is a temporary support layer and the other outermost layer is a protective layer, the temporary support layer and the protective layer come into contact with each other in the roll obtained by winding such a laminate.

[0160] The photosensitive resin laminate roll of the present disclosure has excellent quality stability over time, similar to the photosensitive resin laminate of the present disclosure, and therefore, even if it is stored in a rolled state for a predetermined period of time, it is expected that a resist pattern with good image quality can be realized by using the photosensitive resin laminate thereafter.

[0161] The photosensitive resin laminate roll of the present disclosure may have a core material for constituting its axial core. A known core material may be used. On the other hand, the photosensitive resin laminate roll of the present disclosure may not have a core material. A roll without a core material can be obtained by a method of winding the photosensitive resin laminate without a core material, or by a method of winding the photosensitive resin laminate around a core material and then removing the core material in the axial direction, for example.

[0162] [Method for forming resist pattern] Another aspect of the present embodiment is a method for forming a resist pattern using the photosensitive resin laminate. Such a method comprises the following steps: a step of laminating the photosensitive resin layer of the photosensitive resin laminate on a substrate (lamination step); A step of exposing a photosensitive resin layer laminated on a substrate (exposure step); and a step of developing the photosensitive resin layer after exposure (developing step); By going through these steps, a resist pattern is formed.

[0163] [Lamination process] In the lamination step, the photosensitive resin layer of the photosensitive resin laminate is laminated on a substrate. Specifically, the lamination step includes the following steps: A step of peeling off the protective layer from the photosensitive resin laminate to expose the photosensitive resin laminate; and laminating the photosensitive resin layer on the substrate so that the exposed photosensitive resin layer contacts the substrate; In the lamination step, a predetermined laminator may be used, and in this case, the photosensitive resin layer may be heated and pressed onto the surface of the substrate.

[0164] Examples of materials for the substrate include copper, stainless steel (SUS), glass, and indium tin oxide (ITO). The heating temperature during lamination is, for example, 40 to 160°C. Thermocompression bonding can be performed by using a laminator equipped with rolls, or by repeatedly passing a laminate of a substrate and a photosensitive resin layer through rolls several times. Thermocompression bonding may be performed in a reduced pressure environment as desired. When laminating the photosensitive resin laminate on a substrate, the lamination surface of the substrate may be smoothed as necessary.

[0165] In addition, the lamination process is a step of drawing out the photosensitive resin laminate from the photosensitive resin laminate roll and laminating the photosensitive resin layer of the photosensitive resin laminate on a substrate; This allows the lamination step to be suitably accomplished using the photosensitive resin laminate roll.

[0166] [Exposure process] In the exposure step, the photosensitive resin layer laminated on the substrate is exposed to light. In the exposure step, specifically, the photosensitive resin layer is exposed using an exposure machine. The exposure can be performed before peeling off the temporary support layer from the photosensitive resin layer, or can be performed after peeling off the temporary support layer from the photosensitive resin layer. In the exposure step, when exposure is performed through a photomask, the exposure amount may be determined by the illuminance of the light source and the exposure time, and may also be measured using an actinometer.

[0167] The exposure step may be performed by direct imaging exposure. In direct imaging exposure, the photosensitive resin layer is exposed by a direct imaging device without using a photomask. A semiconductor laser or an ultra-high pressure mercury lamp with a wavelength of 350 to 410 nm is used as the light source. When the imaging pattern is controlled by a computer, the exposure dose may be determined by the illuminance of the exposure light source and the moving speed of the substrate.

[0168] In the exposure step, the method of irradiating the exposure light is preferably at least one method selected from the group consisting of projection exposure, proximity exposure, contact exposure, direct imaging exposure, and electron beam direct writing, and more preferably projection exposure or direct imaging exposure.

[0169] The exposure process is a step of heating the substrate and the exposed photosensitive resin layer after the exposure and before the development step (post-exposure heating 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. By carrying out the heating step, good resolution and good adhesion can be easily achieved. Heating may be carried out using an infrared or far-infrared heating furnace, hot air, a thermostatic bath, a hot plate, a hot air dryer, an infrared dryer, a hot roll, or the like.

[0170] The time elapsed from the exposure step to the heating step, more precisely, the time from the completion of exposure (i.e., the stop of exposure) to the start of heating, is preferably 10 to 600 seconds, more preferably 20 to 300 seconds. The time from the start of heating to the stop of heating is preferably 1 to 120 seconds, more preferably 5 to 60 seconds.

[0171] [Development process] In the development step, the photosensitive resin layer after exposure is developed. In the developing step, specifically, the unexposed portion of the photosensitive resin layer after exposure is removed with a developer using a developing device. This results in a resist pattern. If a temporary support layer is laminated on the photosensitive resin layer, the temporary support layer is peeled off from the photosensitive resin layer before the developing step.

[0172] The alkaline aqueous solution in the developer is preferably an aqueous solution of Na2CO3, K2CO3, tetramethylammonium hydroxide, or the like. The alkaline aqueous solution is selected according to the properties of the photosensitive resin layer, and for example, an aqueous Na2CO3 solution with a concentration of 0.2 to 2 mass % is used. The developer may contain a surfactant and / or an antifoaming agent, and may also contain a small amount of an organic solvent to promote development. In the development step, the temperature of the developer is preferably kept constant within the range of 20 to 40°C.

[0173] The development step preferably includes, after development: a step of washing the substrate and the resist pattern with water (water washing step); It is preferable that the washing water has the following characteristics. The washing step facilitates the removal of the developer remaining on the substrate and the resist pattern. Examples of the washing water used in the washing step include pure water and industrial water. From the viewpoint of achieving good resolution and facilitating the formation of a resist pattern with high rectangularity, a polyvalent metal salt may be mixed into the washing water at a concentration of 0.001 to 1 mass % in accordance with the properties of the photosensitive resin layer. Examples of the polyvalent metal salt include MgSO4. In the washing step, the temperature of the washing water is preferably kept constant within the range of 20 to 40°C.

[0174] The developing step includes, after the development, and after the development and the water washing, a step of heating the substrate and the formed resist pattern (post-development heating step); In this heating step, the heating temperature is preferably 60 to 300° C. By carrying out this heating step, the chemical resistance of the resist pattern is easily improved. Heating may be carried out using an infrared or far-infrared heating furnace, hot air, or the like.

[0175] [Conductor pattern manufacturing method] A further aspect of this embodiment is a method for producing a conductor pattern using the above-described photosensitive resin laminate. Such a method comprises the following steps: A step of obtaining a substrate on which a resist pattern is formed (a step of producing a substrate with a resist pattern); A step of performing an etching process or a plating process on the substrate on which the resist pattern has been formed, and forming a conductor pattern (conductor pattern forming step); a step of peeling the resist pattern from the substrate on which the conductive pattern is formed (peeling step); Includes:

[0176] [Process for Producing a Substrate with a Resist Pattern] In the process of producing a substrate having a resist pattern, a substrate having a resist pattern formed thereon is obtained. For this process, the above-mentioned section "Method of forming a resist pattern" can be referred to, and a substrate having a resist pattern can be obtained in this manner.

[0177] [Conductor pattern forming process]

[0178] In the conductive pattern forming step, the substrate on which the resist pattern has been formed is subjected to etching or plating to form a conductive pattern. Specifically, in the conductive pattern forming step, a known etching method or plating method is used to form a conductive pattern on the surface (e.g., copper surface) of the substrate (e.g., metal plate, metal-coated insulating plate, etc., as described above) exposed by development.

[0179] The etching treatment is carried out, 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 an aqueous solution of hydrochloric acid, an aqueous solution of ferric chloride, or a mixture thereof.

[0180] The plating process is carried out in accordance with a known plating method by developing (removing) the exposed portion and then plating the exposed portion of the substrate with metal (for example, metal plating with a copper sulfate plating solution) or solder.

[0181] [Peeling process] In the peeling step, the resist pattern is peeled off from the substrate on which the conductor pattern has been formed. By removing the resist pattern from the substrate, a wiring board (for example, a printed wiring board) having a desired conductor pattern is obtained.

[0182] In the stripping step, specifically, 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 also organic amine-based aqueous solutions. The stripping solution may contain a small amount of a water-soluble solvent. Examples of the water-soluble solvent include alcohol. The temperature of the stripping solution in the stripping step is preferably within a range of 40 to 70°C. The stripping time may be set appropriately.

[0183] [Other embodiments] The present invention is not limited to the above-described embodiment, and can be practiced in various modified forms within the scope of the invention.

[0184] The above embodiment has been described with reference to a photosensitive resin laminate consisting of only a temporary support layer, a photosensitive resin layer, and a protective layer. In this case, the temporary support layer and the photosensitive resin layer are in contact with each other, and the photosensitive resin layer and the protective layer are in contact with each other. In a roll formed by winding such a laminate, the temporary support layer and the protective layer are also in contact with each other.

[0185] On the other hand, in other embodiments, the photosensitive resin laminate may have layers (other layers) other than the temporary support layer, the photosensitive resin layer, and the protective layer. For example, the photosensitive resin laminate may have other layers on the side of the temporary support layer opposite the photosensitive resin layer, between the temporary support layer and the photosensitive resin layer, between the photosensitive resin layer and the protective layer, and / or on the side of the protective layer opposite the photosensitive resin layer. As long as the other layers do not contradict the gist of the present invention, the photosensitive resin laminates, etc. in other embodiments will have the same effects as those described in the above embodiments.

[0186] Other layers include an "intermediate layer" disposed 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 produced 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. Other layers include a "release layer" disposed on the opposite side of the protective layer from the photosensitive resin layer.

[0187] On the other hand, if the other layer is a thin film (for example, 0.5 μm or less), the thickness of the other layer may be ignored for the purposes of the present invention. In one embodiment, even if the protective layer in the photosensitive resin laminate has a release layer on the side opposite to the photosensitive resin layer (the outermost layer side), if the thickness of the release layer is 0.5 μm or less, for the purposes of the present invention, the photosensitive resin laminate roll obtained by winding the photosensitive resin laminate is considered to be such that "the protective layer and the temporary support layer are in contact with each other."

[0188] The temporary support layer, the photosensitive resin layer, and / or the protective layer may each be composed of a single layer or multiple layers. When composed of multiple layers, the total thickness of the layers may be treated as the thickness of the layer.

[0189] The temporary support layer has a function of supporting the photosensitive resin layer (support function), and the protective layer has a function of protecting the photosensitive resin layer (protective function). On the other hand, the temporary support layer may have both a support function and a protective function, and the protective layer may have both a protective function and a protective function. In these cases, the film that is expected to be peeled off first from the photosensitive resin layer in the method of forming a resist pattern, or the film that has less adhesive strength to the photosensitive resin layer, can be treated as the protective layer. [Example]

[0190] The present embodiment will be described below with reference to examples and comparative examples. However, the present embodiment is not limited to the following examples. Regarding the examples and comparative examples, various productions, measurements, evaluations, etc. were carried out by the following methods.

[0191] [Preparation of Evaluation Sample: Example 1] [Synthesis of component (A)] Solution (a) was prepared by mixing the types of monomers (copolymerization components) shown in the table below with 3.0 parts by mass of azobisisobutyronitrile in the amounts shown in the table below (unit: parts by mass). 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 dropwise to the mixture in the flask at a constant rate over 4 hours, and the mixture was then stirred at 80°C for 2 hours.

[0192] Next, solution (b) was prepared 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 at a constant rate over 10 minutes, followed by stirring at 80°C for 3 hours. The mixture in the flask was then further heated to 90°C over 30 minutes and then maintained at 90°C for 2 hours. Stirring was then stopped, and the mixture in the flask was cooled to room temperature (25°C). This resulted in solutions containing components (A-1) to (A-3) as alkali-soluble polymers, respectively.

[0193] [Table 1]

[0194] [(Weight average molecular weight) The weight-average molecular weights of the components (A-1) to (A-3) contained in each solution were calculated by gel permeation chromatography (GPC) using a calibration curve of standard polystyrene. The GPC conditions are shown below. (GPC conditions) Pump: JASCO PU-4580 Degasser: JASCO DG-2080-53 Column oven: JASCO CO-1560 Columns: 4 in total (Shodex): KF-807 x 1, KF-806M x 2, KF-802.5 x 1 Eluent: tetrahydrofuran Measurement temperature: 40℃ Flow rate: 1.00mL / min Detector: JASCO RI-1530

[0195] [Photosensitive Resin Laminate] The components shown in the table below (the numbers for each component indicate the amount of solid content (parts by mass)) were stirred and mixed with ethanol measured to give a solid content concentration of 60%, so that the amount of each component as solid content was as shown in the table below, to obtain a coating solution.

[0196] In Table 4 below, The proportion of compounds having a molecular weight of 900 or more in all B-1 compounds was 87 mass %, and the proportion of compounds having a molecular weight of 900 or more in all B-3 compounds was 79 mass %. The proportion of compounds having a molecular weight of 540 or less in all B-4 compounds was 54 mass %. That is, the content of (b1) the compound having a molecular weight of 540 or less and two or more ethylenically unsaturated bonds relative to the solid content of the photosensitive resin composition was calculated by multiplying the content of the B-4 compound relative to the solid content of the photosensitive resin composition by the proportion of the compound having a molecular weight of 540 or less in all of the B-4 compounds. a value obtained by multiplying the content of the B-1 compound relative to the solid content of the photosensitive resin composition by the proportion of the compounds having a molecular weight of 900 or more in the entire B-1 compound; and The content of (b2) compounds having a molecular weight of 900 or more and 3 to 6 ethylenically unsaturated bonds was calculated as the sum of the content of B-3 compound relative to the solid content of the photosensitive resin composition, multiplied by the proportion of compounds having a molecular weight of 900 or more in all of the B-3 compounds, and the result. The contents of the (b1) and (b2) compounds were measured using an ACQUITY (registered trademark) Advanced Polymer Chromatography (APC) system (manufactured by Waters) under the following measurement conditions. Solvent used: Tetrahydrofuran Flow rate: 0.5mL / min Column: XT45 x 3 Detector: Differential refractometer or UV-visible absorption spectrometer

[0197] A 16 μm thick polyethylene terephthalate film (Toray Industries, QS71) was used as the temporary support layer, and the above coating liquid was applied to its surface using a bar coater, followed by drying for 2.5 minutes in a dryer at 95°C. This resulted in a 25 μm thick photosensitive resin layer being formed on the temporary support layer. Next, a protective layer shown in the table below was laminated on the side of the photosensitive resin layer opposite the temporary support layer, thereby obtaining a photosensitive resin laminate.

[0198] [Table 2]

[0199] [Photosensitive Resin Laminate Roll] The photosensitive resin laminate obtained above was wound around a predetermined core material to obtain a photosensitive resin laminate roll.

[0200] [Formation of Resist Pattern] <Surface preparation of the board> The surface of a copper-clad laminate with a total thickness of 0.4 mm, laminated with 18 μm-thick rolled copper foil, was prepared. The surface was then washed with a 10% by mass H2SO4 aqueous solution and then with pure water. The washed copper-clad laminate was preheated to 60°C.

[0201] <Lamination> While peeling off the protective layer from the photosensitive resin laminate, the laminate was laminated to a copper-clad laminate preheated to 60°C using a hot roll laminator (AL-700, manufactured by Asahi Kasei Corporation) 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 produced a substrate for evaluation. The air pressure during lamination was set to 0.35 MPa, and the lamination speed was set to 1.5 m / min.

[0202] <Exposure> One hour after lamination, the evaluation substrate was exposed to light at a wavelength of 365 nm using a predetermined exposure mask pattern with a projection exposure machine (UX-23101 manufactured by Ushio Inc.).

[0203] <Heating> One minute after exposure, the evaluation substrate was heated by passing it through a hot roll laminator (AL-700, manufactured by Asahi Kasei Corporation) set at 105° C. at a speed of 3 m / min.

[0204] <Developing> The temporary support layer was peeled off from the evaluation substrate. Then, using an alkaline developer (manufactured by Fuji Kiko Co., Ltd., a dry film developer), the photosensitive resin layer was developed by spraying a 1% by mass Na2CO3 aqueous solution at 30°C for a predetermined time. Then, the photosensitive resin layer was washed by spraying pure water for a predetermined time. This resulted in a resist pattern on the evaluation substrate.

[0205] [Fabrication of Conductive Pattern] Using the substrate with the resist pattern obtained above, a conductor pattern could be produced by a conventional method.

[0206] [Example 2] to [Example 11], and [Comparative Example 1] to [Comparative Example 2] A photosensitive resin laminate and a photosensitive resin laminate roll were produced, and further a resist pattern was formed, and a conductor pattern was produced (Example) based on the same method as in Example 1, except that the items described in the table were changed as shown in the table. In addition, except that the items described in the table were changed as shown in the table, an attempt was made to prepare a photosensitive resin laminate and a photosensitive resin laminate roll based on the same method as in Example 1, and further an attempt was made to form a resist pattern and an attempt was made to prepare a conductor pattern (Comparative Example).

[0207] [Measurement and Evaluation] [Thickness] The thickness tr (μm) of the photosensitive resin layer and the thickness tp (μm) of the protective layer were both measured using a non-contact in-line thickness meter such as the AccureX series manufactured by Hutec Corporation.

[0208] First, the thickness of the evaluation sample (photosensitive resin laminate) prepared above was measured at 1 mm intervals along the width direction within a range of 97% of the entire width direction length, centered on the center of the width direction, to obtain thickness data. The average value of the obtained thickness data was calculated and used as the thickness tr (μm) of the photosensitive resin layer.

[0209] The thickness data for the protective layer was also obtained using the same method. The average value of the obtained thickness data was calculated and used as the thickness tp (μm) of the protective layer. Note that the catalog value may be used as a reference for the thickness tp of the protective layer.

[0210] [Image quality] In order for a resist pattern formed using a photosensitive resin laminate to have good imaging properties, it is necessary for both adhesion and resolution to be good. That is, the smaller the sum of the "adhesion line width" and the "resolution line width" described below, the better the imaging properties.

[0211] <Adhesion> The evaluation was carried out using the mask pattern shown in Figure 1, in which the line width (L) / space width (S) ratio was x / x {x = 1 to 11 (varied in 0.5 μm intervals)} (unit: μm). That is, the substrate that had been subjected to the above-mentioned surface preparation and lamination was exposed to light at an optimum exposure dose using this mask pattern. Then, the above-mentioned heating and development treatment was carried out to form a resist pattern.

[0212] FIG. 1 is a plan view showing an example of the configuration of a mask pattern. In the figure, in an area 100 on the mask, an area that transmits the exposure light is indicated by the reference numeral 10 (transmitting area 10), and an area that does not transmit the exposure light is indicated by the reference numeral 1 (light-shielding area 1). In the figure, the light-shielding area 1 is indicated by diagonal lines.

[0213] The transparent region 10 has a predetermined width and extends in the x direction, and a plurality of such transparent regions 10 are arranged at predetermined intervals in the width direction (y direction). In this example, the unexposed portions of the photosensitive resin layer are removed through the above-mentioned development process, so that, theoretically, based on the mask pattern of Figure 1, a resist pattern having an L / S corresponding to the width of the transparent region 10 (L: line) and the width of the light-shielding region 1 (S: space) is expected to be formed.

[0214] The resulting resist pattern was observed under an optical microscope at 100x magnification to obtain an observation image. In the observation image, the smallest line width formed without the line portion (exposed portion) becoming meandering or missing was obtained as the "adhesion line width (unit: μm)." The smaller this value, the better the adhesion.

[0215] <Resolution> Evaluation was carried out using the mask pattern shown in Figure 2, in which the line width (L) / space width (S) ratio was x / x {x = 1 to 11 (varied in 0.5 μm intervals)} (unit: μm). That is, the substrate that had been subjected to the above-mentioned surface preparation and lamination was exposed to light at an optimum exposure dose using this mask pattern. Then, a resist pattern was formed by carrying out the above-mentioned heating and development treatment.

[0216] FIG. 2 is a plan view showing an example of the configuration of a mask pattern. In the figure, a transmissive region 10 and a light-shielding region 1 are shown in region 100A of the mask. The light-shielding region 1 has a predetermined width and extends in the x direction, and a plurality of such light-shielding regions 1 are arranged in the width direction (y direction) at predetermined intervals. Based on the mask pattern of Figure 2, it is theoretically expected that a resist pattern having an L / S corresponding to the width of the transmissive region 10 (L: line) and the width of the light-shielding region 1 (S: space) will be formed, just as in the case based on the mask pattern of Figure 1.

[0217] The resulting resist pattern was observed under an optical microscope at 100x magnification to obtain an observation image. In the observation image, the minimum line width at which the line portion (exposed portion) was removed without meandering or chipping and the space portion (unexposed portion) was removed without residue was obtained as the "resolved line width (unit: μm)." The smaller this value, the better the resolution.

[0218] <Image quality> The sum of the above "contact line width (unit: μm)" and the above "resolution line width (unit: μm)" was obtained as the value of "image quality (unit: μm)." The image quality was then evaluated according to the following criteria. (Evaluation criteria) Excellent (E:◎): Image quality (unit: μm) is less than 12 μm Good (G: 〇): Image quality (unit: μm) is 12 μm or more and less than 13 μm Acceptable (A:△): Image quality (unit: μm) is 13 μm or more and less than 14 μm Unacceptable (P: ×): Image quality (unit: μm) is 14 μm or more

[0219] <Quality stability over time (bleed resistance)> The photosensitive resin laminate was cut into three pieces measuring 200 mm long x 250 mm wide, and the three photosensitive resin laminates were stacked so that the temporary support layer and the protective layer were in contact with each other, thereby obtaining a measurement sample.

[0220] The measurement sample is sandwiched between metal plates and heated to 40°C before being placed in a press. 2 The sample was left for 2 hours while applying a pressure of 1000 kJ / cm. After 2 hours, the sample was removed and allowed to cool in an external environment (temperature: 23°C, humidity: 50%). The sample was then attached to the base of a friction tester (Toyo Seiki Seisakusho TR-2) with the temporary support layer on top and the protective film on the bottom (base side).

[0221] After fixing the measurement sample to a pedestal at a total of eight locations (four corners and four sides) to prevent wrinkles from forming on the measurement sample, a sled with a mass of 200 g was placed on the upper surface (the surface on the temporary support layer side) of the measurement sample via a dummy substrate (bare wafer). That is, a flat dummy substrate (a substrate with a cross-sectional size of 28 mm × 30 mm) was attached to the sled, and the sled was then placed on the upper surface of the measurement sample via the dummy substrate.

[0222] A 1 kg weight was placed on the sled, and 20 seconds were allowed to pass. The sled was then slid over a distance of 70 mm at a speed of 100 mm / min on the top surface of the measurement sample (the surface on the temporary support layer side), and the coefficient of friction (static coefficient of friction between the temporary support layer and the dummy substrate) was measured. The number of measurements (n) was 5, and the average value was calculated. The bleeding resistance was evaluated according to the following criteria. The measurements were performed under the above-mentioned external environment.

[0223] A small value of the obtained friction coefficient indicates that the degree of transfer of the photosensitive resin component to the temporary support layer via the protective layer is small, i.e., quality stability over time is ensured (excellent bleeding resistance). (Evaluation criteria) Excellent (E: 〇): Average friction coefficient is less than 4.5N Good (G: △): Average friction coefficient is 4.5N or more and less than 5.5N Unacceptable (P: ×): Average friction coefficient is 5.5N or more

[0224] <Sensitivity stability> The optimum exposure dose (mJ) was determined for each of the photosensitive resin laminates 3 days after preparation and 30 days after preparation. The optimum exposure dose (mJ) was determined as the exposure dose at which the line width of the cured resist pattern obtained after exposure and development (line width (L) / space width (S) = 8 μm / 8 μm) was 8 μm. The optimum exposure dose (mJ) was used to evaluate the sensitivity stability according to the following criteria. A smaller difference in the optimum exposure dose indicates better sensitivity stability. (Evaluation criteria) Excellent (E: 〇): The difference in optimal exposure is less than 15% Good (G: △): The difference in the optimum exposure is 15% or more but less than 20% Unacceptable (P: ×): The difference in optimal exposure is 20% or more.

[0225] <Layered> The copper alloy substrate subjected to the above <Substrate surface preparation> was preheated in an oven at 60°C for 10 minutes. A photosensitive resin laminate with a film thickness of 10 µm was laminated onto the copper alloy substrate at a speed of 3 m / min and exposed to light. Thereafter, the photosensitive resin layer was observed under a microscope from the temporary support layer side. 2 The number of trapped air bubbles (lamina air count) in the observation area was counted. The lamination property was evaluated using the lamination air count according to the following criteria. (Evaluation criteria) Good(E:〇) :10cm 2 The number of lamiairs is 0 Good(G:△) :10cm 2 The number of laminae is 1 to 3 or less. Not possible (P: ×): 10cm 2 In the case of 4 or more lamiairs

[0226] The results of the above are shown in the table below. In addition, in the table, "Content of multifunctional (B) component" refers to the content of (B) components having three or more functionalities, "(A) / (B)" indicates the ratio of the content of the (A) component to the content of the (B) component {(A) component / (B) component}, "EO" and "PO" represent ethylene oxide and propionate oxide, respectively.

[0227] [Table 3]

[0228] [Table 4]

[0229] As can be seen from the above table, it was confirmed that the examples make it possible to provide a photosensitive resin laminate that can realize a resist pattern with good imaging properties and ensure quality stability over time.

[0230] Regarding quality stability over time, in the above evaluation, multiple photosensitive resin laminate samples were laminated so that the temporary support layer and the protective layer were in contact with each other. However, it is expected that quality stability over time will be ensured even in the case of a similar "photosensitive resin laminate roll" in terms of the temporary support layer and the protective layer being in contact with each other.

[0231] Furthermore, with regard to the quality stability over time, it was confirmed that the quality stability over time can be ensured even under the severe environment of heating and pressurization, and therefore it is expected that bleeding can be suppressed for an even longer period of time under a normally expected storage environment (for example, room temperature and atmospheric pressure). [Industrial Applicability]

[0232] According to the present invention, it is possible to provide a photosensitive resin laminate that can realize a resist pattern with good imaging properties and ensure quality stability over time. Such a photosensitive resin laminate can be widely used as a photosensitive resin laminate for forming a resist pattern on a printed wiring board or the like. [Explanation of symbols]

[0233] 1: Shade area 10:Transparent area 100,100A: Area in the mask L: Line S: Space

Claims

1. A photosensitive resin laminate comprising a temporary support layer, a photosensitive resin layer containing a photosensitive resin composition, and a protective layer, The photosensitive resin composition comprises the following components: (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator, Including, The component (B) is (b1) a compound having a molecular weight of 540 or less and having two or more ethylenically unsaturated bonds; Including, The thickness tr (μm) of the photosensitive resin layer and the thickness tp (μm) of the protective layer are expressed by the following formula: tp≧25 (1) 1≦tp / tr≦3 (2) The photosensitive resin laminate satisfies both of the above requirements.

2. The photosensitive resin composition further comprises the following component: (D) Polymerization inhibitor 2. The photosensitive resin laminate according to claim 1, wherein the component (D) comprises a compound having a boiling point of 280°C or higher.

3. 3. The photosensitive resin laminate according to claim 2, wherein the compound having a boiling point of 280°C or higher includes at least one selected from the group consisting of phenothiazine, a phenothiazine derivative, and a catechol derivative.

4. 3. The photosensitive resin laminate according to claim 1, wherein the compound (b1) is a compound having two ethylenically unsaturated bonds.

5. 3. The photosensitive resin laminate according to claim 1, wherein the content of the compound (b1) is 1.5 to 5.0 mass % relative to the solid content of the photosensitive resin composition.

6. 3. The photosensitive resin laminate according to claim 1, wherein the thickness tp (μm) of the protective layer is 2.0 times or more the content (mass%) of the (b1) compound relative to the solid content of the photosensitive resin composition.

7. The component (B) further comprises: (b2) a compound having a molecular weight of 900 or more and 3 to 6 ethylenically unsaturated bonds; The photosensitive resin laminate according to claim 1 or 2, comprising:

8. 8. The photosensitive resin laminate according to claim 7, wherein the ratio of the content of the compound (b1) to the content of the compound (b2) {(b1) compound / (b2) compound} is 0.1 to 1.

0.

9. 3. The photosensitive resin laminate according to claim 1, wherein the ratio of the content of the component (A) to the content of the component (B) {component (A) / component (B)} is 1.30 or more.

10. 3. The photosensitive resin laminate according to claim 1, wherein the ratio of the content of the component (A) to the content of the component (B) {component (A) / component (B)} is 1.50 or more.

11. 3. The photosensitive resin laminate according to claim 1, wherein the ratio of the content of the component (A) to the content of the component (B) {component (A) / component (B)} is 1.69 or less.

12. The following ingredients: (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator, a step of applying a photosensitive resin composition containing the above compound onto a temporary support layer to form a coating film; a step of drying the coating film to obtain a photosensitive resin layer; a step of laminating a protective layer on the photosensitive resin layer on the side opposite to the temporary support layer; Including, The component (B) is (b1) a compound having a molecular weight of 540 or less and having two or more ethylenically unsaturated bonds; Including, The thickness tr (μm) of the photosensitive resin layer and the thickness tp (μm) of the protective layer are expressed by the following formula: tp≧25 (1) 1≦tp / tr≦3 (2) The method for producing a photosensitive resin laminate satisfies both of the above.

13. The step of forming the coating film includes: a step of dissolving the photosensitive resin composition in a solvent to obtain a coating liquid; A step of applying the coating liquid onto a temporary support layer; The method for producing a photosensitive resin laminate according to claim 12, comprising:

14. The photosensitive resin composition further comprises the following component: (D) Polymerization inhibitor Including, The component (D) contains a compound having a boiling point of 280°C or higher, The boiling point of the solvent is Ts (°C) and the boiling point of the compound having a boiling point of 280°C or higher is Td (°C), which satisfies the following formula: Td-Ts≧150... (3) The method for producing a photosensitive resin laminate according to claim 12 or 13, wherein the above formula (1) is satisfied.

15. A photosensitive resin laminate roll including a temporary support layer, a photosensitive resin layer containing a photosensitive resin composition, and a protective layer, The photosensitive resin composition comprises the following components: (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator, Including, The component (B) is (b1) a compound having a molecular weight of 540 or less and having two or more ethylenically unsaturated bonds; Including, The thickness tr (μm) of the photosensitive resin layer and the thickness tp (μm) of the protective layer are expressed by the following formula: tp≧25 (1) 1≦tp / tr≦3 (2) The photosensitive resin laminate roll satisfies both of the above requirements.

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