Photosensitive resin composition, laminate and use

Abstract

The invention discloses a photosensitive resin composition, a laminated body and application, and belongs to the technical field of high polymer materials. The photosensitive resin composition of the present application includes an alkali-soluble resin, a urethane (meth) acrylate compound, and a photoinitiator; wherein the content of an isocyanate group in the photosensitive resin composition is 20 to 700 ppm. The composition has excellent adhesive force on the surface of a base material after forming a film, can bear sand blasting impact during sand blasting treatment on the base material, and is not easy to fall off a resin layer, and especially for a base material such as glass with very small surface roughness, the resin layer still has excellent adhesive force and does not fall off during sand blasting.

Description

Technical Field

[0001] The present application relates to the technical field of polymer materials, and in particular, to a photosensitive resin composition, a laminate, and an application. Background Art

[0002] Sandblasting is usually used to selectively engrave patterns formed on materials such as glass and ceramics. In sandblasting, first, a photosensitive resin composition layer is laminated on the material to be processed, and then selective area exposure and development are sequentially performed to expose the areas that need to be sandblasted, forming a resist pattern as a mask material in sandblasting. Then, sandblasting is carried out. Finally, the photosensitive resin layer is removed, and a desired relief pattern is formed on the surface of the material to be processed.

[0003] As the photosensitive resin layer for sandblasting, in terms of performance, it is required to have good adhesion to the substrate. During the sandblasting of the substrate, it is required to withstand the sandblasting impact without the resin layer peeling off. However, for substrates such as glass, the surface roughness is extremely low, and the surface roughness may be 0.1 micrometer or less. The adhesion of the photosensitive resin layer will become particularly poor. When sandblasting the glass surface laminated with the photosensitive resin layer as a mask, the mask is likely to peel off and thus fail.

[0004] In order to improve the adhesion of the photosensitive resin layer to the substrate, the prior art CN1082679C discloses a urethane resin prepared from a polyester polyol with an acid value lower than 70 mgKOH / g and a molecular weight of 1000 - 30000, and an alkali-soluble polymer with an acid value of 50 - 250 mgKOH / g, in a ratio of 30:70 - 95:5, and 0.1 - 20 parts of a photoinitiator, to reduce the electrostatic accumulation during sandblasting, thereby reducing the peeling of fine patterns. However, from the perspective of improving the product yield, it is necessary to provide a more excellent resist composition for substrates with a very low surface roughness such as glass to be sandblasted, to reduce the possibility of mask peeling during sandblasting. Summary of the Invention

[0005] The main object of the present application is to provide a photosensitive resin composition, a laminate, and an application, to solve the problem of low adhesion of the photosensitive resin during sandblasting in the prior art.

[0006] To achieve the above object, according to one aspect of the present application, there is provided a photosensitive resin composition, including an alkali-soluble resin, a urethane (meth)acrylate, and a photoinitiator; wherein, the content of isocyanate groups in the photosensitive resin composition is 20 - 700 ppm.

[0007] Further, the content of isocyanate groups in the photosensitive resin composition is 50 to 670 ppm.

[0008] Further, based on parts by weight, the photosensitive resin composition includes 29 to 70 parts by weight of an alkali-soluble resin, 20 to 70 parts by weight of a urethane (meth)acrylate compound, and 1 to 5 parts by weight of a photoinitiator.

[0009] Further, the photosensitive resin composition further includes 0.005 to 2 parts by weight of an isocyanate group-containing compound.

[0010] Further, the molecular structural formula of the isocyanate group-containing compound is Formula (I) or Formula (II), or the isocyanate group-containing compound is obtained by reacting a hydroxyl group-containing compound with a compound containing at least two isocyanate groups;

[0011] (I);

[0012] Among them, in Formula (I), R is an alkyl group, an aryl group, a substituted alkyl group, a substituted aryl group, an acylalkyl group, or an acryloyloxyalkyl group;

[0013] (II);

[0014] Among them, in Formula (II), G is an alkylene group, an arylene group, a substituted alkylene group, or a substituted arylene group.

[0015] Further, the alkyl group in Formula (I) is a C1-C6 alkyl group, the substituted alkyl group is a C1-C6 substituted alkyl group, the alkyl group in the acylalkyl group is a C1-C6 alkyl group, and the alkyl group in the acryloyloxyalkyl group is a C1-C6 alkyl group.

[0016] Further, the alkylene group in Formula (II) is a C1-C6 alkylene group, and the substituted alkylene group is a C1-C6 substituted alkylene group.

[0017] Further, the hydroxyl group-containing compound is a hydroxyalkyl (meth)acrylate and / or a polyol.

[0018] Further, the compound containing at least two isocyanate groups is selected from at least one of hexamethylene diisocyanate, trimethylhexane diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, or isophorone diisocyanate.

[0019] Further, the isocyanate group-containing compound represented by Formula (I) is 2-isocyanatoethyl acrylate or hexyl isocyanate.

[0020] Further, the isocyanate group-containing compound represented by formula (II) is selected from at least one of hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate.

[0021] Further, the urethane (meth) acrylate is a polyether-based urethane compound and / or a polyester-based urethane compound.

[0022] Further, the alkali-soluble resin is selected from at least one of an acrylic copolymer, a urethane compound having a carboxyl group in its structure, and a cellulose compound having a carboxyl group in its structure.

[0023] Further, the polyether-based urethane compound is a urethane compound having a polyether repeating unit and a (meth) acryloyloxy group-terminated amino group in its molecular chain segment.

[0024] Further, the polyester-based urethane compound is a urethane compound having a polyester repeating unit and a (meth) acryloyloxy group-terminated amino group in its molecular chain segment.

[0025] Further, the weight average molecular weight of the urethane compound having a carboxyl group in its structure is 1,000 to 40,000.

[0026] Further, the acid value of the urethane compound having a carboxyl group in its structure is 30 to 70 mg KOH / g.

[0027] Further, the urethane compound having a carboxyl group in its structure is obtained by a first reaction of a polyhydroxycarboxylic acid compound and a diisocyanate compound to obtain a first reactant, a second reaction of the first reactant and a polyol compound having two hydroxyl groups at its molecular ends to obtain a second reactant, and a third reaction of the second reactant and a (meth) acrylate compound having one hydroxyl group in its molecular structure.

[0028] Further, the weight average molecular weight of the acrylic copolymer is 10,000 to 120,000.

[0029] Further, the acid value of the acrylic copolymer is 97 to 200 mg KOH / g.

[0030] Further, the acrylic copolymer is obtained by copolymerizing at least one carboxyl group-containing copolymerization unit monomer I and at least one carboxyl group-free copolymerization unit monomer II.

[0031] Further, the acid value of the cellulose compound having a carboxyl group in its structure is 80 to 200 mg KOH / g.

[0032] According to a second aspect of the present application, a laminate is provided, including a support film layer and a resist film layer stacked in sequence; the resist film layer is a film layer formed after drying the above photosensitive resin composition.

[0033] According to a third aspect of the present application, there is provided an application of the above photosensitive resin composition or the resist film in the above laminate in the manufacturing of circuit lines of printed circuit boards and selective engraving sandblasting treatment.

[0034] Applying the technical solution of the present application, a photosensitive resin composition, a laminate and an application are provided. By controlling the isocyanate group content in the composition formed by an alkali-soluble resin, a urethane (meth) acrylate compound and a photoinitiator to be 20 - 700 ppm, the composition can have very excellent adhesion on the surface of the substrate after film formation, and can withstand sandblasting impact during sandblasting treatment of the substrate without resin layer peeling off. Especially for substrates with very small surface roughness such as glass, the resin layer still has excellent adhesion and will not peel off during sandblasting. Description of the Drawings

[0035] The specification drawings forming a part of the present application are used to provide a further understanding of the present application. The schematic embodiments of the present application and their descriptions are used to explain the present application and do not constitute an improper limitation of the present application. In the drawings:

[0036] Figure 1 A schematic structural diagram of a laminate formed by the photosensitive resin composition of Example 1 of the present application is shown.

[0037] Reference Signs:

[0038] 1, support film layer; 2, resist film layer; 3, cover film layer. Detailed Embodiments

[0039] It should be noted that, without conflict, the embodiments in the present application and the features in the embodiments can be combined with each other. The present application will be described in detail below with reference to the drawings and embodiments.

[0040] As mentioned in the background art, on the one hand, after the photosensitive resin undergoes exposure and development, it needs to have good adhesion on the glass substrate, be able to withstand the erosion of the developer, and the fine pattern mask does not fall off; on the other hand, during sandblasting treatment, the mask withstands the sandblasting impact, and the fine pattern mask is easily peeled off from the surface of the substrate, that is, the resin material has insufficient adhesion on the substrate such as glass and is not sufficient to resist the sandblasting impact force, resulting in peeling off.

[0041] Therefore, the present application provides a photosensitive resin composition, which includes an alkali-soluble resin, a urethane (meth)acrylate compound, and a photoinitiator; wherein, the content of isocyanate groups in the photosensitive resin composition is 20 to 700 ppm.

[0042] In the present application, the content of isocyanate groups in the composition formed by the alkali-soluble resin, the urethane (meth)acrylate compound, and the photoinitiator is controlled to be 20 to 700 ppm. Here, the content of isocyanate groups is the total content of free NCO groups in the composition system. By controlling the specific content of NCO groups, the film formed by this composition can have very excellent adhesion on the surface of the substrate. When the substrate is sandblasted, it can withstand the sandblasting impact without the resin layer peeling off. Especially for substrates with very small surface roughness such as glass, the resin layer still has excellent adhesion and will not peel off during sandblasting. For example, the dot adhesion before sandblasting can reach 150 to 170 μm, and the dot adhesion after sandblasting can reach 240 to 270 μm. At the same time, the adhesion will not be too large to affect the subsequent removal of the resin layer. Since the isocyanate group has good adhesion to substrates such as glass, the weight content of this group needs to be controlled to 20 to 700 ppm, such as any value among 20, 50, 100, 200, 300, 400, 500, 600, 700 ppm or the range value between any two of them; when the content is too low, the adhesion of the resin layer to substrates such as glass and ceramics is not significantly improved, and when the dosage is too high, the resin composition system becomes unstable and the adhesion decreases; the role of the alkali-soluble resin in the resin composition is to make the photosensitive resin composition developable, and the urethane (meth)acrylate compound is used to provide the main body for the subsequent resin film layer formed by exposure cross-linking and make the mask have better sandblasting impact resistance.

[0043] In order to further improve the adhesion, in some embodiments, the content of isocyanate groups in the photosensitive resin composition is controlled to be 50 to 670 ppm. By regulating the content of isocyanate groups within a more preferred range, the resin layer has more excellent adhesion during sandblasting and is not easily peeled off.

[0044] For convenient use, in some embodiments, the photosensitive resin composition can be formulated into a photosensitive resin composition solution with a solvent; the solvent includes methyl ethyl ketone; the solid content of the photosensitive resin composition solution is 30 to 60%. By regulating the solid content, it is beneficial to the later coating process.

[0045] In order to more precisely control the content of isocyanate groups in the resin composition, in some embodiments, the photosensitive resin composition includes 29 to 70 parts by weight of an alkali-soluble resin, 20 to 70 parts by weight of a urethane (meth)acrylate compound, and 1 to 5 parts by weight of a photoinitiator; for example, the number of parts by weight of the alkali-soluble resin is any value among 29, 30, 35, 40, 45, 50, 55, 60, 65, 70 parts or a range value between any two of them, the number of parts by weight of the urethane (meth)acrylate compound is any value among 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70 or a range value between any two of them, and the number of parts by weight of the photoinitiator is any value among 1, 2, 3, 4, 5 or a range value between any two of them; further preferably, the number of parts by weight of the alkali-soluble resin is 30 to 55 parts, the number of parts by weight of the urethane (meth)acrylate compound is 30 to 70 parts, and the number of parts by weight of the photoinitiator is 1.5 to 3 parts. By defining the ratios of the three components in the resin composition, it is not only easy to control the content of isocyanate groups in the resin composition to reach the required value, but also more conducive to the crosslinking of each compound after later exposure, thereby optimizing the flexibility, adhesion, curing strength, developability, removability, and anti-abrasive blasting impact and non-peeling performance of the resin film layer.

[0046] In order to more easily control the content of isocyanate groups in the resin composition, in addition to the isocyanate groups that may be contained in the raw materials, a compound containing isocyanate groups can also be added externally; in some embodiments, 0.005 to 2 parts by weight of a compound containing isocyanate groups is added; the addition amount is any value among 0.005, 0.01, 0.05, 0.1, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, 2 or a range value between any two of them; for another example, the number of parts by weight of the added compound containing isocyanate groups is 0.01 to 2 parts by weight. After adding the above-mentioned parts by weight of a compound containing isocyanate groups externally to the resin composition and increasing its content, it is beneficial to the adhesion of the resin layer to the substrate.

[0047] In order to precisely control the content of isocyanate groups, in some embodiments, the molecular structural formula of the compound containing isocyanate groups is selected as formula (I) or formula (II); (I); wherein, in formula (I), R is an alkyl group, an aryl group, a substituted alkyl group, a substituted aryl group, an acyl alkyl group or an acryloyloxy alkyl group; further optionally, the alkyl group is a C1-C6 alkyl group, the substituted alkyl group is a C1-C6 substituted alkyl group, the alkyl group in the acyl alkyl group is a C1-C6 alkyl group, and the alkyl group in the acryloyloxy alkyl group is a C1-C6 alkyl group; specifically, the compound containing isocyanate groups shown in formula (I) is 2-isocyanatoethyl acrylate or hexyl isocyanate. (II); wherein, in formula (II), G is an alkylene group, an arylene group, a substituted alkylene group or a substituted arylene group; further optionally, the alkylene group is an alkylene group having 1 to 6 carbon atoms, and the substituted alkylene group is a substituted alkylene group having 1 to 6 carbon atoms; specifically, the isocyanate group-containing compound represented by formula (II) is selected from at least one of hexamethylene diisocyanate, trimethylhexane diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate. The isocyanate group-containing compound can also be obtained by reacting a hydroxyl group-containing compound with a compound having at least two isocyanate groups, and there is a residue of NCO group in the product; optionally, the hydroxyl group-containing compound is a hydroxyalkyl (meth)acrylate and / or a polyol; the compound having at least two isocyanate groups is selected from at least one of hexamethylene diisocyanate, trimethylhexane diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate or isophorone diisocyanate. For example, the polyol and isophorone diisocyanate are reacted at a reaction temperature of 45 to 85 °C for 2 to 5 h, and then further reacted with hydroxyethyl methacrylate at 45 - 90 °C for 2 - 10 h.

[0048] The above-mentioned various types of isocyanate group-containing compounds selected in the present application have good compatibility, reactivity with other components in the resin composition and are beneficial to the performance of the final resin composition. By precisely controlling the content and type of isocyanate groups, for example, D-1: isophorone diisocyanate, D-2: 2-isocyanatoethyl acrylate, D-3: hexyl isocyanate, D-4: the reaction product of polyester polyol and isophorone diisocyanate, and further reacted with hydroxyethyl methacrylate, the content of isocyanate groups in the product is 0.3%; a photosensitive resin composition with excellent performance can be prepared to meet the requirement that the resin film layer does not fall off during the sandblasting protection process.

[0049] In order to improve the compatibility of urethane (meth)acrylate with other components, its reactivity, and the performance of the final resin composition, it is necessary to screen the types of urethane (meth)acrylate used; in some embodiments, the urethane (meth)acrylate is a polyether-based urethane compound and / or a polyester-based urethane compound; optionally, the polyether-based urethane compound is a urethane compound containing polyether repeating units and (meth)acryloyloxy end-capped groups in the molecular chain segment; the polyester-based urethane compound is a urethane compound containing polyester repeating units and (meth)acryloyloxy end-capped groups in the molecular chain segment. By screening out the appropriate types of urethane (meth)acrylate compounds, it is more conducive to improving the sandblasting resistance; for example, B-1: CN965 (Sartomer, polyester-based urethane compound), B-2: CN966 (Sartomer, polyester-based urethane compound). Using the above types of urethane (meth)acrylate is beneficial for preparing a photosensitive resin composition with excellent performance to meet the requirement that the resin film layer does not fall off during the sandblasting protection process.

[0050] In order to further optimize the comprehensive performance of the resin composition, it is necessary to screen the types of alkali-soluble resins; in some embodiments, the alkali-soluble resin is selected from at least one of an acrylic copolymer, a urethane compound containing a carboxyl group in the structure, and a cellulose compound containing a carboxyl group in the structure. Selecting the above types of alkali-soluble resins can optimize the comprehensive performance of the photosensitive resin composition to meet specific requirements during the sandblasting protection process. For example, the introduction of an acrylic copolymer can reduce the peeling of the resist pattern caused by static electricity generated during the sandblasting process, thereby improving the sandblasting impact resistance. The urethane compound can enhance the flexibility of the resist pattern, thereby improving the sandblasting impact resistance, while the cellulose compound can improve the storage stability of the composition layer and avoid flow and wrinkling during the storage of the composition layer; combining the above characteristics, a photosensitive resin composition with good sandblasting resistance and storage stability can be prepared, which is suitable for the sandblasting protection and treatment of fine patterns.

[0051] In some embodiments, the weight-average molecular weight of the acrylic copolymer is from 10,000 to 120,000; optionally from 50,000 to 100,000; the acid value of the acrylic copolymer is from 97 to 200 mg KOH / g; optionally from 130 to 180 mg KOH / g; by precisely controlling the molecular weight and acid value of the acrylic copolymer, an optimal performance balance point can be obtained, which can not only provide good developability (due to moderate acid value and molecular weight), but also maintain appropriate mechanical strength and coating properties (moderate molecular weight). By adjusting the above parameters, a photosensitive resin composition that can meet the requirements for fine pattern formation and maintain stability during the sandblasting process can be prepared. This type of acrylic copolymer can be obtained by copolymerizing at least one carboxyl group-containing comonomer I and at least one carboxyl group-free comonomer II. For example, comonomer I is selected from at least one of itaconic acid, crotonic acid, acrylic acid, methacrylic acid, maleic acid semi-ester, maleic acid, fumaric acid, vinyl acetic acid, and vinyl acetic anhydride. Comonomer II is selected from at least one of methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, (meth)acrylonitrile, glycidyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, N,N-dimethylaminobutyl (meth)acrylate, N,N-diethylaminobutyl (meth)acrylate, (meth)acrylamide, N-hydroxymethylacrylamide, N-butoxymethylacrylamide, styrene, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, nonylphenol (meth)acrylate, and alkoxylated nonylphenol (meth)acrylate. The acid value and molecular weight of the acrylic acid obtained by copolymerizing the above types of comonomer I and comonomer II can be adjusted within the above ranges, which is beneficial for the acrylic copolymer to have good mechanical strength and developability. Further, for example, the acrylic copolymer is obtained by copolymerizing methacrylic acid, methyl methacrylate, and butyl acrylate; further, the weight ratio of methacrylic acid, methyl methacrylate, and butyl acrylate is (20 to 30):(50 to 60):(15 to 25).

[0052] In some embodiments, to improve the development effect, flexibility, and adhesion of the resin composition, the weight-average molecular weight of the urethane compound containing a carboxyl group in the structure is 1000 - 40000; if the molecular weight is too high, it is not conducive to development; if the molecular weight is too low, the flexibility and water resistance of the composition after curing become poor, ultimately resulting in poor adhesion resistance to sandblasting impact and poor adhesion resistance to sandblasting impact. The acid value of the urethane compound containing a carboxyl group in the structure is 30 - 70 mg KOH / g; it can be optionally 40 - 60 mgKOH / g. If the acid value is too low, it is not conducive to development; if the acid value is too high, the water resistance of the composition after curing becomes poor, ultimately resulting in poor adhesion of the cured layer to the substrate. By precisely controlling the molecular weight and acid value, good developability (due to a moderate acid value) can be provided, and appropriate mechanical strength and coating properties (moderate molecular weight) can be maintained.

[0053] In some embodiments, the urethane compound containing a carboxyl group in the structure is obtained by a first reaction of a polyhydroxycarboxylic acid compound and a diisocyanate compound to obtain a first reactant, and then the first reactant and a polyol compound having two hydroxyl groups at the molecular ends undergo a second reaction to obtain a second reactant, and the second reactant and a (meth)acrylate compound having one hydroxyl group in the molecular structure undergo a third reaction. More specifically, the molar ratio of the polyhydroxycarboxylic acid compound, the diisocyanate compound, the polyol compound having two hydroxyl groups at the molecular ends, and the (meth)acrylate compound having one hydroxyl group in the molecular structure is (0.4 - 0.6):(0.8 - 1.2):(0.2 - 0.3):(0.4 - 0.6); the temperature of the first reaction is 45 - 85°C, and the time of the first reaction is 2 - 5 h; the temperature of the second reaction is 45 - 90°C, and the time of the second reaction is 2 - 10 h.

[0054] In some embodiments, the diisocyanate compound is selected from at least one of hexamethylene diisocyanate, trimethylhexane diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate; further preferably hexamethylene diisocyanate. Selecting the above raw materials as the reaction raw materials for the urethane (meth)acrylate compound is more conducive to the adhesion of the resin film layer to the substrate.

[0055] In some embodiments, the polyhydroxycarboxylic acid compound is dimethylolpropionic acid and / or dimethylolbutyric acid; further preferably dimethylolpropionic acid; the above carboxyl group provides sufficient alkali solubility, enabling the resin film layer to dissolve quickly during the development process and improving the pattern clarity.

[0056] In some embodiments, from the perspective of developability, the weight-average molecular weight of the polyol compound having two hydroxyl groups at the molecular terminals is 200 to 4,000; the polyol compound having two hydroxyl groups at the molecular terminals is a polyether polyol and / or a polyester polyol; from the perspective of adhesion, a polyester polyol is further preferably used. For example, the polyether polyol is selected from at least one of polyethylene glycol, polypropylene glycol, polytetrahydrofuran diol, poly-1,5-pentanediol, ethylene oxide-propylene oxide copolymer diol, and tetrahydrofuran-propylene oxide copolymer diol; the polyester polyol is a polyester polyol obtained by polycondensation of a dicarboxylic acid and a diol compound, or a polylactone polyol obtained by ring-opening polymerization of a lactone, or a polycarbonate diol obtained by reacting compound A and compound B, where compound A is bisphenol A or 1,4-dihydroxycyclohexane, and compound B is diphenyl carbonate or phosgene; among them, the dicarboxylic acid is selected from at least one of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, and terephthalic acid; the diol compound is selected from at least one of ethylene glycol, propylene glycol, 1,4-butanediol, hexanediol, 1,4-dihydroxycyclohexane, and bisphenol A; the lactone is caprolactone.

[0057] In some embodiments, the (meth)acrylate compound having one hydroxyl group in the molecular structure is selected from at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate; more preferably, it can be hydroxyethyl methacrylate.

[0058] In some embodiments, the urethane compound having a carboxyl group in the structure is obtained by a first reaction of dimethylolpropionic acid and hexamethylene diisocyanate to obtain a first reactant, a second reaction of the first reactant and a polyester polyol to obtain a second reactant, and a third reaction of the second reactant and hydroxyethyl methacrylate.

[0059] In some embodiments, the acid value of the cellulose compound having a carboxyl group in the structure is 80 to 200 mg KOH / g. It can be 120 to 200 mg KOH / g. If the acid value is too low, it is not conducive to development; if the acid value is too high, the water resistance of the composition after curing becomes poor, and ultimately the adhesion of the cured layer to the substrate becomes poor. Controlling the acidity is more conducive to developability; the compound is, for example, at least one of cellulose acetate phthalate, cellulose propionate phthalate, cellulose acetate propionate phthalate, cellulose acetate succinate, cellulose propionate succinate, cellulose acetate propionate succinate, cellulose acetate maleate, cellulose propionate maleate, and cellulose acetate propionate maleate; more preferably, it can be cellulose acetate phthalate.

[0060] In some embodiments, the photosensitive resin composition further includes 0.1 to 0.5 parts by weight of a silane coupling agent; for example, any value among 0.1, 0.2, 0.3, 0.4, 0.5 or a range value between any two of them; for another example, it is 0.2 to 0.5 parts by weight. By adding a silane coupling agent to the resin composition, the adhesion of the resin film layer to the substrate can be further improved; controlling the addition ratio is beneficial to the stability of the composition system and good adhesion. For example, the above silane coupling agent can be selected from vinyltrifluorosilane, vinyltriethoxysilane, vinyltri(β-methoxyethoxy)silane, γ-glycidylpropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl-trimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl-methyl-trimethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, anilinomethyltrimethoxysilane, anilinomethyltriethoxysilane, vinylbenzylaminoethylaminopropyltrimethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, ureidopropyltriethoxysilane, bis(triethoxysilylpropyl)disulfide, and bis(triethoxysilylpropyl)tetrasulfide. Using the above-preferred silane coupling agent has good compatibility with other components of the resin, which can not only improve the adhesion of the resin film layer but also make the resin composition system have good stability. Further, considering the system stability, γ-methacryloxypropyltrimethoxysilane (commercial grade KH570) can be selected as the silane coupling agent.

[0061] In some embodiments, the photosensitive resin composition further comprises 1 to 5 parts by weight of a photopolymerizable compound; for example, any value among 1, 2, 3, 4, 5 parts or a range value between any two of them; for another example, 2 to 4 parts by weight.By further adding a photopolymerizable compound to the resin composition, a crosslinking reaction occurs during subsequent exposure, and together with other components such as an alkali-soluble urethane (meth)acrylate resin and a urethane (meth)acrylate compound, it promotes the curing performance of the resin film layer, such as certain toughness, strength, excellent adhesion, etc.; The photopolymerizable compound that can achieve the above effects well can be selected from lauryl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, phenoxyethyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, bisphenol A di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, ethoxylated propoxylated bisphenol A di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polyethylene glycol propylene glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, glycerol tri(meth)acrylate, propoxylated glycerol tri(meth)acrylate, ethoxylated glycerol tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, ethoxylated propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol tri(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate, ethoxylated propoxylated pentaerythritol tri(meth)acrylate, ethoxylated propoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, ethoxylated dipentaerythritol tri(meth)acrylate, propoxylated dipentaerythritol tri(meth)acrylate, ethoxylated propoxylated dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, ethoxylated dipentaerythritol tetra(meth)acrylate, propoxylated dipentaerythritol tetra(meth)acrylate, ethoxylated propoxylated dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol penta(meth)acrylate, propoxylated dipentaerythritol penta(meth)acrylate, ethoxylated propoxylated dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, and ethoxylated propoxylated dipentaerythritol hexa(meth)acrylate, at least one of them.By selecting the above-mentioned type of photopolymerizable compound, the photocuring performance of the photosensitive resin composition can be improved, the adhesion of the resin film layer to the substrate can be enhanced by forming more crosslinking points, and at the same time, good mechanical strength and corrosion resistance of the coating can be ensured; the above-mentioned type of compound selected has two or more reactive functional groups, which can react quickly under exposure conditions to form a dense network structure; by adjusting the type and content of the photopolymerizable compound, the curing speed and crosslinking density of the resist layer can be optimized to achieve the best sandblasting protection effect; for another example, the addition of F-1 (ethoxylated bisphenol A diacrylate) and F-2 (ethoxylated trimethylolpropane triacrylate) can improve the photocuring efficiency of the photosensitive resin composition and the performance of the resist layer, especially for pattern retention and substrate protection during photolithographic exposure and sandblasting processes.

[0062] In some embodiments, the photosensitive resin composition further includes 0.1 to 0.3 parts by weight of other additives; for example, 0.1, 0.2, 0.3; for example, 0.15 to 0.2 parts by weight; wherein, the other additives include dyes such as diamond green and victoria blue B, photochromic agents such as colorless crystal violet, color-forming heat stabilizers, plasticizers, pigments, fillers, flame retardants, inhibitors, leveling agents, stripping promoters, antioxidants, fragrances, imaging agents, thermal crosslinking agents, etc. The types of these additives can be selected according to the actual situation and controlled within the above-mentioned addition ratio range, without affecting the overall adhesion, stability, etc. of the resin.

[0063] In some embodiments, the photoinitiator is selected from at least one of 2,4,5-triaryl imidazole dimers, derivatives of 2,4,5-triaryl imidazole dimers, tetraethyl Michler's ketone, N-phenylglycine, acridine compounds, pyrazoline compounds, coumarin compounds, and thiol compounds. For example, the derivatives of 2,4,5-triaryl imidazole dimers are selected from at least one of 2-(o-chlorophenyl)-4,5-diphenyl imidazole dimer, 2-(o-chlorophenyl)-4,5-bis(methoxyphenyl) imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenyl imidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenyl imidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenyl imidazole dimer; for another example, the acridine compounds are selected from at least one of 9-phenyl acridine, 9-(p-methylphenyl) acridine, 9-(p-ethylphenyl) acridine, 9-(p-n-propylphenyl) acridine, 9-(p-isopropylphenyl) acridine, 9-(p-n-butylphenyl) acridine, 9-(p-tert-butylphenyl) acridine, 9-(p-methoxyphenyl) acridine, 9-(p-ethoxyphenyl) acridine, 9-(p-propoxyphenyl) acridine, 9-(p-aminophenyl) acridine, 9-(p-dimethylaminophenyl) acridine, 9-(p-diethylaminophenyl) acridine, 9-(p-chlorophenyl) acridine, 9-(p-bromophenyl) acridine, 9-(p-carboxyphenyl) acridine, 9-(m-methylphenyl) acridine, 9-(m-n-propylphenyl) acridine, 9-(m-isopropylphenyl) acridine, 9-(m-n-butylphenyl) acridine, 9-(m-tert-butylphenyl) acridine, 9-(m-methoxyphenyl) acridine, 9-(m-ethoxyphenyl) acridine, 9-(m-propoxyphenyl) acridine, 9-(m-aminophenyl) acridine, 9-(m-dimethylaminophenyl) acridine, 9-(m-diethylaminophenyl) acridine, 9-(m-chlorophenyl) acridine, and 9-(m-bromophenyl) acridine; further for example, the pyrazoline compounds are selected from 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline and / or phenyl-3-(4-isopropylstyryl)-5-(4-isopropylphenyl)-pyrazoline; further for example, the thiol compounds are selected from at least one of ethanedithiol, 1,4-dimethylthiobenzene, butanediol dithioglycolate, butanediol dithioglycolate, ethylene glycol dithioglycolate, trimethylolpropane trithioglycolate, butanediol dithiopropionate, trimethylolpropane trithiopropionate, pentaerythritol tetrathiopropionate, pentaerythritol tetrathioglycolate, tri(2-hydroxyethyl) trithiopropionate, tris(2-hydroxyethyl) isocyanurate-tris(mercapto propionate), diethanolamine-tris(mercapto propionate), diethylene glycol-bis(mercapto propionate), and benzyl mercaptopropionate; further select C-1: 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole (strong electron) and / or C-2: tetraethyl Michler's ketone (strong electron).By optimizing the type and addition amount of the photoinitiator, higher photocuring efficiency can be achieved, the exposure time can be reduced, the economic benefits of the production process can be improved, and at the same time, the resin film layer can be ensured to have good protective performance and corrosion resistance.

[0064] In some embodiments, the photosensitive resin composition comprises 29 to 70 parts by weight of an alkali-soluble resin, 20 to 70 parts by weight of a urethane (meth)acrylate compound, 1 to 5 parts by weight of a photoinitiator, 0.005 to 0.5 parts of an isocyanate group-containing compound, including 0 to 0.5 parts of a silane coupling agent, 0 to 5 parts of a photopolymerizable compound, and 0 to 0.3 parts of other additives;

[0065] Among them, the alkali-soluble resins A-1 and A-2 are acrylic copolymers, specifically obtained by copolymerizing methacrylic acid, methyl methacrylate and butyl acrylate in a weight ratio of (20 to 30):(50 to 60):(15 to 25); the alkali-soluble resin A-3 is cellulose acetate phthalate, with a specific acid value of 150 to 170 mgKOH / g; the alkali-soluble resin A-4 is an alkali-soluble urethane resin, and the specific preparation method is as follows: dimethylolpropionic acid and hexamethylene diisocyanate undergo a first reaction to obtain a first reactant, the first reactant and a polyester polyol undergo a second reaction to obtain a second reactant, and the second reactant and hydroxyethyl methacrylate undergo a third reaction to obtain; the molar ratio of dimethylolpropionic acid, hexamethylene diisocyanate, polyester polyol, and hydroxyethyl methacrylate is (0.4 to 0.6):(0.8 to 1.2):(0.2 to 0.3):(0.4 to 0.6) in sequence; the temperature of the first reaction is 45 to 85 °C, and the time of the first reaction is 2 to 5 h; the temperature of the second reaction is 45 to 90 °C, and the time of the second reaction is 2 to 10 h; the urethane (meth)acrylate compounds B-1, CN965 (Sartomer), and B-2, CN966 (Sartomer); the isocyanate group-containing compounds D-1: isophorone diisocyanate, D-2: 2-isocyanatoethyl acrylate, D-3: hexyl isocyanate, D-4: obtained by the following method: the reaction product of a polyester polyol and isophorone diisocyanate is further reacted with hydroxyethyl methacrylate; the molar ratio of the polyester polyol, isophorone diisocyanate, and hydroxyethyl methacrylate is in sequence: (0.2 to 0.3):(0.4 to 0.6):(0.4 to 0.6), the reaction temperature of the polyester polyol and isophorone diisocyanate is 45 to 85 °C, and the reaction time is 2 to 5 h; the reaction temperature for further reaction with hydroxyethyl methacrylate is 45 to 90 °C, and the feeding ratio, reaction time and temperature are controlled to make the isocyanate group content be 0.001 to 1%.

[0066] In the present application, “(meth)” means being substituted by a methyl group or not being substituted by a methyl group; for example, a urethane (meth)acrylate compound means a urethane acrylate compound or a urethane methacrylate compound. In the present application, “( )” in the part of the silane coupling agent is the writing method of the chemical name; for example, vinyltris(β-methoxyethoxy)silane.

[0067] According to the second aspect of the present application, there is provided a laminate including a support film layer 1 and a resist film layer 2 which are sequentially stacked; the resist film layer 2 is a film layer formed after drying the above photosensitive resin composition; alternatively, the laminate may also be composed of a support film layer 1, a resist film layer 2, and a cover film layer 3 which are sequentially stacked, as Figure 1 shown.

[0068] In some embodiments, the preparation method of the above laminate includes: weighing each component of the above photosensitive resist composition and dissolving them in an organic solvent according to the above mass ratio to obtain a mixed solution, then coating the mixed solution on a colorless transparent support film and drying it to obtain a resist film; then, laminating a polymer cover film for protecting the resist above the resist film to finally obtain a resist laminate. The coating can be carried out by a reverse roll coater, a gravure coater, a comma coater, a curtain coater, etc.; the drying can be carried out by infrared drying, hot air drying, etc., the drying temperature is 50~120°C, and the drying time can be adjusted according to the concentration of the solution, generally 1~20 minutes.

[0069] The colorless transparent support film can be a film such as low-density polyethylene, high-density polyethylene, polypropylene, polyester, polyethylene terephthalate, polycarbonate, polyarylate, etc. For the resist composition, in order to avoid the influence of moisture on its physical properties and coating conditions, it is preferably that the colorless transparent support film is a polyethylene terephthalate, polyethylene or polypropylene film; more preferably a polyethylene terephthalate film. The thickness of the colorless transparent support film is 10~50μm, preferably 10~30μm. The polymer cover film is selected as a resin film with low moisture permeability and easy peeling, which can be transparent or opaque, preferably a polyethylene terephthalate, polyethylene or polypropylene film, with a thickness of 5~100μm.

[0070] According to the third aspect of the present application, there is provided an application of the above photosensitive resin composition or the resist film in the above laminate in the manufacture of circuits of printed circuit boards and selective engraving sandblasting treatment.

[0071] The following further describes the present application in detail with specific examples, and these examples should not be construed as limiting the scope claimed by the present application.

[0072] All raw materials used in the examples of the present application are of the prior art and are commercially available.

[0073] In the examples and comparative examples of this application, the content of the NCO group was detected by the di-n-butylamine-n-butyl acetate method.

[0074] Example 1

[0075] Mix each component in proportion according to the formula in Table 1, and then stir well until completely dissolved to prepare a resist composition solution with a solid content of 46 - 50%. Use a coater to evenly coat it on the surface of a PET film (thickness 15 μm) as the support film layer 1, and place it in an oven at 95°C for 6 - 20 minutes. According to different evaluation requirements, a resist film layer 2 with a thickness of 100 μm is formed. Then, attach a polyethylene film with a thickness of 100 μm as the covering film layer 3 on its surface, and thus a photosensitive dry film with a three-layer structure is obtained, as Figure 1 shown.

[0076] A alkali-soluble resin:

[0077] A-1: Acrylic copolymer, prepared by using an existing polymerization method. The formula and main technical indicators are as follows:

[0078] Methacrylic acid / methyl methacrylate / butyl acrylate = 22 / 56 / 20 (weight ratio); Mw = 61000, solid content acid value = 143.3 mgKOH / g, solid content = 40%;

[0079] A-2: Acrylic copolymer, prepared by using an existing polymerization method. The formula and main technical indicators are as follows:

[0080] Methacrylic acid / methyl methacrylate / butyl acrylate = 24 / 56 / 20 (weight ratio); Mw = 90000, solid content acid value = 156.4 mgKOH / g, solid content = 40%;

[0081] A-3: Cellulose acetate phthalate (Aladdin chemical reagent), acid value: 162 mgKOH / ;

[0082] A-4: Alkali-soluble urethane resin, obtained by the following method:

[0083] 67 g (0.5 mol) of dimethylolpropionic acid and 168.2 g (1 mol) of hexamethylene diisocyanate were added to a three-necked flask, and the temperature was raised to 70 °C. The reaction was carried out for 4 h, then 260 g (0.26 mol) of a polyester polyol (XCP-1000N, hydroxyl value: 112 mg KOH / g, Asahi Kasei Chemicals), 0.6 g of dibutyltin dilaurate were added, and the temperature was raised to 80 °C. The reaction was continued for 2.5 h, then 0.05 g of MEHQ was added, and 65 g (0.5 mol) of hydroxyethyl methacrylate was added. The reaction was continued until the NCO% = 0.001%, and then the product was discharged; acid value: 50.1 mg KOH / g;

[0084] B: Carbamate (meth)acrylate:

[0085] B-1: Polyester-based carbamate (meth)acrylate compound, Sartomer CN965 (polyester-based carbamate compound, NCO% = 0.001%);

[0086] B-2: Polyester-based carbamate (meth)acrylate compound, Sartomer CN966 (polyester-based carbamate compound, NCO% = 0.001%);

[0087] B-3: Polyether-based carbamate (meth)acrylate compound, Sartomer PRO33112 (polyether-based carbamate compound, NCO% = 0.001%);

[0088] C Photoinitiator:

[0089] C-1: 2,2’,4-Tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4’,5’-diphenyl-1,1’-diimidazole (Strong Electron);

[0090] C-2: Tetraethyl Michler's ketone (Strong Electron);

[0091] D Isocyanate group-containing compound:

[0092] D-1: Isophorone diisocyanate;

[0093] D-2: 2-Isocyanatoethyl acrylate;

[0094] D-3: Hexyl isocyanate;

[0095] D-4: Isocyanate group-containing compound, prepared by the following method:

[0096] Put 260 g (0.26 mol) of polyester polyol (XCP-1000N, Asahi Kasei Chemicals, molecular weight: 1000), 0.4 g of dibutyltin dilaurate into a three-necked flask, heat up to 70 °C, and slowly add dropwise 111.15 g (0.5 mol) of isophorone diisocyanate. React for 4 h, then add 65 g (0.5 mol) of 2-hydroxyethyl methacrylate, heat up to 80 °C, and continue to react until NCO% = 0.3% (the content of unreacted NCO groups in the product system), and then discharge the material;

[0097] E silane coupling agent:

[0098] E-1: Silane coupling agent KH570;

[0099] F photo-polymerizable monomer:

[0100] F-1: Ethoxylated bisphenol A diacrylate (Sartomer);

[0101] F-2: Ethoxylated trimethylolpropane triacrylate (Sartomer);

[0102] G other additives:

[0103] G-1: Leuco crystal violet (Aladdin);

[0104] Solvent: Methyl ethyl ketone.

[0105] Example 2-11

[0106] The difference between Example 2-11 and Example 1 is that the formulation of the photosensitive resin composition is different, as shown in Table 1 and Table 2 specifically.

[0107] Example 12

[0108] The difference between Example 12 and Example 11 is that the formulation of the photosensitive resin composition is different, as shown in Table 2 specifically.

[0109] Example 13

[0110] The difference between Example 13 and Example 8 is that the formulation of the photosensitive resin composition is different, as shown in Table 2 specifically.

[0111] Example 14

[0112] The difference between Example 14 and Example 7 is that the formulation of the photosensitive resin composition is different, as shown in Table 2 specifically.

[0113] Example 15

[0114] The difference between Example 15 and Example 7 is that the formulation of the photosensitive resin composition is different, as shown in Table 2 specifically.

[0115] Example 16

[0116] Example 16 is different from Example 8 in that the formulations of the photosensitive resin compositions are different, as specifically shown in Table 2.

[0117] Example 17

[0118] Example 17 is different from Example 11 in that the formulations of the photosensitive resin compositions are different, as specifically shown in Table 2.

[0119] Comparative Example 1

[0120] Comparative Example 1 is different from Example 11 in that the formulations of the photosensitive resin compositions are different, as specifically shown in Table 2.

[0121] Comparative Example 2

[0122] Comparative Example 2 is different from Example 6 in that the formulations of the photosensitive resin compositions are different, as specifically shown in Table 2.

[0123] Test Example

[0124] The adhesion of the photosensitive resin compositions prepared in Examples 1 to 17 and Comparative Examples 1 to 2 was detected, and the results are shown in Table 1.

[0125] Film laminating: Use Changzhou Changyao Electronics CYL-M25 for film laminating. The film laminating pressure is 4 Kg / cm 2 , the speed is 0.5 m / min, and the temperature is 100 °C. Stack the photosensitive dry film with the protective film removed and the photosensitive resin layer on the borosilicate glass substrate.

[0126] Exposure: After film laminating, let the sample stand for more than 15 min. Use Hongshengxiang HSX-LEDS5 exposure machine for exposure. Use stouffer 21-step exposure ruler to measure the exposure grid number, and control the exposure grid number within 10 grids.

[0127] Development: After exposure, let the sample stand for more than 15 min. The development temperature is 30 °C, and the pressure is 1.5 Kg / cm 2 , the developer is 0.2 wt% sodium carbonate aqueous solution, the development time is 1.6 times the minimum development time, and after development, wash with water and dry.

[0128] Evaluation of adhesion before sandblasting: Use a dot matrix reticle with dot size = n microns (n ranges from 120 to 400, 20 dots of the same size in each row, increasing by 10 in each row in sequence, a total of 29 rows), and a photomask with a dot matrix pattern with a dot center distance of 3000 microns (the dot area is the exposed area, and other areas are non-exposed areas) for exposure and development, and then wash with water and dry. Observe with a magnifying glass. The row in which all dots in the row are completely non-detached is the adhesion limit value of the sample. The smaller the adhesion limit value, the better the adhesion of the dry film.

[0129] Evaluation of adhesion after sandblasting: For the samples used in the evaluation of adhesion before sandblasting described above, continue to use 800# SiC micropowder to perform sandblasting treatment on the glass substrate (spraying pressure: 0.2 MPa) until the depth reaches 200 microns. Observe with a magnifying glass. The row in which all the dots in the row are completely non-detached is the adhesion limit value of the sample. The smaller the adhesion limit value, the better the adhesion of the dry film.

[0130]

[0131]

[0132] The data in Table 1 and Table 2 show that in Examples 1 to 17, by controlling the isocyanate group content in the composition formed by an alkali-soluble resin, a urethane (meth)acrylate compound, and a photoinitiator to 20 to 700 ppm, the composition has very excellent adhesion on the surface of a substrate with very small surface roughness such as glass after film formation. When sandblasting the substrate, it can withstand the sandblasting impact and is not prone to resin layer peeling. For example, the adhesion before sandblasting can reach 150 to 190 μm, and the adhesion after sandblasting can reach 240 to 280 μm. At the same time, the adhesion is not too large to affect the subsequent removal of the resin layer. In Comparative Examples 1 to 2, due to inappropriate adjustment of the component ratios, the NCO content is too small or too large, and the adhesion of the resin film before sandblasting reaches 200 to 240 μm, and the adhesion after sandblasting reaches 300 to 330 μm; the adhesion decays in both cases. It can be seen that controlling the NCO content in the resin composition within a suitable range can make the resin film layer have good adhesion before and after sandblasting, which is operable.

[0133] It should be noted that the terms "first", "second", etc. in the description and claims of this application are used to distinguish similar objects, and do not necessarily have to be used to describe a specific order or sequence. It should be understood that such terms can be interchanged under appropriate circumstances so that the embodiments of the present application described herein can be implemented in an order other than those described herein, for example.

[0134] The above are only the preferred embodiments of the present application and are not used to limit the present application. For those skilled in the art, the present application can have various changes and modifications. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A photosensitive resin composition, characterized in that, The photosensitive resin composition comprises an alkali-soluble resin, a urethane (meth)acrylate, and a photoinitiator; wherein, the content of isocyanate groups in the photosensitive resin composition is 20 to 700 ppm.

2. The photosensitive resin composition according to claim 1, wherein The content of isocyanate groups in the photosensitive resin composition is 50 to 670 ppm.

3. The photosensitive resin composition according to claim 1, wherein Based on parts by weight, the photosensitive resin composition comprises 29 to 70 parts by weight of the alkali-soluble resin, 20 to 70 parts by weight of the urethane (meth)acrylate compound, and 1 to 5 parts by weight of the photoinitiator.

4. The photosensitive resin composition according to claim 3, wherein The photosensitive resin composition further comprises 0.005 to 2 parts by weight of an isocyanate group-containing compound.

5. The photosensitive resin composition according to claim 4, wherein, The molecular structural formula of the isocyanate group-containing compound is Formula (I) or Formula (II), or the isocyanate group-containing compound is obtained by reacting a hydroxyl group-containing compound with a compound containing at least two isocyanate groups; （I）； wherein, in Formula (I), R is an alkyl group, an aryl group, a substituted alkyl group, a substituted aryl group, an acylalkyl group, or an acryloyloxyalkyl group; (II); wherein, in Formula (II), G is an alkylene group, an arylene group, a substituted alkylene group, or a substituted arylene group.

6. The photosensitive resin composition according to claim 5, wherein The alkyl group in Formula (I) is a C1-C6 alkyl group, the substituted alkyl group is a C1-C6 substituted alkyl group, the alkyl group in the acylalkyl group is a C1-C6 alkyl group, and the alkyl group in the acryloyloxyalkyl group is a C1-C6 alkyl group; and / or, the alkylene group in Formula (II) is a C1-C6 alkylene group, and the substituted alkylene group is a C1-C6 substituted alkylene group; and / or, the hydroxyl group-containing compound is a (meth)acrylic acid hydroxyalkyl ester and / or a polyol; and / or, the compound containing at least two isocyanate groups is selected from at least one of hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, or isophorone diisocyanate.

7. The photosensitive resin composition according to any one of claims 1 to 6, characterized in that, The urethane (meth)acrylate is a polyether-based urethane compound and / or a polyester-based urethane compound; and / or, the alkali-soluble resin is selected from at least one of an acrylic copolymer, a urethane compound containing a carboxyl group in its structure, and a cellulose compound containing a carboxyl group in its structure.

8. The photosensitive resin composition according to claim 7, wherein The polyether-based urethane compound is a urethane compound having a polyether repeating unit and a (meth)acryloyloxy end group in its molecular chain segment; and / or, the polyester-based urethane compound is a urethane compound having a polyester repeating unit and a (meth)acryloyloxy end group in its molecular chain segment; and / or, the weight average molecular weight of the urethane compound containing a carboxyl group in its structure is 1000 to 40000; and / or, the acid value of the urethane compound containing a carboxyl group in its structure is 30 to 70 mg KOH / g; And / or, the urethane compound containing a carboxyl group in the structure is obtained by reacting a polyhydroxy carboxylic acid compound with a diisocyanate compound to obtain a first reactant, reacting the first reactant with a polyol compound having two hydroxyl groups at the molecular ends to obtain a second reactant, and reacting the second reactant with a (meth)acrylate compound having one hydroxyl group in the molecular structure; And / or, the weight average molecular weight of the acrylic copolymer is 10,000 to 120,000; And / or, the acid value of the acrylic copolymer is 97 to 200 mg KOH / g; And / or, the acrylic copolymer is obtained by copolymerizing at least one copolymerization unit monomer I containing a carboxyl group and at least one copolymerization unit monomer II not containing a carboxyl group; And / or, the acid value of the cellulose compound containing a carboxyl group in the structure is 80 to 200 mg KOH / g.

9. A laminate comprising a support film layer and a resist film layer stacked in sequence; characterized in that, The resist film layer is a film layer formed after drying the photosensitive resin composition according to any one of claims 1 to 8.

10. Use of the resist film in the photosensitive resin composition according to any one of claims 1 to 8 or the laminate according to claim 9 in the production of a circuit or selective engraving sandblasting treatment of a printed circuit board.

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