Photosensitive resin film, and application of the same

Abstract

To provide a photosensitive resin film, and an application of the same.SOLUTION: In a photosensitive resin film, an absolute value of a first derivative of a weight percentage to a time within a range of 0 to 40 minutes is higher than 0.1% / min and is not higher than 1.0% / min when the photosensitive resin film is subjected to thermogravimetric analysis under a condition of heating to 200°C from 40°C by a rate of 5°C / min, and holding a temperature of 200°C for 10 minutes.SELECTED DRAWING: None

Description

Technical Field

[0001] Priority Claim This application claims the priority of Taiwan Patent Application No. 113100428 filed on January 4, 2024, and Chinese Patent Application No. 202410010517.2 filed on January 4, 2024. The subject matters of these patent applications are incorporated herein by reference in their entirety.

[0002] Field of the Invention This application provides a photosensitive resin film, particularly a thick photosensitive resin film, and applications thereof.

Background Art

[0003] A photosensitive resin film is a film that undergoes chemical changes after exposure and is used as a photoresist film in the field of electronics. Depending on the changes after exposure, the photoresist film can be classified into a positive photoresist film and a negative photoresist film. In a positive photoresist film, the exposed part of the photoresist film dissolves during development, and the unexposed part of the photoresist film remains. In a negative photoresist film, the unexposed part of the photoresist film dissolves during development, and the exposed part of the photoresist film remains. Benefit In the printed circuit board (PCB) industry, a photoresist film is used in an etching process or an electroplating process to form a circuit pattern. Due to the increasing complexity and size of electronic components, the PCB industry demands a thick photoresist film with a high ratio of depth to width. However, conventional photoresist films often exhibit low storage characteristics, adhesiveness, and / or operability, thus causing defects in subsequent etching processes or electroplating processes.

[0004]

Summary of the Invention

Problems to be Solved by the Invention

[0005] From the perspective of the above technical problems, the object of the present invention is to provide a photosensitive resin film having excellent storage characteristics, adhesiveness, and operability. This photosensitive resin film can be used in various fields of electronics that require high-precision etching or electroplating processes.

Means for Solving the Problems

[0006] Accordingly, an object of the present invention is to provide a photosensitive resin film, which when subjected to thermogravimetric analysis under the condition of heating from 40°C to 200°C at a rate of 5°C / min and maintaining a temperature of 200°C for 10 minutes, has an absolute value of the first derivative of the weight percentage with respect to time in the range of 0 to 40 minutes higher than 0.1% / min and not higher than 1.0% / min.

[0007] In some embodiments of the present invention, when the photosensitive resin film is subjected to the above thermogravimetric analysis, the weight loss percentage of the photosensitive resin film within the range of 0 to 20 minutes is higher than 0% by weight and not higher than 10% by weight, preferably in the range of 2% to 10% by weight.

[0008] In some embodiments of the present invention, the photosensitive resin film has a thickness of 60 μm to 600 μm.

[0009] In some embodiments of the present invention, the photosensitive resin film is a dry film.

[0010] In some embodiments of the present invention, the photosensitive resin film contains (A) an alkali-soluble polymer, (B) a component of an ethylenically unsaturated compound, and (C) a photopolymerization initiator.

[0011] In some embodiments of the present invention, the component (B) of the ethylenically unsaturated compound contains one or more difunctional acrylate-based compounds.

[0012] In some embodiments of the present invention, the amount of the difunctional acrylate-based compound based on the weight of the component (B) of the ethylenically unsaturated compound is 60% by weight or more.

[0013] Other of the present invention ObjectiveIt is to provide a composite film including the photosensitive resin film and a protective film on at least one surface of the photosensitive resin film.

[0014] In some embodiments of the present invention, the protective film is selected from the group consisting of polyethylene terephthalate films, polyolefin films, and composites thereof.

[0015] In order to clarify the above problems, technical features, and advantages of the present invention in more detail, the present invention will be described in detail below with reference to some specific embodiments.

Embodiments for Carrying Out the Invention

[0016] Some specific embodiments of the present invention will be described in detail. However, the present invention may be embodied in various embodiments and should not be limited to the embodiments described herein.

[0017] Unless otherwise explained, the expressions "a", "the", etc. described in this specification and the claims should include both singular and plural forms.

[0018] Unless otherwise explained, the expressions "first", "second", etc. described in this specification and the claims do not have special meanings and are only used to distinguish the described elements or components. These expressions are not used to represent priorities.

[0019] Unless otherwise explained, the terms "(meth)acrylic acid", "(meth)acrylate", etc. are intended to cover both aspects where the functional groups within the parentheses are included and those where they are not included. For example, the term "(meth)acrylic acid" is intended to cover both acrylic acid and methacrylic acid. The term "methyl (meth)acrylate" is intended to cover both methyl acrylate and methyl methacrylate.

[0020] In this specification and the claims, the weight-average molecular weight (Mw) is measured by gel permeation chromatography (GPC) and calculated by comparison with polystyrene standard samples. The unit of the weight-average molecular weight (Mw) is "g / mol".

[0021] The main effect of the present invention over the prior art is to provide a thick photosensitive resin film having excellent storage properties, adhesiveness, and operability by controlling the first derivative of the weight percentage with respect to time in thermogravimetric analysis. The photosensitive resin film of the present invention and its applications will be described in detail below.

[0022] 1. Photosensitive Resin Film The photosensitive resin film of the present invention can be a positive photoresist film or a negative photoresist film. In some embodiments of the present invention, the photosensitive resin film is a negative photoresist film. That is, after exposure of the photosensitive resin film, the unexposed portions are dissolved in the developing process and the exposed portions remain.

[0023] As will be discussed in the following sections, prior to the use of the photosensitive resin film, a protective film providing functions of protection and support is provided on the surface of the photosensitive resin film to facilitate the storage of the photosensitive resin film and protect it from the incorporation of foreign substances or damage, thereby forming the structure of a hybrid film. Unless otherwise explained, the terms "thickness" and "thermogravimetric properties" described in this specification and the claims refer to the photosensitive resin film itself and do not include other parts such as the protective film used in combination with the photosensitive resin film.

[0024] In some embodiments of the present invention, the photosensitive resin film is a dry film, that is, a photosensitive resin film with a low solvent content. The above-mentioned low solvent content means that the amount of the solvent based on the total weight of the photosensitive resin film is 0.1 wt% to 8 wt%, more particularly 0.1 wt% to 7 wt%. In contrast to ink-like and liquid wet films, dry films are less likely to flow or deform due to their low solvent content and can be attached to a substrate without the need for additional processes such as coating or drying. Therefore, dry films are easy to control and have good operability.

[0025] The photosensitive resin film of the present invention can have a large thickness. In particular, the photosensitive resin film of the present invention can have a thickness of 60 μm to 600 μm. For example, the thickness of the photosensitive resin film of the present invention can be 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm, 190 μm, 200 μm, 210 μm, 220 μm, 230 μm, 240 μm, 250 μm, 260 μm, 270 μm, 280 μm, 290 μm, 300 μm, 310 μm, 320 μm, 330 μm, 340 μm, 350 μm, 360 μm, 370 μm, 380 μm, 390 μm, 400 μm, 410 μm, 420 μm, 430 μm, 440 μm, 450 μm, 460 μm, 470 μm, 480 μm, 490 μm, 500 μm, 510 μm, 520 μm, 530 μm, 540 μm, 550 μm, 560 μm, 570 μm, 580 μm, 590 μm, or 600 μm, or can be between any two of these recited values. The thicker the photosensitive resin film, the thicker the possible thickness for plating the metal conductive layer when the photosensitive resin film is used as a photoresist film. Therefore, the photosensitive resin film of the present invention is particularly suitable for 2.5D and 3D integrated circuit packages and is useful for patterning before plating the conductive layer.

[0026] The photosensitive resin film of the present invention can be formed with a single photosensitive resin layer or by laminating two or more photosensitive resin layers. For example, the photosensitive resin film of the present invention can laminate 2, 3, or 4 photosensitive resin layers, but the present invention is not limited thereto.

[0027] 1.1. Thermogravimetric Characteristics of Photosensitive Resin Film The photosensitive resin film of the present invention has specific thermogravimetric characteristics. In particular, when the photosensitive resin film is heated from 40 °C (i.e., the temperature at the 0-second time point) to 200 °C at a rate of 5 °C / min and subjected to thermogravimetric analysis under the condition of maintaining the temperature of 200 °C for 10 minutes, the absolute value of the first derivative of the weight percentage with respect to time (i.e., d(weight%) / dt) within the range of 0 to 40 minutes is higher than 0.1% / min and not higher than 1.0% / min, preferably in the range of 0.2% / min to 1.0% / min. For example, when the photosensitive resin film is subjected to thermogravimetric analysis under the above conditions, the absolute value of the first derivative of the weight percentage with respect to time within the range of 0 to 40 minutes can be 0.11% / min, 0.13% / min, 0.15% / min, 0.17% / min, 0.19% / min, 0.21% / min, 0.23% / min, 0.25% / min, 0.27% / min, 0.29% / min, 0.31% / min, 0.33% / min, 0.35% / min, 0.37% / min, 0.39% / min, 0.41% / min, 0.43% / min, 0.45% / min, 0.47% / min, 0.49% / min, 0.51% / min, 0.53% / min, 0.55% / min, 0.57% / min, 0.59% / min, 0.61% / min, 0.63% / min, 0.65% / min, 0.67% / min, 0.69% / min, 0.71% / min, 0.73% / min, 0.75% / min, 0.77% / min, 0.79% / min, 0.81% / min, 0.83% / min, 0.85% / min, 0.87% / min, 0.89% / min, 0.91% / min, 0.93% / min, 0.95% / min, 0.97% / min, 0.99% / min, or 1.0% / min, or fall within the range between any two of these described values.

[0028] The expression "the absolute value of the first derivative of the weight percentage with respect to time within the range of 0 to 40 minutes is higher than 0.1% / min and not higher than 1.0% / min" means that at all time points within the range of 0 to 40 minutes, the first derivative of the weight percentage with respect to time is higher than 0.1% / min and not higher than 1.0% / min. Therefore, if the absolute value of the first derivative of the weight percentage with respect to time within the range of 0 to 40 minutes has a minimum value higher than 0.1% / min and a maximum value not higher than 1.0% / min, it can be confirmed that the photosensitive resin film exhibits the above-mentioned thermogravimetric characteristics of the present invention. Conversely, if the absolute value of the first derivative of the weight percentage with respect to time within the range of 0 to 40 minutes has a minimum value not higher than 0.1% / min or a maximum value higher than 1.0% / min, it can be confirmed that the photosensitive resin film does not exhibit the above-mentioned thermogravimetric characteristics of the present invention.

[0029] In the present invention, the first derivative of the weight percentage with respect to time is obtained by subjecting the photosensitive resin film to thermogravimetric analysis and analyzing the derivative thermogravimetric curve. Specifically, the thermogravimetric analysis is performed under the following operating conditions. Under the above operating conditions, the protective films are removed from both surfaces of the photosensitive resin film, and two sections are created along the transverse direction (TD) and the machine direction (MD) of the photosensitive resin film to obtain a sample of 5 mg to 30 mg. The furnace of the thermogravimetric analyzer is heated from room temperature to 40°C at a heating rate of 5°C / min and maintained at a temperature of 40°C. The sample is placed in the furnace of the thermogravimetric analyzer. Air with a flow rate of 40 mL / min is used as the purge gas for balance, and air with a flow rate of 100 mL / min is used as the purge gas for the sample. The sample is heated from 40°C to 200°C at a heating rate of 5°C / min and maintained at a temperature of 200°C for 10 minutes. During the operation, the weight loss is recorded every 0.5 seconds, and a thermogravimetric measurement curve of the weight percentage with respect to time within the range of 0 to 40 minutes calculated from the start of heating at a heating rate of 5°C / min is obtained. The first derivative is calculated from the thermogravimetric measurement curve to obtain a derivative thermogravimetric measurement curve. In some embodiments of the present invention, a photosensitive resin film cut into 20 mg is used as the sample.

[0030] When the photosensitive resin film is subjected to thermogravimetric analysis under the above conditions, the weight loss percentage of the photosensitive resin film within the range of 0 to 20 minutes is preferably higher than 0% by weight and not higher than 10% by weight, more preferably in the range of 2% to 10% by weight, and even more preferably in the range of 2.2% to 9.5% by weight. For example, when the photosensitive resin film is subjected to thermogravimetric analysis under the above conditions, the weight loss percentage of the photosensitive resin film within the range of 0 to 20 minutes can be 0.5% by weight, 1% by weight, 1.5% by weight, 2% by weight, 2.5% by weight, 3% by weight, 3.5% by weight, 4% by weight, 4.5% by weight, 5% by weight, 5.5% by weight, 6% by weight, 6.5% by weight, 7% by weight, 7.5% by weight, 8% by weight, 8.5% by weight, 9% by weight, 9.5% by weight, or 10% by weight, or within the range between any two of these described values. The weight loss percentage of the photosensitive resin film within the range of 0 to 20 minutes is obtained from the above thermogravimetric measurement curve.

[0031] In some embodiments of the present invention, when the photosensitive resin film is subjected to thermogravimetric analysis under the above conditions, the weight loss percentage of the photosensitive resin film within the range of 0 to 10 minutes is not higher than 3% by weight. For example, when the photosensitive resin film is subjected to thermogravimetric analysis under the above conditions, the weight loss percentage of the photosensitive resin film within the range of 0 to 10 minutes can be 0.5% by weight, 1% by weight, 1.5% by weight, 2% by weight, 2.5% by weight, or 3% by weight, or within the range between any two of these described values. The weight loss percentage of the photosensitive resin film within the range of 0 to 10 minutes is obtained from the above thermogravimetric measurement curve.

[0032] In thermogravimetric analysis, the temperature at which the weight loss percentage of the photosensitive resin film reaches 3% by weight with respect to the initial weight when installed in the thermogravimetric measurement analyzer is designated as "T d3 ". In some embodiments of the present invention, T d3 of the photosensitive resin film is preferably 90 °C or higher. For example, T d3It can be 90°C or higher, 100°C or higher, 110°C or higher, 120°C or higher, 125°C or higher, 130°C or higher, 135°C or higher, 140°C or higher, 145°C or higher, 150°C or higher, 155°C or higher, 160°C or higher, 165°C or higher, 170°C or higher, 175°C or higher, 180°C or higher, 185°C or higher, 190°C or higher, 195°C or higher, or 200°C or higher, or within the range between two of the values described above.

[0033] In thermogravimetric analysis, the temperature at which the weight loss percentage of the photosensitive resin film reaches 5% by weight with respect to the initial weight when installed in the thermogravimetric measurement analyzer is defined as "T d5 ". In some embodiments of the present invention, the T d5 of the photosensitive resin film is preferably 90°C or higher, more preferably 105°C or higher, and even more preferably 115°C or higher. For example, the T d5 of the photosensitive resin film can be 110°C or higher, 120°C or higher, 125°C or higher, 130°C or higher, 135°C or higher, 140°C or higher, 145°C or higher, 150°C or higher, 155°C or higher, 160°C or higher, 165°C or higher, 170°C or higher, 175°C or higher, 180°C or higher, 185°C or higher, 190°C or higher, 195°C or higher, or 200°C or higher, or within the range between two of the values described above.

[0034] In thermogravimetric analysis, the temperature at which the weight loss percentage of the photosensitive resin film reaches 10% by weight with respect to the initial weight when installed in the thermogravimetric measurement analyzer is defined as "T d10 ". In some embodiments of the present invention, the T d10 of the photosensitive resin film is preferably 140°C or higher, more preferably 145°C or higher. For example, the T d10 of the photosensitive resin film can be 145°C or higher, 150°C or higher, 155°C or higher, 160°C or higher, 165°C or higher, 170°C or higher, 175°C or higher, 180°C or higher, 185°C or higher, 190°C or higher, 195°C or higher, or 200°C or higher, or within the range between two of the values described above.

[0035] The thermogravimetric properties of the photosensitive resin film of the present invention can be controlled, for example, by adjusting the components of the photosensitive resin film or the process conditions of the photosensitive resin film (e.g., drying conditions). Those skilled in the art can prepare a photosensitive resin film having the above thermogravimetric properties based on the description in the specification of the present application, particularly based on the specific description of the examples. to investigate When the photosensitive resin film is subjected to thermogravimetric analysis under the above conditions, on the premise that the absolute value of the first derivative of the weight percentage with respect to time within the range of 0 to 40 minutes is higher than 0.1% / min and not higher than 1.0% / min, the components of the photosensitive resin film can be adjusted as necessary. In some embodiments of the present invention, the photosensitive resin film contains (A) an alkali-soluble polymer, (B) a component of an ethylenically unsaturated compound, and (C) a photopolymerization initiator. The photosensitive resin film can contain a small amount of solvent and optionally further contain additives.

[0036] 1.2. Components of Photosensitive Resin Film Examples of the alkali-soluble polymer include, but are not limited to, carboxy-containing acrylic polymers, carboxy-containing vinyl aromatic polymers, carboxy-containing norbornene polymers, carboxy-containing epoxy polymers, carboxy-containing amide polymers, carboxy-containing amide epoxy polymers, carboxy-containing alkyd polymers, and carboxy-containing phenolic polymers. The above alkali-soluble polymers can be used alone or in combination. In some embodiments of the present invention, the alkali-soluble polymer is a carboxy-containing acrylic polymer.

[0037] 1.2.1. (A) Alkali-Soluble Polymer

[0038] ​For example, an alkali-soluble polymer can be obtained by polymerizing one or more carboxy-containing polymerizable monomers or by copolymerizing other polymerizable monomers not containing carboxyl and one or more carboxy-containing polymerizable monomers. Accordingly, the alkali-soluble polymer can contain one or more repeating units derived from the carboxy-containing polymerizable monomer, or can contain one or more repeating units derived from the carboxy-containing polymerizable monomer and one or more repeating units derived from other polymerizable monomers.

[0039] In some embodiments of the present invention, the alkali-soluble polymer has repeating units derived from at least one first polymerizable monomer and repeating units derived from at least one second polymerizable monomer, and the first polymerizable polymer contains carboxy. Examples of the first polymerizable monomer include, but are not limited to, (meth)acrylic acid, α-bromo(meth)acrylic acid, α-chloro(meth)acrylic acid, β-phthalimido(meth)acrylic acid, β-styryl(meth)acrylic acid, propiolic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, and maleic acid. The second polymerizable monomer does not contain carboxy. Examples of the second polymerizable monomer include (meth)acrylate compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 1-methylcyclopentyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 2-butyl-2-adamantyl (meth)acrylate, tetrahydrofurfurylmethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate; (meth)acrylonitrile; vinyl ester compounds such as vinyl acetate and vinyl n-butyrate; vinyl aromatic compounds such as styrene, vinyl naphthalene, 3-acetoxystyrene, 4-acetoxystyrene, vinyltoluene, and α-methylstyrene; norbornene; acrylamide; maleate compounds such as monomethyl maleate, monoethyl maleate, and monoisopropyl maleate; and derivatives of the above polymerizable monomers, but are not limited thereto.The above-mentioned first polymerizable monomer and second polymerizable monomer can be used alone or in combination.

[0040] In a preferred embodiment of the present invention, an alkali-soluble polymer can be obtained by copolymerizing (meth)acrylic acid and one or more (meth)acrylate compounds. Accordingly, the alkali-soluble polymer contains repeating units derived from (meth)acrylic acid and repeating units derived from (meth)acrylate compounds. The weight ratio of (meth)acrylic acid to (meth)acrylate compound can be 1:20 to 1:1, more particularly 1:6 to 1:4. For example, the weight ratio of (meth)acrylic acid to (meth)acrylate compound can be 1:20, 1:19, 1:18, 1:17, 1:16, 1:15, 1:14, 1:13, 1:12, 1:11, 1:10, 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, or 1:1, or can fall within the range between any two of these recited values.

[0041] The weight average molecular weight (Mw) of the alkyl-soluble polymer can be 10,000 to 180,000, preferably 40,000 to 80,000. For example, the weight average molecular weight of the alkyl-soluble polymer can be 10,000, 15,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, 50,000, 55,000, 60,000, 65,000, 70,000, 75,000, 80,000, 85,000, 90,000, 95,000, 100,000, 105,000, 110,000, 115,000, 120,000, 125,000, 130,000, 135,000, 140,000, 145,000, 150,000, 155,000, 160,000, 165,000, 170,000, 175,000, or 180,000, or can fall within the range between two of these recited values.

[0042] In the photosensitive resin film of the present invention, the amount of the alkyl-soluble polymer based on the total weight of the photosensitive resin film can be in the range of 20% by weight to 85% by weight, particularly 40% by weight to 80% by weight, more particularly 50% by weight to 75% by weight. For example, the amount of the alkyl-soluble polymer based on the total weight of the photosensitive resin film can be 20% by weight, 22.5% by weight, 25% by weight, 27.5% by weight, 30% by weight, 32.5% by weight, 35% by weight, 37.5% by weight, 40% by weight, 42.5% by weight, 45% by weight, 47.5% by weight, 50% by weight, 52.5% by weight, 55% by weight, 57.5% by weight, 60% by weight, 62.5% by weight, 65% by weight, 67.5% by weight, 70% by weight, 72.5% by weight, 75% by weight, 77.5% by weight, 80% by weight, 82.5% by weight, or 85% by weight, or can fall within the range between any two of these recited values.

[0043] 1.2.2. (B) Component of Ethylenically Unsaturated Compound The ethylenically unsaturated compound represents a compound having at least one reactive ethylene functional group, preferably a bifunctional compound having two reactive ethylene functional groups. In some embodiments of the present invention, the components of the ethylenically unsaturated compound include monofunctional or polyfunctional acrylate compounds, preferably bifunctional acrylate compounds. Examples of acrylate compounds include, but are not limited to, ethoxylated bisphenol-A dimethacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated bisphenol-A diacrylate, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, polypropylene glycol diacrylate, tris((meth)acryloyloxy isocyanate) hexamethylene isocyanurate, ethoxylated urethane di(meth)acrylate, propoxylated urethane di(meth)acrylate, ethoxylated / propropoxylated urethane di(meth)acrylate, ethoxylated tris(methacryloyloxy isocyanate) hexamethylene isocyanurate, acrylated tris(methacryloyloxy isocyanate) hexamethylene isocyanurate, and ethoxylated / propropoxylated tris(methacryloyloxy isocyanate) hexamethylene isocyanurate. Further, based on the weight of the components of the ethylenically unsaturated compound, the amount of the bifunctional acrylate compound is preferably 60% by weight or more. For example, based on the weight of the components of the ethylenically unsaturated compound, the amount of the bifunctional acrylate compound can be 60% by weight, 62.5% by weight, 65% by weight, 67.5% by weight, 70% by weight, 72.5% by weight, 75% by weight, 77.5% by weight, 80% by weight, 82.5% by weight, 85% by weight, 87.5% by weight, 90% by weight, 92.5% by weight, 95% by weight, 97.5% by weight, or 100% by weight, or within the range between any two of these recited values.

[0044] In some embodiments of the present invention, the components of the ethylenically unsaturated compound include at least one of ethoxylated bisphenol-A dimethacrylate and trimethylolpropane triacrylate.

[0045] In the photosensitive resin film of the present invention, the amount of the ethylenically unsaturated compound component based on the total weight of the photosensitive resin film can be in the range of 5% by weight to 70% by weight, particularly 15% by weight to 50% by weight, more particularly 20% by weight to 45% by weight. For example, the amount of the ethylenically unsaturated compound component based on the total weight of the photosensitive resin film can be 5% by weight, 7.5% by weight, 10% by weight, 12.5% by weight, 15% by weight, 17.5% by weight, 20% by weight, 22.5% by weight, 25% by weight, 27.5% by weight, 30% by weight, 32.5% by weight, 35% by weight, 37.5% by weight, 40% by weight, 42.5% by weight, 45% by weight, 47.5% by weight, 50% by weight, 52.5% by weight, 55% by weight, 57.5% by weight, 60% by weight, 62.5% by weight, 65% by weight, 67.5% by weight, or 70% by weight, or can fall within the range between any two of the values described above.

[0046] 1.2.3. (C) Photoinitiator A photoinitiator represents a substance that can initiate a polymerization reaction in the presence of light. The type of photoinitiator is not particularly limited. Examples of photoinitiators include, but are not limited to, imidazole-based compounds, ketone-based compounds, quinone-based compounds, benzoin-based or benzoin ether-based compounds, polyhalogenated compounds, triazine-based compounds, organic peroxide compounds, onium compounds, and other common well-known photoinitiators. The above-mentioned photoinitiators can be used alone or in combination.

[0047] Examples of imidazole-based compounds include, but are not limited to, 2,4,5-triarylimidazole dimers such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0048] Examples of ketone compounds include, but are not limited to, benzophenone, 4,4-bis(dimethylamino)benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, xanthone, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, acridone, α-hydroxyacetophenone, α-aminoacetophenone, α-hydroxycycloalkylphenone, and dialkylacetophenone.

[0049] Examples of quinone compounds include, but are not limited to, camphorquinone, benzanthraquinone, 2-tert-butylanthraquinone, and 2-methylanthraquinone.

[0050] Examples of benzoin or benzoin ether compounds include, but are not limited to, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin phenyl ether.

[0051] Examples of polyhalogenated compounds include, but are not limited to, carbon tetrabromide, phenyltribromomethyl sulfone, and phenyltrichloromethyl ketone.

[0052] Examples of triazine compounds include, but are not limited to, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methoxy-4,6-bis(trichloromethyl)-s-triazine, 2-amino-4,6-bis(trichloromethyl)-s-triazine, and 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine.

[0053] Examples of organic peroxide compounds include, but are not limited to, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, benzoyl peroxide, di-tert-butyl isophthalate peroxide, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, tert-butyl peroxybenzoate, a,a'-bis(tert-butylperoxyisopropyl)benzene, dicumyl peroxide, and 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone.

[0054] Examples of onium compounds include diaryliodonium salts or triarylsulfonium salts obtained by combining diphenyliodonium, 4,4'-dichlorodiphenyliodonium, 4,4'-dimethoxydiphenyliodonium, 4,4'-di-tert-butyldiphenyliodonium, 4-methyl-4'-isopropyldiphenyliodonium, or 3,3'-dinitrodiphenyliodonium with chloride, bromide, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, tetrakis(pentafluorophenyl)borate, or trifluoromethanesulfonic acid, but are not limited to these.

[0055] Examples of other common well-known photoinitiators include, but are not limited to, fluorine, bisacylphosphine oxide, azinium compounds, organoboron compounds, phenylglyoxylate, and titanocene.

[0056] In some embodiments of the present invention, the photoinitiator is an imidazole-based compound or a ketone-based compound.

[0057] In the photosensitive resin film of the present invention, the amount of the photoinitiator based on the total weight of the photosensitive resin film can be in the range of 0.1% by weight to 15% by weight, particularly 0.5% by weight to 10% by weight, more particularly 1% by weight to 5% by weight. For example, the amount of the photoinitiator based on the total weight of the photosensitive resin film can be 0.1% by weight, 0.5% by weight, 1% by weight, 1.5% by weight, 2% by weight, 2.5% by weight, 3% by weight, 3.5% by weight, 4% by weight, 4.5% by weight, 5% by weight, 5.5% by weight, 6% by weight, 6.5% by weight, 7% by weight, 7.5% by weight, 8% by weight, 8.5% by weight, 9% by weight, 9.5% by weight, 10% by weight, 10.5% by weight, 11% by weight, 11.5% by weight, 12% by weight, 12.5% by weight, 13% by weight, 13.5% by weight, 14% by weight, 14.5% by weight, or 15% by weight, or can fall within the range between any two of these recited values.

[0058] 1.2.4. Solvent In the present invention, the photosensitive resin film can further contain a solvent. The solvent is an inert solvent that can dissolve or disperse the components of the photosensitive resin film and does not react with these components.

[0059] In some embodiments of the present invention, the photosensitive resin film contains a solvent having a boiling point in the range of 55°C to 120°C, preferably 60°C to 90°C. For example, the boiling point of the solvent can be 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 100°C, 110°C, or 120°C, or can fall within the range between any two of these recited values. Examples of solvents having a boiling point in the range of 55°C to 120°C include, but are not limited to, methyl acetate, ethyl acetate, acetone, methyl ethyl ketone, propylene glycol methyl ether, methanol, ethanol, n-propanol, and isopropanol. The above solvents can be used alone or in combination.

[0060] In the photosensitive resin film of the present invention, the amount of the solvent based on the total weight of the photosensitive resin film can be in the range of 0.1% by weight to 8% by weight, more particularly in the range of 0.1% by weight to 7% by weight. For example, the amount of the solvent based on the total weight of the photosensitive resin film can be 0.1% by weight, 0.5% by weight, 1% by weight, 1.5% by weight, 2% by weight, 2.5% by weight, 3% by weight, 3.5% by weight, 4% by weight, 4.5% by weight, 5% by weight, 5.5% by weight, 6% by weight, 6.5% by weight, 7% by weight, 7.5% by weight, or 8% by weight, or can fall within the range between any two of the values described herein.

[0061] 1.2.5. Optional Component When the photosensitive resin film is subjected to thermogravimetric analysis under the above conditions, on the premise that the absolute value of the first derivative of the weight percentage with respect to time within the range of 0 to 40 minutes is higher than 0.1% / min and not higher than 1.0% / min, the photosensitive resin film can further contain additives to improve the characteristics of the photoresist film. Examples of the additives include, but are not limited to, light absorbers, dyes, pigments, radical initiators, and surfactants. The above additives can be used alone or in combination.

[0062] 1.3. Preparation of Photosensitive Resin Film The method for preparing the photosensitive resin film of the present invention is not particularly limited. Those skilled in the art can prepare the photosensitive resin film based on the description in the specification of this application, particularly based on the specific description of the examples. For example, when preparing a photosensitive resin film containing the above-exemplified components, the preparation method includes the following steps: (A) a step of uniformly mixing each component of the photosensitive resin film including an alkali-soluble polymer, (B) a component of an ethylenically unsaturated compound, (C) a photopolymerization initiator, and any other optional additives with a stirrer; a step of dissolving or dispersing these in a solvent to form a resin composition; a step of coating the resin composition on a substrate; and a step of drying the coated resin composition to obtain a photosensitive resin film.

[0063] The coating method of the resin composition of the present invention is not particularly limited and can be an existing coating method in this technical field. Examples of existing coating methods include, but are not limited to, gravure coating, reverse roll coating, die coating, air knife coating, knife coating, rod coating, knife rod coating, curtain coating, knife coating, transfer roll coating, extrusion press coating, dip coating, kiss coating, spray coating, calendar coating, and extrusion coating. In some embodiments of the present invention, the coating method of the resin composition is preferably knife coating, rod coating, knife rod coating, or die coating.

[0064] The drying temperature can be adjusted according to the composition of the photosensitive resin film. Generally, the drying temperature can be in the range of 55°C to 120°C. For example, the drying temperature can be 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, or 120°C, or within the range between two of these described values. The drying time can be adjusted according to the composition of the photosensitive resin film. Generally, the drying time can be 20 minutes to 60 minutes. For example, the drying time can be 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, or 50 minutes, or within the range between two of these described values.

[0065] 2. Application of Photosensitive Resin Film The photosensitive resin film of the present invention can be used as a photoresist film and is applied in various fields of electronic engineering. Generally, before using the photosensitive resin film, both surfaces of the photosensitive resin film can be covered with a protective film that provides protection and support. This facilitates the storage of the photosensitive resin film and protects the photosensitive resin film from the intrusion of foreign substances or damage. Accordingly, the present invention also provides a composite film including the above-mentioned photosensitive resin film and a protective film on at least one surface of the photosensitive resin film. In a preferred embodiment of the present invention, the protective film is provided on both surfaces of the photosensitive resin film, and the materials of the protective films on different surfaces of the photosensitive resin film can be the same or different.

[0066] The type of the protective film is not particularly limited and can be any conventional film known in the art. For example, the protective film can be selected from the group consisting of polyethylene terephthalate films (PET films), polyolefin films, and composites thereof. Examples of polyolefin films include, but are not limited to, polyethylene films (PE films) and polypropylene films (PP films), such as biaxially oriented polypropylene films. The composite can be a composite of a polyethylene terephthalate film and a polyolefin film, or a composite of different polyolefin films. In a preferred embodiment of the present invention, the composite film includes a PET film on one surface of the photosensitive resin film and a PE film on the other surface of the photosensitive resin film.

[0067] The method for preparing the composite film of the present invention is not particularly limited and can be any method known in the art. Those skilled in the art can prepare the composite film based on the description in the specification of the present application. For example, the composite film can be prepared in a process of providing a laminate by stacking protective films on both surfaces of a photosensitive resin film, and a process of obtaining the composite film by pressing the laminate. Alternatively, in a process of coating a resin composition for forming a photosensitive resin film on a first protective film, drying the coated resin composition to form a photosensitive resin film on the first protective film, and then adhering a second protective film on the surface of the photosensitive resin film that is not in contact with the first protective film, the composite film can be prepared. Alternatively, in a process of extruding a resin composition for forming a photosensitive resin film into a gap between two protective films maintained at a predetermined distance, and then drying the extruded resin composition to form a photosensitive resin film between the two protective films, the composite film can be prepared.

Examples

[0068] 3. Examples 3.1. Test Method [Thermogravimetric Analysis of Photosensitive Resin Film] The PE protective film or PET protective film of the prepared composite film was removed from both surfaces of the photosensitive resin film. Subsequently, two slices were made along the transverse direction (TD) and the flow direction (MD), and 20 mg of the photosensitive resin film was provided as a sample. The furnace of the thermogravimetric analyzer (model: TA TGA Q500, TA Instruments) was heated from room temperature to 40 °C at a heating rate of 5 °C / min, and the temperature was maintained at 40 °C. The sample was placed in the furnace of the thermogravimetric analyzer, and air at a flow rate of 40 mL / min was used as the purge gas for the balance, and air at a flow rate of 100 mL / min was used as the purge gas for the sample. Subsequently, the sample was heated from 40 °C to 200 °C at a heating rate of 5 °C / min, and the temperature of 200 °C was maintained for 10 minutes. During the operation, the weight loss was recorded every 0.5 seconds, and using the analysis software (Universal Analysis V4.5A Build 4.5.0.5), a thermogravimetric measurement curve of the weight percentage with respect to time within the range of 0 to 40 minutes, calculated from the start of heating at a heating rate of 5 °C / min, was obtained. Using the same analysis software, the first derivative was calculated from the thermogravimetric measurement curve to obtain a derivative thermogravimetric curve. From the derivative thermogravimetric curve, the first derivative of the weight percentage with respect to time can be obtained. The weight loss percentage of the photosensitive resin film within the range of 0 to 20 minutes and the weight loss percentage of the photosensitive resin film within the range of 0 to 10 minutes (T d5 and T d10 ) are obtained from the thermogravimetric curve.

[0069] [Wrinkle Test of Photosensitive Resin Film] The prepared composite film was wound into a slit roll having a length of 30 m and a width of 300 mm and placed at a temperature of 23°C to 27°C for 12 hours. Thereafter, a 5-m length of the composite film was drawn out from the slit roll, and the PE protective film of the composite film was peeled off. Thereafter, the surface of the photosensitive resin film was visually observed. The number of wrinkles having a length of 10 mm or more and a width of 1 mm or more present within the range of 3 m to 5 m of the photosensitive resin film was recorded. If no wrinkles having a length of 10 mm or more and a width of 1 mm or more are seen, it indicates that the photosensitive resin film has excellent storage characteristics and operability.

[0070] [100-Grid Adhesion Test of the Thermal Photosensitive Resin Film] According to ASTM D3359, the 100-grid adhesion test of the photosensitive resin film was conducted in the following manner. A copper-clad laminate having a thickness of 1.6 mm (model: CCP-308, Chang Chun Prastics Co., Ltd.) was prepared. The copper foil of the copper-clad laminate had a thickness of 35 μm. The copper-clad laminate was subjected to brush polishing using a #320 non-woven fabric brush wheel and a #600 non-woven fabric brush wheel. The surface temperature of the copper foil of the copper-clad laminate was adjusted to 50°C. The PE protective film on the surface of the prepared composite film was peeled off. Along the PET protective film, the photosensitive resin film was stacked on the surface of the copper foil such that the photosensitive resin film faced the surface of the copper foil of the copper-clad laminate and laminated with a laminator to provide a sample. The lamination temperature was 80°C, the lamination pressure was 3.0 kg / cm 2 and the lamination speed was 2.0 mm / min. The PET film on the sample was peeled off, and the photosensitive resin film of the sample was cut with a knife into 100 grids of 10×10 squares having an interval of 1 mm to 1.2 mm. A transparent tape (model: 3M Transparent 600) manufactured by 3M Company was adhered to the surface of the grid photosensitive resin film. The tape was quickly peeled off at an angle of 45° with respect to the substrate. For all the grids, the number of grids from which the photosensitive resin film was peeled off was calculated and recorded as a percentage. A low percentage of grids from which the photosensitive resin film was peeled off indicates that the photosensitive resin film adhered better to the copper-clad laminate.

[0071] 3.2. Preparation and Test of Photosensitive Resin Film 3.2.1. Synthesis of Alkali-Soluble Polymer According to the following Synthesis Examples 1 to 5, a carboxy-containing acrylic polymer was prepared as an alkali-soluble polymer.

[0072] [Synthesis Example 1] As copolymerization monomers, 15 g of methacrylic acid, 60 g of methyl methacrylate, and 25 g of butyl acrylate were mixed with 0.5 g of azobisisoheptyl nitrile to prepare Solution a1. Separately, 0.5 g of azobisisoheptyl nitrile was dissolved in 20 g of ethyl acetate solvent to prepare Solution b1.

[0073] A flask equipped with a stirrer, a reflux condenser, a thermometer, and a pipette was prepared. 80 g of ethyl acetate solvent was added to the flask and heated to 70°C. Solution a1 was dropped into the flask at a constant rate over 3 hours, and the solution in the flask was maintained at a temperature of 70°C and stirred for 2 hours. While continuously maintaining the solution in the flask at a temperature of 70°C, Solution b1 was dropped into the flask at a constant rate over 0.5 hour, and the solution in the flask was maintained at a temperature of 70°C and stirred for 5 hours. Then, the solution in the flask was heated to 90°C and stirred for 5 hours to complete the reaction. After the reaction was completed, the resulting product was cooled to room temperature to obtain a carboxy-containing acrylic polymer A (hereinafter referred to as Polymer A) having a weight average molecular weight of 55,000 and a solid content of 50% by weight.

[0074] [Synthesis Example 2] As copolymerization monomers, 15 g of methacrylic acid, 65 g of methyl methacrylate, and 20 g of butyl acrylate were mixed with 0.5 g of azobisisoheptyl nitrile to prepare Solution a2. Separately, 0.5 g of azobisisoheptyl nitrile was dissolved in 20 g of methyl acetate solvent to prepare Solution b2.

[0075] Prepare a flask equipped with a stirrer, a reflux condenser, a thermometer and a pipette, add 102.2 g of methyl acetate solvent to the flask, and heat it to 70 °C. Drop solution a2 into the flask at a constant rate over 3 hours, maintain the solution in the flask at a temperature of 70 °C, and stir for 2 hours. While continuously maintaining the solution in the flask at a temperature of 70 °C, drop solution b2 into the flask at a constant rate over 0.5 hours, maintain the solution in the flask at a temperature of 70 °C, and stir for 5 hours. Then, heat the solution in the flask to 90 °C and stir for 5 hours to complete the reaction. After the reaction is completed, cool the resulting product to room temperature to obtain a carboxy-containing acrylic polymer B (hereinafter referred to as polymer B) having a weight average molecular weight of 65,000 and a solid content of 45 wt%.

[0076] [Synthesis Example 3] As a copolymer monomer, 20 g of methacrylic acid, 40 g of methyl methacrylate, and 40 g of 2-ethylhexyl acrylate were mixed with 0.5 g of azobisisoheptyl nitrile to prepare solution a3. Separately, 0.5 g of azobisisoheptyl nitrile was dissolved in 20 g of acetone solvent to prepare solution b3.

[0077] Prepare a flask equipped with a stirrer, a reflux condenser, a thermometer and a pipette, add 80 g of acetone solvent to the flask, and heat it to 70 °C. Drop solution a3 into the flask at a constant rate over 3 hours, maintain the solution in the flask at a temperature of 70 °C, and stir for 2 hours. While continuously maintaining the solution in the flask at a temperature of 70 °C, drop solution b3 into the flask at a constant rate over 0.5 hours, maintain the solution in the flask at a temperature of 70 °C, and stir for 5 hours. Then, heat the solution in the flask to 90 °C and stir for 5 hours to complete the reaction. After the reaction is completed, cool the resulting product to room temperature to obtain a carboxy-containing acrylic polymer C (hereinafter referred to as polymer C) having a weight average molecular weight of 55,000 and a solid content of 50 wt%.

[0078] [Synthesis Example 4] As the copolymerizable monomers, 20 g of methacrylic acid, 60 g of methyl methacrylate, and 20 g of butyl acrylate were mixed with 0.5 g of azobisisoheptyl nitrile to prepare solution a4. Separately, 0.5 g of azobisisoheptyl nitrile was dissolved in 20 g of propylene glycol methyl ether (PGME) solvent to prepare solution b4.

[0079] A flask equipped with a stirrer, a reflux condenser, a thermometer, and a pipette was prepared, 80 g of propylene glycol methyl ether solvent was added to the flask, and it was heated to 70 °C. Solution a4 was added dropwise to the flask at a constant rate over 3 hours, the solution in the flask was maintained at a temperature of 70 °C, and it was stirred for 2 hours. While continuously maintaining the solution in the flask at a temperature of 70 °C, solution b4 was added dropwise to the flask at a constant rate over 0.5 hours, the solution in the flask was maintained at a temperature of 70 °C, and it was stirred for 5 hours. Then, the solution in the flask was heated to 90 °C and stirred for 5 hours to complete the reaction. After the reaction was completed, the resulting product was cooled to room temperature to obtain a carboxy-containing acrylic polymer D (hereinafter referred to as polymer D) having a weight average molecular weight of 50,000 and a solid content of 50 wt%.

[0080] [Synthesis Example 5] As the copolymerizable monomers, 15 g of acrylic acid, 65 g of methyl methacrylate, and 20 g of butyl acrylate were mixed with 0.5 g of azobisisoheptyl nitrile to prepare solution a5. Separately, 0.5 g of azobisisoheptyl nitrile was dissolved in 20 g of ethyl acetate solvent to prepare solution b5.

[0081] Prepare a flask equipped with a stirrer, a reflux condenser, a thermometer and a pipette, add a mixed solvent of 20 g of ethanol and 60 g of ethyl acetate to the flask, and heat it to 70 °C. Drop solution a5 into the flask at a constant rate over 3 hours, maintain the solution in the flask at a temperature of 70 °C, and stir for 2 hours. While continuously maintaining the solution in the flask at a temperature of 70 °C, drop solution b5 into the flask at a constant rate over 0.5 hours, maintain the solution in the flask at a temperature of 70 °C, and stir for 5 hours. Then, heat the solution in the flask to 90 °C and stir for 5 hours to complete the reaction. After the reaction is completed, cool the resulting product to room temperature to obtain a carboxy-containing acrylic polymer E (hereinafter referred to as polymer E) having a weight average molecular weight of 70,000 and a solid content of 50% by weight.

[0082] 3.2.2. Preparation of Photoresist Film Information on the raw materials used in the following examples and comparative examples is shown in Table 1 below.

[0083]

Table 1

[0084] According to the ratios shown in Table 2-1 and Table 2-2, the components were mixed and stirred for 1.5 hours to mix them uniformly, thereby obtaining a resin composition. According to the coating conditions and drying conditions shown in Table 2-1 and Table 2-2, the obtained resin composition was coated on a PET film that functions as a protective film using a Kodaira wound rod. The coated resin composition was dried in an oven. Then, the surface of the dried resin composition was covered with a PE film that functions as a protective film. Thereby, photosensitive resin films (i.e., composite films) covered with the protective films of Examples 1 to 11 (E1 to E11) and Comparative Examples 1 to 7 (CE1 to CE7) were obtained.

[0085]

Table 2-1

[0086]

Table 2-2

[0087] 3.2.3. Test of Photosensitive Resin Film According to the above test method, the first derivative of the weight percentage with respect to time, thermogravimetric analysis regarding the weight loss percentage within the range of 0 to 20 minutes, wrinkles, and 100-grid adhesion characteristics were used to test the characteristics of the photosensitive resin films of Examples 1 to 11 and Comparative Examples 1 to 7. The results are shown in Table 3-1 and Table 3-2.

[0088]

Table 3-1

[0089]

Table 3-2

[0090] As shown in Table 3-1 and Table 3-2, the photosensitive resin films of Examples 1 to 11 of the present invention do not include wrinkles. This indicates good storage characteristics and operability. These photosensitive resin films also show a low peeling percentage (<5%) in the 100-grid adhesion test. This indicates good adhesion to the copper-clad laminate. In contrast, the photosensitive resin films of Comparative Examples 1 to 7 cannot achieve good storage characteristics, operability, and adhesiveness simultaneously. Comparative Examples 1 to 6 show that when the absolute value of the first derivative of the weight percentage with respect to time within the range of 0 to 40 minutes is higher than the specific range of the present invention, wrinkles are generated in the photosensitive resin film, indicating low storage characteristics and operability. Comparative Example 7 shows that when the absolute value of the first derivative of the weight percentage with respect to time within the range of 0 to 40 minutes is lower than the specific range of the present invention, the photosensitive resin film shows an extremely high peeling percentage (>65%) in the 100-grid adhesion test, indicating low adhesion to the copper-clad laminate.

[0091] Furthermore, even if Comparative Examples 3, 4, and 7 have the same weight loss percentage of the photosensitive resin film within the range of 0 to 20 minutes as the embodiments described in the examples, the absolute value of the first derivative of the weight percentage with respect to time within the range of 0 to 40 minutes cannot achieve the inventive effects of good storage characteristics, operability, and adhesiveness unless it is within a specific range. From this, it is revealed that the basic technical means of the present invention is actually to control the absolute value of the first derivative of the weight percentage with respect to time within the range of 0 to 40 minutes in thermogravimetric analysis to be within a specific range.

[0092] Furthermore, from the related research of the inventor, even if the weight loss percentage of the photosensitive resin film within the range of 0 to 10 minutes, T d5 , or T d10 is the same as the embodiments described in the examples, it is shown that the inventive effects of good storage characteristics, operability, and adhesiveness cannot be achieved unless the absolute value of the first derivative of the weight percentage with respect to time within the range of 0 to 40 minutes is within a specific range. From this, it is revealed that the basic technical means of the present invention is actually to control the absolute value of the first derivative of the weight percentage with respect to time within the range of 0 to 40 minutes in thermogravimetric analysis to be within a specific range.

[0093] The above embodiments explain the principles and effects of the present invention and show its inventive features. Those skilled in the art can make various changes and exchanges based on the disclosed and proposed invention. Therefore, the protection scope of the present invention is defined by the appended claims.

Claims

1. When a photosensitive resin film is heated from 40°C to 200°C at a rate of 5°C / min and subjected to thermogravimetric analysis under the condition of maintaining the temperature of 200°C for 10 minutes, the absolute value of the first derivative of the weight percentage with respect to time within the range of 0 to 40 minutes is higher than 0.1% / min and not higher than 1.0% / min, the photosensitive resin film.

2. When the photosensitive resin film is subjected to the thermogravimetric analysis, the weight loss percentage of the photosensitive resin within the range of 0 to 20 minutes is higher than 0 wt% and not higher than 10 wt%, the photosensitive resin film according to Claim 1.

3. The weight loss percentage of the photosensitive resin film within the range of 0 to 20 minutes is in the range of 2 wt% to 10 wt%, the photosensitive resin film according to Claim 2.

4. Having a thickness of 60 μm to 600 μm, the photosensitive resin film according to Claim 1.

5. A dry film, the photosensitive resin film according to Claim 1.

6. (A) An alkali-soluble polymer, (B) A component of an ethylenically unsaturated compound, and (C) A photoinitiator, the photosensitive resin film according to Claim 1.

7. The component (B) of the ethylenically unsaturated compound contains one or more difunctional acrylate-based compounds, the photosensitive resin film according to Claim 6.

8. The amount of the difunctional acrylate-based compound based on the weight of the component (B) of the ethylenically unsaturated compound is 60 wt% or more, the photosensitive resin film according to Claim 7.

9. The photosensitive resin film according to any one of Claims 1 to 8, and A composite film including a protective film on at least one surface of the photosensitive resin film.

10. The protective film is selected from the group consisting of a polyethylene terephthalate film, a polyolefin film, and a composite thereof, the composite film according to Claim 9.

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