Photosensitive resin laminate and its application

Abstract

To provide a photosensitive resin laminate and application thereof.SOLUTION: The photosensitive resin laminate comprises two or more photosensitive resin layers and includes a second component. When the photosensitive resin laminate is characterized by gas chromatography with added toluene as an internal standard, the retention time of an elution peak of the second component ranges from 0.55 min to 1.30 min, the retention time of the added toluene ranges from 1.32 min to 1.65 min, and the formula in the figure is satisfied (in the formula, the amount of the added toluene and the weight of the photosensitive resin laminate are represented in grams (g)). The photosensitive resin laminate has a total thickness of 100 μm to 600 μm.SELECTED DRAWING: None

Description

[Technical Field]

[0001] Priority claim This application claims priority to U.S. Provisional Patent Application No. 63 / 536,189, filed September 1, 2023, and Chinese Patent Application No. 202410010516.8, filed January 4, 2024, the subject matter of which is incorporated herein by reference in its entirety.

[0002] FIELD OF THE INVENTION The present application provides a photosensitive resin laminate, particularly a photosensitive resin laminate having a large total thickness, and applications of the photosensitive resin laminate. [Background technology]

[0003] Photosensitive resin films are films that undergo chemical changes after exposure and are used in the electronics industry as photoresist films. Depending on the changes they undergo after exposure, photoresist films can be classified as positive and negative. In positive photoresist films, the exposed portions of the photoresist film dissolve during development, leaving the unexposed portions behind. In negative photoresist films, the unexposed portions of the photoresist film dissolve during development, leaving the exposed portions behind.

[0004] In the printed circuit board (PCB) industry, photoresist films are used in etching or electroplating procedures to form circuit patterns. Due to the increasing complexity and size of electronic components, the printed circuit board industry requires thicker photoresist films with higher depth-to-width ratios. However, conventional photoresist films often exhibit poor adhesion or contain bubbles or wrinkles, which can lead to defects in subsequent etching or electroplating procedures. Summary of the Invention [Problem to be solved by the invention]

[0005] In view of the above technical problems, the present invention aims to provide a solution for improving the adhesion, storage properties, and operability of photoresist films. Through research, it has been found that these technical problems can be addressed by a photosensitive resin laminate consisting of multiple photosensitive resin layers.

[0006] Therefore, an object of the present invention is to provide a photosensitive resin laminate comprising two or more photosensitive resin layers and containing a second component, When the photosensitive resin laminate is characterized by gas chromatography using added toluene as an internal standard, the retention time of the elution peak of the second component is in the range of 0.55 minutes to 1.30 minutes, the retention time of the added toluene is in the range of 1.32 minutes to 1.65 minutes, and the following formula is satisfied:

number

[0007] In some embodiments of the present invention, the photosensitive resin laminate is dissolved in propylene glycol methyl ether together with added toluene as an internal standard to prepare a solution, and the solution is tested under the following conditions to perform gas chromatography: <Conditions> A stainless steel column with a column length of 3 m, an outer diameter of 1 / 8 inch, and a column wall thickness of 0.02 inch is used; a porous polymer stationary phase is used as the packing; a flow rate of 20 ml / min and a supply pressure of 5 kgf / cm 2of helium is used as the carrier gas; stepwise heating conditions are applied: 80°C for 0.1 min, heating from 80°C to 96°C at a heating rate of 4°C / min, heating from 96°C to 135°C at a heating rate of 10°C / min, and holding at 135°C for 2 min; the injection port temperature is 180°C; the solution injection volume is 3 μl; and a thermal conductivity detector is used at 200°C.

[0008] In some embodiments of the present invention, the two or more photosensitive resin layers each independently have a thickness of 50 μm to 300 μm.

[0009] In some embodiments of the present invention, the photosensitive resin laminate comprises 2 to 4 photosensitive resin layers.

[0010] In some embodiments of the present invention, the two or more photosensitive resin layers are each independently a dry film.

[0011] In some embodiments of the present invention, the two or more photosensitive resin layers each independently contain (A) an alkali-soluble polymer, (B) an ethylenically unsaturated compound component, and (C) a photopolymerization initiator.

[0012] In some embodiments of the present invention, the ethylenically unsaturated compound, component (B), comprises one or more difunctional acrylate compounds.

[0013] In some embodiments of the present invention, the amount of the difunctional acrylate compound based on the weight of the ethylenically unsaturated compound, component (B), is 60% by weight or more.

[0014] Another object of the present invention is to provide a composite laminate comprising the above-mentioned photosensitive resin laminate and a non-photosensitive resin film on at least one surface of the photosensitive resin laminate.

[0015] In some embodiments of the present invention, the non-photosensitive resin film is selected from the group consisting of polyethylene terephthalate film, polyolefin film, and composites thereof.

[0016] In order to make the above-mentioned objects, technical features and advantages of the present invention more apparent, the present invention will be described in detail below with reference to some specific embodiments. DETAILED DESCRIPTION OF THE INVENTION

[0017] Some specific embodiments of the present invention will now be described in detail, however, the present invention may be embodied in various embodiments and should not be limited to the embodiments set forth herein.

[0018] Unless otherwise stated, the expressions "a," "the," etc. used in the specification and claims are intended to include both the singular and the plural forms.

[0019] Unless otherwise specified, the terms "first," "second," etc. used in this specification and claims have no special meaning and are used only to distinguish between the elements or components described. These terms are not used to indicate priority.

[0020] Unless further explained, the terms "(meth)acrylic acid," "(meth)acrylate," etc. are intended to cover both embodiments with and without the functional group within the parentheses. 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.

[0021] In this specification and claims, weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC) and calculated by comparison with a standard sample. The unit of weight average molecular weight (Mw) is "g / mol."

[0022] The advantage of the present invention over the prior art is that it provides a thick photosensitive resin laminate with excellent adhesion, storage properties, and handling properties by controlling the gas chromatography properties of the photosensitive resin laminate. The photosensitive resin laminate of the present invention and its applications are described in detail below.

[0023] 1. Photosensitive resin laminate The photosensitive resin laminate of the present invention comprises two or more photosensitive resin layers and contains a second component. The second component can be contained in a photosensitive resin layer of the photosensitive resin laminate. In some embodiments of the present invention, the photosensitive resin laminate comprises two to four photosensitive resin layers, and each photosensitive resin layer contains the second component.

[0024] In some embodiments of the present invention, the photosensitive resin laminate is essentially free of toluene. That is, the amount of toluene based on the total weight of the photosensitive resin laminate is 0.5 wt% or less. For example, the amount of toluene based on the total weight of the photosensitive resin laminate can be 0.5 wt%, 0.45 wt%, 0.4 wt%, 0.35 wt%, 0.3 wt%, 0.25 wt%, 0.2 wt%, 0.15 wt%, 0.1 wt%, 0.05 wt%, or 0.01 wt%. In some embodiments of the present invention, the photosensitive resin laminate is free of toluene.

[0025] The photosensitive resin laminate of the present invention can be used as a positive photoresist film or a negative photoresist film. In some embodiments of the present invention, the photosensitive resin laminate is used as a negative photoresist film. That is, after exposure of the photoresist film, the unexposed parts are dissolved in the development process, leaving the exposed parts.

[0026] The total thickness of the photosensitive resin laminate of the present invention is in the range of 100 μm to 600 μm, for example, 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, The thickness of the photosensitive resin laminate can be 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 between these two values. The thicker the photosensitive resin laminate, the thicker the thickness that can be used for plating a metal conductive layer when the photosensitive resin laminate is used as a photoresist film. Therefore, the photosensitive resin laminate is particularly suitable for packaging 2.5D and 3D integrated circuits, and is useful for patterning before plating a conductive layer.

[0027] 1.1. Gas chromatographic characteristics of photosensitive resin laminate The photosensitive resin laminate of the present invention has specific gas chromatography characteristics. In particular, when the photosensitive resin laminate is characterized by gas chromatography using added toluene as an internal standard, the retention time of the elution peak of the second component is in the range of 0.55 to 1.30 minutes, and the retention time of the added toluene is in the range of 1.32 to 1.65 minutes, satisfying the following formula:

number

[0028] In the above formula, "0.1% to 7.0%" means that the value obtained by calculating the left side of the equation can be in the range of 0.1% to 7.0%. For example, in the above formula, the value obtained by calculating the left side of the equation can be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 3.10%, 3.11%, 3.12%, 3.13%, 3.14%, 3.15%, 3.16%, 3.17%, 3.18%, 3.19%, 3.20%, 3.21%, 3.22%, 3.23%, 3.24%, 3.25%, 3.26%, 3.27%, 3.28%, 3.29%, 3.30%, 3.31%, 3.32%, 3.33%, 3.34%, 3.35%, 3.36%, 3.37%, 3.38%, 3.39%, 3.40%, 3.41%, 3.42%, 3.43%, 3.44%, 3.45%, 3.46%, 3.47%, 3.48%, 3.49%, 3.50%, The variance may be 6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5.0%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6.0%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%, 6.6%, 6.7%, 6.8%, 6.9%, or 7.0%, or within a range between any two of these recited values.

[0029] Gas chromatography is performed by dissolving the photosensitive resin laminate in propylene glycol methyl ether with added toluene as an internal standard to form a solution, and testing the solution under the following conditions: <Conditions> A stainless steel column with a column length of 3 m, an outer diameter of 1 / 8 inch, and a column wall thickness of 0.02 inch is used; a porous polymer stationary phase is used as the packing; a flow rate of 20 ml / min and a supply pressure of 5 kgf / cm 2 of helium is used as the carrier gas; stepwise heating conditions are applied: 80°C for 0.1 min, heating from 80°C to 96°C at a heating rate of 4°C / min, heating from 96°C to 135°C at a heating rate of 10°C / min, and holding at 135°C for 2 min; the injection port temperature is 180°C; the solution injection volume is 3 μl; and a thermal conductivity detector is used at 200°C. In the above test conditions, the porous polymer stationary phase can be a column with model number: CRS BX-10 (Heng Yi Enterprise Company).

[0030] The weight of the photosensitive resin laminate used in gas chromatography can be in the range of 11 g to 19.5 g. The amount of added toluene used in gas chromatography can be in the range of 0.45 g to 0.55 g. For example, the weight of the photosensitive resin laminate can be 11 g, 11.5 g, 12 g, 12.5 g, 13 g, 13.5 g, 14 g, 14.5 g, 15 g, 15.5 g, 16 g, 16.5 g, 17 g, 17.5 g, 18 g, 18.5 g, or 19 g, or any value between these two values. The amount of added toluene can be 0.45 g, 0.46 g, 0.47 g, 0.48 g, 0.49 g, 0.50 g, 0.51 g, 0.52 g, 0.53 g, 0.54 g, or 0.55 g, or any value between these two values. In gas chromatography, the weight of the photosensitive resin laminate used is preferably 25 to 35 times the amount of added toluene, thereby achieving a better signal-to-noise ratio. In some embodiments of the present invention, the weight of the photosensitive resin laminate used in gas chromatography is 15 g, and the amount of added toluene is in the range of 0.50 g to 0.53 g.

[0031] The weight of propylene glycol methyl ether used in gas chromatography can be in the range of 55 g to 65 g. For example, the weight of propylene glycol methyl ether used in gas chromatography can be 55 g, 56 g, 57 g, 58 g, 59 g, 60 g, 61 g, 62 g, 63 g, 64 g, or 65 g, or any value between these two values. In gas chromatography, the retention time of propylene glycol methyl ether is slower than the retention time of added toluene. In some embodiments of the present invention, the elution peak of propylene glycol methyl ether corresponds to a retention time of 1.9 minutes to 6.9 minutes.

[0032] 1.2. Photosensitive resin layer The photosensitive resin laminate of the present invention may be composed of two or more photosensitive resin layers. For example, the photosensitive resin laminate of the present invention may be composed of two, three, or four photosensitive resin layers, but the present invention is not limited thereto. Each photosensitive resin layer may independently have a thickness in the range of 50 μm to 300 μm. For example, the photosensitive resin layers can each independently have a thickness of 50 μm, 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, or 300 μm, or a thickness within a range between two of these recited values.

[0033] In some embodiments of the present invention, the photosensitive resin layer is a dry film. This means that the photosensitive resin film has a low solvent content. The term "low solvent content" refers to a solvent content of 0.1% to 8% by weight, more particularly 0.1% to 7% by weight, based on the total weight of the photosensitive resin film. In contrast to ink-like and liquid-like wet films, dry films are less likely to flow or deform due to their low solvent content, and can be applied to a substrate without the need for additional processes such as coating or drying. Therefore, dry films are easier to control and easier to handle.

[0034] As long as the photosensitive resin laminate satisfies the above-mentioned chromatographic properties, the compositions of the two or more photosensitive resin layers forming the photosensitive resin laminate can be adjusted as necessary. The compositions of the two or more different photosensitive resin layers can be the same or different. In some embodiments of the present invention, the photosensitive resin layers each independently contain (A) an alkali-soluble polymer, (B) an ethylenically unsaturated compound component, (C) a photopolymerization initiator, a second component, and optional additives.

[0035] 1.2.1.(A) Alkali-soluble polymer Examples of alkali-soluble polymers include, but are not limited to, carboxy-containing acrylic acid 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 alkali-soluble polymers described above can be used alone or in combination. In some embodiments of the present invention, the alkali-soluble polymer is a carboxy-containing acrylic acid polymer.

[0036] For example, an alkali-soluble polymer can be obtained by polymerizing one or more carboxy-containing polymerizable monomers or copolymerizing one or more carboxy-containing polymerizable monomers with other polymerizable monomers that do not contain carboxyl groups. Thus, the alkali-soluble polymer can contain one or more repeating units derived from the carboxy-containing polymerizable monomer, or one or more repeating units derived from the carboxy-containing polymerizable monomer and one or more repeating units derived from the other polymerizable monomer.

[0037] In some embodiments of the present invention, the alkali-soluble polymer has a repeating unit derived from at least one first polymerizable monomer and a repeating unit derived from at least one second polymerizable monomer, and the first polymerizable monomer contains a carboxyl group. 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 a carboxyl group. Examples of the second polymerizable monomer include 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-based compounds such as (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-based compounds such as vinyl acetate and vinyl n-butylate; vinyl aromatic-based compounds such as styrene, vinyl naphthalene, 3-acetoxystyrene, 4-acetoxystyrene, vinyl toluene, and α-methylstyrene; norbornene; acrylamide; maleate-based compounds such as monomethyl maleate, monoethyl maleate, and monoisopropyl maleate; and derivatives of the above polymerizable monomers, but are not limited to these.The first polymerizable monomer and the second polymerizable monomer may be used alone or in combination.

[0038] In a preferred embodiment of the present invention, an alkali-soluble polymer can be obtained by copolymerizing (meth)acrylic acid with one or more (meth)acrylate compounds. Thus, 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 compounds 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 compounds 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 any range between any two of these values.

[0039] 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, 1 The value may be 0.05,000, 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 a range between any two of these recited values.

[0040] The amount of the alkyl-soluble polymer based on the weight of the photosensitive resin layer in which it is present can be 20% to 85% by weight, particularly 40% to 80% by weight, and more particularly 50% to 75% by weight. For example, the amount of alkyl-soluble polymer based on the weight of the photosensitive resin layer in which it is present can be 20 wt%, 22.5 wt%, 25 wt%, 27.5 wt%, 30 wt%, 32.5 wt%, 35 wt%, 37.5 wt%, 40 wt%, 42.5 wt%, 45 wt%, 47.5 wt%, 50 wt%, 52.5 wt%, 55 wt%, 57.5 wt%, 60 wt%, 62.5 wt%, 65 wt%, 67.5 wt%, 70 wt%, 72.5 wt%, 75 wt%, 77.5 wt%, 80 wt%, 82.5 wt%, or 85 wt%, or any range between any two of these recited values.

[0041] 1.2.2.(B) Ethylenically unsaturated compound components The ethylenically unsaturated compound refers to a compound having at least one reactive ethylenic functional group, and is preferably a difunctional compound having two reactive ethylenic functional groups. In some embodiments of the present invention, the ethylenically unsaturated compound component includes a monofunctional or polyfunctional acrylate compound, and preferably a difunctional acrylate compound. 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)acryloxyisocyanate)hexamethylene isocyanurate, ethoxylated urethane di(meth)acrylate, propoxylated urethane di(meth)acrylate, ethoxylated / propoxylated urethane di(meth)acrylate, ethoxylated tris(methacryloxyisocyanate)hexamethylene isocyanurate, acrylated tris(methacryloxyisocyanate)hexamethylene isocyanurate, and ethoxylated / propoxylated tris(methacryloxyisocyanate)hexamethylene isocyanurate. Furthermore, in each photosensitive resin layer, the amount of the difunctional acrylate compound based on the weight of the ethylenically unsaturated compound components in each photosensitive resin layer is preferably 60 wt% or more. For example, the amount of the difunctional acrylate compound based on the weight of the ethylenically unsaturated compound components in each photosensitive resin layer can be 60 wt%, 62.5 wt%, 65 wt%, 67.5 wt%, 70 wt%, 72.5 wt%, 75 wt%, 77.5 wt%, 80 wt%, 82.5 wt%, 85 wt%, 87.5 wt%, 90 wt%, 92.5 wt%, 95 wt%, 97.5 wt%, or 100 wt%, or within a range between these two values.

[0042] In some embodiments of the present invention, the ethylenically unsaturated compound component includes at least one of ethoxylated bisphenol-A dimethacrylate and trimethylolpropane triacrylate.

[0043] The amount of the ethylenically unsaturated compound component based on the weight of the photosensitive resin layer in which the ethylenically unsaturated compound component is present can be in the range of 5% by weight to 70% by weight, particularly 15% by weight to 50% by weight, and more particularly 20% by weight to 45% by weight. For example, the amount of the ethylenically unsaturated compound component based on the weight of the photosensitive resin layer in which the ethylenically unsaturated compound component is present can be 5 wt%, 7.5 wt%, 10 wt%, 12.5 wt%, 15 wt%, 17.5 wt%, 20 wt%, 22.5 wt%, 25 wt%, 27.5 wt%, 30 wt%, 32.5 wt%, 35 wt%, 37.5 wt%, 40 wt%, 42.5 wt%, 45 wt%, 47.5 wt%, 50 wt%, 52.5 wt%, 55 wt%, 57.5 wt%, 60 wt%, 62.5 wt%, 65 wt%, 67.5 wt%, or 70 wt%, or within a range between any two of these recited values.

[0044] 1.2.3.(C) Photopolymerization initiator A photopolymerization initiator refers to a substance capable of initiating a polymerization reaction in the presence of light. The type of photopolymerization initiator is not particularly limited. Examples of photopolymerization initiators 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 commonly known photopolymerization initiators. The photopolymerization initiators may be used alone or in combination.

[0045] Examples of the imidazole compound 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.

[0046] 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.

[0047] Examples of quinone compounds include, but are not limited to, camphorquinone, benzanthraquinone, 2-tert-butylanthraquinone, and 2-methylanthraquinone.

[0048] 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.

[0049] Examples of polyhalogenated compounds include, but are not limited to, carbon tetrabromide, phenyl tribromomethyl sulfone, and phenyl trichloromethyl ketone.

[0050] 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.

[0051] 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.

[0052] Examples of onium compounds include, but are not limited to, 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.

[0053] Other common well-known examples of photoinitiators include, but are not limited to, fluorine, bisacylphosphine oxides, azinium compounds, organoboron compounds, phenylglyochelates, and titanocenes.

[0054] In some embodiments of the present invention, the photoinitiator is an imidazole-based compound or a ketone-based compound.

[0055] The amount of photopolymerization initiator based on the weight of the photosensitive resin layer in which the photopolymerization initiator is present can be in the range of 0.1 wt % to 15 wt %, particularly 0.5 wt % to 10 wt %, more particularly 1 wt % to 5 wt %. For example, the amount of photoinitiator based on the weight of the photosensitive resin layer in which the photoinitiator is present can be 0.1 wt%, 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%, 10 wt%, 10.5 wt%, 11 wt%, 11.5 wt%, 12 wt%, 12.5 wt%, 13 wt%, 13.5 wt%, 14 wt%, 14.5 wt%, or 15 wt%, or within a range between any two of these recited values.

[0056] 1.2.4. Second Component In the present invention, the second component refers to a component that contributes to an elution peak with a retention time in the range of 0.55 minutes to 1.30 minutes when the photosensitive resin laminate is characterized by gas chromatography using added toluene as an internal standard. The second component can be present in at least one photosensitive resin layer, and preferably in all photosensitive resin layers that form the photosensitive resin laminate.

[0057] In some embodiments of the present invention, the second component of the photosensitive resin layer can each independently be at least one of an inert ester, ketone, ether, or alcohol having a boiling point in the range of 55°C to 90°C. The term "inert ester, ketone, ether, or alcohol" refers to an ester, ketone, ether, or alcohol that is miscible with but does not react with the other components of the photosensitive resin layer. For example, the second component can include at least one of methyl acetate, ethyl acetate, acetone, methyl ethyl ketone, methanol, ethanol, and isopropanol.

[0058] 1.2.5. Optional Additives As long as the photosensitive resin laminate satisfies the above-mentioned chromatographic properties, the two or more photosensitive resin layers forming the photosensitive resin laminate may further contain additives to improve the properties of the photosensitive resin layers. Examples of additives include, but are not limited to, solvents, light absorbers, dyes, pigments, radical initiators, and surfactants. The additives may be used alone or in combination.

[0059] 1.3. Preparation of photosensitive resin laminate The method for preparing the photosensitive resin laminate of the present invention is not particularly limited. Those skilled in the art can prepare a photosensitive resin laminate based on the description of the present application, particularly the specific description in the examples. For example, a method for preparing a photosensitive resin laminate containing the above-mentioned components includes uniformly mixing each component of the photosensitive resin film, including (A) an alkali-soluble polymer, (B) an ethylenically unsaturated compound component, (C) a photopolymerization initiator, a second component, and optional additives, using a mixer. The mixture is then dissolved or dispersed in a solvent to form a photosensitive solution, which is then coated on a substrate. The coated photosensitive solution is dried to obtain a photosensitive resin layer. These steps can be repeated, optionally changing the composition of the photosensitive solution, to obtain additional photosensitive resin layers. Finally, the obtained photosensitive resin layers are stacked, pressed, or bonded together to obtain a photosensitive resin laminate.

[0060] The method for coating the photosensitive solution is not particularly limited and can be any coating method known in the art. Examples of known coating methods include, but are not limited to, gravure coating, reverse roll coating, die coating, air scraper coating, scraper coating, rod coating, scraper 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 method for coating the photosensitive solution is preferably scraper coating, rod coating, scraper rod coating, or die coating.

[0061] In some embodiments of the present invention, the coated photosensitive solution can be heated at a temperature in the range of 70°C to 200°C for 1 to 40 minutes, preferably at 100°C to 180°C for 1 to 40 minutes, in order to dry the photosensitive resin layer to an appropriate extent.

[0062] The detailed method for preparing the photosensitive resin laminate will be described in the following examples.

[0063] 2. Application of photosensitive resin laminate The photosensitive resin laminate of the present invention can be used as a photoresist film and is applied in various electronic engineering fields. Generally, before using the photoresist film, both surfaces of the photoresist film can be covered with a protective film that provides protection and support. This facilitates storage of the photoresist film and protects the photoresist film from contamination or damage by foreign substances. Similarly, a protective film can be provided on both sides of the photosensitive resin laminate. The protective film is preferably a non-photosensitive resin film.

[0064] Therefore, the present invention also provides a composite film comprising the above-mentioned photosensitive resin laminate and a non-photosensitive resin film on at least one surface of the photosensitive resin laminate. In a preferred embodiment of the present invention, the non-photosensitive resin films are provided on both surfaces of the photosensitive resin laminate, and the materials of the non-photosensitive resin films on the two different surfaces of the photosensitive resin laminate can be the same or different.

[0065] The type of non-photosensitive resin film is not particularly limited and can be any conventional material known in the art. For example, the non-photosensitive resin film that can be used in the present invention can be selected from the group consisting of polyethylene terephthalate film (PET film), polyolefin film, and composites thereof. Examples of polyolefin films include, but are not limited to, polyethylene film (PE film) and polypropylene film (PP film), such as oriented polypropylene film. 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 laminate comprises a PET film on one surface of the photosensitive resin laminate and a PE film on the other surface of the photosensitive resin laminate.

[0066] The method for preparing the composite laminate of the present invention is not particularly limited and can be any method known in the art. Those skilled in the art can prepare a composite laminate based on the description of the present specification. For example, a composite laminate can be prepared by stacking non-photosensitive resin films on both surfaces of a photosensitive resin laminate to form a stacked body, and then pressing the stacked body to obtain a composite laminate. Alternatively, a composite film can be prepared by forming a photosensitive resin layer between two non-photosensitive resin films by coating or extrusion. The non-photosensitive resin film on the surface of the photosensitive resin layer that will contact the other photosensitive resin layer can be peeled off, followed by stacking and pressing to obtain a composite laminate.

[0067] Detailed methods for preparing composite laminates are described in the examples below. [Example]

[0068] 3. Working Example 3.1. Test Method [Number of layers of photosensitive resin laminate] The prepared composite laminate was cut into 10 mm x 15 mm pieces along the transverse direction (TD) and machine direction (MD) at random locations. The PE and PET films were removed from both surfaces of the photopolymer laminate. The photopolymer laminate was placed on the analysis platform of a microscope (model number: Olympus MX51) along with a jig. The sample position was adjusted to ensure that the cut surface of the sample was perpendicular to the viewing angle of the objective lens. The cut surface was observed under a fluorescent filter, a 10x objective lens (model number: MPlanFL N), and a 10x eyepiece. The presence of clear interfaces between layers indicated that the sample had a laminated structure. Each identified interface was counted to determine the number of layers in the photopolymer laminate (= "number of identified interfaces + 1").

[0069] [Gas chromatography of photosensitive resin laminate] The PE and PET films of the composite laminate were removed from both surfaces of the photosensitive resin laminate. The prepared composite laminate was cut into 15 g samples along the transverse direction (TD) and machine direction (MD) at random positions. The obtained photosensitive resin laminate sample was dissolved in 60 g of propylene glycol methyl ether, and 0.50 g to 0.53 g of toluene was added as an internal standard to create a solution. Gas chromatography was performed under the following conditions. <Conditions> A stainless steel column with a column length of 3 m, an outer diameter of 1 / 8 inch, and a column wall thickness of 0.02 inch was used; CRS BX-10 (Heng Yi Enterprise Company) was used as the packing material; the flow rate was 20 ml / min and the supply pressure was 5 kgf / cm 2of helium is used as the carrier gas; stepwise heating conditions are applied: 80°C for 0.1 min, heating from 80°C to 96°C at a heating rate of 4°C / min, heating from 96°C to 135°C at a heating rate of 10°C / min, and holding at 135°C for 2 min; the injection port temperature is 180°C; the solution injection volume is 3 μl; and a thermal conductivity detector is used at 200°C. Analysis was performed using analytical software Qchrom V1.2 from Scientific Information Service Company. Calculations were performed according to the following formula, and the obtained values ​​were recorded as "Gas Chromatography Calculation Results."

number

[0070] [Air bubble analysis of photosensitive resin laminate] The prepared composite laminate was cut at random positions into 10 mm x 15 mm pieces along the transverse direction (TD) and machine direction (MD). The PE film was removed. The resulting photosensitive resin laminate was placed on a transparent glass sheet, with the PET film on top facing the transparent glass. This assembly was placed in a laminator under the following conditions: lamination speed 0.5 m / min, lamination pressure 3.0 kg / cm. 2 , and pressed at a lamination temperature of 25°C. Then, the PET film was removed. The obtained photosensitive resin laminate was placed on a black flat substrate along with glass, and exposed to light with an exposure energy of 100 mJ / cm. 2 The photopolymer laminate was exposed to light until it reached a thickness of 100 μm. A 1% aqueous solution of Na2CO3 at 30°C was used as the developer, and the photopolymer laminate was immersed in the developer along with the glass for 10 minutes. After development, the photopolymer laminate was removed along with the glass, washed with pure water for 10 seconds, and air-dried. An arbitrary 5 cm x 5 cm area was selected in the center of the glass and observed. This area was divided into 5 mm x 5 mm subareas, and the subareas were successively observed for bubbles using a microscope with a 10x eyepiece. The number of bubbles whose major axis was longer than 0.5 times the total thickness of the photopolymer laminate was recorded.

[0071] [Wrinkle test for photosensitive resin laminate] The prepared composite laminate was wound into a slit roll having a length of 30 m and a width of 300 mm and left at a temperature of 23 to 27°C for 16 hours. A 5-m-long composite laminate was then pulled out from the slit roll, and the PE protective film on the composite laminate was peeled off. The surface of the photosensitive resin laminate was then visually inspected. The number of wrinkles having a length of 10 mm or more and a width of 1 mm or more present within a 3 to 5 m area of ​​the photosensitive resin laminate was recorded. The absence of wrinkles having a length of 10 mm or more and a width of 1 mm or more indicated that the photosensitive resin laminate had excellent storage properties and operability.

[0072] [100-grid adhesion test of thermally engineered resin laminate] A 100-grid adhesion test of the photosensitive resin laminate was conducted in accordance with ASTM D3359 using the following method. A copper-clad laminate (Model: CCP-308, Chang Chun Plastics Co., Ltd.) with a thickness of 1.6 mm was prepared. The copper foil of the copper-clad laminate was 35 μm thick. The copper-clad laminate was subjected to brush polishing using a #320 nonwoven brush wheel and a #600 nonwoven brush wheel. The temperature of the copper foil surface of the copper-clad laminate was adjusted to 50°C. The PE film on the surface of the prepared composite laminate was peeled off. The photosensitive resin laminate, along with the PET film, was stacked on the surface of the copper foil so that the photosensitive resin laminate faced the copper foil surface of the copper-clad laminate. The stack was laminated using a laminator to provide the sample. The lamination temperature was 80°C, and the lamination pressure was 3.0 kg / cm. 2 The lamination speed was 2.0 mm / min. The PET film on the sample was peeled off, and the photopolymer laminate of the sample was cut into a grid of 100 10 × 10 squares with spacing of 1 mm to 1.2 mm using a knife. A transparent tape (Model: 3M Transparent 600) manufactured by 3M Company was adhered to the surface of the grid photopolymer laminate. The tape was quickly peeled off at a 45° angle to the substrate. The number of grids from which the photopolymer laminate was peeled off was calculated and recorded as a percentage. A lower percentage indicates better adhesion of the photopolymer laminate to the copper-clad laminate.

[0073] 3.2. Preparation method 3.2.1. Synthesis of alkali-soluble polymers According to the following Synthesis Examples 1 to 7, carboxy-containing acrylic acid polymers were prepared as alkali-soluble polymers.

[0074] [Synthesis Example 1] Solution a1 was prepared by mixing 15 g of methacrylic acid, 60 g of methyl methacrylate, and 25 g of butyl acrylate as copolymerization monomers with 1.8 g of azobisisoheptylnitrile. Separately, solution b1 was prepared by dissolving 0.7 g of azobisisoheptylnitrile in 20 g of ethyl acetate.

[0075] A flask equipped with a stirrer, reflux condenser, thermometer, and pipette was prepared. 80 g of ethyl acetate was added to the flask and heated to 70°C. Solution a1 was added dropwise to the flask at a constant rate over 3 hours, and the solution in the flask was maintained at 70°C and stirred for 2 hours. While continuously maintaining the solution in the flask at 70°C, solution b1 was added dropwise to the flask at a constant rate over 0.5 hours, and the solution in the flask was maintained at 70°C and stirred for 5 hours. The solution in the flask was then 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 acid-based polymer A (hereinafter referred to as polymer A) having a weight-average molecular weight of 55,000 and a solids content of 50% by weight.

[0076] [Synthesis Example 2] Solution a2 was prepared by mixing 15 g of methacrylic acid, 65 g of methyl methacrylate, and 20 g of butyl acrylate as copolymerization monomers with 0.8 g of azobisisoheptylnitrile. Separately, solution b2 was prepared by dissolving 0.5 g of azobisisoheptylnitrile in 20 g of methyl acetate.

[0077] A flask equipped with a stirrer, reflux condenser, thermometer, and pipette was prepared. 102.2 g of methyl acetate was added to the flask and heated to 70°C. Solution a2 was added dropwise to the flask at a constant rate over 3 hours, and the solution in the flask was maintained at 70°C and stirred for 2 hours. While continuously maintaining the solution in the flask at 70°C, solution b2 was added dropwise to the flask at a constant rate over 0.5 hours, and the solution in the flask was maintained at 70°C and stirred for 5 hours. The solution in the flask was then 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 acid-based polymer B (hereinafter referred to as polymer B) having a weight-average molecular weight of 65,000 and a solids content of 45% by weight.

[0078] [Synthesis Example 3] Solution a3 was prepared by mixing 20 g of methacrylic acid, 40 g of methyl methacrylate, and 40 g of 2-ethylhexyl acrylate as copolymerization monomers with 1.2 g of azobisisoheptylnitrile. Separately, solution b3 was prepared by dissolving 0.5 g of azobisisoheptylnitrile in 20 g of acetone.

[0079] A flask equipped with a stirrer, reflux condenser, thermometer, and pipette was prepared. 80 g of acetone was added to the flask and heated to 70°C. Solution a3 was added dropwise to the flask at a constant rate over 3 hours, and the solution in the flask was maintained at 70°C and stirred for 2 hours. While continuously maintaining the solution in the flask at 70°C, solution b3 was added dropwise to the flask at a constant rate over 0.5 hours, and the solution in the flask was maintained at 70°C and stirred for 6 hours. The solution in the flask was then heated to 90°C and stirred for 4 hours to complete the reaction. After the reaction was completed, the resulting product was cooled to room temperature to obtain a carboxy-containing acrylic acid-based polymer C (hereinafter referred to as polymer C) having a weight-average molecular weight of 55,000 and a solids content of 50% by weight.

[0080] [Synthesis Example 4] Solution a4 was prepared by mixing 20 g of methacrylic acid, 60 g of methyl methacrylate, and 20 g of butyl acrylate as copolymerization monomers with 1 g of azobisisoheptylnitrile. Separately, solution b4 was prepared by dissolving 0.5 g of azobisisoheptylnitrile in 20 g of methyl ethyl ketone.

[0081] A flask equipped with a stirrer, reflux condenser, thermometer, and pipette was prepared. 80 g of methyl ethyl ketone was added to the flask and heated to 70°C. Solution a4 was added dropwise to the flask at a constant rate over 4 hours, and the solution in the flask was maintained at 70°C and stirred for 2 hours. While continuously maintaining the solution in the flask at 70°C, solution b4 was added dropwise to the flask at a constant rate over 0.5 hours, and the solution in the flask was maintained at 70°C and stirred for 5 hours. The solution in the flask was then 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 acid-based polymer D (hereinafter referred to as polymer D) having a weight-average molecular weight of 50,000 and a solids content of 50 wt%.

[0082] [Synthesis Example 5] Solution a5 was prepared by mixing 20 g of methacrylic acid, 60 g of methyl methacrylate, and 20 g of butyl acrylate as copolymerization monomers with 1 g of azobisisoheptylnitrile. Separately, solution b5 was prepared by dissolving 0.5 g of azobisisoheptylnitrile in a mixed solvent of 10 g of propylene glycol methyl ether (PGME) and 10 g of ethyl acetate.

[0083] A flask equipped with a stirrer, reflux condenser, thermometer, and pipette was prepared. A mixed solvent of 40 g of propylene glycol methyl ether and 40 g of ethyl acetate was added to the flask and heated to 70°C. Solution a5 was added dropwise to the flask at a constant rate over 3 hours, and the solution in the flask was maintained at 70°C and stirred for 2 hours. While continuously maintaining the solution in the flask at 70°C, solution b5 was added dropwise to the flask at a constant rate over 0.5 hours, and the solution in the flask was maintained at 70°C and stirred for 5 hours. The solution in the flask was then 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 acid-based polymer E (hereinafter referred to as Polymer E) having a weight-average molecular weight of 50,000 and a solids content of 50 wt%.

[0084] [Synthesis Example 6] Solution a6 was prepared by mixing 15 g of acrylic acid, 65 g of methyl methacrylate, and 20 g of hydroxyethyl methacrylate as copolymerization monomers with 1 g of azobisisoheptylnitrile. Separately, solution b6 was prepared by dissolving 0.5 g of azobisisoheptylnitrile in a mixed solvent of 4 g of ethanol and 16 g of ethyl acetate.

[0085] A flask equipped with a stirrer, reflux condenser, thermometer, and pipette was prepared. A mixed solvent of 16 g of ethanol and 64 g of ethyl acetate was added to the flask and heated to 70°C. Solution a6 was added dropwise to the flask at a constant rate over 3 hours, and the solution in the flask was maintained at 70°C and stirred for 2 hours. While continuously maintaining the solution in the flask at 70°C, solution b6 was added dropwise to the flask at a constant rate over 0.5 hours, and the solution in the flask was maintained at 70°C and stirred for 5 hours. The solution in the flask was then 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 acid-based polymer F (hereinafter referred to as polymer F) having a weight-average molecular weight of 50,000 and a solids content of 50% by weight.

[0086] [Synthesis Example 7] Solution a7 was prepared by mixing 20 g of methacrylic acid, 45 g of methyl methacrylate, and 35 g of 2-ethylhexyl acrylate as copolymerization monomers with 1.9 g of azobisisoheptylnitrile. Separately, solution b7 was prepared by dissolving 0.5 g of azobisisoheptylnitrile in a mixed solvent of 2 g of methanol and 18 g of methyl acetate.

[0087] A flask equipped with a stirrer, reflux condenser, thermometer, and pipette was prepared. A mixed solvent of 8 g of methanol and 72 g of methyl acetate was added to the flask and heated to 70°C. Solution a7 was added dropwise to the flask at a constant rate over 3 hours, and the solution in the flask was maintained at 70°C and stirred for 2 hours. While continuously maintaining the solution in the flask at 70°C, solution b7 was added dropwise to the flask at a constant rate over 0.5 hours, and the solution in the flask was maintained at 70°C and stirred for 5 hours. The solution in the flask was then 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 acid-based polymer G (hereinafter referred to as polymer G) having a weight-average molecular weight of 45,000 and a solids content of 50 wt%.

[0088] 3.2.2. Preparation of photosensitive solution Information regarding the raw materials used in the preparation of the following photosensitive solutions is provided in Table 1 below.

[0089] [Table 1]

[0090] A mixed solution was obtained by mixing the photopolymerization initiator, additives, and THF solvent according to the components and ratios shown in Table 2 and stirring for 30 minutes. Next, the carboxy-containing acrylic acid polymer and ethylenically unsaturated compound components prepared in each synthesis example were added to the mixed solution and stirred for 1 hour to obtain photosensitive solutions A to H.

[0091] [Table 2]

[0092] 3.2.3. Preparation of photosensitive resin laminate According to Tables 3-1 to 3-3, photosensitive resin laminates of Examples E1 to E12 and Comparative Examples CE1 to CE15 were prepared to the desired thickness. Specifically, the resulting photosensitive solution was coated onto a PET film using a Kodaira wire-wound rod. The coated photosensitive solution was dried in an oven to form a photosensitive resin layer on the PET film. A PE film was then stacked on the surface of the photosensitive resin layer that was not in contact with the PET film, resulting in photosensitive resin layers 1, 2, 3, and 4, each coated on both surfaces.

[0093] The PE film was removed from photosensitive resin layer 1, and the PET film was removed from photosensitive resin layer 2. Photosensitive resin layer 1 and photosensitive resin layer 2 were pressed together with the surfaces of the photosensitive resin layers facing each other, resulting in a photosensitive resin laminate including photosensitive resin layer 1 and photosensitive resin layer 2.

[0094] The PE film was removed from photosensitive resin layer 1, and the PET film was removed from photosensitive resin layer 2. Photosensitive resin layer 1 and photosensitive resin layer 2 were pressed together with the surfaces of the photosensitive resin layers facing each other. Subsequently, the PE film was removed from photosensitive resin layer 2, and the PET film was removed from photosensitive resin layer 3. Photosensitive resin layer 3 was adhered to the surface of photosensitive resin layer 2 that was not adhered to photosensitive resin layer 1, and they were pressed together, resulting in a photosensitive resin laminate including photosensitive resin layer 1, photosensitive resin layer 2, and photosensitive resin layer 3.

[0095] The PE film was removed from photosensitive resin layer 1, and the PET film was removed from photosensitive resin layer 2. Photosensitive resin layer 1 and photosensitive resin layer 2 were pressed together with their respective surfaces facing each other. Next, the PE film was removed from photosensitive resin layer 2, and the PET film was removed from photosensitive resin layer 3. Photosensitive resin layer 3 was bonded to the surface facing the surface of photosensitive resin layer 2 that was not bonded to photosensitive resin layer 1. Furthermore, the PE film was removed from photosensitive resin layer 3, and the PET film was removed from photosensitive resin layer 4. Photosensitive resin layer 4 was bonded to the surface facing the surface of photosensitive resin layer 3 that was not bonded to photosensitive resin layer 2, and then pressed. As a result, a photosensitive resin laminate including photosensitive resin layer 1, photosensitive resin layer 2, photosensitive resin layer 3, and photosensitive resin layer 4 was obtained.

[0096] [Table 3-1]

[0097] [Table 3-2]

[0098] [Table 3-3]

[0099] 3.3. Testing of photosensitive resin laminates According to the above-mentioned test methods, the properties of the photosensitive resin laminates or photosensitive resin layers of Examples E1 to E12 and Comparative Examples CE1 to CE15 were tested, including the number of layers of the photosensitive resin laminate, the calculation results of gas chromatography, bubbles, wrinkles, and 100-grid adhesion properties. The results are shown in Tables 4-1 to 4-3.

[0100] [Table 4-1]

[0101] [Table 4-2]

[0102] [Table 4-3]

[0103] As shown in Tables 4-1 to 4-3, the photosensitive resin laminates of the present invention do not contain air bubbles or wrinkles as defects. This indicates that the photosensitive resin laminates have good handling and storage properties. In addition, the photosensitive resin laminates of Examples E1 to E12 exhibit low peel percentages (<5%) in a 100-grid adhesion test. This indicates good adhesion to copper-clad laminates.

[0104] In contrast, the photosensitive resin laminates of Comparative Examples CE1 to CE10 and CE15 exhibit air bubble defects and wrinkles. Furthermore, these photosensitive resin laminates exhibit poor operability and storage properties because the gas chromatography calculation results are higher than the specific range (higher than 7.0%). The photosensitive resin laminates of Comparative Examples CE11 to CE13 exhibit air bubble defects. Furthermore, these photosensitive resin laminates exhibit poor adhesion because the gas chromatography calculation results are lower than the specific range (lower than 0.1%). In particular, Comparative Example CE13 has a photosensitive resin laminate structure, but the gas chromatography calculation results are lower than the specific range, so it still fails to achieve the effects of the present invention. Comparative Example CE15 has a photosensitive resin laminate structure and a thickness of 600 μm, but the gas chromatography calculation results are higher than the specific range, so it still fails to achieve the effects of the present invention. This emphasizes the importance of the technical features of gas chromatography specified in the present invention.

[0105] On the other hand, Comparative Example CE14 shows that even if the technical characteristics for gas chromatography of the present invention are satisfied, defects such as bubbles and wrinkles still occur if the photosensitive resin film does not have a laminate structure. This emphasizes the importance of having a photosensitive resin laminate structure while also satisfying the technical characteristics for gas chromatography specified in the present invention.

[0106] Furthermore, comparisons between Example E4 and Comparative Example CE4, Example E2 and Comparative Example CE5, Example E7 and Comparative Example CE6, and Example E11 and Comparative Example CE9 show that even if the total thickness is ideal, the comparative examples that do not have two or more photosensitive resin layers cannot satisfy the above formula, resulting in the presence of many bubbles and wrinkles. This highlights the importance of the technical feature of having a photosensitive resin laminate structure.

[0107] The above embodiments illustrate the principles and effects of the present invention and demonstrate its inventive features. Those skilled in the art can make various modifications and replacements based on the disclosure and suggestions of the invention described. Therefore, the protection scope of the present invention is defined by the appended claims.

Claims

1. A photosensitive resin laminate comprising two or more low-solvent-content photosensitive resin layers and containing a second component, When the photosensitive resin laminate is characterized by gas chromatography using added toluene as an internal standard, the retention time of the elution peak of the second component is in the range of 0.55 minutes to 1.30 minutes, the retention time of the added toluene is in the range of 1.32 minutes to 1.65 minutes, and the following formula is satisfied: [Equation 1] (wherein the amount of toluene added and the weight of the photosensitive resin laminate are expressed in grams (g).) the photosensitive resin laminate has a total thickness of 100 μm to 600 μm, the second component is selected from one or more of methyl acetate, ethyl acetate, acetone, methyl ethyl ketone, methanol, ethanol, isopropanol, and propylene glycol methyl ether; The photosensitive resin laminate was dissolved in propylene glycol methyl ether together with added toluene as an internal standard to prepare a solution, and gas chromatography was performed by testing the solution under the following conditions: <Conditions> A stainless steel column with a column length of 3 m, an outer diameter of 1 / 8 inch, and a column wall thickness of 0.02 inch is used; a porous polymer stationary phase is used as the packing; a flow rate of 20 ml / min and a supply pressure of 5 kgf / cm 2 of helium was used as the carrier gas; stepwise heating conditions were applied: 80°C for 0.1 minutes, followed by heating from 80°C to 96°C at a heating rate of 4°C / min, heating from 96°C to 135°C at a heating rate of 10°C / min, and then holding at 135°C for 2 minutes; the temperature of the injection port was 180°C; the injection volume of the solution was 3 μl; and a thermal conductivity detector was used at 200°C. The amount of the solvent based on the total weight of the photosensitive resin film is 0.1% by weight to 7% by weight.

2. 2. The photosensitive resin laminate according to claim 1, wherein the two or more photosensitive resin layers each independently have a thickness of 50 μm to 300 μm.

3. 2. The photosensitive resin laminate according to claim 1, which comprises 2 to 4 photosensitive resin layers.

4. 2. The photosensitive resin laminate according to claim 1, wherein the two or more photosensitive resin layers are each independently a dry film.

5. Two or more photosensitive resin layers are independently (A) an alkali-soluble polymer, (B) an ethylenically unsaturated compound component, and The photosensitive resin laminate according to claim 1 , further comprising (C) a photopolymerization initiator.

6. 6. The photosensitive resin laminate according to claim 5, wherein the ethylenically unsaturated compound component (B) comprises one or more difunctional acrylate compounds.

7. 7. The photosensitive resin laminate according to claim 6, wherein the amount of the bifunctional acrylate compound is 60% by weight or more based on the weight of the ethylenically unsaturated compound component (B).

8. The photosensitive resin laminate according to any one of claims 1 to 7, and A composite laminate comprising a non-photosensitive resin film on at least one surface of a photosensitive resin laminate.

9. 9. The composite laminate according to claim 8, wherein the non-photosensitive resin film is selected from the group consisting of polyethylene terephthalate film, polyolefin film, and composites thereof.

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