Compound for preparing photoresist film, photosensitive resin composition and photosensitive laminated body

Abstract

The present invention relates to a compound for preparing a photoresist film, a photosensitive resin composition, and a photosensitive laminate, the compound serving as an adhesion promoter gives consideration to both adhesion and resolution compared to conventional benzotriazole and derivatives thereof, and is easy to remove by alkaline water development, acidic etching, or a pickling process before electroplating. Therefore, the corresponding photosensitive resin composition and the photosensitive laminated body have good post-processing compatibility, and are suitable for precise manufacturing of printed circuit boards.

Description

Technical Field

[0001] This invention belongs to the field of photosensitive materials technology, specifically relating to a compound for preparing photoresist films, a photosensitive resin composition, and a photosensitive laminate. Background Technology

[0002] Printed circuit boards are typically manufactured using photolithography, which specifically refers to the following method: a photoresist film, which serves as a resist material, is stacked on a substrate, such as a copper-clad laminate. The pattern is then exposed, and the exposed portion of the photosensitive resin composition is polymerized and cured. The unexposed portion is removed using a developer, thereby forming a resist pattern on the substrate. Subsequently, etching or plating is performed to form a conductor pattern, and then the resist pattern is peeled off from the substrate.

[0003] In recent years, with the increasing density of smart devices, the linewidth / spacing (L / S) of circuits has been reduced to below 15 / 15μm. Against this backdrop, the interfacial adhesion between the resist material and the copper surface has become a key factor affecting pattern accuracy. Microscopically, the copper-photoresist interface often contains microcracks, insufficiently cured areas, and channels with highly polar groups, which can easily lead to the penetration of etching solution along the interface, causing lateral etching and even pattern detachment.

[0004] To improve adhesion, benzotriazole (BTA) and its derivatives are often added to photoresist films. However, these compounds currently in use still have some drawbacks. For example, the amount of BTA added needs to be precisely controlled; even a slight overdose can easily lead to etching defects or reduced electroplating adhesion due to difficulty in removal by acid etching after development. Another example is that while carboxylated 5-carboxybenzotriazole or 4-carboxybenzotriazole are easily removed in subsequent acid etching processes, they form a carboxyl-rich layer at the copper-photoresist interface in the exposed area. This hydrophilic carboxyl-rich layer can form penetration channels for the etching solution, easily causing lateral etching and resist pattern detachment under certain etching process conditions. Furthermore, the long-chain alkyl derivatives of BTA are too hydrophobic, making them difficult to remove completely even in subsequent conventional processes, leading to etching defects or reduced electroplating adhesion. Therefore, existing BTA-based adhesion promoters struggle to balance adhesion and post-processing compatibility within the same process framework.

[0005] In summary, a long-standing "adhesion-residue removal" paradox exists in this field: introducing adhesion-enhancing groups onto the benzotriazole backbone often results in difficult removal, while introducing groups with easy-to-remove properties sacrifices adhesion. Traditional solutions, such as adjusting the amount of BTA added or introducing long-chain alkyl groups, cannot simultaneously meet the triple requirements of high adhesion, low residue, and resistance to lateral etching in precise patterns below 15 / 15μm. Summary of the Invention

[0006] The primary objective of this invention is to provide a compound for preparing photoresist films that balances adhesion and post-processing compatibility.

[0007] A second objective of the present invention is to provide a photosensitive resin composition containing the above-mentioned compound for preparing photoresist films.

[0008] A third objective of the present invention is to provide a photosensitive laminate containing the above-described photosensitive resin composition.

[0009] To achieve the first objective mentioned above, the present invention provides a compound for preparing photoresist films, the compound being represented by the following formula (I) or (II): Wherein, R1 is an acid-hydrolyzable carboxyl protecting group or an alkaline-hydrolyzable carboxyl protecting group. When R1 is an acid-hydrolyzable carboxyl protecting group, the compound can be hydrolyzed under conditions of pH < 2. When R1 is an alkaline-hydrolyzable carboxyl protecting group, the compound can be hydrolyzed under conditions of pH > 10.

[0010] Furthermore, the acid-hydrolyzed carboxyl protecting group is selected from at least one of tertiary alkyl, acetal, silyl, enol, aryl or heteroaryl substituted tertiary alkyl, ketal imine, β-keto, glycosidic, and epoxyalkyl.

[0011] Furthermore, the acid-hydrolyzed carboxyl protecting group is tert-butyl, 1-methylcyclohexyl, 2-tetrahydropyranyl, 2-tetrahydrofuranyl, 1-ethoxyethyl, tert-butyldimethylsilyl, triethylsilyl, or dimethylethylsilyl.

[0012] Furthermore, the alkaline hydrolysis carboxyl protecting group is a benzene ring activated by an electron-withdrawing group, and / or the alkaline hydrolysis carboxyl protecting group is p-nitrophenyl or pentafluorobenzene.

[0013] Furthermore, the alkaline hydrolysis carboxyl protecting group is a 1-succinimide group.

[0014] To achieve the second objective mentioned above, the present invention provides a photosensitive resin composition comprising (A) an alkali-soluble adhesive polymer, (B) a photopolymerizable compound containing ethylene unsaturated double bonds, (C) a photopolymerization initiator, (D) a mixture of additives, and (E) the aforementioned compound for preparing a photoresist film.

[0015] Furthermore, (E) the aforementioned compound used to prepare the photoresist film accounts for 50 to 1500 ppm of the total weight of the photosensitive resin composition.

[0016] Furthermore, (E) the aforementioned compound used to prepare the photoresist film accounts for 150 to 1000 ppm of the total weight of the photosensitive resin composition.

[0017] Furthermore, (A) the weight-average molecular weight of the alkali-soluble adhesive polymer is 20K to 300K, and the acid value is 100 to 260 mg KOH / g.

[0018] To achieve the third objective mentioned above, the present invention provides a photosensitive laminate comprising a support layer and a photosensitive resin layer formed from the aforementioned photosensitive resin composition.

[0019] The compound involved in this invention for preparing photoresist films, as an adhesion promoter, is easier to remove by alkaline water development, acid etching, or pre-electroplating pickling processes while taking into account both adhesion and resolution, compared to existing benzotriazole and its derivatives. Therefore, the corresponding photosensitive resin composition and photosensitive laminate have good post-processing compatibility and are suitable for the precision manufacturing of printed circuit boards. Attached Figure Description

[0020] Figure 1 This is a cross-sectional structural schematic diagram of an embodiment of the photosensitive laminate of the present invention.

[0021] Figure 2 These are optical microscope images of the specimens corresponding to Example 3 after undergoing an initial test under simulated acidic lateral erosion.

[0022] Figure 3 This is an optical microscope image of the specimen corresponding to Comparative Example 2 after undergoing a simulated acidic lateral erosion initial wheel test. Detailed Implementation

[0023] The preferred embodiments of the present invention will now be described in detail. Furthermore, in the present invention, (meth)acrylic acid refers to acrylic acid and the corresponding methacrylic acid, and (meth)acrylate refers to acrylate and the corresponding methacrylate. In addition, in the present invention, the term "process" is not limited to a single process; even if it cannot be clearly distinguished from other processes, it is included as long as the intended function of the process is achieved. Furthermore, in this specification, the numerical range indicated by "~" represents a range including the minimum and maximum values ​​respectively before and after "~", "wt%" represents mass percentage, and "vol%" represents volume percentage.

[0024] [Photosensitive Resin Composition] The photosensitive resin composition provided by this invention comprises: (A) an alkali-soluble adhesive polymer, (B) a photopolymerizable compound containing ethylene unsaturated double bonds, (C) a photopolymerization initiator, (D) a mixture of additives, and (E) an adhesion promoter. Wherein, (E) the adhesion promoter comprises at least one BTA derivative as shown in formula (I) or (II): Wherein, R1 is an acid-hydrolyzed carboxyl protecting group or an alkaline-hydrolyzed carboxyl protecting group. When R1 is an acid-hydrolyzed carboxyl protecting group, the above BTA derivative is hydrolyzed at pH < 2 to generate the corresponding carboxylbenzotriazole and the corresponding byproduct. When R1 is an alkaline-hydrolyzed carboxyl protecting group, the above BTA derivative is hydrolyzed at pH > 10 to generate the salt of the corresponding carboxylbenzotriazole.

[0025] The BTA end of both types of BTA derivatives can anchor to the copper surface, forming a strong adsorption layer on the copper surface. When a specific group is selected as the acid-hydrolyzed carboxyl protecting group R1, a molecular adsorption layer of the aforementioned BTA derivative remains on the copper surface in the exposed area after alkaline development. This adsorption layer is not hydrolyzed after development, but it can undergo acid-catalyzed hydrolysis during the standard pickling process before etching or electroplating. After the acid-hydrolyzed carboxyl protecting group R1 is removed, 5-carboxybenzotriazole or 4-carboxybenzotriazole, which are easily removed by acid pickling, are formed. Alternatively, when a specific group is selected as the alkaline-hydrolyzed carboxyl protecting group R1, the aforementioned BTA derivative can undergo alkaline-catalyzed hydrolysis during alkaline development to remove the alkaline-hydrolyzed carboxyl protecting group R1, generating a carboxyl group and the corresponding salt. Therefore, in the non-exposed area after alkaline development, the adsorbed substance on the copper surface is the salt of the hydrolyzed BTA derivative, corresponding to the salt of 5-carboxybenzotriazole or 4-carboxybenzotriazole. Therefore, in both of the above situations, the copper surface in the non-exposed area can eventually form easily removable 5-carboxybenzotriazole, 4-carboxybenzotriazole, or their corresponding salts. In the exposed area after development, the adsorbed molecular layer formed by the above-mentioned BTA derivatives on the copper surface is fully protected by the photosensitive resin layer that acts as a photoresist film, preventing it from being eroded by alkaline or acidic hydrolysis. Therefore, the overall interface hydrophobicity is still maintained.

[0026] The various components of the photosensitive resin composition of the present invention will be described in further detail below.

[0027] (A) Alkali-soluble adhesive polymer The alkali-soluble adhesive polymer (A) used in this invention is selected from at least one of acrylic resins, epoxy resins, amide resins, amide-epoxy resins, alkyd resins, and phenolic resins. Acrylic resins are preferred. Acrylic resins are obtained by free radical polymerization of polymerizable monomers, the essential monomers of which include (meth)acrylic acid, alkyl (meth)acrylates, styrene, and styrene derivatives, and may also include other auxiliary monomer components.

[0028] The aforementioned alkyl methacrylates can be exemplified by compounds conforming to the general formula R2-COO-C(R3)=CH2, as well as compounds in which the alkyl group is replaced by a hydroxyl group, an epoxy group, a halogen group, etc. In the general formula R2-COO-C(R3)=CH2, R3 represents a hydrogen atom or a methyl group, and R2 represents an alkyl group having 1 to 12 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, benzyl, and their structural isomers. These monomers can be used alone or in combination of two or more.

[0029] The aforementioned (meth)acrylic acid includes acrylic acid and methacrylic acid, with methacrylic acid being more preferred. Considering the balance between alkali developability and alkali resistance, the range of (meth)acrylic acid monomer relative to the total polymerizable monomers used in polymerization is 15–40 wt%, more preferably 20–35 wt%, and the acid value range of the (A) alkali-soluble adhesive polymer of the present invention is 100–260 mg KOH / g.

[0030] Furthermore, for the purpose of improving adhesion and chemical resistance, styrene or styrene derivatives are preferably used as the polymerizing monomers for the alkali-soluble adhesive polymer (A) in this invention. When styrene or styrene derivatives are used as copolymer components, the amount used relative to all polymerizing monomers used in polymerization is 10 to 60 wt%, more preferably 15 to 50 wt%, to improve adhesion and chemical resistance. When the content of styrene or styrene derivatives is controlled at 10 wt% or more, the photosensitive resin layer tends to have improved adhesion; when controlled at 50 wt% or less, the increase in peeling time caused by the enlargement of the release liner can be suppressed.

[0031] The above-mentioned (A) alkali-soluble adhesive polymer can be used alone or in combination of two or more. When two or more are used in combination, examples include two or more (A) alkali-soluble adhesive polymers composed of different copolymer components, two or more (A) alkali-soluble adhesive polymers with different weight-average molecular weights, and two or more (A) alkali-soluble adhesive polymers with different dispersities.

[0032] The aforementioned (A) alkali-soluble adhesive polymer can be prepared by conventional methods, such as by thermally or UV-excited free radical polymerization of alkyl methacrylate with (meth)acrylic acid, styrene, etc. The weight-average molecular weight (Mw) of the obtained polymer is preferably 20K to 300K, more preferably 40K to 120K, and particularly preferably 50K to 80K. If the total amount of (A) alkali-soluble adhesive polymer and the photopolymerizable compound containing ethylene unsaturated double bonds (B) described later is 100 parts by weight, then (A) alkali-soluble adhesive polymer is preferably 50 to 70 parts.

[0033] (B) Photopolymerizable compounds containing ethylene unsaturated double bonds Photopolymerizable compounds refer to compounds that can participate in photopolymerization reactions, specifically compounds containing carbon-carbon double bonds. Considering the balance between improving resolution, developability, and masking ability, bisphenol A-based (meth)acrylate compounds are preferred, with an amount preferably 5–25 wt% relative to the total amount of component (A) and component (B), more preferably 7–20 wt%. Specific material options include, but are not limited to, 2,2-bis(4-((meth)acryloyloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxypolypropoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxypolybutoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloyloxypolyethoxypolypropoxy)phenyl)propane, etc. The above-mentioned substances can be used alone or in combination of two or more. In addition, the number of hydrophilic ethoxy, propoxy, and butoxy groups in the molecule can be adjusted. For example, 2,2-bis(4-((meth)acryloyloxypentadecethoxy)phenyl)propane (BPA30EODMA, trade name MIRAMER M2301), 2,2-bis(4-((meth)acryloyloxypentadecethoxy)phenyl)propane (BPA10EODMA, trade name MIRAMER M2101) and 2,2-bis(4-(acryloyloxydiethoxy)phenyl)propane (BPA4EODMA, trade name MIRAMER M241) can be mixed in a certain proportion.

[0034] To balance aperture control and reproducibility, polyethylene glycol di(meth)acrylates with 4 to 10 ethylenes can be used, such as PEG400DMA (trademark name MIRAMER M281) and PPG400DA (trademark name MIRAMER M2040). Among the aforementioned photopolymerizable compounds, from the perspective of aperture control reliability and enhanced resolution, trimethylolpropane polyethylene tri(meth)acrylates containing 1 to 21 ethylenes are preferred, such as TMP(EO)15TA (trademark name MIRAMER M3150) and TMP(EO)9TA (trademark name MIRAMER M3190).

[0035] To reduce peeling time, decrease fragment size, and improve yield and efficiency, monomers containing one (meth)acrylate group, i.e., monofunctional (meth)acrylates, such as nonylphenoxy octaetheneoxy(meth)acrylate (NP8EOA, trade name MIRAMER M166) and 4-(ethoxy)nonylphenol acrylate (NP(EO)4A, trade name MIRAMER M164), can be used. The amount used is preferably 5–15 wt%, more preferably 5–10 wt%, relative to the total amount of component (A) and component (B).

[0036] In addition, component (B) can also be a hydrophilic POSS compound containing photopolymerizable vinyl double bonds. This hydrophilic POSS compound with photopolymerizable vinyl double bonds refers to a compound molecule possessing POSS (SiO₂) bonds. 1.5 ) n (n=6, 8, 10, 12) Cage structure.

[0037] If, by weight, the total amount of (A) the alkali-soluble adhesive polymer and (B) the photopolymerizable compound containing ethylene unsaturated double bonds (described later) is 100 parts, then (B) the photopolymerizable compound containing ethylene unsaturated double bonds is preferably 30 to 55 parts, and particularly preferably 30 to 50 parts. When the content of component (B) is within the above range, the photosensitivity and coating properties of the photosensitive resin composition are relatively good.

[0038] (C) Photopolymerization initiator (C) Photopolymerization initiators can be selected from aromatic ketones such as benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-acetone-1, quinones such as alkyl anthraquinones, benzoin alkyl ethers and other benzoin ether compounds, benzoin and alkylbenzoin and other benzoin compounds, benzoin derivatives such as benzoinoyl dimethyl ketal, 2,4,5-triarylimidazolium dimers such as 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer and 2,4,5-triarylimidazolium dimer, etc. These can be used alone or in combination of two or more.

[0039] As a 2,4,5-triarylimidazolium dimer, for example, with respect to 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, BCIM (o-chlorohexaarylbisimidazole, Changzhou Qiangli Electronic New Materials Co., Ltd.) can be selected. If the total amount of (A) the alkali-soluble binder polymer and (B) the photopolymerizable compound containing ethylene unsaturated double bonds is 100 parts by weight, then the amount of (C) the photopolymerization initiator can be set to 0.1 to 10 parts, preferably 1 to 7 parts, and more preferably 3 to 5 parts.

[0040] (D) Auxiliary agent mixture (D) The additive mixture includes sensitizing pigments selected from components capable of efficiently absorbing photons in the wavelength range of 360nm to 420nm and efficiently transferring energy to (C) the photopolymerization initiator. Examples of sensitizing pigments include dialkylaminobenzophenones (such as 4,4'-bis(diethylamino)benzophenone, abbreviated as EMK), anthraquinones, coumarins, xanthones, oxazoles, benzoxazoles, thiazoles, benzothiazoles, triazoles, stilbene, triazines, thiophenes, naphthalenedicarboximides, triarylamines, 9-phenylacridine, and acridine derivatives such as 1,7-(9,9'-acridyl)heptane. These can be used alone or in combination of two or more. Regarding the amount of sensitizing pigment, if the total amount of component (A) and component (B) is 100 parts by weight, the amount of sensitizing pigment is preferably set to 0.05 to 5 parts by weight, and more preferably 0.1 to 3 parts by weight.

[0041] (D) The additive mixture may also include dyes such as malachite green, Victoria blue, brilliant green, and methyl violet; photochromic agents such as tribromophenyl sulfone, colorless crystal violet, diphenylamine, benzylamine, triphenylamine, diethylaniline, o-chloroaniline, and tert-butylcatechol; heat-resistant agents; plasticizers such as p-toluenesulfonamide; pigments; fillers; defoamers; flame retardants; adhesion promoters; leveling agents; peeling accelerators; antioxidants; fragrances; developers; thermal crosslinking agents; and polymerization inhibitors (e.g., p-tert-butylcatechol). (D) The additive mixture may include one or more of the above-mentioned additives, and the substances corresponding to each class of additives may be used alone or in combination of two or more. If the total amount of components (A) and (B) is 100 parts by weight, then the total amount of the above-mentioned type of additives is preferably set to 0.01 to 2 parts.

[0042] (E) Adhesion promoter (E) Adhesion promoters refer to BTA derivatives based on formula (I) or (II) above. When a specific group is selected as the acid-hydrolyzed carboxyl protecting group R1, an adsorbed layer of the above-mentioned BTA derivative molecules remains on the copper surface in the non-exposed area after alkaline water development. This adsorbed layer is not hydrolyzed after development, but can undergo acid-catalyzed hydrolysis in the standard pickling process before etching or electroplating. After the acid-hydrolyzed carboxyl protecting group R1 is removed, 5-carboxybenzotriazole or 4-carboxybenzotriazole, which are easily removed by acid pickling, are formed. Alternatively, when a specific group is selected as the alkaline hydrolyzed carboxyl protecting group R1, the above-mentioned BTA derivative can undergo alkaline-catalyzed hydrolysis during alkaline water development to remove the alkaline hydrolyzed carboxyl protecting group R1 and generate carboxyl groups and corresponding salts. Therefore, in the non-exposed area after alkaline water development, the salt of the hydrolyzed BTA derivative, i.e., the salt corresponding to 5-carboxybenzotriazole or 4-carboxybenzotriazole, is adsorbed on the copper surface.

[0043] The difference between compounds corresponding to formulas (I) and (II) lies in the fact that hydrolysis produces 5-carboxybenzotriazole and 4-carboxybenzotriazole, respectively. These two benzotriazole derivatives exhibit no significant difference in properties on copper surfaces; therefore, compounds corresponding to formulas (I) and (II) can be considered equivalent. However, from the perspective of synthesizing compounds corresponding to formulas (I) and (II), 5-carboxybenzotriazole, as a precursor, is relatively inexpensive; therefore, compounds conforming to formula (I) are preferred. In the following descriptions, unless otherwise specified, the application of the [BTA]-COO-R1 type adhesion promoter in photosensitive resin compositions will be illustrated using the synthesis method and specific application of the compound corresponding to formula (I).

[0044] In practical applications, suitable alkali-sensitive or acid-sensitive hydrolyzable groups can be selected as acid-hydrolyzable carboxyl protecting groups or alkali-hydrolyzable carboxyl protecting groups R1. However, the selected groups also need to be matched with the actual alkaline development, acid etching, and pickling process conditions before electroplating of the photosensitive resin composition. It is well known in the industry that the alkaline development process in PCB manufacturing typically uses aqueous solutions of Na2CO3, K2CO3, and TMAOH (tetramethylammonium hydroxide), with the most common being a 0.8–1.2 wt% Na2CO3 aqueous solution, a pH range of 10.5–12.5, a process temperature of 28–35℃, and a development time of 30–90 seconds. Commonly used acidic etching solution systems in PCB manufacturing etching processes include, for example, a CuCl2 etching solution system with a pH < 1, a process temperature of 45–50℃, and a processing time of 120–180 seconds; or an FeCl3 etching solution system with a pH < 1, a process temperature of 40–45℃, and a processing time of 150–240 seconds. Commonly used pickling solution systems in the pre-plating pickling process of PCB manufacturing include, for example, a sulfuric acid-sodium persulfate system with pH < 1, a process temperature of 25-35℃, and a treatment time of 30-90s; another example is a sulfuric acid-hydrogen peroxide system with pH < 1, a process temperature of 25-35℃, and a treatment time of 30-60s; and yet another example is a sulfonic acid activation system with pH 1-2, which can be used at room temperature and has a treatment time of 30-60s.

[0045] The acid-hydrolyzed carboxyl protecting group R1 can be selected from at least one of tertiary alkyl, acetal, silyl, enol, aryl or heteroaryl substituted tertiary alkyl, ketal imine, β-keto, glycosidic, and epoxyalkyl.

[0046] Considering that the acid hydrolysis of the carboxyl protecting group R1 needs to match the acid etching or pre-pickling process in PCB manufacturing, the [BTA]-COO-R1 acid hydrolysis adhesion promoter is preferably at least one of tertiary alkyl esters, cyclic acetal alkyl esters, acetal esters, and alkylsilyl ester benzotriazole derivatives. Tertiary alkyl esters hydrolyze to produce carboxylic acids and alcohols, with representative molecules shown in formulas BTA-1 and BTA-2. Representative molecules of cyclic acetal alkyl esters include 2-tetrahydropyranyl ester (formula BTA-3) and 2-tetrahydrofuranyl ester (formula BTA-4), which can hydrolyze under acidic conditions to produce free carboxylic acids and corresponding hydroxyaldehyde byproducts. Representative molecules of acetal esters include formula BTA-5, which hydrolyzes under acidic conditions to produce carboxylic acids, acetaldehyde, and ethanol. Representative alkyl silanes include tert-butyldimethylsilane (BTA-6), triethylsilane (BTA-7), and ethyldimethylsilane (BTA-8). Under acidic conditions, these three molecules hydrolyze to produce carboxylic acids and their corresponding silanols. Those skilled in the art will recognize that other acid-sensitive carboxyl protecting groups satisfying the above hydrolysis kinetics can be equivalently substituted.

[0047] Considering the raw materials, synthesis difficulty, and storage stability, the [BTA]-COO-R1 acid hydrolysis type adhesion promoter is more preferably at least one of benzotriazole tert-butyl ester, 1-methyl-1-cyclohexyl ester, 2-tetrahydropyran ester, 2-tetrahydrofuran ester, 1-ethoxyethyl ester, 1-methoxy-1-methylethyl ester, triethylsilyl ester, tert-butyldimethylsilyl ester, and dimethyl-n-propylsilyl ester.

[0048] The alkaline hydrolysis carboxyl protecting group R1 is selected from an aromatic ring activated by an electron-withdrawing group, an N-linked activated imide, i.e., [BTA]-COO-R1. Alkaline hydrolysis type adhesion promoters can be benzene ring activated esters or succinimide activated esters of benzotriazole derivatives, including but not limited to p-nitrophenyl ester, pentafluorophenyl ester, and N-hydroxysuccinimide ester-type benzotriazole derivatives.

[0049] Common alkyl esters conforming to the general formula -COO-R (where R can be methyl, ethyl, or propyl) can theoretically undergo saponification and hydrolysis, but significant hydrolysis requires a long time under strongly alkaline conditions and high temperatures. This does not match the aforementioned common alkaline water development process well. Therefore, it is necessary to select a strong electron-withdrawing group to activate the COO-R1 portion of [BTA]-COO-R1 to ensure rapid hydrolysis even under weakly alkaline conditions. For example, BTA-9 uses p-nitrophenyl for activation, BTA-10 uses 1-succinimide, and BTA-11 uses pentafluorophenyl. To achieve rapid hydrolysis under weakly alkaline developing conditions, the carboxyl protecting group R1 is preferably pentafluorophenyl. Although its raw material cost is relatively high, its perfluorinated substitution structure can endow the [BTA]-COO-R1 adhesion promoter with excellent thermal and light stability, enabling it to withstand the high temperature environment (80-120°C) during the laminate manufacturing process, and to complete hydrolysis within 30 seconds in 1wt% Na2CO3 developing solution.

[0050] The [BTA]-COO-R1 type adhesion promoter is present in the photosensitive composition at a concentration of 50 ppm to 1500 ppm. If the addition amount is too low, for example, below 50 ppm, it will be difficult to form a sufficient adsorption layer on the copper surface; if the addition amount is too high, for example, above 1.5‰ (1500 ppm), it will not only increase the raw material cost but also bring the risk of decreased production stability and finished product storage stability of the photosensitive product. The preferred addition amount is 150 ppm to 1000 ppm.

[0051] (F) Solvent Considering the two main applications of the photosensitive resin composition of the present invention—namely, the photosensitive resin layer in the photosensitive laminate and the photosensitive resin coating—both require dissolving and preparing a solution during manufacturing, at least one organic solvent is necessary. The aforementioned organic solvent can be selected from commonly used organic solvents in the relevant field without particular limitation. Examples include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, propylene glycol monomethyl ether, and mixtures thereof. In the preparation of the photosensitive laminate mentioned later, the above-mentioned (A) alkali-soluble adhesive polymer, (B) photopolymerizable compound containing ethylene unsaturated double bonds, (C) photopolymerization initiator, (D) additive mixture, and (E) adhesion promoter need to be dissolved in the above-mentioned organic solvent to form a solution with a solid content of 30–60 wt% (hereinafter referred to as "photosensitive resin composition coating solution") for use.

[0052] [Photosensitive laminar flow] A cross-sectional structural schematic diagram of an embodiment of the photosensitive laminate of the present invention is shown below. Figure 1As shown, it is configured to have a support film 11, a photosensitive resin layer 12 formed on the support film 11 from the above-described photosensitive resin composition, and a protective film 13 covering the photosensitive resin layer 12. The support film 11 can be a polymer film with heat resistance and solvent resistance, such as polyethylene terephthalate, polypropylene, polyethylene, and polyester. The thickness of the support film 11 ranges from 5 to 100 μm, preferably from 10 to 30 μm. The protective film 13 is preferably a protective film with a lower adhesive force to the photosensitive resin layer 12 than the adhesive force of the support film 11 to the photosensitive resin layer 12, such as a polyethylene film, polypropylene film, or polyethylene terephthalate film. The preferred thickness of the protective film 13 is from 15 to 30 μm.

[0053] The aforementioned photosensitive laminate can be manufactured by a manufacturing method comprising the following steps: dissolving (A) an alkali-soluble adhesive polymer, (B) a photopolymerizable compound containing ethylene unsaturated double bonds, (C) a photopolymerization initiator, (D) a mixture of additives, and (E) an adhesion promoter in an organic solvent to obtain a photosensitive resin composition coating liquid; coating the aforementioned photosensitive resin composition coating liquid onto a support film 11 to form a coating layer; drying the aforementioned coating layer to form a photosensitive resin layer 12; and pressing a protective film 13 onto the photosensitive resin layer 12. The above steps can be performed using known manufacturing equipment such as roller coaters, corner roller coaters, gravure coaters, air knife coaters, die coaters, doctor blade coaters, and spray coaters.

[0054] The shape of the photosensitive laminate of the present invention is not particularly limited. For example, it can be in sheet form or it can be wound on a core to form a roll structure.

[0055] <Synthetic Example 1> BTA-11 molecule 27.7 g (0.170 mol) of 5-carboxybenzotriazole was suspended in 110 mL of anhydrous toluene, and 58.5 mL (0.808 mol) of thionyl chloride was added dropwise at 0–5 °C. After the addition was complete, the mixture was heated to 78 °C and refluxed for 4 hours. The solvent and excess thionyl chloride were then removed by vacuum distillation to obtain crude 5-benzotriazole formyl chloride.

[0056] The crude 5-benzotriazole carboxyl chloride was dissolved in 20 mL of anhydrous toluene and added dropwise at 0–5 °C to a solution of pentafluorophenol (31.3 g, 0.170 mol) and triethylamine (34.4 g, 0.340 mol) in anhydrous toluene (110 mL). After the addition was complete, the reaction mixture was stirred at room temperature for 2 h. The reaction solution was washed with 5 wt% NaHCO3 aqueous solution (2 × 100 mL) and water (100 mL), dried over anhydrous MgSO4, and concentrated under reduced pressure. The residue was recrystallized from toluene / n-hexane (1:3, v / v) and dried under vacuum at 50 °C for 8 h to give 48.6 g of a white solid product. The yield was calculated to be 87%, and the purity was determined to be 98.6% by HPLC.

[0057] <Synthetic Example 2> BTA-1 molecule 5-Carboxybenzotriazole (39.9 g, 0.244 mol) and tert-butanol (21.7 g, 0.293 mol) were dissolved in anhydrous dichloromethane (160 mL), and N,N-dimethylpyridine (DMAP, 2.4 g, 0.020 mol) was added. The mixture was cooled to 0–5 °C in an ice bath, and N,N'-dicyclohexylcarbodiimide (DCC, 50.4 g, 0.244 mol) was added in portions. After the addition was complete, the mixture was heated to room temperature and stirred for 12 h. The dicyclohexylurea (DCU) precipitate was removed by filtration. The filtrate was washed successively with 5 wt% NaHCO3 aqueous solution and water. After drying and concentrating the organic phase, the product was recrystallized from ethyl acetate / n-hexane (1:3, v / v) and dried under vacuum at 50 °C to give 50.3 g of white solid product. The yield was calculated to be 89%, and the purity of the product was 99.1% as determined by HPLC.

[0058] <Synthetic Example 3> BTA-3 molecule 5-Carboxybenzotriazole (31.7 g, 0.194 mol) and 3,4-dihydro-2H-pyran (19.6 g, 0.233 mol) were dissolved in anhydrous dichloromethane (126 mL), and p-toluenesulfonic acid (0.16 g) was added. The mixture was stirred at room temperature for 4 h. The reaction solution was washed with saturated NaHCO3 aqueous solution (2 × 80 mL) and water (100 mL), dried over anhydrous Na2SO4, and concentrated under reduced pressure. The residue was recrystallized from ethyl acetate / n-hexane (1:3, v / v) and dried under vacuum at 50 °C for 6 h to give 43.7 g of white solid product. The yield was calculated to be 91%, and the purity of the product was determined to be 98.4% by HPLC.

[0059] <Synthetic Example 4> BTA-5 molecule 5-Carboxybenzotriazole (34.8 g, 0.213 mol) and acetaldehyde dimethyl acetal (19.5 g, 0.216 mol) were dissolved in anhydrous dichloromethane (139 mL), and p-toluenesulfonic acid (p-TsOH, 0.17 g) was added. The mixture was stirred at room temperature for 6 h. The reaction solution was washed successively with saturated NaHCO3 aqueous solution and water. After drying and concentrating the organic phase, it was recrystallized from ethyl acetate / n-hexane (1:3, v / v) and dried under vacuum at 50 °C to give 47.8 g of white solid product. The yield was calculated to be 90%, and the purity of the product was 98.3% as determined by HPLC.

[0060] <Synthetic Example 5> BTA-8 molecule 5-Carboxybenzotriazole (36.3 g, 0.222 mol) and triethylamine (27.0 g, 0.267 mol) were dissolved in anhydrous tetrahydrofuran (145 mL) and cooled to 0–5 °C in an ice bath. Dichloromethylethylsilane (27.3 g, 0.223 mol) was added dropwise. After the addition was complete, the mixture was brought to room temperature and stirred for 2 h. The reaction solution was washed successively with 1 wt% dilute hydrochloric acid and water, dried, and the organic phase was concentrated. The solution was then recrystallized from n-hexane / ethyl acetate (4:1, v / v) and dried under vacuum at 40 °C to give 50.6 g of a white solid product. The yield was calculated to be 92%, and the purity of the product was 98.8% as determined by HPLC.

[0061] Triethylamine, acting as an acid absorbent, ensures complete silanization, while dichloromethylethylsilane is added in excess at 0.5% to compensate for trace amounts of moisture loss. The recrystallization solvent ratio (n-hexane:ethyl acetate = 4:1, v / v) was optimized experimentally to maximize the removal of disilination byproducts.

[0062] <Synthesis Example 6> (A) Alkali-soluble adhesive polymer Add 370 mL of butanone and 185 mL of ethylene glycol methyl ether to the reactor, purge with nitrogen for 30 min, and then heat to 78 °C. Separately, prepare a monomer / initiator solution by mixing 220 g of methacrylic acid (MAA), 88 g of methyl methacrylate (MMA), 176 g of benzyl methacrylate (BzMA), 396 g of styrene (St), 6.6 g of azobisisobutyronitrile (AIBN), and 200 mL of butanone. Add the monomer / initiator solution dropwise to the reactor at a uniform rate over 3 h at 78 °C. After the addition is complete, stir the reaction mixture at 78–80 °C for 2 h. Then, dissolve 2.2 g of azobisisobutyronitrile (AIBN) in 25 mL of ethylene glycol methyl ether and add it to the reactor all at once. Continue the reaction at 80 °C for 1 h. Finally, the reaction system was heated to 85℃ and aged for 2 hours, then cooled to room temperature to obtain a viscous and transparent solution with a total mass of about 2.00 kg. The solid content was determined to be 44.0 wt%, the weight average molecular weight was about 65,000 (determined by GPC polystyrene standard), and the acid value was 158 mg KOH / g.

[0063] Preparation of coating solution for photosensitive resin composition The photosensitive resin composition was prepared according to the materials and proportions shown in Table 1, and the corresponding coating solution was prepared. The values ​​in the table represent the mass parts of the corresponding components. After mixing and stirring to dissolve the components, the mixture was filtered through a 2 μm filter membrane under positive pressure to obtain the photosensitive resin composition coating solution that can be used to prepare photosensitive laminates.

[0064] Table 1: Formulation Table of Coating Solution for Photosensitive Resin Composition Production of photosensitive laminates The photosensitive resin compositions corresponding to the example groups and comparative groups in Table 1 were uniformly coated onto polyethylene terephthalate (PET) films with a thickness of 15 μm and dried in a hot air convection dryer at 80°C for 30 min, forming a photosensitive resin layer with a film thickness of approximately 25 μm. A polypropylene (PP) protective film was then adhered to this photosensitive resin layer to obtain a photosensitive laminate having a PET support film, a photosensitive resin layer, and a PP protective film.

[0065] Fabrication of stacked bodies The epoxy fiberglass copper-clad laminate undergoes a pretreatment process, which includes grinding the copper surface of the laminate, washing it with water, and then drying it with an air stream. The pretreated copper-clad laminate is heated to 80°C, and while peeling off the PP protective film from the aforementioned photosensitive laminate, the photosensitive resin layer is laminated in such a manner that it comes into contact with the copper surface. Lamination is performed using a 110°C hot roller at a pressing pressure of 0.40 MPa and a roller speed of 1.5 m / min. This results in a laminate formed by sequentially stacking the copper-clad laminate, the photosensitive resin layer, and the PET support film. This laminate can be used in exposure, development processes, and various evaluation tests.

[0066] [Evaluation Test] (1) Analysis and Adhesion Base Test: The aforementioned laminate was placed in a Saite LDI exposure machine as a specimen and exposed at 405nm with a 0.89x lens. The exposure energy corresponding to the ST value between 18±2 was determined according to the Stouffer 41-grid exposure scale. The exposure pattern was an array of patterns L / S=x / x,x / 400,3x / x. After exposure, the specimen was developed and rinsed clean, and then placed under an optical microscope. The tester observed the pattern and recorded the results in Table 2.

[0067] (2) Water contact angle of copper surface: The copper after acid washing is superhydrophilic, and the 5-carboxyphenyltriazole adsorbed on the copper surface also exhibits superhydrophilicity after reacting with the alkali in the developer to form a salt. However, BTA and its [BTA]-COO-R1 type derivatives are hydrophobic. Therefore, the state of the [BTA]-COO-R1 adsorption layer can be evaluated by measuring the water contact angle on the copper surface to determine whether it has been completely hydrolyzed in the developing process or completely removed by acid washing. The specific process is as follows: Take the specimens corresponding to the example group and the comparative example group that have undergone the aforementioned exposure treatment and divide them into developing group and acid washing group for testing. For the developing group, only the developing treatment is performed and then the water contact angle of the exposed area of ​​the copper surface is tested. For the acid washing group, the developing treatment and acid washing treatment are performed in sequence and then the water contact angle of the exposed area of ​​the copper surface is tested. The above developing treatment used a 1wt% Na2CO3 aqueous solution at a process temperature of 30℃ for 60s. The above acid washing treatment used a 10vol% H2SO4 solution at a process temperature of 25℃ for 90s. Before testing the water contact angle, both the developing and acid washing samples were rinsed with pure water and dried with nitrogen. Five different sites were taken from each sample for testing, and the average value was recorded in Table 2.

[0068] (3) Adhesive tape method for interfacial adhesion (ASTM D3359): This evaluates the bonding strength between the photosensitive resin layer, which acts as a photoresist film in the exposed area, and the copper interface, reflecting the effect of BTA derivatives on improving the adhesion of the photosensitive resin layer. The specific procedure is as follows: Take the specimens corresponding to the example group and the comparative group that have undergone the aforementioned exposure treatment, and use a cross-cutting knife to make 1mm × 1mm squares (#11 blade, 100 squares) in the exposed area (i.e., the area covered by the photoresist film). Use 3M #600 or #610 type adhesive tape to quickly peel it off at a 180° angle. Refer to the ASTM D3359 standard, that is, according to the six levels from 5B (no peeling) to 0B (>65% peeling), the test results are rated. Each specimen is tested 3 times, and the average value is recorded as the test result in Table 2.

[0069] (4)Color change by CuCl2 solution corrosion: It is used to quickly evaluate whether the organic molecule adsorption layer remaining on the exposed copper surface between the resist patterns formed after exposure and development on the copper surface hinders subsequent pickling. The specific process is as follows: The specimens corresponding to the example group and the comparative example group after the aforementioned exposure and development treatments are immersed in a 5wt% aqueous CuCl2 solution for 1 minute and then observed under an optical microscope to check the color change of the exposed copper surface between the L / S = 15 / 15 μm photolithography lines. If the copper color uniformly darkens between the lines, it indicates that the BTA or its derivative molecule adsorption layer in this area can be successfully cleaned during subsequent pickling, and it can be judged as qualified; if the copper surface between the lines partially or completely retains the original copper color, it indicates that the BTA or its derivative molecule adsorption layer in this area hinders subsequent pickling and may cause etching defects and poor electroplating adhesion defects, and it should be judged as unqualified.

[0070] (5)Simulated acidic undercut width: To evaluate whether lateral corrosion occurs at the bottom of the resist pattern during subsequent acidic etching treatment, and to reflect whether a "hydrophilic channel" is formed at the copper-photoresist film interface. The specific process is as follows: Take the aforementioned laminate corresponding to the example group and the comparative example group as specimens, expose them with an energy of 130 mJ to form a rectangular exposure area array of 0.4 × 1.0 mm, develop them in a 1wt% aqueous Na2CO3 solution at a process temperature of 30 °C for 60 s, then rinse them clean with pure water and dry them with hot air. Subsequently, pickle them with a 10vol% H2SO4 solution for 90 s and then immerse them in a 25 °C CuCl2 / HCl simulated acidic etching solution and let them stand for 15 minutes. Take them out, rinse them clean, and observe and measure the undercut width under an optical microscope.

[0071] (6)Storage stability: Verify whether the photosensitive resin layer containing BTA or its derivatives decomposes during the storage of the photosensitive laminate, resulting in a shortened storage duration of the photosensitive laminate product. Referring to the master roll storage specification, store the photosensitive laminate master rolls (i.e., the rolls formed by winding the photosensitive laminate mentioned above) corresponding to the example group and the comparative example group in an indoor environment with a temperature range of 10 - 20 °C and a relative humidity of 50 - 65%, protected from light for 3 months, and then test them according to the test methods in the aforementioned (1) - (5) items. If each index does not change significantly, it is judged as qualified for storage stability, otherwise it is judged as unqualified. The results of each of the above tests are shown in Table 2.

[0072] Table 2: Evaluation test results Next, the effects of BTA and its derivatives on the properties of the photosensitive laminate product are evaluated according to Table 2.

[0073] (1) Basic tests on resolution and adhesion: The test results of the example group and the comparative example group show that BTA and its different derivatives have no significant effect on the photosensitivity and resolution and adhesion performance of the photosensitive laminate products.

[0074] (2) Copper surface water contact angle: After alkaline water development treatment, both Example 1 and Comparative Example 2 showed superhydrophilicity, while the other examples and Comparative Example 1 showed hydrophobicity. For Example 1, BTA-11 molecules containing alkaline hydrolysis carboxyl protecting groups were used. The 5-carboxybenzotriazole formed by hydrolysis could be neutralized by alkali to form a superhydrophilic salt. Comparative Example 2 used 5-carboxybenzotriazole, which was also neutralized by alkali after development to form a superhydrophilic salt. The hydrophobic state of the other examples and Comparative Example 1 indicates that the adsorbed molecules were not hydrolyzed by alkali, proving that BTA-1, BTA-3, BTA-5, and BTA-8 molecules with acid-hydrolyzable carboxyl protecting groups are stable in alkaline solutions and do not undergo hydrolysis.

[0075] After pickling, the bare copper exhibited superhydrophilicity (contact angle <10°). Examples 1-5 and Comparative Example 2 were all superhydrophilic after pickling, indicating that the adsorbed molecular layer on the copper surface was removed after hydrolysis. However, Comparative Example 1 did not reach a superhydrophilic state because it used BTA as an adhesion promoter, indicating that a large number of BTA molecules remained on the copper surface.

[0076] (3) Adhesion of the tape method interface: The adhesion of Examples 3, 4, 5 and Comparative Example 2 is relatively good.

[0077] (4) CuCl2 solution etching and coloring: Except for Comparative Example 1 which uses BTA, the BTA derivatives used in each example and Comparative Example 2 do not interfere with the subsequent etching and electroplating processes.

[0078] (5) Simulated acid etching side etching width: An extreme 15-minute immersion simulation test was used to simulate the interface stability between the photoresist film and copper during the acid etching process. It was found that Comparative Example 2, which used 5-carboxybenzotriazole, experienced severe side etching, while the side etching width of the other examples could be controlled within a small range. See Figure 3 The rectangular area within the photograph's field of view represents the photoresist film coverage area of ​​the specimen corresponding to Comparative Example 2. For easier observation, a portion of the photoresist film within area B was scraped away, revealing blurred edges on the copper surface and significant lateral etching (approximately 36 μm). For comparison, see [reference needed]. Figure 2 The rectangular area within the field of view of the photograph is the area covered by the photoresist film of the corresponding specimen in Example 3. After scraping off the photoresist film in area A, it can be seen that the edge shape of area A is regular and the degree of lateral etching is extremely low (optical microscopes cannot perform high-precision measurements, so the lateral etching level is judged as <5μm).

[0079] (6) Storage stability: After 3 months of storage, the differences in various test indicators of the photosensitive laminar material master roll were not significant, indicating that the [BTA]-COO-R1 derivatives in the example group have good storage stability in the photosensitive laminar material products, which meets the requirements of photosensitive laminar materials for storage performance.

[0080] Based on the above analysis, it can be concluded that: BTA-11 molecules: are hydrolyzed during alkaline water development and neutralized to form the sodium salt of 5-carboxybenzotriazole, which has slightly poor adhesion but can effectively reduce the width of side etching. BTA-1 molecule: stable in alkaline water development, hydrolyzes to form 5-carboxybenzotriazole in subsequent acid washing, with slightly poor adhesion, which can effectively reduce the width of side etching. BTA-3 molecules: stable in alkaline water development, hydrolyze to form 5-carboxybenzotriazole in subsequent acid washing, with good adhesion and can effectively reduce the width of side etching; BTA-5 molecules: stable in alkaline water development, hydrolyze to form 5-carboxybenzotriazole in subsequent acid washing, with good adhesion and can effectively reduce the width of side etching; BTA-8 molecules: stable in alkaline water development, hydrolyze to form 5-carboxybenzotriazole in subsequent acid washing, with good adhesion and can effectively reduce the width of side etching; BTA: Stable in alkaline water development and acid pickling, but difficult to be completely removed by acid etching, leading to defects in subsequent etching and electroplating processes. It has slightly poor adhesion and can reduce the width of side etching, but it is not conducive to precision etching and electroplating. 5-Carboxybenzotriazole: It is neutralized in alkaline water development and is easily removed during acid washing or etching. It has good adhesion, but due to its hydrophilicity, it forms side etching channels at the copper-photoresist interface, resulting in a large amount of side etching. It is also not conducive to the stability of fine resist patterns in precision etching or electroplating processes.

[0081] The various embodiments in this specification are described in a progressive manner, with each embodiment focusing on the differences from other embodiments. The same or similar parts between the various embodiments can be referred to each other.

[0082] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A compound for preparing photoresist films, characterized in that, The compound is represented by either formula (I) or formula (II): Wherein, R1 is an acid-hydrolyzable carboxyl protecting group or an alkaline-hydrolyzable carboxyl protecting group. When R1 is an acid-hydrolyzable carboxyl protecting group, the compound can be hydrolyzed under conditions of pH < 2. When R1 is an alkaline-hydrolyzable carboxyl protecting group, the compound can be hydrolyzed under conditions of pH > 10.

2. The compound for preparing photoresist films as described in claim 1, characterized in that: The acid-hydrolyzed carboxyl protecting group is selected from at least one of tertiary alkyl, acetal, silyl, enol, aryl or heteroaryl substituted tertiary alkyl, ketal imine, β-keto, glycosidic, and epoxyalkyl.

3. The compound for preparing photoresist films as described in claim 2, characterized in that: The acid-hydrolyzed carboxyl protecting group is tert-butyl, 1-methylcyclohexyl, 2-tetrahydropyranyl, 2-tetrahydrofuranyl, 1-ethoxyethyl, tert-butyldimethylsilyl, triethylsilyl, or dimethylethylsilyl.

4. The compound for preparing photoresist films as described in claim 1, characterized in that: The alkaline hydrolysis carboxyl protecting group is an aromatic ring activated by an electron-withdrawing group, and / or the alkaline hydrolysis carboxyl protecting group is p-nitrophenyl or pentafluorophenyl.

5. The compound for preparing photoresist films as described in claim 1, characterized in that: The alkaline hydrolysis carboxyl protecting group is a 1-succinimide group.

6. A photosensitive resin composition, characterized in that: The compound comprising (A) an alkali-soluble adhesive polymer, (B) a photopolymerizable compound containing ethylene unsaturated double bonds, (C) a photopolymerization initiator, (D) a mixture of additives and (E) the compound for preparing a photoresist film as described in any one of claims 1 to 5.

7. The photosensitive resin composition according to claim 6, characterized in that: (E) The compound for preparing the photoresist film as described in any one of claims 1 to 5 comprises 50 to 1500 ppm of the total weight of the photosensitive resin composition.

8. The photosensitive resin composition according to claim 6, characterized in that: (E) The compound for preparing the photoresist film as described in any one of claims 1 to 5 comprises 150 to 1000 ppm of the total weight of the photosensitive resin composition.

9. The photosensitive resin composition according to claim 6, characterized in that: (A) The weight-average molecular weight of the alkali-soluble adhesive polymer is 20K to 300K, and the acid value is 100 to 260 mg KOH / g.

10. A photosensitive laminate, characterized in that: It comprises a support layer and a photosensitive resin layer formed from the photosensitive resin composition according to any one of claims 6 to 9.

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