Photosensitive resin film and application thereof

Abstract

The invention provides a photosensitive resin film and an application thereof. When the photosensitive resin film is heated from 40 DEG C to 200 DEG C at a heating rate of 5 DEG C / min and then is subjected to thermogravimetric analysis at a constant temperature of 200 DEG C for 10 minutes, the absolute value of the primary differential of wt% with respect to time in the range of 0-40 minutes is greater than 0.1% / min and not greater than 1.0% / min.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin film, and more particularly to a photosensitive resin film with a high thickness, and the application of the photosensitive resin film. Background Art

[0002] A photosensitive resin film is a resin film that undergoes a chemical change upon exposure to light, and it can be used as a photoresist film in various electronic fields. Photoresist films are classified into positive photoresist films and negative photoresist films according to the changes after exposure and development. After exposure, the exposed part of the positive photoresist film will dissolve during development, and the pattern of the unexposed part will be left after development. After exposure, the unexposed part of the negative photoresist film will dissolve during development, and the pattern of the exposed part will be left after development.

[0003] In the printed circuit board (PCB) industry, it is necessary to use a photoresist film for etching or electroplating processes to form circuit patterns. Due to the increasing complexity and size of electronic components, the demand for thick photoresist films with a high aspect ratio in the printed circuit board industry is gradually increasing. However, existing photoresist films still have problems such as poor storage stability, adhesion, and / or operability, resulting in defects in subsequent electroplating or etching processes, which urgently need to be solved. Summary of the Invention

[0004] In view of the above technical problems, the present invention aims to provide a photosensitive resin film with excellent storage stability, adhesion, and operability, which can be used in various electronic fields that require high-precision etching or electroplating processes.

[0005] Therefore, an object of the present invention is to provide a photosensitive resin film, wherein when the photosensitive resin film is subjected to thermogravimetric analysis at a heating rate of 5 °C / minute from 40 °C to 200 °C and then held at 200 °C for 10 minutes, the absolute value of the first derivative of the weight percentage with respect to time in the range of 0 to 40 minutes is greater than 0.1% / minute and not greater than 1.0% / minute.

[0006] In some embodiments of the present invention, in the thermogravimetric analysis, the weight loss percentage of the photosensitive resin film within 0 to 20 minutes is greater than 0 wt% and not greater than 10 wt%, preferably 2 wt% to 10 wt%.

[0007] In some embodiments of the present invention, the thickness of the photosensitive resin film is 60 microns to 600 microns.

[0008] In some embodiments of the present invention, the photosensitive resin film is a dry film.

[0009] In some embodiments of the present invention, the photosensitive resin film comprises: (A) an alkali-soluble polymer; (B) a component containing an ethylenically unsaturated compound; and (C) a photoinitiator.

[0010] In some embodiments of the present invention, the component (B) containing an ethylenically unsaturated compound comprises a bifunctional acrylate compound.

[0011] In some embodiments of the present invention, based on the weight of the component (B) containing an ethylenically unsaturated compound, the content of the bifunctional acrylate compound is 60% by weight or more.

[0012] Another object of the present invention is to provide a composite film comprising the photosensitive resin film as described above and a protective film located on at least one surface of the photosensitive resin film.

[0013] In some embodiments of the present invention, the protective film is selected from the following group: polyethylene terephthalate film, polyolefin film, and the aforementioned composite.

[0014] To make the above objects, technical features, and advantages of the present invention more obvious and understandable, the following will be described in detail with some specific embodiments. Detailed Description of Embodiments

[0015] The following will specifically describe some specific embodiments according to the present invention; however, the present invention can be practiced in many different forms and should not be construed as limited to what is stated in the specification.

[0016] Unless otherwise specified, the terms "a", "the", and similar terms used in this specification and the claims should be understood to include both singular and plural forms.

[0017] Unless otherwise specified, the terms "first", "second", and similar terms used in this specification and the claims are only used to distinguish the described elements or components and have no special meaning in themselves, nor are they used to represent a sequence.

[0018] Unless otherwise specified, the terms "(meth)acrylic acid", "(meth)acrylate", and similar terms used in this specification are intended to cover cases with and without the groups in parentheses. For example, "(meth)acrylic acid" is intended to cover acrylic acid and methacrylic acid, and "(meth)acrylate" is intended to cover acrylate and methacrylate.

[0019] In this specification and the claims, the weight-average molecular weight (Mw) is measured by gel permeation chromatography (GPC), compared with polystyrene standards, and converted, and its unit is "grams per mole (g / mol)".

[0020] The efficacy of the present invention compared to the prior art lies particularly in providing a photosensitive resin film with high thickness, good storage stability, adhesion, and operability by controlling the first derivative value of weight percentage with respect to time in thermogravimetric analysis. The following provides a detailed description of the photosensitive resin film of the present invention and its applications.

[0021] 1. Photosensitive Resin Film

[0022] 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, the unexposed part of the photosensitive resin film will dissolve during development, and the pattern of the exposed part will be left after development.

[0023] As will be described below, before use, the photosensitive resin film generally forms a composite film structure by covering a protective film with protective and supporting functions on the surface to facilitate the storage of the photosensitive resin film and prevent the photosensitive resin film from adhering to foreign objects or being damaged. In this article, unless otherwise stated, properties such as "thickness" and "thermogravimetric properties" are for the photosensitive resin film itself and do not include other parts such as the protective film used in combination with it.

[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 low solvent content means that the content of the solvent is 0.1 wt% to 8 wt%, more specifically 0.1 wt% to 7 wt% based on the total weight of the photosensitive resin film. Compared with 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 the substrate without additional processes such as coating and drying, so they have the advantages of being easy to control and having good operability.

[0025] The photosensitive resin film of the present invention can have a high thickness. Specifically, the thickness of the photosensitive resin film of the present invention can be from 60 micrometers to 600 micrometers, such as 60 micrometers, 70 micrometers, 80 micrometers, 90 micrometers, 100 micrometers, 110 micrometers, 120 micrometers, 130 micrometers, 140 micrometers, 150 micrometers, 160 micrometers, 170 micrometers, 180 micrometers, 190 micrometers, 200 micrometers, 210 micrometers, 220 micrometers, 230 micrometers, 240 micrometers, 250 micrometers, 260 micrometers, 270 micrometers, 280 micrometers, 290 micrometers, 300 micrometers, 310 micrometers, 320 micrometers, 330 micrometers, 340 micrometers, 350 micrometers, 360 micrometers, 370 micrometers, 380 micrometers, 390 micrometers, 400 micrometers, 410 micrometers, 420 micrometers, 430 micrometers, 440 micrometers, 450 micrometers, 460 micrometers, 470 micrometers, 480 micrometers, 490 micrometers, 500 micrometers, 510 micrometers, 520 micrometers, 530 micrometers, 540 micrometers, 550 micrometers, 560 micrometers, 570 micrometers, 580 micrometers, 590 micrometers, or 600 micrometers, or within the range formed by any two of the above values. The higher the thickness of the photosensitive resin film, the higher the thickness of the metal conduction layer that can be plated when used as a photoresist film. Therefore, it is particularly suitable for 2.5D and 3D integrated circuit packaging and can be used for patterning applications before electroplating the conduction layer.

[0026] The photosensitive resin film of the present invention can be formed by a single layer of photosensitive resin or by stacking two or more layers of photosensitive resin. For example, the photosensitive resin film of the present invention can be formed by stacking two, three, or four layers of photosensitive resin, but the present invention is not limited thereto.

[0027] 1.1. Thermogravimetric properties of the photosensitive resin film

[0028] The photosensitive resin film of the present invention has specific thermogravimetric properties. Specifically, when the photosensitive resin film is subjected to thermogravimetric analysis at a heating rate of 5 °C / minute from 40 °C (i.e., the temperature at the 0th second) to 200 °C and then held at 200 °C for 10 minutes, the absolute value of the first derivative of the weight % with respect to time (i.e., d(weight %) / dt) within the range of 0 to 40 minutes is greater than 0.1% / minute and not greater than 1.0% / minute, preferably 0.2% / minute to 1.0% / minute. 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 % with respect to time within the range of 0 to 40 minutes can be 0.11% / minute, 0.13% / minute, 0.15% / minute, 0.17% / minute, 0.19% / minute, 0.21% / minute, 0.23% / minute, 0.25% / minute, 0.27% / minute, 0.29% / minute, 0.31% / minute, 0.33% / minute, 0.35% / minute, 0.37% / minute, 0.39% / minute, 0.41% / minute, 0.43% / minute, 0.45% / minute, 0.47% / minute, 0.49% / minute, 0.51% / minute, 0.53% / minute, 0.55% / minute, 0.57% / minute, 0.59% / minute, 0.61% / minute, 0.63% / minute, 0.65% / minute, 0.67% / minute, 0.69% / minute, 0.71% / minute, 0.73% / minute, 0.75% / minute, 0.77% / minute, 0.79% / minute, 0.81% / minute, 0.83% / minute, 0.85% / minute, 0.87% / minute, 0.89% / minute, 0.91% / minute, 0.93% / minute, 0.95% / minute, 0.97% / minute, 0.99% / minute, or 1.0% / minute, or within the range formed by any two of the above values.

[0029] The statement that the absolute value of the first derivative of the weight % with respect to time within the range of 0 to 40 minutes is greater than 0.1% / minute and not greater than 1.0% / minute means that at any time point within the range of 0 to 40 minutes, the absolute value of the first derivative of the weight % with respect to time is greater than 0.1% / minute and not greater than 1.0% / minute. Therefore, if the minimum value of the absolute value of the first derivative of the weight % with respect to time within the range of 0 to 40 minutes of the photosensitive resin film is greater than 0.1% / minute and the maximum value is not greater than 1.0% / minute, it can be determined that the photosensitive resin film has the thermogravimetric property characteristics of the present invention. Conversely, if the minimum value of the absolute value of the first derivative of the weight % with respect to time within the range of 0 to 40 minutes of the photosensitive resin film is not greater than 0.1% / minute, or the maximum value is greater than 1.0% / minute, it can be determined that the photosensitive resin film does not have the thermogravimetric property characteristics of the present invention.

[0030] In the present invention, the first derivative of weight % with respect to time is obtained by performing thermogravimetric analysis on the photosensitive resin film and then obtaining a derivative thermogravimetric curve. Specifically, the thermogravimetric analysis is performed as follows: After removing the protective film from both sides of the photosensitive resin film, the photosensitive resin film is cut into samples of 5 mg to 30 mg by cutting twice in the transverse direction (TD) and the machine direction (MD) respectively; the heating furnace of the thermogravimetric analyzer is heated from room temperature to 40 °C at a heating rate of 5 °C / min and held at 40 °C; the sample is placed in the heating furnace of the thermogravimetric analyzer, air with a flow rate of 40 ml / min is used as the purge gas for the 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 then held at 200 °C for 10 minutes. During the heating and subsequent holding process, the weight loss is recorded every 0.5 seconds, and a thermogravimetric curve of weight % versus time in the range from the start of heating at a rate of 5 °C / min to 40 minutes is obtained; the first derivative of this thermogravimetric curve is taken to obtain a derivative thermogravimetric curve. In some embodiments of the present invention, a photosensitive resin film cut into 20 mg is used as the sample.

[0031] When the photosensitive resin film is subjected to thermogravimetric analysis under the aforementioned conditions, the percentage of weight loss within 0 to 20 minutes is preferably greater than 0 wt% and not greater than 10 wt%, more preferably 2 wt% to 10 wt%, and particularly preferably 2.2 wt% to 9.5 wt%. For example, when the photosensitive resin film is subjected to thermogravimetric analysis under the aforementioned conditions, the percentage of weight loss within 0 to 20 minutes can be 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, or 10 wt%, or within the range formed by any two of the above values. The percentage of weight loss within 0 to 20 minutes is obtained from the aforementioned thermogravimetric curve.

[0032] In some embodiments of the present invention, when the photosensitive resin film is subjected to thermogravimetric analysis under the aforementioned conditions, it has a weight loss percentage of not more than 3% by weight within 0 to 10 minutes. For example, when the photosensitive resin film is subjected to thermogravimetric analysis under the aforementioned conditions, the weight loss percentage within 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 formed by any two of the above values. The weight loss percentage within 0 to 10 minutes is obtained from the aforementioned thermogravimetric curve.

[0033] In this thermogravimetric analysis, the temperature corresponding to when the weight loss percentage of the photosensitive resin film reaches 3% by weight relative to the initial weight when placed in the thermogravimetric analyzer is "T d3 ". In some embodiments of the present invention, the T d3 of the photosensitive resin film is preferably 90 °C or higher. For example, the T d3 of the photosensitive resin film 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 formed by any two of the above values.

[0034] In this thermogravimetric analysis, the temperature corresponding to when the weight loss percentage of the photosensitive resin film reaches 5% by weight relative to the initial weight when placed in the thermogravimetric analyzer is "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 particularly 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 formed by any two of the above values.

[0035] In this thermogravimetric analysis, the temperature corresponding to when the weight loss percentage of the photosensitive resin film reaches 10% by weight relative to the initial weight when placed in the thermogravimetric analyzer is "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 d10It 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 formed by any two of the above values.

[0036] The thermogravimetric properties of the photosensitive resin film of the present invention can be adjusted, for example, by adjusting the composition of the photosensitive resin film or the process conditions (such as drying conditions) of the photosensitive resin film. Those skilled in the art to which the present invention pertains, based on the teachings of this specification, especially the specific examples in the embodiments, should be able to implement the photosensitive resin film having the above thermogravimetric properties.

[0037] 1.2. Composition of the photosensitive resin film

[0038] 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 greater than 0.1% / min and not greater than 1.0% / min, the composition of the photosensitive resin film can be adjusted as needed. In some embodiments of the present invention, the photosensitive resin film contains: (A) an alkali-soluble polymer, (B) a component containing an ethylenically unsaturated compound, and (C) a photoinitiator, and may contain a low content of a solvent and further contain additives as needed.

[0039] 1.2.1. (A) Alkali-soluble polymer

[0040] Examples of the alkali-soluble polymer include, but are not limited to, polymers having a carboxyl group, such as acrylic polymers having a carboxyl group, vinyl aromatic polymers having a carboxyl group, norbornene polymers having a carboxyl group, epoxy polymers having a carboxyl group, amide polymers having a carboxyl group, amide epoxy polymers having a carboxyl group, alkyd polymers having a carboxyl group, and phenolic polymers having a carboxyl group. Each of the above alkali-soluble polymers can be used alone or in combination. In some embodiments of the present invention, the alkali-soluble polymer is an acrylic polymer having a carboxyl group.

[0041] The alkali-soluble polymer can be obtained, for example, by polymerizing one or more polymerizable monomers having a carboxyl group, or by copolymerizing one or more polymerizable monomers having a carboxyl group with other polymerizable monomers without a carboxyl group. Therefore, it can contain repeating units derived from polymerizable monomers having a carboxyl group, or contain repeating units derived from polymerizable monomers having a carboxyl group and repeating units of other polymerizable monomers.

[0042] 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, wherein the first polymerizable monomer has a carboxyl group, and examples thereof 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 have a carboxyl group, and examples thereof include, but are not limited to, (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-methyladamantyl 2-(meth)acrylate, 2-ethyladamantyl 2-(meth)acrylate, 2-butyladamantyl 2-(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate; (meth)acrylonitrile; vinyl ester compounds, such as vinyl acetate, vinyl n-butyrate; vinyl aromatic compounds, such as styrene, vinyl naphthalene, 3-acetoxystyrene, 4-acetoxystyrene, vinyltoluene, α-methylstyrene; norbornene; acrylamide; maleate compounds, such as monomethyl maleate, monoethyl maleate, monoisopropyl maleate; and derivatives of the aforementioned polymerizable monomers. The first monomer and the second monomer may be used independently alone or in combination.

[0043] In a preferred embodiment of the present invention, the alkali-soluble polymer is obtained by copolymerizing (meth)acrylic acid with one or more (meth)acrylate compounds, and thus 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 compounds may be from 1:20 to 1:1, more specifically from 1:6 to 1:4. For example, the weight ratio of (meth)acrylic acid to (meth)acrylate compounds may 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 within the range formed by any two of the above values.

[0044] The weight average molecular weight (Mw) of the alkali-soluble polymer may be from 10,000 to 180,000, preferably from 40,000 to 80,000. For example, it may 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 within the range formed by any two of the above values.

[0045] In the photosensitive resin film of the present invention, the content of the alkali-soluble polymer may be from 20% by weight to 85% by weight based on the total weight of the photosensitive resin film, more specifically from 40% by weight to 80% by weight, and even more specifically from 50% by weight to 75% by weight. For example, the content of the alkali-soluble polymer may 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 within the range formed by any two of the above values.

[0046] 1.2.2. (B) Component containing ethylenically unsaturated compounds

[0047] The ethylenically unsaturated double bond compound refers to a compound having at least one reactive ethylenic functional group, preferably a bifunctional compound having two reactive ethylenic functional groups. In some embodiments of the present invention, the ethylenically unsaturated double bond compound comprises a monofunctional or polyfunctional acrylate compound, and the monofunctional or polyfunctional acrylate compound is preferably a bifunctional acrylate compound. Examples thereof 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)acryloyloxyisocyanate) hexamethylene diisocyanate, ethoxylated allophanate di(meth)acrylate, propoxylated allophanate di(meth)acrylate, ethoxylated / propoxylated allophanate di(meth)acrylate, ethoxylated tris((meth)acryloyloxyisocyanate) hexamethylene diisocyanate, acrylated tris((meth)acryloyloxyisocyanate) hexamethylene diisocyanate, ethoxylated / propoxylated tris((meth)acryloyloxyisocyanate) hexamethylene diisocyanate. In addition, based on the total weight of the component of the ethylenically unsaturated double bond compound, the content of the bifunctional acrylate compound is preferably 60% by weight or more, such as 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 formed by any two of the above values.

[0048] In some embodiments of the present invention, the component of the ethylenically unsaturated double bond compound comprises at least one of ethoxylated bisphenol A dimethacrylate and trimethylolpropane triacrylate.

[0049] In the photosensitive resin film of the present invention, the content of the component containing an ethylenically unsaturated double bond compound may be 5% by weight to 70% by weight, more specifically 15% by weight to 50% by weight, and even more specifically 20% by weight to 45% by weight, based on the total weight of the photosensitive resin film. For example, the content of the component containing an ethylenically unsaturated double bond compound may 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 within the range constituted by any two of the above values.

[0050] 1.2.3. (C) Photoinitiator

[0051] A photoinitiator refers to a substance that can initiate a polymerization reaction under the action of light. The types of photoinitiators are not particularly limited, and examples thereof include, but are not limited to, imidazole compounds, ketone compounds, quinone compounds, benzoin or benzoin ether compounds, polyhalogen compounds, triazine compounds, organic peroxides, onium salt compounds, and other common photoinitiators in the art. Each of the foregoing photoinitiators can be used independently alone or in combination.

[0052] Examples of the foregoing imidazole compounds include, but are not limited to, 2,4,6-triaryl imidazole dimers, such as 2-(o-chlorophenyl)-4,5-diphenyl imidazole dimer, 2-(o-chlorophenyl)-4,5-bis(m-methoxyphenyl) imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenyl imidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenyl imidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenyl imidazole dimer.

[0053] Examples of the foregoing ketone compounds include, but are not limited to, benzophenone, 4,4-bis(dimethylamino) benzophenone, 4-methoxy-4'-dimethylamino benzophenone, 4,4'-dimethoxy benzophenone, 4-dimethylamino benzophenone, 4-dimethylamino acetophenone, xanthone, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, acridone, α-hydroxy acetophenone, α-amino acetophenone, α-hydroxy cycloalkyl phenyl ketone, and dialkoxy acetophenone.

[0054] Examples of the foregoing quinone compounds include, but are not limited to, camphorquinone, benzyl anthraquinone, 2-tert-butyl anthraquinone, and 2-methyl anthraquinone.

[0055] Examples of the aforementioned benzoin or benzoin ether compounds include, but are not limited to, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin phenyl ether.

[0056] Examples of the aforementioned polyhalogen compounds include, but are not limited to, carbon tetrabromide, phenyl tribromomethyl sulfone, and phenyl trichloromethyl ketone.

[0057] Examples of the aforementioned 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.

[0058] Examples of the aforementioned organic peroxides include, but are not limited to, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, benzoyl peroxide, di-tert-butyl m-phthalate peroxide, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, tert-butyl peroxybenzoate, α,α'-bis(tert-butylperoxyisopropyl)benzene, dicumyl peroxide, and 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone.

[0059] Examples of the aforementioned onium salt compounds include, but are not limited to, diaryliodonium salts and triarylsulfonium salts obtained by combining biphenyliodonium, 4,4'-dichlorobiphenyliodonium, 4,4'-dimethoxybiphenyliodonium, 4,4'-di-tert-butylbiphenyliodonium, 4-methyl-4'-isopropyl-biphenyliodonium, or 3,3'-dinitrobiphenyliodonium with chloride, bromide, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, and tetrakis(pentafluorophenyl)borate or trifluoromethanesulfonic acid.

[0060] Examples of the aforementioned other common photoinitiators in the art include, but are not limited to, fluorene, bisacylphosphine oxide compounds, azinium compounds, organoboron compounds, phenylglyoxylate, and titanocene.

[0061] In some embodiments of the present invention, the photoinitiator is an imidazole-based compound or a ketone-based compound.

[0062] In the photosensitive resin film of the present invention, the content of the photoinitiator may be from 0.1% by weight to 15% by weight, more specifically from 0.5% by weight to 10% by weight, and even more specifically from 1% by weight to 5% by weight, based on the total weight of the photosensitive resin film. For example, relative to the total weight of the photosensitive resin film, the content of the photoinitiator may 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 within the range formed by any two of the above values.

[0063] 1.2.4. Solvent

[0064] In the present invention, the photosensitive resin film may further contain a solvent. The solvent is an inert solvent that can dissolve or disperse the components of the photosensitive resin film but does not react with these components.

[0065] In some embodiments of the present invention, the photosensitive resin film contains a solvent, and the solvent has a boiling point of 55°C to 120°C, preferably 60°C to 90°C. For example, the boiling point of the solvent may 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 within the range formed by any two of the above values. Examples of the solvent having a boiling point 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. Each of the foregoing solvents may be used alone or in combination.

[0066] In the photosensitive resin film of the present invention, the content of the solvent may be from 0.1% by weight to 8% by weight, specifically from 0.1% by weight to 7% by weight, based on the total weight of the photosensitive resin film. For example, relative to the total weight of the photosensitive resin film, the content of the solvent may 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 within the range formed by any two of the above values.

[0067] 1.2.5. Optional Additives

[0068] When the photosensitive resin film is subjected to thermogravimetric analysis under the above-mentioned conditions, and the absolute value of the first derivative of the weight percentage with respect to time within the range of 0 to 40 minutes is greater than 0.1% / minute and not greater than 1.0% / minute, the photosensitive resin film of the present invention may further contain additives to specifically improve the properties of the photoresist film. Examples of the additives include, but are not limited to, light absorbers, dyes, pigments, radical inhibitors, and surfactants. Each of these additives can be used alone or in any combination.

[0069] 1.3. Preparation of the photosensitive resin film

[0070] There is no particular limitation on the method for preparing the photosensitive resin film of the present invention. Those skilled in the art to which the present invention pertains can prepare the photosensitive resin film based on the disclosure of the present specification, especially the specific examples in the embodiments. Taking the preparation of a photosensitive resin film having the exemplary composition described above as an example, each component of the photosensitive resin film, including (A) an alkali-soluble polymer, (B) an ethylenically unsaturated double bond-containing compound, (C) a photoinitiator, and other optional additives, can be uniformly mixed and dissolved or dispersed in a solvent with a stirrer to form a resin composition, and then the resulting resin composition is coated on a substrate and dried to obtain the photosensitive resin film.

[0071] In the present invention, there is no particular limitation on the coating method of the resin composition, and any coating method known in the art to which the present invention pertains can be used, including but not limited to gravure coating, reverse roll coating, die coating, air knife coating, blade coating, rod coat, bar coating, curtain coating, knife coating, transfer roll coating, extrusion coating, impregnation coating, kiss coating, spray coating, calendar coat, and extrusion coating. In some embodiments of the present invention, the coating method of the resin composition is preferably blade coating, rod coat, bar coating, or die coating.

[0072] The drying temperature can be adjusted according to the composition of the photosensitive resin film. Generally, it can be 55°C to 120°C, such as 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, or 120°C, or within the range formed by any two of the above values. The drying time can be adjusted according to the composition of the photosensitive resin film. Generally, it can be 20 minutes to 60 minutes, such as 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, or 50 minutes, or within the range formed by any two of the above values.

[0073] 2. Application of the photosensitive resin film

[0074] The photosensitive resin film of the present invention can be used as a photoresist film and further applied to various electronic fields. Generally, before use, protective films that can provide protection and support functions are coated on both surfaces of the photosensitive resin film to facilitate the storage of the photosensitive resin film and prevent the photosensitive resin film from adhering to foreign objects or being damaged. Therefore, the present invention further provides a composite film, which comprises the photosensitive resin film of the present invention as described above and a protective film formed on at least one surface of the photosensitive resin film. In a preferred embodiment of the present invention, the protective film is formed on both surfaces of the photosensitive resin film, and the materials of the protective films formed on both surfaces of the photosensitive resin film can be the same or different.

[0075] There is no particular limitation on the type of the protective film, and various materials existing in the technical field to which the present invention pertains can be used. For example, the protective film applicable to the present invention can be selected from the following group: polyethylene terephthalate film (PET film), polyolefin film, and the aforementioned composites. Examples of the polyolefin film include, but are not limited to, polyethylene film (PE film) and polypropylene film (PP film), such as oriented polypropylene film, and the composite can be a composite of polyethylene terephthalate film and polyolefin film, or a composite of different polyolefin films. In a preferred embodiment of the present invention, the composite film comprises a PET film formed on one surface of the photosensitive resin film and a PE film formed on the other surface of the photosensitive resin film.

[0076] There is no particular limitation on the preparation method of the composite film of the present invention, and methods existing in the technical field to which the present invention pertains can be used. Those skilled in the technical field to which the present invention pertains can prepare the composite film based on the disclosure of the present specification. For example, the protective film can be laminated on both surfaces of the photosensitive resin film to provide a laminate, and the laminate can be pressed to obtain the composite film. Alternatively, the resin composition for forming the photosensitive resin film can be first coated on the first protective film and dried to form a photosensitive resin film on the first protective film, and then a second protective film can be pasted on the surface of the photosensitive resin film that does not contact the first protective film, thereby obtaining the composite film. Alternatively, the resin composition for forming the photosensitive resin film can also be extruded between two protective films with a fixed spacing, and then dried to form a photosensitive resin film between the two protective films.

[0077] 3. Examples

[0078] 3.1. Measuring methods

[0079] [Thermogravimetric analysis of the photosensitive resin film]

[0080] After removing the PE protective film and the PET protective film in the prepared composite film from both sides of the photosensitive resin film, cut the photosensitive resin film of 20 mg into samples by cutting twice in the transverse direction (TD) and the longitudinal direction (MD); heat the furnace of the thermogravimetric analyzer (model: TA TGA Q500, purchased from TA Instruments) from room temperature to 40 °C at a heating rate of 5 °C / min and hold at 40 °C; place the sample in the furnace of the thermogravimetric analyzer, use air with a flow rate of 40 mL / min as the purge gas for the balance, and use air with a flow rate of 100 mL / min as the purge gas for the sample; heat the sample from 40 °C to 200 °C at a heating rate of 5 °C / min, and then hold at 200 °C for 10 minutes. During the heating and holding process after the temperature rise, record the weight loss every 0.5 seconds, and use the analysis software Universal Analysis V4.5A Build 4.5.0.5 to plot the thermogravimetric curve of weight% against time in the range of 0 to 40 minutes starting from the start of heating at a heating rate of 5 °C / min; perform the first derivative on the thermogravimetric curve using this analysis software to obtain the derivative thermogravimetric curve. Obtain the first derivative of weight% against time from the derivative thermogravimetric curve obtained above; and obtain the weight loss percentage within 0 to 20 minutes, the weight loss percentage within 0 to 10 minutes, T d5 and T d10 .

[0081] [Wrinkling Test of Photosensitive Resin Film]

[0082] Wind the prepared composite film into a slit roll with a length of 30 m and a width of 300 mm, and place it at a temperature of 23 °C to 27 °C for 12 hours. Then, pull out 5 m of the composite film from the slit roll and tear off the PE protective film, and observe the surface of the photosensitive resin film with the naked eye, and record the number of wrinkles with a length of more than 10 mm and a width of more than 1 mm existing on the photosensitive resin film at the position where 3 m to 5 m is pulled out. If no wrinkles with a length of more than 10 mm and a width of more than 1 mm are observed, it means that the storage stability and operability of the photosensitive resin film are good.

[0083] [Cross-Cut Test of Adhesion of Photosensitive Resin Film]

[0084] The cross-cut adhesion test of the photosensitive resin film was carried out in the following manner according to ASTM D3359. A copper foil laminate with a thickness of 1.6 mm (purchased from Changchun Artificial Resin Co., Ltd., model CCP-308), where the copper foil thickness is 35 μm, was prepared. It was abraded using a #320 non-woven brush wheel and a #600 non-woven brush wheel, and the surface temperature of the copper foil of the copper foil laminate was adjusted to 50°C. The PE protective film on the surface of the prepared composite film was removed, and then the photosensitive resin film together with the PET protective film thereon was stacked on the copper foil surface with the photosensitive resin film facing the copper foil surface of the copper foil laminate, and then laminated with a laminating machine to obtain a sample, where the lamination temperature was 80°C, the lamination pressure was 3.0 kg / cm², and the lamination speed was 2.0 m / min. The PET protective film on the sample was removed, and the photosensitive resin film on the sample was cut into 100 squares of 10×10 at intervals of 1 mm to 1.2 mm with a blade. A transparent tape produced by 3M Company (model: 3M transparent tape 600) was closely attached to the surface of the photosensitive resin film at the cutting position, and then the tape was pulled up forcefully at an angle of 45 degrees to the substrate, and the percentage of the number of squares where the photosensitive resin film peeled off in the total number of squares was calculated and recorded. The lower the percentage of the number of squares where the photosensitive resin film peeled off in the total number of squares, the better the adhesion of the photosensitive resin film to the copper foil laminate.

[0085] 3.2. Preparation and testing of photosensitive resin

[0086] 3.2.1. Synthesis of alkali-soluble polymer

[0087] The acrylic polymer having a carboxyl group was prepared as an alkali-soluble polymer according to the following Synthesis Examples 1 to 5.

[0088] [Synthesis Example 1]

[0089] 15 g of methacrylic acid, 60 g of methyl methacrylate, 25 g of butyl acrylate as copolymerization monomers were mixed with 0.5 g of azobisisoheptonitrile to obtain solution a1. In addition, 0.5 g of azobisisoheptonitrile was dissolved in 20 g of ethyl acetate solvent to obtain solution b1.

[0090] A flask equipped with a stirrer, a reflux cooler, a thermometer, and a dropper was prepared, 80 g of ethyl acetate solvent was added to the flask, and the flask was heated to 70°C, and then the solution a1 was dripped into the flask at a fixed rate for a total of 3 hours, and then the temperature of the solution in the flask was maintained at 70°C and stirred for 2 hours. Then, the temperature of the solution in the flask was continued to be maintained at 70°C, and the solution b1 was dripped into the flask at a fixed rate for a total of 0.5 hours, and then the temperature of the solution in the flask was maintained at 70°C and stirred for 5 hours. After that, the solution in the flask was heated to 90°C and stirred for 5 hours to allow the reaction to proceed fully. After the reaction was completed, the product was cooled to room temperature to obtain an acrylic acid polymer A having a carboxyl group (hereinafter also referred to as "polymer A"), whose weight average molecular weight was 55,000 and solid content was 50% by weight.

[0091] [Synthesis example 2]

[0092] 15 g of methacrylic acid, 65 g of methyl methacrylate, 20 g of butyl acrylate and 0.5 g of azobisisoheptanitrile as copolymer monomers were mixed to prepare solution a2. Separately, 0.5 g of azobisisoheptanitrile was dissolved in 20 g of methyl acetate solvent to prepare solution b2.

[0093] A flask equipped with a stirrer, a reflux cooler, a thermometer, and a dropper was prepared, 102.2 g of methyl acetate solvent was added to the flask, and the mixture was heated to 70°C. Solution a2 was then added dropwise to the flask at a fixed rate for a total of 3 hours, and the temperature of the solution in the flask was maintained at 70°C and stirred for 2 hours. Then, the temperature of the solution in the flask was continued to be maintained at 70°C, and solution b2 was added dropwise to the flask at a fixed rate for a total of 0.5 hours, and the temperature of the solution in the flask was maintained at 70°C and stirred for 5 hours. After that, the solution in the flask was heated to 90°C and stirred for 5 hours to allow the reaction to proceed sufficiently. After the reaction was completed, the resultant was cooled to room temperature to obtain an acrylic acid polymer B having a carboxyl group (hereinafter also referred to as "polymer B") having a weight average molecular weight of 65,000 and a solid content of 45% by weight.

[0094] [Synthesis example 3]

[0095] 20 g of methacrylic acid, 40 g of methyl methacrylate, 40 g of 2-ethylhexyl acrylate and 0.5 g of azobisisohexyl nitrile as copolymer monomers were mixed to prepare solution a3. In addition, 0.5 g of azobisisohexyl nitrile was dissolved in 20 g of acetone solvent to prepare solution b3.

[0096] A flask equipped with a stirrer, a reflux cooler, a thermometer, and a dropper was prepared, 80 g of acetone solvent was added to the flask, and heated to 70°C, and then solution a3 was dripped into the flask at a fixed rate for a total of 3 hours, and then the temperature of the solution in the flask was maintained at 70°C and stirred for 2 hours. Then, the temperature of the solution in the flask was continued to be maintained at 70°C, and solution b3 was dripped into the flask at a fixed rate for a total of 0.5 hours, and then the temperature of the solution in the flask was maintained at 70°C and stirred for 5 hours. After that, the solution in the flask was heated to 90°C and stirred for 5 hours to allow the reaction to proceed fully. After the reaction was completed, the product was cooled to room temperature to obtain an acrylic acid polymer C having a carboxyl group (hereinafter also referred to as "polymer C"), whose weight average molecular weight was 55,000 and solid content was 50% by weight.

[0097] [Synthesis Example 4]

[0098] 20 g of methacrylic acid, 60 g of methyl methacrylate, 20 g of butyl acrylate and 0.5 g of azobisisoheptanenitrile as copolymer monomers were mixed to prepare solution a4. In addition, 0.5 g of azobisisoheptanenitrile was dissolved in 20 g of propylene glycol methyl ether (PGME) solvent to prepare solution b4.

[0099] A flask equipped with a stirrer, a reflux cooler, a thermometer, and a dropper was prepared, 80 grams of propylene glycol methyl ether solvent was added to the flask, and heated to 70°C, and then solution a4 was dripped into the flask at a fixed rate for a total of 3 hours, and then the temperature of the solution in the flask was maintained at 70°C and stirred for 2 hours. Then, the temperature of the solution in the flask was continued to be maintained at 70°C, and solution b4 was dripped into the flask at a fixed rate for a total of 0.5 hours, and then the temperature of the solution in the flask was maintained at 70°C and stirred for 5 hours. After that, the solution in the flask was heated to 90°C and stirred for 5 hours to allow the reaction to proceed fully. After the reaction was completed, the resultant was cooled to room temperature to obtain an acrylic acid polymer D (hereinafter also referred to as "polymer D") having a carboxyl group, the weight average molecular weight of which was 50,000 and the solid content was 50% by weight.

[0100] [Synthesis example 5]

[0101] 15 g of acrylic acid, 65 g of methyl methacrylate, 20 g of butyl acrylate and 0.5 g of azobisisoheptanitrile as copolymer monomers were mixed to prepare solution a5. Separately, 0.5 g of azobisisoheptanitrile was dissolved in 20 g of ethyl acetate solvent to prepare solution b5.

[0102] A flask equipped with a stirrer, a reflux cooler, a thermometer, and a dropper was prepared, a mixed solvent of 20 g of ethanol and 60 g of ethyl acetate was added to the flask, and the mixture was heated to 70°C. Then, solution a5 was added dropwise to the flask at a fixed rate for a total of 3 hours, and then the temperature of the solution in the flask was maintained at 70°C and stirred for 2 hours. Then, the temperature of the solution in the flask was continued to be maintained at 70°C, and solution b5 was added dropwise to the flask at a fixed rate for a total of 0.5 hours, and then the temperature of the solution in the flask was maintained at 70°C and stirred for 5 hours. Thereafter, the solution in the flask was heated to 90°C and stirred for 5 hours to allow the reaction to proceed sufficiently. After the reaction was completed, the product was cooled to room temperature to obtain an acrylic acid polymer E having a carboxyl group (hereinafter also referred to as "polymer E") having a weight average molecular weight of 70,000 and a solid content of 50% by weight.

[0103] 3.2.2. Preparation of photosensitive resin film

[0104] In the following embodiments and comparative examples, the raw material information used is shown in Table 1.

[0105] Table 1

[0106]

[0107]

[0108] The components were mixed according to the component ratios shown in Tables 2-1 and 2-2, and stirred for 1.5 hours to mix uniformly, thereby obtaining a resin composition. Thereafter, according to the coating and drying conditions shown in Tables 2-1 and 2-2, the obtained resin composition was coated on a PET film as a protective film using a Kodaira wire rod, and then the coated resin composition was dried in an oven, and then a PE film as a protective film was covered on the surface of the dried resin composition, thereby obtaining the protective film-coated photosensitive resin films (i.e., composite films) of Examples 1 to 11 and Comparative Examples 1 to 7.

[0109] Table 2-1

[0110]

[0111] Table 2-2

[0112]

[0113] 3.2.3. Testing of photosensitive resin film

[0114] The properties of the photosensitive resin films of Examples 1 to 11 and Comparative Examples 1 to 7 were measured according to the measurement methods described above, including the first derivative of the weight percentage with respect to time in thermogravimetric analysis, the weight loss percentage within 0 to 20 minutes, wrinkles, and the crosshatch adhesion property, and the results were recorded in Tables 3-1 and 3-2 below.

[0115] Table 3-1

[0116]

[0117] Table 3-2

[0118]

[0119] As shown in Tables 3-1 and 3-2, the photosensitive resin films of Examples 1 to 11 of the present invention did not produce wrinkles, indicating good storage stability and operability, and showed a low peeling ratio (<5%) in the crosshatch test, indicating good adhesion to the copper foil laminate. In contrast, the photosensitive resin films of Comparative Examples 1 to 7 could not simultaneously have good storage stability, operability, and adhesion. Comparative Examples 1 to 6 showed that if the absolute value of the first derivative of the weight percentage with respect to time within the range of 0 to 40 minutes was higher than the specified range of the present invention, wrinkles would occur in the photosensitive resin film, indicating poor storage stability and operability. Comparative Example 7 showed that if the absolute value of the first derivative of the weight percentage with respect to time within the range of 0 to 40 minutes was lower than the specified range of the present invention, the photosensitive resin film showed an extremely high peeling ratio (>65%) in the crosshatch test, indicating poor adhesion to the copper foil laminate.

[0120] In addition, Comparative Examples 3, 4, and 7 showed that even if the weight loss percentage of the photosensitive resin film within 0 to 20 minutes was similar to the exemplified scheme of the examples, as long as the absolute value of the first derivative of the weight percentage with respect to time within the range of 0 to 40 minutes was not within the specified range, the inventive effects of good storage stability, operability, and adhesion could not be provided. This shows that the technical focus of the present invention indeed lies in adjusting the absolute value of the first derivative of the weight percentage with respect to time of the photosensitive resin film within the range of 0 to 40 minutes in the thermogravimetric analysis to the specified range.

[0121] In addition, the related research of the inventors also showed that even when the weight loss percentage of the photosensitive resin film within 0 to 10 minutes, T d5 , T d10 was similar to or equivalent to the exemplified scheme of the examples, as long as the absolute value of the first derivative of the weight percentage with respect to time within the range of 0 to 40 minutes was not within the specified range, the inventive effects of good storage stability, operability, and adhesion could not be provided. This also shows that the technical focus of the present invention indeed lies in adjusting the absolute value of the first derivative of the weight percentage with respect to time of the photosensitive resin film within the range of 0 to 40 minutes in the thermogravimetric analysis to the specified range.

[0122] The above embodiments are only illustrative of the principles and effects of the present invention and illustrate the technical features of the present invention, rather than being used to limit the protection scope of the present invention. Any changes or arrangements that can be easily made by those familiar with the technology without departing from the technical principles of the present invention fall within the scope claimed by the present invention.

Claims

1. A photosensitive resin film, characterized in that, When the photosensitive resin film is subjected to thermogravimetric analysis under the conditions of heating from 40°C to 200°C at a heating rate of 5°C / minute and then maintaining a constant temperature of 200°C for 10 minutes, the absolute value of the first derivative of the weight percentage with respect to time in the range of 0 to 40 minutes is greater than 0.1% / minute and not greater than 1.0% / minute.

2. The photosensitive resin film according to claim 1, wherein In this thermogravimetric analysis, the weight loss percentage of the photosensitive resin film within 0 to 20 minutes is greater than 0 weight% and not greater than 10 weight%.

3. The photosensitive resin film according to claim 2, wherein The weight loss percentage of the photosensitive resin film within 0 to 20 minutes is 2 weight% to 10 weight%.

4. The photosensitive resin film according to claim 1, wherein Its thickness is 60 micrometers to 600 micrometers.

5. The photosensitive resin film according to claim 1, wherein It is a dry film.

6. The photosensitive resin film according to claim 1, wherein It contains: (A) an alkali-soluble polymer; (B) a component containing an ethylenically unsaturated compound; and (C) a photoinitiator.

7. The photosensitive resin film according to claim 6, wherein The component (B) containing an ethylenically unsaturated compound contains a bifunctional acrylate compound.

8. The photosensitive resin film according to claim 7, wherein Based on the weight of the component (B) containing an ethylenically unsaturated compound, the content of the bifunctional acrylate compound is 60 weight% or more.

9. A composite film, characterized in that, It contains: the photosensitive resin film according to any one of claims 1 to 8; and a protective film located on at least one surface of the photosensitive resin film.

10. The composite film according to claim 9, wherein, The protective film is selected from the following group: polyethylene terephthalate film, polyolefin film, and the aforementioned composite.

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