A method for preparing a photosensitive resin, a photosensitive resin prepared thereby, and applications thereof

Abstract

The application provides a preparation method of a photosensitive resin, the photosensitive resin prepared therefrom and application, and relates to the technical field of photosensitive paste. The preparation method of the photosensitive resin comprises the following steps: in the presence of a polymerization inhibitor and a catalyst, carrying out a polymerization reaction on o-cresol formaldehyde epoxy resin and an unsaturated dibasic acid in an organic solvent to obtain an intermediate P; in the presence of a polymerization inhibitor and a catalyst, carrying out a grafting reaction on the intermediate P and 3-glycidyl ether oxypropyl triethoxysilane in an organic solvent to obtain an intermediate P-O; in the presence of a polymerization inhibitor and a catalyst, carrying out a reaction on the intermediate P-O and an acid anhydride compound in an organic solvent to obtain the photosensitive resin P-O-S. The photosensitive resin has good chemical bonding strength and film-forming property on a substrate, has excellent wetting and dispersion stability to an inorganic phase, has good developing resolution and developing appearance, and has good application prospect in the photosensitive paste.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of photosensitive paste, in particular to a preparation method of photosensitive resin, photosensitive resin prepared therefrom and application. BACKGROUND

[0002] At present, high-end industries such as artificial intelligence, 5G communication, new display screen, intelligent automobile, integrated circuit and flexible circuit board are booming in China, which also promotes the midstream electronic component industry to develop towards the goal of small size, high density wiring, multi-functional integration and high reliability. Electronic paste is one of the key materials for manufacturing these electronic components, mainly serving as wiring conductive, insulation protection, via hole and current conduction control inside and outside the device, and its performance will have a decisive influence on the processing size and precision, mechanical properties, electrical properties, heat dissipation properties and device reliability.

[0003] Limited by the development of screen printing equipment and screen printing process technology, traditional screen printing type electronic paste has been unable to meet the manufacturing process requirements of high-end electronic components with wiring density of line width / line spacing (L / S) ≤50 μm / 50 μm and via hole diameter (R) ≤50 μm, so it is necessary to develop new type electronic paste and supporting process. Photosensitive paste is a kind of photosensitive electronic paste which is applied by combining screen printing technology and photolithography technology, and its advantage is that it can be used for film forming on various size substrates by using the flexibility and convenience of screen printing technology, and then the solubility contrast of paste film exposed area and non-exposed area in alkaline solution can be changed by photochemical reaction caused by photolithography technology to realize fine line width / line spacing ≤50um / 50um or / and via hole diameter R ≤50um.

[0004] Photosensitive resin is a core key raw material in photosensitive paste, and plays a decisive contribution role in the dispersion stability, film forming property, development resolution, development line fineness and adhesion of photosensitive paste. At present, the photosensitive resin used in photosensitive paste is mostly traditional modified epoxy acrylate resin, but this kind of resin still faces some performance problems: (1) it is difficult to achieve high resolution result of 15um / 15um and below after development due to poor adhesion; (2) it is prone to line breakage in low molecular weight and high acid value state, and it is prone to line thick edge and incomplete development when the molecular weight is high; (3) the adhesion contribution ability of the resin itself is limited, and additional adhesion promoting functional additives need to be added to improve the overall adhesion of the photosensitive paste system.

[0005] In view of this, the present application is proposed. SUMMARY

[0006] One of the purposes of the present application is to provide a preparation method of a photosensitive resin, in particular, a preparation method of a photosensitive resin for a photosensitive paste soluble in a weak alkali solution, the preparation method taking o-cresol formaldehyde epoxy resin as a matrix, and sequentially performing an epoxy ring-opening reaction, a coupling modification and an anhydride modification based on the matrix, so that the photosensitive resin has good chemical bonding strength and film-forming property on substrates such as ceramics, metal oxides and glass, and also has excellent wetting and dispersion stability for inorganic phases such as metal powder, ceramic powder and inorganic glass powder, and further endows the photosensitive resin with good development resolution and development appearance.

[0007] The second purpose of the present application is to provide a photosensitive resin prepared by the above-mentioned preparation method of a photosensitive resin.

[0008] The third purpose of the present application is to provide an application of the photosensitive resin in the preparation of a photosensitive paste, and the photosensitive resin prepared by the present application has a good application prospect in photosensitive pastes such as photosensitive silver paste, photosensitive silver-coated copper paste and photosensitive ceramic paste.

[0009] In order to achieve the above-mentioned purposes of the present application, the following technical solutions are adopted:

[0010] In the first aspect, the present application provides a preparation method of a photosensitive resin, the preparation method of the photosensitive resin comprising:

[0011] (1) in the presence of a polymerization inhibitor and a catalyst, polymerizing o-cresol formaldehyde epoxy resin and an unsaturated dibasic acid in an organic solvent to obtain an intermediate P;

[0012] (2) in the presence of a polymerization inhibitor and a catalyst, grafting the intermediate P and 3-glycidyl ether oxypropyl triethoxysilane in an organic solvent to obtain an intermediate P-O;

[0013] (3) in the presence of a polymerization inhibitor and a catalyst, reacting the intermediate P-O and an anhydride compound in an organic solvent to obtain the photosensitive resin P-O-S.

[0014] Further, in steps (1) and (2), the intermediate P includes any one or a combination of at least two of the intermediates represented by the following formulae Pa~Pc:

[0015] ;

[0016] Formula Pa;

[0017] ;

[0018] Formula Pb;

[0019]

[0020] Formula Pc;

[0021] wherein x is an integer between 4 and 14.

[0022] Further, step (1) specifically comprises:

[0023] The organic solvent and the o-cresol formaldehyde epoxy resin are mixed, stirred and warmed to a first stage temperature for dissolution; after dissolution, a polymerization inhibitor and a catalyst are added, stirred and dissolved and warmed to a second stage temperature; after the temperature is stabilized, an organic solution of the unsaturated dibasic acid is added dropwise and the second stage temperature is maintained for a polymerization reaction to obtain the intermediate P.

[0024] Further, in step (1), the molar ratio of the unsaturated dibasic acid to the epoxy groups in the o-cresol formaldehyde epoxy resin is (0.85-1.2):1.

[0025] Further, in step (1), the unsaturated dibasic acid includes any one or a combination of at least two of methylene succinic acid, maleic acid or glutaconic acid.

[0026] Further, in step (1), the first stage temperature is 65-80°C.

[0027] Further, in step (1), the second stage temperature is 95-110°C.

[0028] Further, in step (1), the organic solution of the unsaturated dibasic acid is added dropwise within 1 h.

[0029] Further, in step (1), the reaction is stopped when the difference between the measured value of the intermediate P and the theoretical acid value is ≤5 mgKOH / g.

[0030] Further, in steps (2) and (3), the intermediate P-O includes any one or a combination of at least two of the intermediates shown in the following formulas Pa-O-Pc-O:

[0031]

[0032] Pa-O;

[0033] ;

[0034] Pb-O;

[0035] ;

[0036] Pc-O;

[0037] wherein n is an integer between 2 and 8 and m is an integer between 2 and 6.

[0038] Further, step (2) specifically comprises:

[0039] controlling the intermediate P at a third stage temperature, adding a polymerization inhibitor and a catalyst to dissolve; after dissolving, adding 3-glycidyloxypropyl triethoxysilane dropwise, and maintaining the third stage temperature to carry out a grafting reaction, to obtain the intermediate P-O.

[0040] Further, the molar ratio of the unsaturated dibasic acid and the 3-glycidyloxypropyl triethoxysilane is 1:(0.12~0.45).

[0041] Further, in step (2), the third stage temperature is 85~95℃.

[0042] Further, in step (2), the time of the grafting reaction is 3~5 h.

[0043] Further, the photosensitive resin P-O-S in step (3) comprises any one or a combination of at least two of the photosensitive resins represented by the following formulas Pa-O-S~Pc-O-S:

[0044] ;

[0045] Formula Pa-O-S;

[0046] ;

[0047] Formula Pb-O-S;

[0048] ;

[0049] Formula Pc-O-S;

[0050] wherein Ra, Rb and Rc are each independently selected from , represents the connecting site of the group;

[0051] wherein M1, M2, M3, M4 are each independently selected from -H or -OH, and the M1, M2, M3, M4 are not simultaneously selected from -H.

[0052] Further, step (3) specifically comprises:

[0053] controlling the intermediate P-O at a fourth stage temperature, adding a polymerization inhibitor and a catalyst to dissolve; after dissolving, adding an organic solution of an acid anhydride compound dropwise, and maintaining the fourth stage temperature to carry out a reaction, to obtain the photosensitive resin P-O-S.

[0054] Further, the structure of the acid anhydride compound is shown in the following formula A:

[0055] ​ ;

[0056] Formula A

[0057] wherein, M1, M2, M3, M4 are each independently selected from -H or -OH, and the M1, M2, M3, M4 are not simultaneously selected from -H.

[0058] Further, the molar ratio of the unsaturated dibasic acid and the acid anhydride compound is 1:(0.8~1.2).

[0059] Further, in step (3), the fourth stage temperature is 75~85℃.

[0060] Further, in step (3), the reaction stopping criterion is: when the difference between the measured value of the photosensitive resin P-O-S and the theoretical acid value is ≤5 mgKOH / g, the reaction is stopped.

[0061] Further, in steps (1)~(3), the organic solvent includes any one or a combination of at least two of ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate or dipropylene glycol methyl ether acetate.

[0062] Further, in steps (1)~(3), the polymerization inhibitor includes p-hydroxyanisole and / or hydroquinone.

[0063] Further, in steps (1)~(3), the polymerization inhibitor is each independently used in an amount of 0.1~0.6% of the mass of the o-cresol novolac epoxy resin.

[0064] Further, in steps (1)~(3), the catalyst includes N,N - dimethylbenzylamine, N,N - any one or a combination of at least two of dimethylbenzylamine, dimethylaniline, triethylamine or triphenylphosphine.

[0065] Further, in steps (1)~(3), the catalyst is each independently used in an amount of 0.4~1.2% of the mass of the o-cresol novolac epoxy resin.

[0066] In a second aspect, the present application provides a photosensitive resin prepared by the method for preparing a photosensitive resin according to the first aspect.

[0067] In a third aspect, the present application provides use of the photosensitive resin according to the second aspect in preparing a photosensitive paste.

[0068] Further, the photosensitive paste includes any one of photosensitive silver paste, photosensitive silver-coated copper paste or photosensitive ceramic paste.

[0069] Compared with the prior art, the present application has the following beneficial effects:

[0070] (1) Compared with the conventional photosensitive o-cresol novolac epoxy acrylate resin, the photosensitive resin prepared by the present application contains flexible siloxane chain segments (-Si(OC2H5)3), which can effectively reduce the glass transition temperature and overall rigidity of the resin system, improve the flexibility and internal stress of the resin. This is conducive to forming a more uniform, dense and crack-free film on the substrate (such as ceramic, glass, metal oxide, etc.), especially during the drying or pre-baking process; in addition, the reaction activity of the double bond of the binary unsaturated acid ester in the photosensitive resin prepared by the present application is moderate, and the molecular structure itself also has a certain flexibility, which has less negative impact on film formation compared with acrylate (especially phenolic epoxy acrylate containing rigid benzene ring).

[0071] (2) The siloxane chain segments in the photosensitive resin prepared by the present application can form firm Si-O-Si or Si-O-M (M=metal) covalent bonds with the hydroxyl groups on the surface of the substrate (such as ceramic, glass, metal oxide, etc.) and inorganic powder particles, significantly improving the chemical bonding strength of the resin and the substrate / powder interface, which can not only improve the adhesion on the substrate, but also increase the wettability of the resin to inorganic powder and the overall stability of the paste. The hydroxyl-containing phthalic anhydride structure in the photosensitive resin prepared by the present application can also form physical adsorption and hydrogen bonding with the surface of the powder, which has the effect of auxiliary improving compatibility and dispersion stability, which is the key to realizing the preparation of high solid content and high performance photosensitive paste.

[0072] (3) The flexible siloxane chain segments and hydroxyl-containing phthalic anhydride structures in the photosensitive resin prepared by the present application can improve the density of the exposed area of the photosensitive material, improve the anti-swelling property of the film layer in the exposed area and the lateral etching of the developing solution, and ensure the smoothness and no burr of the pattern edge; the hydroxyl-containing phthalic anhydride structure in the photosensitive resin has acidic carboxyl and acidic phenolic hydroxyl groups, and the binary unsaturated acid ester structure also contains acidic carboxyl groups, which can greatly improve the hydrophilicity and dissolution rate of the unexposed area, forming a strong contrast with the insoluble exposed area, which can meet the harsh requirements of high-precision photosensitive paste on developing resolution and contrast. DETAILED DESCRIPTION

[0073] Unless otherwise defined, scientific and technical terms used in connection with the present application shall have the meanings that are commonly understood by those of ordinary skill in the art. The meaning and scope of the terms should be clear; however, in the event of any latent ambiguity, definitions provided herein take precedent over any dictionary or extrinsic definition. In this application, the use of "or" means "and / or" unless otherwise stated. Moreover, the use of the "a", "an" or "the" are the generic and open-ended first choice of a grammatical component that states conditions conditions of placing restrict the component to a single instance but to one or more instances unless otherwise indicated by context. In addition, the use of the terms "including", "comprising" and other forms is intended to be equivalent in meaning to "including but not limited to".

[0074] It should be noted that specific details are set forth in the following description in order to provide a thorough understanding of the application. However, the application can be practiced without many of the details described in this description, which are not essential to the practice of the application. It is also possible in this description that some concepts have not been presented in order to not obscure the related details.

[0075] The technical solutions of the present application will be described clearly and completely below in combination with the embodiments. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor are within the scope of protection of the present application.

[0076] In order to achieve the above-mentioned purpose of the present application, the following technical solutions are adopted:

[0077] In a first aspect, the present application provides a preparation method of a photosensitive resin, the preparation method of the photosensitive resin comprising:

[0078] (1) polymerizing o-cresol formaldehyde epoxy resin and unsaturated dibasic acid in an organic solvent in the presence of a polymerization inhibitor and a catalyst to obtain an intermediate P;

[0079] (2) grafting the intermediate P and 3-glycidyl ether oxypropyl triethoxysilane in an organic solvent in the presence of a polymerization inhibitor and a catalyst to obtain an intermediate P-O;

[0080] (3) reacting the intermediate P-O and an acid anhydride compound in an organic solvent in the presence of a polymerization inhibitor and a catalyst to obtain the photosensitive resin P-O-S.

[0081] In the present application, the photosensitive resin takes o-cresol formaldehyde epoxy resin as a matrix, and epoxy ring-opening reaction, coupling modification and acid anhydride modification are successively carried out on the basis thereof, so that the photosensitive resin has good chemical bonding strength and film-forming property on substrates such as ceramics, metal oxides and glass, and also has excellent wetting and dispersion stability for inorganic phases such as metal powder, ceramic powder and inorganic glass powder, and further endows the photosensitive resin with good development resolution and development appearance. In addition, the photosensitive resin prepared by the present application has good application prospect in photosensitive silver paste, photosensitive silver-coated copper paste, photosensitive ceramic paste and other photosensitive paste.

[0082] As an optional embodiment, in step (1) and step (2), the intermediate P comprises any one of the following intermediates of formulae Pa~Pc or a combination of at least two of them:

[0083] ;

[0084] Formula Pa;

[0085] ;

[0086] Formula Pb;

[0087]

[0088] Formula Pc.

[0089] As an optional embodiment, x is an integer between 4~14, for example, it can be 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14.

[0090] As an optional embodiment, step (1) specifically comprises:

[0091] The organic solvent and the o-cresol formaldehyde epoxy resin are mixed, stirred and heated to the first stage temperature for dissolution; after dissolution, the polymerization inhibitor and the catalyst are added, stirred and dissolved and heated to the second stage temperature; after the temperature is stable, the unsaturated dibasic acid organic solution is added dropwise and the second stage temperature is maintained for polymerization reaction to obtain the intermediate P.

[0092] As an optional embodiment, in step (1), the molar ratio of the unsaturated dibasic acid to the epoxy group in the o-cresol formaldehyde epoxy resin is (0.85~1.2):1, specifically but not limitedly, 0.85:1, 0.86:1, 0.87:1, 0.88:1, 0.89:1, 0.9:1, 0.91:1, 0.92:1, 0.93:1, 0.94:1, 0.95:1, 0.96:1, 0.97:1, 0.98:1, 0.99:1, 1:1, 1.01:1, 1.02:1, 1.03:1, 1.04:1, 1.05:1, 1.06:1, 1.07:1, 1.08:1, 1.09:1, 1.1:1, 1.11:1, 1.12:1, 1.13:1, 1.14:1, 1.15:1, 1.16:1, 1.17:1, 1.18:1, 1.19:1 or 1.2:1, etc.

[0093] As an optional embodiment, in step (1), the o-cresol formaldehyde epoxy resin can be any one of o-cresol formaldehyde epoxy resin NPCN-701, NPCN-702, NPCN-703, NPCN-704 produced by Changchun Company in Taiwan, China, or o-cresol formaldehyde epoxy resin EOCN6650, EOCN6700, EOCN6800, EOCN6900 produced by Hunan Jia Shengde Material Science and Technology Co., Ltd.

[0094] As an optional embodiment, in step (1), the unsaturated dibasic acid includes any one or a combination of at least two of methylene butanedioic acid, maleic acid or glutaconic acid.

[0095] As an optional embodiment, in step (1), the first stage temperature is 65-80℃, specifically but not limitedly, 65℃, 66℃, 67℃, 68℃, 69℃, 70℃, 71℃, 72℃, 73℃, 74℃, 75℃, 76℃, 77℃, 78℃, 79℃ or 80℃, etc.

[0096] As an optional embodiment, in step (1), the second stage temperature is 95-110℃, specifically but not limitedly, 95℃, 96℃, 97℃, 98℃, 99℃, 100℃, 101℃, 102℃, 103℃, 104℃, 105℃, 106℃, 107℃, 108℃, 109℃ or 110℃, etc.

[0097] As an optional embodiment, in step (1), the organic solution of the unsaturated dibasic acid is added dropwise within 1 h, specifically but not limitedly, 1 h, 58 min, 56 min, 55 min, 54 min, 52 min, 50 min, 48 min, 46 min, 45 min, 44 min, 42 min, 40 min, etc.

[0098] As an optional embodiment, in step (1), the reaction is stopped when the difference between the measured value of the intermediate P and the theoretical acid value is ≤5 mgKOH / g, specifically but not limitedly, 5 mgKOH / g, 4.5 mgKOH / g, 4 mgKOH / g, 3.5 mgKOH / g, 3 mgKOH / g, 2.5 mgKOH / g, 2 mgKOH / g, 1.5 mgKOH / g, 1 mgKOH / g, etc.

[0099] As an optional embodiment, step (1) specifically includes the following steps:

[0100] Into a four-mouth round bottom flask equipped with a mechanical stirring paddle, a thermometer, a reflux condenser and a thermometer, an organic solvent and o-cresol formaldehyde epoxy resin are sequentially added, and under a certain stirring speed, the temperature is raised to the first stage temperature for sufficient dissolution. After complete dissolution, a certain amount of polymerization inhibitor and catalyst is added to the round bottom flask for sufficient stirring and dissolution. After dissolution is complete, the temperature is raised to the second stage temperature. After the temperature is stable, the previously dissolved unsaturated dibasic acid organic solution is slowly added dropwise through a constant pressure funnel, and the addition is completed within 1 hour. The second stage temperature is maintained for a period of time. The acid value is tested at each time interval, and when the difference between the measured value and the theoretical acid value is less than or equal to 5 mgKOH / g, the reaction is stopped, and the intermediate P is obtained.

[0101] As an optional embodiment, in steps (2) and (3), the intermediate P-O includes any one or a combination of at least two of the intermediates represented by the following formulas Pa-O~Pc-O:

[0102]

[0103] Pa-O;

[0104] ;

[0105] Pb-O;

[0106] ;

[0107] Pc-O.

[0108] As an optional embodiment, n is an integer between 2~8, for example, it can be 2, 3, 4, 5, 6, 7, 8.

[0109] As an optional embodiment, m is an integer between 2~6, for example, it can be 2, 3, 4, 5, 6.

[0110] As an optional embodiment, step (2) specifically includes:

[0111] The intermediate P is controlled at the third stage temperature, and a polymerization inhibitor and a catalyst are added for dissolution. After dissolution, 3-glycidyl ether oxypropyl triethoxysilane is added dropwise, and a grafting reaction is carried out at the third stage temperature to obtain the intermediate P-O.

[0112] As an optional embodiment, the molar ratio of the unsaturated dibasic acid and 3-glycidyloxypropyl triethoxysilane is 1: (0.12-0.45), specifically but not limitedly, 1:0.12, 1:0.14, 1:0.16, 1:0.18, 1:0.2, 1:0.22, 1:0.24, 1:0.26, 1:0.28, 1:0.3, 1:0.32, 1:0.34, 1:0.36, 1:0.38, 1:0.4, 1:0.42, 1:0.44 or 1:0.45, etc.

[0113] As an optional embodiment, in step (2), the third-stage temperature is 85-95℃, specifically but not limitedly, 85℃, 86℃, 87℃, 88℃, 89℃, 90℃, 91℃, 92℃, 93℃, 94℃ or 95℃, etc.

[0114] As an optional embodiment, in step (2), the time of the grafting reaction is 3-5 h, specifically but not limitedly, 3 h, 3.2 h, 3.4 h, 3.5 h, 3.6 h, 3.8 h, 4 h, 4.2 h, 4.4 h, 4.5 h, 4.6 h, 4.8 h, 5 h, etc.

[0115] As an optional embodiment, step (2) specifically comprises:

[0116] The temperature of the intermediate P is controlled at the third-stage temperature, and a small amount of polymerization inhibitor and catalyst is added into the round-bottom flask for dissolution, and after the dissolution is completed, 3-glycidyloxypropyl triethoxysilane is slowly added dropwise through a constant-pressure funnel for a modification reaction for 3-5 h, to obtain the intermediate P-O.

[0117] As an optional embodiment, the photosensitive resin P-O-S in step (3) comprises any one or a combination of at least two of the photosensitive resins represented by the following formulas Pa-O-S-Pc-O-S:

[0118] ;

[0119] Formula Pa-O-S;

[0120] ;

[0121] Formula Pb-O-S;

[0122] ;

[0123] Formula Pc-O-S;

[0124] wherein Ra, Rb and Rc are each independently selected from , represents the linking site of the group;

[0125] M1, M2, M3, M4 are each independently selected from -H or -OH, and the M1, M2, M3, M4 are not simultaneously selected from -H.

[0126] As an optional implementation, step (3) specifically comprises:

[0127] The intermediate P-O is controlled at the fourth stage temperature, and a polymerization inhibitor and a catalyst are dissolved; after dissolution, an organic solution of the acid anhydride compound is added dropwise, and the reaction is carried out at the fourth stage temperature to obtain the photosensitive resin P-O-S.

[0128] As an optional implementation, the structure of the acid anhydride compound is as shown in the following formula A:

[0129] ;

[0130] Formula A

[0131] M1, M2, M3, M4 are each independently selected from -H or -OH, and the M1, M2, M3, M4 are not simultaneously selected from -H.

[0132] As an optional implementation, the molar ratio of the unsaturated dibasic acid and the acid anhydride compound and the acid anhydride compound is 1:(0.8~1.2), and specifically but not limitedly, 1:0.80, 1:0.82, 1:0.84, 1:0.86, 1:0.88, 1:0.9, 1:0.92, 1:0.94, 1:0.96, 1:0.98, 1:1, 1:1.02, 1:1.04, 1:1.06, 1:1.08, 1:1.1, 1:1.12, 1:1.14, 1:1.16, 1:1.18 or 1:1.2, etc.

[0133] As an optional implementation, in step (3), the fourth stage temperature is 75~85℃, and specifically but not limitedly, 75℃, 76℃, 77℃, 78℃, 79℃, 80℃, 81℃, 82℃, 83℃, 84℃ or 85℃, etc.

[0134] As an optional implementation, in step (3), the reaction stopping criterion is that when the difference between the measured value of the photosensitive resin P-O-S and the theoretical acid value is ≤5 mgKOH / g, the reaction is stopped, and specifically but not limitedly, 5 mgKOH / g, 4.5 mgKOH / g, 4 mgKOH / g, 3.5 mgKOH / g, 3 mgKOH / g, 2.5 mgKOH / g, 2 mgKOH / g, 1.5 mgKOH / g, 1 mgKOH / g, etc.

[0135] As an optional implementation, step (3) specifically includes:

[0136] The reaction solution of intermediate PO was maintained at the fourth stage temperature, and a certain amount of polymerization inhibitor and catalyst were added. Then, a pre-dissolved acid anhydride compound was slowly added dropwise using a constant pressure funnel. After the addition was completed, the acid value was measured every half hour until the difference between the measured acid values ​​of the last two samples was less than or equal to 5 mgKOH / g. The reaction was then stopped, and some organic solvent was removed by vacuum distillation to obtain the photosensitive resin POS product.

[0137] As an optional implementation, in steps (1) to (3), the organic solvent includes any one or a combination of at least two of ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, or dipropylene glycol methyl ether acetate.

[0138] As an optional implementation, in steps (1) to (3), the polymerization inhibitor includes p-hydroxyanisole and / or hydroquinone.

[0139] As an optional implementation, in steps (1) to (3), the amount of the polymerization inhibitor is independently 0.1 to 0.6% of the mass of the o-crestyrene epoxy resin, specifically but not limited to 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, etc.

[0140] As an optional implementation, in steps (1) to (3), the catalyst includes N,N -Dimethylbenzylamine, N,N - Any one or a combination of at least two of dimethylaniline, triethylamine, or triphenylphosphine.

[0141] As an optional implementation, in steps (1) to (3), the amount of the catalyst is independently 0.4 to 1.2% of the mass of the o-crestyrene epoxy resin, specifically but not limited to 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, etc.

[0142] In a second aspect, the present invention provides a photosensitive resin, which is prepared by the photosensitive resin preparation method described in the first aspect.

[0143] Thirdly, the present invention provides an application of the photosensitive resin as described in the second aspect in the preparation of photosensitive paste.

[0144] As an optional embodiment, the photosensitive paste comprises any one of photosensitive silver paste, photosensitive silver-coated copper paste or photosensitive ceramic paste.

[0145] The application is further illustrated by the following examples. Unless otherwise specified, the materials in the examples are prepared according to the existing methods or directly purchased from the market.

[0146] Example 1

[0147] This example provides a photosensitive resin P a1 -O-S1, the photosensitive resin P a1 The synthesis process of the photosensitive resin P

[0148] (1) Preparation of intermediate P a1

[0149] A four-necked round-bottom flask equipped with a mechanical stirring paddle, a thermometer, a reflux condenser and a thermometer was charged with diethylene glycol methyl ether acetate and o-cresol formaldehyde epoxy resin NPCN-702 in sequence, and was heated to 75°C under stirring at a speed of 200 rpm / min until complete dissolution. After complete dissolution, 0.3% of p-hydroxyanisole and 1% of N,N dimethylbenzylamine relative to the mass of the o-cresol formaldehyde epoxy resin were added to the round-bottom flask for complete dissolution under stirring. After complete dissolution, the temperature was increased to 100°C, and a pre-dissolved solution of itaconic acid (with a molar ratio of itaconic acid to epoxy groups in the o-cresol formaldehyde epoxy resin of 1:1) was slowly added dropwise through a constant-pressure funnel at a temperature of 100°C. The addition was completed within 1 h, and the reaction was maintained at a temperature of 100°C for a period of time. The acid value was tested every half hour, and the reaction was stopped when the difference between the measured value and the theoretical acid value was ≤5 mgKOH / g, thereby obtaining the intermediate P a1 ;

[0150] (2) Preparation of intermediate P a1 -O

[0151] The temperature of the intermediate P a1 prepared in step (1) was controlled at 90°C, and a small amount of p-hydroxyanisole (0.2% relative to the mass of the o-cresol formaldehyde epoxy resin) and N,N dimethylbenzylamine (0.8% relative to the mass of the o-cresol formaldehyde epoxy resin) were added to the round-bottom flask for dissolution. After complete dissolution, a modification reaction was performed by slowly adding 3-glycidyloxypropyl triethoxysilane with a molar amount of 0.15 relative to itaconic acid through a constant-pressure funnel for 4 h, thereby obtaining the intermediate P a1 -O.

[0152] (3) Preparation of photosensitive resin P a1 -O-S1

[0153] The intermediate P obtained in step (2) a1 The reaction solution was maintained at 80°C, and a small amount of hydroxyanisole (0.1% relative to the mass of o-cresyl epoxy resin) was added. N,N - Dimethylbenzylamine (0.6% relative to o-cresyl formaldehyde epoxy resin) was then slowly added dropwise using a constant pressure funnel. A pre-dissolved 3-hydroxyphthalic anhydride solution (3-hydroxyphthalic anhydride molar amount relative to itaconic acid was 1.2) was added dropwise. After the addition was completed, samples were taken every half hour to measure the acid value. The reaction was stopped when the difference between the measured acid values ​​of the last two samples was ≤5 mgKOH / g. The organic solvent was then removed by vacuum distillation to obtain the photosensitive resin Pa1-O-S1.

[0154] The structural formula of the photosensitive resin Pa1-O-S1 is shown below:

[0155] ;

[0156] Where Ra is .

[0157] Example 2

[0158] This embodiment provides a photosensitive resin P a1 -O-S2, the photosensitive resin P a1 The synthesis process of -O-S2 is as follows:

[0159] (1) Preparation of intermediate P a1

[0160] Diethylene glycol methyl ether acetate and o-cresyl formaldehyde epoxy resin NPCN-702 were added sequentially to a four-necked round-bottom flask equipped with a mechanical stirrer, thermometer, reflux condenser, and thermometer. The mixture was heated to 75°C at a stirring speed of 200 rpm / min until fully dissolved. After complete dissolution, 0.3% p-hydroxyanisole and 1% p-hydroxyanisole (based on the mass of o-cresyl formaldehyde epoxy resin) were added to the round-bottom flask. N,N - Dissolve dimethylbenzylamine thoroughly by stirring. After dissolution, continue heating to 100℃. Once the temperature stabilizes, slowly add a pre-dissolved hot solution of itaconic acid (in which the molar ratio of itaconic acid to the epoxy group in o-cresyl formaldehyde epoxy resin is 1:1) dropwise using a constant pressure funnel. Complete the addition within 1 hour and maintain the temperature at 100℃ for a period of time. Take samples every half hour to test the acid value. Stop the reaction when the difference between the measured value and the theoretical acid value is ≤5 mgKOH / g, thus obtaining intermediate P. a1 ;

[0161] (2) Preparation of intermediate P a1 -O

[0162] The intermediate P obtained in step (1)a1 The temperature was controlled at 90℃, and a small amount of p-hydroxyanisole (0.2% relative to the mass of o-cresyl epoxy resin) was added to the round-bottom flask. N,N - Dimethylbenzylamine (0.8% relative to the mass of o-cresolaldehyde epoxy resin) was dissolved, and after dissolution, 3-glycidyl etheroxypropyltriethoxysilane (0.15 molar amount relative to itaconic acid) was slowly added dropwise through a constant pressure funnel to carry out the modification reaction for 4 h, thus obtaining intermediate P. a1 -O;

[0163] (3) Preparation of photosensitive resin P a1 -O-S2

[0164] The reaction solution of intermediate Pa1-O was maintained at 80°C, and a small amount of hydroxyanisole (0.1% relative to the mass of o-cresyl epoxy resin) was added. N,N - Dimethylbenzylamine (0.6% relative to o-cresyl formaldehyde epoxy resin) was then slowly added dropwise using a constant pressure funnel. A pre-dissolved 3,6-dihydroxyphthalic anhydride solution (3,6-dihydroxyphthalic anhydride molar amount relative to itaconic acid was 1.2) was added dropwise. After the addition was completed, samples were taken every half hour to measure the acid value. The reaction was stopped when the difference between the measured acid values ​​of the last two samples was less than or equal to 5 mgKOH / g. The organic solvent was then removed by vacuum distillation to obtain the photosensitive resin Pa1-O-S2.

[0165] The structural formula of the photosensitive resin Pa1-O-S2 is shown below:

[0166] ;

[0167] Where Ra is .

[0168] Example 3

[0169] This embodiment provides a photosensitive resin P b1 -O-S1, the photosensitive resin P b1 The synthesis process of -O-S1 is as follows:

[0170] (1) Preparation of intermediate P b1

[0171] Ethylene glycol methyl ether acetate and o-cresyl formaldehyde epoxy resin NPCN-702 were added sequentially to a four-necked round-bottom flask equipped with a mechanical stirrer, thermometer, reflux condenser, and thermometer. The mixture was heated to 75°C at a stirring speed of 200 rpm / min until fully dissolved. After complete dissolution, 0.3% p-hydroxyanisole and 1% p-hydroxyanisole (based on the mass of the o-cresyl formaldehyde epoxy resin) were added to the round-bottom flask. N,N- Dissolve dimethylbenzylamine thoroughly by stirring. After dissolution, continue heating to 100℃. Once the temperature stabilizes, slowly add a pre-dissolved hot maleic acid solution (in which the molar ratio of maleic acid to the epoxy group in o-cresyl formaldehyde epoxy resin is 1:1) dropwise using a constant pressure funnel. Complete the addition within 1 hour and maintain the reaction at 100℃ for a period of time. Samples are taken every half hour to test the acid value. The reaction is stopped when the difference between the measured value and the theoretical acid value is less than or equal to 5 mgKOH / g, yielding intermediate P. b1 ;

[0172] (2) Preparation of intermediate P b1 -O

[0173] The intermediate P obtained in step (1) b1 The temperature was controlled at 90℃, and a small amount of p-hydroxyanisole (0.2% relative to the mass of o-cresyl epoxy resin) was added to the round-bottom flask. N,N Dimethylbenzylamine (0.8% relative to the mass of o-cresolaldehyde epoxy resin) was dissolved, and after dissolution, 3-glycidyl etheroxypropyltriethoxysilane (0.15 molar amount relative to maleic acid) was slowly added dropwise through a constant pressure funnel to carry out the modification reaction for 4 h, thereby obtaining intermediate P. b1 -O;

[0174] (3) Preparation of photosensitive resin P b1 -O-S1

[0175] The intermediate P obtained in step (2) b1 The reaction solution was maintained at 80°C, and a small amount of hydroxyanisole (0.1% relative to the mass of o-cresyl epoxy resin) was added. N,N - Dimethylbenzylamine (0.6% relative to o-cresyl formaldehyde epoxy resin) was then slowly added dropwise using a constant pressure funnel. A pre-dissolved 3-hydroxyphthalic anhydride solution (3-hydroxyphthalic anhydride molar amount relative to itaconic acid was 1.2) was added dropwise. After the addition was completed, samples were taken every half hour to measure the acid value. The reaction was stopped when the difference between the measured acid values ​​of the last two samples was ≤5 mgKOH / g. The organic solvent was then removed by vacuum distillation to obtain the photosensitive resin Pb1-O-S1.

[0176] The structural formula of the photosensitive resin Pb1-O-S1 is shown below:

[0177] ;

[0178] Among them, R b for .

[0179] Example 4

[0180] This embodiment provides a photosensitive resin Pb2 -O-S3, the photosensitive resin P b2 The synthesis process of -O-S3 is as follows:

[0181] (1) Preparation of intermediate P b2

[0182] Diethylene glycol methyl ether acetate and o-cresyl formaldehyde epoxy resin EOCN6650 were added sequentially to a four-necked round-bottom flask equipped with a mechanical stirrer, thermometer, reflux condenser, and thermometer. The mixture was heated to 75°C at a stirring speed of 200 rpm / min until fully dissolved. After complete dissolution, 0.3% p-hydroxyanisole and 1% p-hydroxyanisole (based on the mass of o-cresyl formaldehyde epoxy resin) were added to the round-bottom flask. N,N - Dissolve dimethylbenzylamine thoroughly by stirring. After dissolution, continue heating to 100℃. Once the temperature stabilizes, slowly add a pre-dissolved hot maleic acid solution (in which the molar ratio of maleic acid to the epoxy group in o-cresyl formaldehyde epoxy resin is 1:1) dropwise using a constant pressure funnel. Complete the addition within 1 hour and maintain the reaction at 100℃ for a period of time. Samples are taken every half hour to test the acid value. The reaction is stopped when the difference between the measured value and the theoretical acid value is less than or equal to 5 mgKOH / g, yielding intermediate P. b2 ;

[0183] (2) Preparation of intermediate P b2 -O

[0184] The intermediate P obtained in step (1) b2 The temperature was controlled at 90℃, and a small amount of p-hydroxyanisole polymerization inhibitor (0.2% relative to the mass of o-cresyl epoxy resin) was added to the round-bottom flask. N,N The dimethylbenzylamine catalyst (0.8% relative to the mass of o-cresolaldehyde epoxy resin) was dissolved. After dissolution, 0.15 molar amount of 3-glycidyl etheroxypropyltriethoxysilane relative to maleic acid was slowly added dropwise through a constant pressure funnel for 4 h to carry out the modification reaction, thus obtaining intermediate P. b2 -O;

[0185] (3) Preparation of photosensitive resin P b2 -O-S3

[0186] The intermediate P obtained in step (2) b2 The reaction solution was maintained at 80°C, and a small amount of hydroxyanisole polymerization inhibitor (0.2% relative to the mass of o-cresyl epoxy resin) was added. N,N- Dimethylbenzylamine catalyst (0.8% relative to o-cresol epoxy resin) was then slowly added dropwise using a constant pressure funnel. A pre-dissolved 4-hydroxyphthalic anhydride solution (4-hydroxyphthalic anhydride molar amount relative to itaconic acid was 1.2) was added dropwise. After the addition was completed, samples were taken every half hour to measure the acid value. The reaction was stopped when the difference between the measured acid values ​​of the last two samples was less than or equal to 5 mgKOH / g. The organic solvent was then removed by vacuum distillation to obtain the photosensitive resin Pb2-O-S3.

[0187] The structural formula of the photosensitive resin Pb2-O-S3 is shown below:

[0188] ;

[0189] Among them, R b for .

[0190] Example 5

[0191] This embodiment provides a photosensitive resin P c1 -O-S1, the photosensitive resin P c1 The synthesis process of -O-S1 is as follows:

[0192] (1) Preparation of intermediate P c1

[0193] Diethylene glycol methyl ether acetate and o-cresyl formaldehyde epoxy resin NPCN-702 were added sequentially to a four-necked round-bottom flask equipped with a mechanical stirrer, thermometer, reflux condenser, and thermometer. The mixture was heated to 75°C at a stirring speed of 200 rpm / min until fully dissolved. After complete dissolution, 0.3% p-hydroxyanisole and 1% p-hydroxyanisole (based on the mass of o-cresyl formaldehyde epoxy resin) were added to the round-bottom flask respectively. N,N - Dissolve dimethylbenzylamine thoroughly by stirring. After dissolution, continue heating to 100℃. Once the temperature stabilizes, slowly add the pre-dissolved hot pentene acid solution (in which the molar ratio of pentene acid to the epoxy group in o-cresyl formaldehyde epoxy resin is 1:1) dropwise using a constant pressure funnel. Complete the addition within 1 hour and maintain the temperature at 100℃ for a period of time. Take samples every half hour to test the acid value. Stop the reaction when the difference between the measured value and the theoretical acid value is less than or equal to 5 mgKOH / g, thus obtaining intermediate P. c1 ;

[0194] (2) Preparation of intermediate P c1 -O

[0195] The intermediate P obtained in step (1) c1 The temperature was controlled at 90℃, and a small amount of p-hydroxyanisole (0.2% relative to the mass of o-cresyl epoxy resin) was added to the round-bottom flask.N,N - dimethylbenzylamine (0.8% relative to the mass of the o-cresol novolac epoxy resin) is dissolved, and after the dissolution is complete, a modification reaction is performed for 4 h by slowly adding 3-glycidyloxypropyltriethoxysilane (0.15 relative to the molar amount of glutaconic acid) using a constant pressure funnel, to obtain the intermediate P c1 -O;

[0196] (3) Preparation of the photosensitive resin P c1 -O-S1

[0197] The intermediate P c1 -O prepared in step (2) is maintained at 80°C in the reaction solution, and a small amount of hydroxyanisole (0.1% relative to the mass of the o-cresol novolac epoxy resin) and N,N - dimethylbenzylamine (0.6% relative to the mass of the o-cresol novolac epoxy resin) are continuously added, and then a previously dissolved 3-hydroxyphthalic anhydride solution (3-hydroxyphthalic anhydride is 1.2 relative to the molar amount of glutaconic acid) is slowly added using a constant pressure funnel, and after the addition is complete, the acid value is measured every half hour until the difference between the measured acid values of the last two samples is less than or equal to 5 mgKOH / g, at which point the reaction is stopped, and a portion of the organic solvent is removed using reduced pressure distillation, to obtain the photosensitive resin Pc1-O-S1.

[0198] The structural formula of the photosensitive resin Pc1-O-S1 is as follows:

[0199]

[0200] wherein R c is .

[0201] Example 6

[0202] This example provides a photosensitive resin P c2 -O-S2, and a synthesis process of the photosensitive resin P c2 -O-S2 is as follows:

[0203] (1) Preparation of the intermediate P c2

[0204] A four-necked round-bottom flask equipped with a mechanical stirring paddle, a thermometer, a reflux condenser, and a thermometer is sequentially charged with diethylene glycol methyl ether acetate and an o-cresol novolac epoxy resin EOCN6650, and is warmed to 75°C under a stirring speed of 200 rpm / min to fully dissolve, and after the dissolution is complete, the round-bottom flask is further charged with 0.3% of hydroxyanisole and 1% of N,N- Dissolve dimethylbenzylamine thoroughly by stirring. After dissolution, continue heating to 100℃. Once the temperature stabilizes, slowly add the pre-dissolved hot pentene acid solution (in which the molar ratio of pentene acid to the epoxy group in o-cresyl formaldehyde epoxy resin is 1:1) dropwise using a constant pressure funnel. Complete the addition within 1 hour and maintain the temperature at 100℃ for a period of time. Take samples every half hour to test the acid value. Stop the reaction when the difference between the measured value and the theoretical acid value is less than or equal to 5 mg KOH / g, thus obtaining intermediate P. c2 ;

[0205] (2) Preparation of intermediate P c2 -O

[0206] The intermediate P obtained in step (1) c2 The temperature was controlled at 90℃, and a small amount of p-hydroxyanisole (0.2% of the mass of o-cresyl epoxy resin) was added to the round-bottom flask. N,N - Dimethylbenzylamine (0.8% relative to the mass of o-cresyl formaldehyde epoxy resin) was dissolved, and after dissolution, 0.15 molar amount of 3-glycidyl etheroxypropyltriethoxysilane relative to pentene edodesic acid was slowly added dropwise through a constant pressure funnel to carry out the modification reaction for 4 h, thus obtaining intermediate P. c2 -O;

[0207] (3) Preparation of photosensitive resin P c2 -O-S2

[0208] The intermediate P obtained in step (2) c2 The reaction solution was maintained at 80°C, and a small amount of hydroxyanisole (0.1% relative to the mass of o-cresyl epoxy resin) was added. N,N - Dimethylbenzylamine (0.6% relative to o-crestyral epoxy resin) was then slowly added dropwise using a constant pressure funnel. A pre-dissolved 3,6-dihydroxyphthalic anhydride solution (3,6-dihydroxyphthalic anhydride molar amount relative to pentenediaic acid was 1.2) was added dropwise. After the addition was completed, samples were taken every half hour to measure the acid value. The reaction was stopped when the difference between the measured acid values ​​of the last two samples was less than or equal to 5 mgKOH / g. The organic solvent was then removed by vacuum distillation to obtain the photosensitive resin Pc2-O-S2.

[0209] The structural formula of the photosensitive resin Pc2-O-S2 is shown below:

[0210]

[0211] Among them, R c for .

[0212] Comparative Example 1

[0213] The present comparative example provides a photosensitive resin P a1 The synthesis process of the photosensitive resin P a1 is as follows:

[0214] A four-necked round-bottom flask equipped with a mechanical stirring paddle, a thermometer, a reflux condenser, and a thermometer was sequentially charged with diethylene glycol methyl ether acetate and o-cresol formaldehyde epoxy resin NPCN-702, and was heated to 75°C under stirring at a speed of 200 rpm / min until fully dissolved. After complete dissolution, 0.3% of p-hydroxyanisole and 1% of N,N-dimethylbenzylamine, relative to the mass of the o-cresol formaldehyde epoxy resin, were added to the round-bottom flask, respectively, and were fully stirred and dissolved. After complete dissolution, the temperature was increased to 100°C, and a pre-dissolved solution of itaconic acid (with a molar ratio of itaconic acid to epoxy groups in the o-cresol formaldehyde epoxy resin of 1:1) was slowly added dropwise through a constant-pressure funnel at a rate of 1 h, and was reacted at a temperature of 100°C for a period of time. The reaction was stopped when the difference between the measured acid value and the theoretical acid value was less than or equal to 5 mgKOH / g, and was sampled every half hour. Then, a portion of the organic solvent was removed by vacuum distillation to obtain the photosensitive resin P a1 .

[0215] The photosensitive resin P a1 has the following structural formula:

[0216] .

[0217] Comparative Example 2

[0218] The present comparative example provides a photosensitive resin P a1 -O, and the synthesis process of the photosensitive resin P a1 -O is as follows:

[0219] (1) Preparation of intermediate P a1

[0220] A four-necked round-bottom flask equipped with a mechanical stirring paddle, a thermometer, a reflux condenser, and a thermometer was sequentially charged with diethylene glycol methyl ether acetate and o-cresol formaldehyde epoxy resin NPCN-702, and was heated to 75°C under stirring at a speed of 200 rpm / min until fully dissolved. After complete dissolution, 0.3% of p-hydroxyanisole and 1% of N,N-dimethylbenzylamine, relative to the mass of the o-cresol formaldehyde epoxy resin, were added to the round-bottom flask, respectively, and were fully stirred and dissolved. After complete dissolution, the temperature was increased to 100°C, and a pre-dissolved solution of itaconic acid (with a molar ratio of itaconic acid to epoxy groups in the o-cresol formaldehyde epoxy resin of 1:1) was slowly added dropwise through a constant-pressure funnel at a rate of 1 h, and was reacted at a temperature of 100°C for a period of time. The reaction was stopped when the difference between the measured acid value and the theoretical acid value was less than or equal to 5 mgKOH / g, and was sampled every half hour. Then, a portion of the organic solvent was removed by vacuum distillation to obtain the photosensitive resin P N,N- Dissolve dimethylbenzylamine thoroughly by stirring. After dissolution, continue heating to 100℃. Once the temperature stabilizes, slowly add a pre-dissolved hot solution of itaconic acid (in which the molar ratio of itaconic acid to the epoxy group in o-cresyl formaldehyde epoxy resin is 1:1) dropwise using a constant pressure funnel. Complete the addition within 1 hour and maintain the reaction at 100℃ for a period of time. Samples are taken every half hour to test the acid value. The reaction is stopped when the difference between the measured value and the theoretical acid value is less than or equal to 5 mgKOH / g, yielding intermediate P. a1 ;

[0221] (2) Preparation of photosensitive resin P a1 -O

[0222] The intermediate P obtained in step (1) a1 The temperature was controlled at 90℃, and a small amount of p-hydroxyanisole (0.2% relative to the mass of o-cresyl epoxy resin) was added to the round-bottom flask. N,N Dimethylbenzylamine (0.8% relative to o-cresolaldehyde epoxy resin) was dissolved, and after that, 3-glycidyl etheroxypropyltriethoxysilane (0.15 molar amount relative to itaconic acid) was slowly added dropwise through a constant pressure funnel for 4 hours to carry out the modification reaction, thus obtaining photosensitive resin P. a1 -O.

[0223] The photosensitive resin P a1 The structural formula for -O is shown below:

[0224] .

[0225] Comparative Example 3

[0226] This comparative example provides a photosensitive resin P b1 -S1, the photosensitive resin P b1 The synthesis process of -S1 is as follows:

[0227] (1) Preparation of intermediate P b1

[0228] Diethylene glycol methyl ether acetate and o-cresyl formaldehyde epoxy resin NPCN-702 were added sequentially to a four-necked round-bottom flask equipped with a mechanical stirrer, thermometer, reflux condenser, and thermometer. The mixture was heated to 75°C at a stirring speed of 200 rpm / min until fully dissolved. After complete dissolution, 0.3% p-hydroxyanisole and 1% p-hydroxyanisole (based on the mass of o-cresyl formaldehyde epoxy resin) were added to the round-bottom flask. N,N- dimethylbenzylamine was dissolved completely under sufficient stirring, and after the dissolution was completed, the temperature was increased to 100°C, and after the temperature was stabilized, a previously dissolved hot solution of maleic acid (in which the molar ratio of maleic acid to epoxy groups in the o-cresol formaldehyde epoxy resin was 1 : 1) was slowly added dropwise using a constant pressure funnel, and the addition was completed within 1 hour, and the reaction was maintained at 100°C for a period of time, and every half hour, a sample was taken to test the acid value, and when the difference between the measured value and the theoretical acid value was less than or equal to 5 mgKOH / g, the reaction was stopped, and the intermediate P was obtained a1 ;

[0229] (2) Preparation of the photosensitive resin P b1 -S1

[0230] The reaction solution of the intermediate P a1 was maintained at 80°C, and a small amount of p-hydroxyanisole (0.2% relative to the mass of the o-cresol formaldehyde epoxy resin) and N,N dimethylbenzylamine (0.8% relative to the mass of the o-cresol formaldehyde epoxy resin) were continuously added, and then a previously dissolved solution of 3-hydroxyphthalic anhydride (the molar amount of 3-hydroxyphthalic anhydride relative to maleic acid was 1.2) was slowly added dropwise using a constant pressure funnel, and after the addition was completed, every half hour, a sample was taken to test the acid value, and until the difference between the measured acid values of the last two samples was less than or equal to 5 mgKOH / g, the reaction was stopped, and then, using a reduced pressure distillation method, part of the organic solvent was removed, and the photosensitive resin P b1 -S1 was obtained.

[0231] The structural formula of the photosensitive resin P b1 -S1 is as follows:

[0232] .

[0233] Comparative Example 4

[0234] This comparative example provides a photosensitive resin P a1 -O-S0, and the synthesis process of the photosensitive resin P a1 -O-S0 is as follows:

[0235] (1) Preparation of the intermediate P a1

[0236] A four-necked round-bottom flask equipped with a mechanical stirring paddle, a thermometer, a reflux condenser, and a thermometer was sequentially charged with diethylene glycol methyl ether acetate and o-cresol formaldehyde epoxy resin NPCN-702, and under a stirring speed of 200 rpm / min, the temperature was increased to 75°C for complete dissolution, and after the dissolution was complete, the round-bottom flask was charged with 0.3% of p-hydroxyanisole and 1% of N,N- Dissolve dimethylbenzylamine thoroughly by stirring. After dissolution, continue heating to 100℃. Once the temperature stabilizes, slowly add a pre-dissolved hot solution of itaconic acid (in which the molar ratio of itaconic acid to the epoxy group in o-cresyl formaldehyde epoxy resin is 1:1) dropwise using a constant pressure funnel. Complete the addition within 1 hour and maintain the temperature at 100℃ for a period of time. Take samples every half hour to test the acid value. Stop the reaction when the difference between the measured value and the theoretical acid value is ≤5 mgKOH / g, thus obtaining intermediate P. a1 ;

[0237] (2) Preparation of intermediate P a1 -O

[0238] The intermediate P obtained in step (1) a1 The temperature was controlled at 90℃, and a small amount of p-hydroxyanisole (0.2% relative to the mass of o-cresyl epoxy resin) was added to the round-bottom flask. N,N - Dimethylbenzylamine (0.8% relative to the mass of o-cresolaldehyde epoxy resin) was dissolved, and after dissolution, 3-glycidyl etheroxypropyltriethoxysilane (0.15 molar amount relative to itaconic acid) was slowly added dropwise through a constant pressure funnel to carry out the modification reaction for 4 h, thus obtaining intermediate P. a1 -O;

[0239] (3) Preparation of photosensitive resin P a1 -O-S0

[0240] The intermediate P obtained in step (2) a1 The reaction solution was maintained at 80°C, and a small amount of hydroxyanisole (0.1% relative to the mass of o-cresyl epoxy resin) was added. N,N - Dimethylbenzylamine (0.6% relative to o-cresyl epoxy resin by mass) was then slowly added dropwise using a constant pressure funnel. A pre-dissolved phthalic anhydride solution (1.2 molar amount of phthalic anhydride relative to itaconic acid) was added dropwise every half hour after the addition was completed. The reaction was stopped when the difference between the measured acid values ​​of the last two samples was less than or equal to 5 mgKOH / g. The organic solvent was then removed by vacuum distillation to obtain the photosensitive resin Pa1-O-S0.

[0241] The structural formula of the photosensitive resin Pa1-O-S0 is shown below:

[0242] ;

[0243] Where Ra is .

[0244] Comparative Example 5

[0245] Commercially available modified o-cresol acrylic resin B-196S (produced by Guangdong Boxing New Material Technology Co., Ltd.).

[0246] Test Example

[0247] Test sample: photosensitive resin provided by Examples 1-6 and photosensitive resin provided by Comparative Examples 1-5;

[0248] Test method:

[0249] (1) Preparation of photosensitive composition: 42 parts of photosensitive resin corresponding to the sample, 0.5 parts of 2-isopropylthioxanthone, 2 parts of 2-methyl-1-(4-methylthiophenyl)-2-morpholine-1-propanone, 46 parts of diethylene glycol methyl ether acetate, 3 parts of 1,6-hexanediol diacrylate, and 6 parts of dipentaerythritol hexaacrylate were dissolved and compounded to prepare a photosensitive composition.

[0250] (2) Process test of photosensitive composition:

[0251] (i) Construction substrate: 50mm*50mm alumina ceramic substrate, 50mm*50mm ITO substrate, 100mm*100mm ITO / PET film; (ii) Gluing: 500rpm*5sec+2500rpm*30sec; (iii) Pre-baking: hot plate, 60℃@10min; (iv) Exposure: i-line UV lithography machine, 150 mj / cm 2 ; (v) Development: 0.6% Na2CO3 developer, development time 23±2℃; (vi) Post-development rinsing: high-pressure water rinsing for 3min; (vii) Post-development drying: high-purity nitrogen blowing.

[0252] (3) Adhesion after curing: the photosensitive composition after curing was tested according to the standard ASTM D3359; development performance: the resolution, line edge, and whether the line was broken of the substrate after development and drying were observed by optical microscope.

[0253] The specific test results are shown in Table 1 below:

[0254] Table 1

[0255]

[0256] As can be seen from Table 1, the photosensitive compositions prepared in Examples 1-6 have good adhesion and development performance, while Comparative Example 1 without the flexible siloxane segment and the hydroxyl phthalic anhydride structure has poor adhesion and development performance; similarly, Comparative Example 2 without the hydroxyl phthalic anhydride structure and Comparative Example 3 without the flexible siloxane segment also cannot exhibit good curing adhesion or (and) development performance; and Comparative Example 4 in which the hydroxyl phthalic anhydride structure is replaced by a non-hydroxyl phthalic anhydride structure also cannot achieve the expected development performance results; and Comparative Example 5 prepared using a commercially available photosensitive modified o-cresol acrylic resin also has poor curing adhesion and development performance due to the reasons such as the strong brittleness of the resin skeleton, insufficient anti-swelling of the exposed area after curing, and insufficient density of carboxyl or phenolic hydroxyl groups in the resin.

[0257] Finally, it should be noted that: the above examples are only used to illustrate the technical solutions of the present application, and not to limit it; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that: it can still modify the technical solutions recorded in the foregoing examples, or make equivalent replacement for part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A method for producing a photosensitive resin, characterized by, The preparation method of the photosensitive resin comprises: (1) in the presence of a polymerization inhibitor and a catalyst, polymerizing o-cresol formaldehyde epoxy resin and unsaturated dibasic acid in an organic solvent to obtain an intermediate P; (2) in the presence of a polymerization inhibitor and a catalyst, grafting the intermediate P and 3-glycidyl ether oxypropyl triethoxysilane in an organic solvent to obtain an intermediate P-O; (3) in the presence of a polymerization inhibitor and a catalyst, reacting the intermediate P-O and an acid anhydride compound in an organic solvent to obtain the photosensitive resin P-O-S; wherein the structure of the acid anhydride compound is shown in the following formula A: ； Formula A wherein M1, M2, M3, M4 are each independently selected from -H or -OH, and the M1, M2, M3, M4 are not simultaneously selected from -H.

2. The method for preparing the photosensitive resin according to claim 1, characterized in that, In steps (1) and (2), the intermediate P comprises any one or a combination of at least two of the intermediates shown in the following formulas Pa~Pc: ； Formula Pa; ； Formula Pb; Formula Pc; wherein x is an integer between 4~14.

3. The method for preparing the photosensitive resin according to claim 1, characterized in that, Step (1) specifically comprises: Mixing the organic solvent and o-cresol formaldehyde epoxy resin, stirring and heating to a first stage temperature for dissolution; after dissolution, adding a polymerization inhibitor and a catalyst, stirring and dissolving and heating to a second stage temperature; after the temperature is stable, adding an organic solution of unsaturated dibasic acid dropwise, and maintaining the second stage temperature for polymerization reaction to obtain the intermediate P.

4. The method of producing a photosensitive resin according to claim 1 or 3, characterized by, In step (1), the molar ratio of the unsaturated dibasic acid to the epoxy group in the o-cresol formaldehyde epoxy resin is (0.85~1.2):

1.

5. The method of producing a photosensitive resin according to claim 1 or 3, characterized by, In step (1), the unsaturated dibasic acid comprises any one or a combination of at least two of methylene butanedioic acid, maleic acid or glutaconic acid.

6. The method for preparing the photosensitive resin according to claim 3, characterized in that, In step (1), the first stage temperature is 65~80℃.

7. The method for preparing the photosensitive resin according to claim 3, characterized in that, In step (1), the second stage temperature is 95~110℃.

8. The method for preparing the photosensitive resin according to claim 3, characterized in that, In step (1), the organic solution of the unsaturated dibasic acid is added dropwise within 1 h.

9. The method for preparing the photosensitive resin according to claim 3, characterized in that, In step (1), the reaction stops when the difference between the measured value of the intermediate P and the theoretical acid value is ≤5 mgKOH / g.

10. The method for preparing the photosensitive resin according to claim 1, characterized in that, In steps (2) and (3), the intermediate P-O comprises any one or a combination of at least two of the intermediates shown in the following formulas Pa-O~Pc-O: Pa-O; ； Pb-O; ； Pc-O; wherein n is an integer between 2~8, and m is an integer between 2~6.

11. The method for preparing the photosensitive resin according to claim 1, characterized in that, Step (2) specifically comprises: Controlling the intermediate P at a third stage temperature, adding a polymerization inhibitor and a catalyst for dissolution; after dissolution, adding 3-glycidyl ether oxypropyl triethoxysilane dropwise, and maintaining the third stage temperature for grafting reaction to obtain the intermediate P-O.

12. The method of producing a photosensitive resin according to claim 1 or 11, characterized by, The molar ratio of the unsaturated dibasic acid to 3-glycidyl ether oxypropyl triethoxysilane is 1:(0.12~0.45).

13. The method for preparing the photosensitive resin according to claim 11, characterized in that, In step (2), the third stage temperature is 85~95℃.

14. The method of producing a photosensitive resin according to claim 1 or 11, characterized by, In step (2), the grafting reaction time is 3~5 h.

15. The method for preparing the photosensitive resin according to claim 1, characterized in that, The photosensitive resin P-O-S in step (3) comprises any one or a combination of at least two of the photosensitive resins shown in the following formulas Pa-O-S~Pc-O-S: ； Formula Pa-O-S; ； Formula Pb-O-S; ； Formula Pc-O-S; wherein Ra, Rb, and Rc are each independently selected from " represents the point of attachment of the group;​ wherein M1, M2, M3, M4 are each independently selected from -H or -OH, and the M1, M2, M3, M4 are not simultaneously selected from -H.

16. The method for preparing the photosensitive resin according to claim 1, characterized in that, Step (3) specifically comprises: controlling the intermediate P-O at a fourth stage temperature, adding a polymerization inhibitor and a catalyst to dissolve; after dissolving, adding an organic solution of an acid anhydride compound dropwise, and maintaining the fourth stage temperature to react, to obtain the photosensitive resin P-O-S.

17. The method for preparing the photosensitive resin according to claim 1, characterized in that, The molar ratio of the unsaturated dibasic acid and the acid anhydride compound is 1:(0.8-1.2).

18. The method for preparing the photosensitive resin according to claim 16, characterized in that, In step (3), the fourth stage temperature is 75-85°C.

19. The method for preparing the photosensitive resin according to claim 16, characterized in that, In step (3), the reaction stops when the difference between the measured value of the photosensitive resin P-O-S and the theoretical acid value is ≤5 mgKOH / g.

20. The method for preparing the photosensitive resin according to claim 1, characterized in that, In steps (1)-(3), the organic solvent includes any one or a combination of at least two of ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, or dipropylene glycol methyl ether acetate.

21. The method for preparing the photosensitive resin according to claim 1, characterized in that, In steps (1)-(3), the polymerization inhibitor includes p-hydroxyanisole and / or hydroquinone.

22. The method for preparing the photosensitive resin according to claim 1, characterized in that, In steps (1)-(3), the amount of the polymerization inhibitor is independently 0.1-0.6% of the mass of the o-cresol formaldehyde epoxy resin.

23. The method for preparing the photosensitive resin according to claim 1, characterized in that, In steps (1) to (3), the catalyst comprises N,N - dimethylbenzylamine, N,N - any one of dimethylamine, diethylamine, triethylamine, or a combination of at least two of dimethylamine, diethylamine, triethylamine.

24. The method for preparing the photosensitive resin according to claim 1, characterized in that, In steps (1)-(3), the amount of the catalyst is independently 0.4-1.2% of the mass of the o-cresol formaldehyde epoxy resin.

25. A photosensitive resin, characterized by, The photosensitive resin is prepared by the method for preparing a photosensitive resin according to any one of claims 1-24.

26. Use of the photosensitive resin according to claim 25 in preparing a photosensitive paste; and / or the photosensitive paste includes any one of a photosensitive silver paste, a photosensitive silver-coated copper paste, or a photosensitive ceramic paste.

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