Photosensitive slurry composition

Abstract

The invention discloses a photosensitive slurry composition. The photosensitive slurry composition comprises an alkali-soluble polymer, an inorganic substance and a curing catalyst. The alkali-soluble polymer contains not less than 35 parts by mass of a polymerizable monomer having an aromatic group, the weight-average molecular weight of the polymerizable monomer is 1000-100000, and the molecular terminal of the polymerizable monomer has a specific functional group such as a carboxyl group, a hydroxyl group or an amino group; according to the composition, the pattern line width expansion phenomenon caused by light scattering of inorganic particles is effectively inhibited through the synergistic effect of all the components, especially the alkali-soluble polymer of a specific structure, and precise fine patterns can be formed. Meanwhile, according to the design, the adaptation of the slurry to a base material is remarkably improved, and good dispersity and storage stability of inorganic particles in a system are ensured. The photosensitive paste composition is particularly suitable for manufacturing high-performance electronic components having fine electrodes or resistance patterns by screen printing, exposure and development processes.

Description

Technical Field

[0001] This invention relates to the field of photosensitive material preparation technology, and specifically to a photosensitive paste composition. Background Technology

[0002] As electronic components continue to evolve towards miniaturization and high performance, higher demands are being placed on the micro-patterning of their internal electrodes, resistors, and other structures. In existing technologies, screen printing is widely used to create such patterns, but its precision is no longer sufficient to meet the ever-increasing demands for miniaturization. Therefore, photosensitive paste technology based on the principle of photoresist is gradually gaining attention. This technology involves applying the paste through screen printing, followed by exposure and development processes, enabling the formation of more refined patterns.

[0003] However, because photosensitive pastes typically contain a large number of inorganic particles, they easily cause scattering and random reflection of the irradiated light during exposure, resulting in the actual linewidth often exceeding the set value, i.e., pattern extension. This phenomenon is particularly pronounced when using pastes containing oxime ester initiators and forming thicker wiring patterns through irradiation with active energy rays such as ultraviolet light.

[0004] To suppress pattern expansion, existing technologies have proposed using acrylic resins with aromatic rings as alkali-soluble polymers (CN115079515A). While this method alleviates linewidth expansion to some extent, it introduces new problems such as decreased substrate adhesion and deterioration of inorganic particle dispersion. Additionally, attempts have been made to improve pattern accuracy by adding free radical scavengers (JP2024033515A), but this method easily leads to uneven curing of the exposed layer in the thickness direction, resulting in defects such as reduced substrate adhesion and pattern cracking.

[0005] Various photosensitive paste compositions have been attempted in the prior art. For example, prior art CN109564385B discloses a "photosensitive resin composition, cured product, interlayer insulating film, TFT active matrix substrate and image display device," which discloses a photosensitive paste composition comprising an alkali-soluble polymer, inorganic matter and a curing catalyst. However, the alkali-soluble polymer used in this patent is lacking in specific functional groups and molecular structure. Its technical solution mainly solves the basic composition problem, but does not conduct in-depth optimization to suppress the pattern linewidth expansion caused by light scattering from inorganic particles. Therefore, in practical applications, it may still face the problem of insufficient pattern accuracy.

[0006] Existing technology CN109324480A discloses a patent for "photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed circuit board." This patent offers an improvement approach, involving the use of an alkali-soluble polymer containing a specific content (more than 35% by mass) of aromatic polymeric monomers with a weight-average molecular weight within a specific range (1000~100000). This design recognizes to some extent the potential benefits of aromatic ring structures in controlling pattern size. However, the alkali-soluble polymer described in this patent does not have specific functional groups endowed at its molecular ends and on its side chains. This deficiency may lead to insufficient reaction sites during the curing process, weak interfacial adhesion (tightness) with the substrate, and poor dispersion stability of inorganic particles in the system, ultimately affecting the overall performance of the molded pattern.

[0007] In summary, although existing technologies have proposed various solutions, none have systematically addressed the key contradiction of simultaneously achieving pattern miniaturization (suppressing linewidth expansion), excellent substrate adhesion, and stable inorganic dispersion. Therefore, the industry urgently needs a novel photosensitive paste composition that, while inheriting the advantages of existing technologies, fundamentally and synergistically enhances these properties through innovative design of the alkali-soluble polymer molecular structure.

[0008] Therefore, the present invention provides a photosensitive paste composition that can achieve micro-patterning while having good substrate adhesion and inorganic material dispersion stability, and effectively suppresses abnormal expansion of pattern linewidth. Summary of the Invention

[0009] The purpose of this invention is to provide a photosensitive paste composition that fills a gap in the current technology.

[0010] The objective of this invention is achieved through the following technical solution: A photosensitive paste composition comprises an alkali-soluble polymer (A), an inorganic substance (B), and a curing catalyst (C); wherein the alkali-soluble polymer (A) contains more than 35 parts by mass of a polymerizable monomer having aromatic groups, which suppresses the light diffusion of inorganic particles to obtain the designed linewidth; its weight average molecular weight is 1,000 to 100,000, ensuring that the prepared paste has good viscosity and excellent screen printing performance; and its molecular ends have functional groups.

[0011] Preferably, the functional groups at the molecular ends of the alkali-soluble polymer (A) are selected from one or more of carboxyl groups, hydroxyl groups or amino groups, which improves the dispersibility of inorganic particles and the adhesion to the substrate.

[0012] Preferably, the molecular side chain of the alkali-soluble polymer (A) has one or more functional groups selected from carboxyl groups and phenolic hydroxyl groups.

[0013] Preferably, the glass transition temperature of the alkali-soluble polymer (A) is 0-150°C, resulting in excellent linearity and good adhesion to the substrate.

[0014] Preferably, relative to 100 parts by weight of the inorganic material (B), the composition contains 1 to 100 parts by weight of the alkali-soluble polymer (A) and 0.1 to 10 parts by weight of the curing catalyst (C).

[0015] The structural features of the alkali-soluble polymer (A) in this invention are as follows: the main chain structure of the alkali-soluble polymer (A) is preferably a (meth)acrylic acid polymer, which is copolymerized from alkyl (meth)acrylic acid esters and other functional monomers; its polymerizable monomer components contain at least 35 parts by mass of monomers with aromatic groups, such as styrene, p-methylstyrene, benzyl (meth)acrylic acid ester, etc., which can suppress the expansion of the wiring pattern and have the effect of generating the same type of line as when irradiated by UV light.

[0016] The polymer's molecular chain ends are designed with specific synthetic techniques to incorporate functional groups such as carboxyl, hydroxyl, or amino groups. These terminal functional groups not only impart the ability to disperse inorganic particles and improve substrate adhesion, but also allow the polymer's side chains to contain carboxyl or phenolic hydroxyl functional groups. These can be used to finely adjust the polymer's solubility, compatibility with inorganic fillers, and the photocurability of the entire photosensitive composition.

[0017] Synthesis methods for alkali-soluble polymer (A): Specifically, the following approaches are included: Free radical copolymerization is a fundamental and practical method; monomers containing aromatic groups, alkyl methacrylates, and functional monomers containing carboxyl or hydroxyl groups (such as (meth)acrylic acid, hydroxyethyl (meth)acrylate) are copolymerized in the presence of a free radical initiator and a chain transfer agent. Preferably, the chain transfer agent is a thiol compound containing a functional group, such as mercaptoacetic acid or mercaptoethanol, to efficiently introduce carboxyl or hydroxyl groups at the polymer chain ends.

[0018] To more precisely control the molecular chain structure and end functionalization, living polymerization methods, such as reversible addition-fragmentation chain transfer polymerization (RAFT) or atom transfer radical polymerization (ATRP), can be used. These methods allow the use of chain transfer agents or initiators with specific functional groups (such as carboxyl or hydroxyl groups) to directly introduce the desired functional groups at the ends of the molecular chains at the end of the polymerization process.

[0019] In addition, post-functionalization modification is also an effective strategy; by reacting pre-synthesized polymers with small molecule reagents containing functional groups (such as succinic anhydride, phthalic anhydride and maleic anhydride), carboxyl groups can be further introduced into the side chains or ends of the polymers, thereby flexibly adjusting the properties of the polymers.

[0020] <Physical Property Requirements of Alkali-Soluble Polymer (A)> Regarding molecular weight, the weight-average molecular weight of the alkali-soluble polymer (A) needs to be controlled between 1,000 and 100,000, preferably between 5,000 and 50,000. This range can well balance the polymer's solubility in solvents, the coating processability of the slurry, and the mechanical properties of the final cured film. The molecular weight and its distribution need to be characterized using gel permeation chromatography with polystyrene as a standard, and the molecular weight distribution index is preferably controlled below 3.

[0021] Its glass transition temperature should be between 0°C and 150°C, preferably between 20°C and 120°C; a suitable glass transition temperature can ensure that the photosensitive paste remains stable during storage and coating, while also possessing appropriate film-forming properties and flowability during pre-baking and subsequent processing. Tg is determined by differential scanning calorimetry (DSC).

[0022] The polymer must possess good alkali solubility; thanks to the functional groups such as carboxyl groups carried on its side chains or ends, the polymer should be able to dissolve readily in dilute alkaline aqueous solutions (such as aqueous solutions of sodium carbonate, magnesium carbonate, or tetramethylammonium hydroxide), which is fundamental to achieving patterning development. Alkali solubility can be assessed by observing its solubility under specified conditions.

[0023] The functional group content of alkali-soluble polymer (A), such as carboxyl or hydroxyl group values, needs to be determined by chemical titration or nuclear magnetic resonance.

[0024] Through the above design and synthesis, the alkali-soluble polymer (A) of the present invention successfully combines good alkali solubility, excellent photosensitive curing properties and good compatibility with inorganic fillers, making it very suitable for preparing high-resolution, high-precision photosensitive paste systems.

[0025] In this specification, (meth)acrylic acid is used as a general term for acrylic acid and methacrylic acid, and can be either acrylic acid or methacrylic acid; (meth)acrylate is used as a general term for acrylate and methacrylate, and can be either acrylate or methacrylate; (meth)acryloyl is used as a general term for acryloyl and methacryloyl, and can be either acryloyl or methacryloyl.

[0026] <Composition of Alkali-Soluble Polymer (A)> Alkali-soluble polymer (A) (hereinafter also referred to as "polymer (A)") is a polymer that has aromatic groups, specific functional groups at the molecular ends, and is alkali-soluble. The weight-average molecular weight of this polymer is 1,000 to 100,000, and the glass transition temperature is 0 to 150°C.

[0027] The main chain structure of polymer (A) is preferably a (meth)acrylic acid polymer, which is formed by copolymerization of polymerizable monomer components including aromatic monomers (a1), alkali-soluble monomers (a2), and other functional monomers (a3).

[0028] <<Aromatic Monomers (a1)>> Aromatic monomers (a1) are polymerizable monomers containing aromatic groups, and their content in the polymerizable monomer composition is more than 35 parts by mass. By containing aromatic monomers (a1), the light diffusion of inorganic particles during the photocuring process can be effectively suppressed, so that the linewidth of the formed pattern is consistent with the design.

[0029] Examples of aromatic monomers (a1) include: styrene (St), α-methylstyrene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, p-methoxystyrene, p-tert-butoxystyrene, divinylbenzene, indene, and other styrene derivatives; benzyl methacrylate (BzMA), 2-phenoxyethyl acrylate (PEA), etc. These monomers can be used alone or in combination of two or more.

[0030] <<Base-soluble monomers (a2)>> Alkali-soluble monomers (a2) are polymerizable monomers that can introduce alkali-soluble functional groups such as carboxyl groups and phenolic hydroxyl groups into polymers. These functional groups endow polymers with solubility in alkaline aqueous solutions (such as aqueous solutions of sodium carbonate, magnesium carbonate, or tetramethylammonium hydroxide), which is the basis for achieving patterned development.

[0031] Examples of alkali-soluble monomers (a2) include: (meth)acrylic acid (AA, MAA), 4-hydroxyphenyl methacrylate, itaconic acid, carboxyethyl (meth)acrylate, crotonic acid, fumaric acid, maleic acid; carboxyl-containing (meth)acrylate monomers such as β-carboxyethyl (meth)acrylate, 5-carboxypentyl (meth)acrylate, mono(meth)acryloyloxyethyl succinate, ω-carboxylated polycaprolactone mono(meth)acrylate; and o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, α-methyl-o-hydroxystyrene, o-piperol, p-hydroxystyrene. Monomers containing phenolic hydroxyl groups, such as vinyl hydroxybenzoate, vinyl m-hydroxybenzoate, 4-hydroxybenzyl methacrylate, vinyl salicylate, vinyl p-hydroxybenzoyloxyacetate, eugenol, isoeugenol, p-isopropenylphenol, o-allylphenol, m-allylphenol, p-allylphenol, 4-hydroxyphenyl methacrylate, 2,2-(o-hydroxyphenyl-4-vinylacetyl)propane, 2,2-(m-hydroxyphenyl-4-vinylacetyl)propane, and 2,2-(p-hydroxyphenyl-4-vinylacetyl)propane.

[0032] In addition, alkali-soluble functional groups can also be introduced through post-processing, for example, by reacting the pre-synthesized polymer with acid anhydride compounds (such as succinic anhydride, phthalic anhydride and maleic anhydride) to obtain an alkali-soluble polymer (a2-1).

[0033] Alkali-soluble monomers (a2) can be used alone or in combination of two or more.

[0034] <<Other Monomers (a3)>> Without prejudice to the purpose of this invention, the polymer (A) may further have structural units derived from other monomers (a3). These other monomers (a3) ​​are used to adjust the polymer's glass transition temperature, flexibility, adhesion, dispersibility, and crosslinking density, etc.

[0035] Other monomers (a3) ​​can be listed as follows: Aliphatic or alicyclic (meth)acrylates (a3-1): such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, nonyl methacrylate, isononyl methacrylate, n-decyl methacrylate, isodecyl methacrylate, lauryl methacrylate, etc., aliphatic (meth)acrylates, cyclohexyl methacrylate, tricyclo[5.2.1.02,6]dec-8-yl methacrylate (TCDMA), isobornyl methacrylate (IBOMA), glycidyl methacrylate (GMA), phenyl methacrylate, etc., are used to adjust the glass transition temperature and flexibility of polymers.

[0036] Hydroxyl monomers (a3-2): such as hydroxyethyl methacrylate (2-HEMA), hydroxypropyl methacrylate, 4-hydroxybutyl acrylate (4-HBA), etc., are used to enhance the adhesion of polymers to substrates and provide crosslinking sites.

[0037] Amino-containing monomers (a3-3): such as dimethylaminoethyl (meth)acrylate, acrylamide, 2-methyl-2-acrylate-2,2,6,6-tetramethyl-4-piperidinyl ester (LA-87), 2-methyl-2-acrylate-1,2,2,4,6-pentamethyl-4-piperidinyl ester (LA-82), etc., are used to improve the dispersibility of polymers. Some amino-containing monomers (a3-3-1) also possess free radical scavenging properties, which help improve polymer stability.

[0038] Crosslinking monomers: such as monomers containing multiple (meth)acryloyl or silane groups, used to further enhance the crosslinking density of the cured film.

[0039] Other monomers (a3) ​​can be used alone or in combination of two or more.

[0040] <Manufacturing of Polymer (A)> Polymer (A) can be prepared by various polymerization methods, and the methods are not particularly limited, but the following methods are preferred:

[0041] (i) Free radical polymerization: A polymerizable monomer composition including aromatic monomers (a1), alkali-soluble monomers (a2), and other monomers (a3) ​​is copolymerized in the presence of a free radical initiator (b2) and a chain transfer agent (b1). This method is fundamental and practical, and is suitable for industrial production.

[0042] Chain transfer agent (b1): Preferably, a thiol compound containing a functional group is used, such as mercaptoacetic acid, mercaptoethanol, 3-mercaptopropionic acid, etc., so as to efficiently introduce functional groups such as carboxyl or hydroxyl groups at the end of the polymer chain.

[0043] Initiator (b2): Examples include azo compound polymerization initiators, peroxide polymerization initiators, and photoradical polymerization initiators. Furthermore, it is more preferable to avoid using a metal catalyst. Polymers (A) manufactured using such polymerization initiators do not contain metal components derived from the catalyst, thus improving the resistance to crosslinking reactions and reducing coloration. Moreover, since depolymerization reactions caused by metal components can be suppressed, cured products with excellent durability can be provided for various applications.

[0044] Examples of azo compound polymerization initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobis(4-methoxy-2,4-dimethylpentanitrile), 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(2,4-dimethylpentanitrile), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carboxynitrile), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylpentanitrile, and 2,2'-... -Azobis(2-amidinylpropane) dihydrochloride, 2,2'-azobis(N,N'-dimethyleneisobutyramidine), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], 2,2'-azobis(isobutyramide) dihydrate, 4,4'-azobis(4-cyanopentanoic acid), 2,2'-azobis(2-cyanopropanol), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide].

[0045] Examples of peroxide-based polymerization initiators include tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, benzoyl peroxide, lauroyl peroxide, hexanoyl hydroperoxide, diisopropyl peroxide dicarbonate, di-2-ethylhexyl peroxide dicarbonate, tert-butyl peroxypentanoate, 2,2-bis(4,4-di-tert-butylperoxycyclohexyl)propane, 2,2-bis(4,4-di-tert-pentylperoxycyclohexyl)propane, 2,2-bis(4,4-di-tert-octylperoxycyclohexyl)propane, 2,2-bis(4,4-di-α-isopropylphenylperoxycyclohexyl)propane, 2,2-bis(4,4-di-tert-butylperoxycyclohexyl)butane, and 2,2-bis(4,4-di-tert-octylperoxycyclohexyl)butane.

[0046] As photoradical polymerization initiators, compounds conventionally used as photoradical polymerization initiators are preferred, such as: benzoin initiators, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, etc.; acetophenone initiators, such as 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexylacetone, 2-methyl-1-[4-(methmercapto)phenyl]-2-morpholino-1-propanone, N,N-dimethylaminoacetophenone, etc.; anthraquinone initiators, such as 2-methylanthraquinone, 1-chloroanthraquinone, 2-pentylanthraquinone, etc.; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, etc. Thioxanone initiators such as 2,4-diisopropylthioxanthone; ketal initiators such as acetophenone dimethyl ketal and benzyl methyl ketal; benzophenone, methyl benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis(diethylamino)benzophenone, michalcone, 4-benzoyl-4'-methyldiphenyl sulfide, and other benzophenone initiators; Acylphosphine oxide initiators such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4'-trimethylpentylphosphine oxide, and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide; oxime-ester initiators such as 1-[4-(phenylmercapto)phenyl]-1,2-octanedione = 2-(O-benzoyl oxime); camphorquinone and α-hydroxy ketone.

[0047] Photoradical polymerization initiators can be used alone or in combination with two or more.

[0048] Photoradical polymerization initiators can be combined with sensitizers. For example, anthracene compounds such as 9,10-dibutoxyanthracene and 9,10-bis(acyloxy)anthracene are preferred as sensitizers.

[0049] One or more polymerization initiators can be used.

[0050] (ii) Living polymerization: To more precisely control the molecular chain structure and terminal functionalization, living radical polymerization methods such as reversible addition-fragmentation chain transfer polymerization (RAFT) or atom transfer radical polymerization (ATRP) can be used. These methods allow the use of chain transfer agents or initiators with specific functional groups (such as carboxyl or hydroxyl groups), thereby introducing the desired functional groups directly at the ends of the molecular chains at the end of the polymerization process.

[0051] (iii) Post-functionalization modification method: By reacting the pre-synthesized polymer with small molecule reagents containing functional groups (such as acid anhydrides), functional groups such as carboxyl groups and hydroxyl groups can be further introduced into the side chain or end of the polymer, thereby flexibly adjusting the properties of the polymer.

[0052] <Polymer (A) Content> The photosensitive paste composition of the present invention may contain one or more polymers (A). The content of polymer (A) in the composition of the present invention is preferably 1 to 100 parts by weight relative to 100 parts by weight of inorganic matter (B).

[0053] Preferably, the inorganic material (B) has an average particle size of 0.01 to 10 μm.

[0054] More preferably, the inorganic material (B) can be a conductor, insulator, magnet, etc. For example, it can be one or more carbon materials selected from alloys of metals such as gold (Au), silver (Ag), copper (Cu), platinum (Pt), palladium (Pd), aluminum (Al), iron (Fe), tungsten (W), molybdenum (Mo), manganese (Mn), nickel (Ni), ruthenium (Ru), and tin (Sn); metals such as silver-coated copper particles; carbon oxides such as silicon dioxide, aluminum oxide, titanium oxide, zinc oxide, zirconium oxide, silicon nitride, silicon carbide, iron oxide, copper oxide, silver oxide, tin oxide, indium oxide, and silver-coated titanium oxide particles; carbon; carbon nanotubes; fullerenes, etc.

[0055] Preferably, the curing catalyst (C) is selected from the group composed of cationic curing catalysts or the group composed of free radical curing catalysts.

[0056] More preferably, the curing catalyst (C) is selected from one or more of the following: Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone; Benzophenone, milchone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives; bis(cyclopentadienyl)titanium dichloride, bis(cyclopentadienyl)diphenyltitanium, bis(cyclopentadienyl)bis(2,3,4,5,6-pentafluorobenzene-1-yl)titanium, bis(cyclopentadienyl)bis(2,3,5,6-tetrafluorobenzene-1-yl)titanium, bis(cyclopentadienyl)bis(2,4,6-trifluorobenzene-1-yl)titanium, bis(cyclopentadienyl)-2,6-difluorobenzene Diocene titanium derivatives include 1-yltitanium, bis(cyclopentadienyl)-2,4-difluorophenyl-1-yltitanium, bis(methylcyclopentadienyl)bis(2,3,4,5,6-pentafluorophenyl-1-yl)titanium, bis(methylcyclopentadienyl)bis(2,6-difluorophenyl-1-yl)titanium, bis(cyclopentadienyl)-2,6-difluoro-3-(pyrrolo-1-yl)phenyl-1-yltitanium, etc. Oxime esters such as 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime) (IrgacureOXE01) and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl] ethyl ketone 1-(O-acetyl oxime).

[0057] Preferably, relative to 100 parts by weight of the inorganic material (B), the composition contains 1 to 100 parts by weight of a curable resin (D).

[0058] More preferably, the curable resin (D) is selected from one or more of tris(2-hydroxyethyl) isocyanurate triacrylate (THEICTA), bisphenol A diacrylate ethoxylate, bisphenol A dimethacrylate ethoxylate, 2-butyl-2-ethyl-1,3-propanediol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane triacrylate, triallyl cyanurate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, triisopropylisocyanurate, pentaerythritol tetraacrylate ethoxylate, ethylene glycol diacrylate (EGDA), ethylene glycol dimethacrylate (EGDMA), trimethylolpropane trimethacrylate (TMPTMA), and tris(2-hydroxyethyl) isocyanurate triacrylate.

[0059] Preferably, the composition contains 1 to 100 parts by mass of solvent (E) relative to 100 parts by mass of inorganic matter (B).

[0060] More preferably, the solvent (E) is selected from organic solvents with a boiling point of 100°C or higher. For example, it is selected from one or more of dipropylene glycol monomethyl ether (DPM), cyclohexanone, propylene glycol monobutyl ether, ethylene glycol ethyl ether acetate, diisobutyl ketone, ethylene glycol butyl ether, propylene glycol butyl ether, ethylene glycol butyl ether acetate, glycol diacetate, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol propyl ether, ethylene glycol hexyl ether, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether, and diethylene glycol butyl ether acetate.

[0061] This application also provides an electronic component made from the above-described photosensitive paste composition.

[0062] The working mechanism of this invention: The photosensitive paste composition of this invention achieves a synergistic improvement in high-precision patterning, excellent substrate adhesion, and good dispersion stability. Its core mechanism lies in the molecular structure design of the alkali-soluble polymer (A) and the synergistic effect between its components. The aromatic groups in this polymer molecule, comprising more than 35 parts by mass, constitute the key to suppressing pattern linewidth expansion. During exposure, these aromatic rings effectively absorb stray light generated by scattering from inorganic particles (B), forming an intrinsic "optical barrier," significantly reducing the ineffective light intensity in non-exposed areas, thereby suppressing unintended cross-linking of the curable resin (D). This ensures a clear dissolution contrast between the illuminated and non-illuminated areas during alkaline development, ultimately resulting in a precise pattern with sharp edges. Simultaneously, the precise introduction of strong polar functional groups such as carboxyl, hydroxyl, or amino groups at the molecular ends achieves a strong adhesion to the substrate. These functional groups located at the molecular chain ends have higher migration capabilities and can form strong hydrogen bonds with the substrate surface, fundamentally overcoming the adhesion reduction problem that may be caused by high aromatic content, and ensuring the interfacial bonding strength of the cured pattern. Furthermore, the polymer's moderate molecular weight (1000~100000) and the optional carboxyl and phenolic hydroxyl groups on its side chains together construct a stable dispersion system: the polymer backbone prevents the aggregation of inorganic particles through steric hindrance, while the side chain functional groups ensure the long-term dispersion stability of inorganic particles during slurry storage and coating processes by enhancing wettability. Finally, under the action of the curing catalyst (C), this precisely molecularly designed system successfully achieved a triple breakthrough in optical precision, interfacial bonding, and material uniformity through coating, exposure, and development processes, providing a patterned solution that meets the stringent requirements of the microelectronics field.

[0063] Due to the application of the above technical solution, the present invention has the following beneficial effects compared with the prior art: 1. This invention can form high-precision, controllable linewidth micro-patterns; the high content of aromatic groups in the alkali-soluble polymer can effectively absorb and suppress the scattering and random reflection of the irradiated light caused by inorganic particles during the exposure process, thereby significantly reducing the abnormal expansion of the pattern, so that the final formed line can accurately conform to the preset size, meeting the stringent requirements of high performance electronic components for miniaturization. 2. The composition of the present invention exhibits excellent substrate adhesion; the functional groups (such as carboxyl, hydroxyl or amino groups) at the ends of the alkali-soluble polymer molecules play a key role; these terminal functional groups act as "anchors" and can form strong physical adsorption with the substrate surface, effectively overcoming the defects of sacrificing adhesion in pursuit of pattern accuracy in the past, ensuring that the cured pattern will not peel off or break from the substrate during subsequent processing and use, and greatly improving the reliability of the product. 3. This invention simultaneously ensures the excellent dispersibility and stability of the slurry system; the specific molecular weight range gives the adhesive moderate rheological properties, while the various functional groups (such as carboxyl groups, phenolic hydroxyl groups, etc.) that can be selected on the molecular side chains can effectively prevent the aggregation and sedimentation of inorganic metal particles in the slurry through steric hindrance or electrostatic interaction, so that the slurry composition is uniform, the storage is stable, and a smooth and defect-free coating can be formed through processes such as screen printing. 4. This invention also provides a high degree of formulation flexibility and performance adjustability; by further limiting the glass transition temperature of the alkali-soluble polymer, the precise ratio of each component, the particle size of the inorganic material, and the type of curing catalyst, the film-forming properties, curing speed, conductivity, and other properties of the slurry can be precisely optimized for different application scenarios (such as forming thick or thin film electrodes, resistors, etc.); and electronic components made from this photosensitive slurry composition have the outstanding advantages of fine structure, stable performance, and high reliability. Detailed Implementation

[0064] To provide a clearer understanding of the technical features, objectives, and effects of this invention, specific implementation schemes are now described in detail.

[0065] The present invention will be further described below with reference to embodiments, but the present invention is not limited to the following embodiments. The implementation conditions used in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions not specified are conventional conditions in the industry. The technical features involved in the various embodiments of the present invention can be combined with each other as long as they do not conflict with each other.

[0066] Synthesis example 1 In a flask equipped with a stirrer, nitrogen inlet tube, thermometer, and reflux condenser, 150 parts by weight of dipropylene glycol monomethyl ether (DPM) as a solvent and 19 parts by weight of methyl methacrylate (MMA), 40 parts by weight of styrene (St), 16 parts by weight of hydroxyethyl methacrylate (2-HEMA), 24 parts by weight of methacrylic acid (MAA), and 1 part by weight of 2-methyl-2-acrylate-2,2,6,6-tetramethyl-4-piperidinyl ester (LA-) as polymerizable monomers were added. 87) Nitrogen gas was introduced into the flask and stirred for 30 minutes to purge the nitrogen gas. Then the temperature was raised to 80°C. While keeping the contents of the flask at 80°C, 0.8 parts by mass of mercaptopropionic acid (BMPA) was added and stirred for 10 minutes. Then 0.5 parts by mass of azobisisobutyronitrile (AIBN) was added. After the first addition of AIBN, 30 minutes later, another 0.5 parts by mass of AIBN was added, and the mixture was kept at 80°C for 16 hours to obtain an alkali-soluble polymer (A1) with 40 wt% non-volatile matter.

[0067] Synthesis example 2 This synthesis example is based on the above synthesis example 1, and is the same as the above synthesis example 1, so it will not be repeated here; In this synthesis example, LA-87 was not added, but 1 part by mass of 2-methyl-2-acrylate-1,2,2,4,6-pentamethyl-4-piperidin ester (LA-82) was added; the preparation method was the same as in Synthesis Example 1, and a non-volatile alkali-soluble polymer (A2) with 40 wt% volatile matter was obtained.

[0068] Synthesis example 3 This synthesis example is based on the above synthesis example 1, and is the same as the above synthesis example 1, so it will not be repeated here; In this synthesis example, LA-87 was not added, but 20 parts by mass of MMA were added; the preparation method was the same as in Synthesis Example 1, and an alkali-soluble polymer (A3) with 40 wt% non-volatile matter was obtained.

[0069] Synthesis example 4 This synthesis example is based on the above synthesis example 1, and is the same as the above synthesis example 1, so it will not be repeated here; In this synthesis example, LA-87 and MMA were not added, but 20 parts by weight of tricyclo[5.2.1.02,6]dec-8-yl methacrylate (TCDMA) were added; the preparation method was the same as in Synthesis Example 1, and a non-volatile alkali-soluble polymer (A4) with 40 wt% volatile content was obtained.

[0070] Synthesis example 5 This synthesis example is based on the above synthesis example 1, and is the same as the above synthesis example 1, so it will not be repeated here; In this synthesis example, LA-87 and MMA were not added, but 20 parts by weight of isobornyl methacrylate (IBOMA) were added; the preparation method was the same as in Synthesis Example 1, and an alkali-soluble polymer (A5) with 40 wt% non-volatile matter was obtained.

[0071] Synthesis example 6 In a flask equipped with a stirrer, nitrogen inlet tube, thermometer, and reflux condenser, 166 parts by mass of DPM as solvent and 14 parts by mass of MMA, 40 parts by mass of St, 16 parts by mass of 2-HEMA, and 30 parts by mass of MAA as polymerizable monomers were added. Nitrogen was introduced into the flask while stirring for 30 minutes to purge the nitrogen, and then the temperature was raised to 80°C. While maintaining the contents of the flask at 80°C, 0.8 parts by mass of BMPA were added and stirred for 10 minutes, followed by 0.5 parts by mass of AIBN. 30 minutes after the first addition of AIBN, another 0.5 parts by mass of AIBN were added, and the mixture was kept at 80°C for 16 hours. Then, 0.1 parts by mass of 4-methoxyphenol (MEHQ) were added. Next, 0.4 parts by mass of N,N-dimethylbenzylamine (DMBA) and 10 parts by mass of glycidyl methacrylate (GMA) were added. The mixture was reacted at 90°C for 16 hours to obtain a non-volatile, alkali-soluble polymer (A6) with 40 wt% volatile content.

[0072] Synthesis Example 7 This synthesis example is based on the above synthesis example 1, and is the same as the above synthesis example 1, so it will not be repeated here; In this synthesis example, LA-87 and BMPA were not added, but 19.35 parts by weight of MMA, 24.65 parts by weight of MAA, and 0.8 parts by weight of 1-thioglycerol (3MP) were added; the preparation method was the same as in Synthesis Example 1, and an alkali-soluble polymer (A7) with 40 wt% non-volatile matter was obtained.

[0073] Synthesis example 8 This synthesis example is based on the above synthesis example 1, and is the same as the above synthesis example 1, so it will not be repeated here; In this synthesis example, LA-87 and BMPA were not added, but 19.35 parts by mass of MMA, 24.65 parts by mass of MAA, and 0.6 parts by mass of mercaptoethanol (2ME) were added; the preparation method was the same as in Synthesis Example 1, and an alkali-soluble polymer (A8) with 40 wt% non-volatile matter was obtained.

[0074] Synthesis example 9 This synthesis example is based on the above synthesis example 1, and is the same as the above synthesis example 1, so it will not be repeated here; In this synthesis example, LA-87, MMA, and St are not added, but 60 parts by weight of benzyl methacrylate (BzMA) are added; the preparation method is the same as in Synthesis Example 1, and an alkali-soluble polymer (A9) with 40 wt% non-volatile matter is obtained.

[0075] Synthesis example 10 This synthesis example is based on the above synthesis example 1, and is the same as the above synthesis example 1, so it will not be repeated here; In this synthesis example, LA-87, MMA, and St are not added, but 60 parts by mass of 2-phenoxyethyl acrylate (PEA) are added; the preparation method is the same as in Synthesis Example 1, and an alkali-soluble polymer (A10) with 40 wt% non-volatile matter is obtained.

[0076] Comparative Synthesis Example 1 In a flask equipped with a stirrer, nitrogen inlet tube, thermometer, and reflux condenser, 150 parts by mass of DPM as a solvent were added. Nitrogen was introduced into the flask while stirring for 30 minutes to purge the nitrogen, and then the temperature was raised to 80°C. Next, 0.5 parts by mass of AIBN were added, followed by the dropwise addition of a mixture of 19.35 parts by mass of MMA, 40 parts by mass of St, 16 parts by mass of 2-HEMA, and 24.65 parts by mass of MAA over a period of 1 hour. After the first addition of AIBN, another 0.5 parts by mass of AIBN was added 30 minutes later, and the temperature was maintained at 80°C for 16 hours to obtain a non-volatile alkali-soluble polymer (A11) with 40 wt% volatile content.

[0077] Comparative Synthesis Example 2 This comparative synthesis example is based on the above synthesis example 1, and is the same as the above synthesis example 1, so it will not be repeated here; In this comparative synthesis example, LA-87 and BMPA were not added, but 19.35 parts by mass of MMA, 24.65 parts by mass of MAA, and 1.1 parts by mass of 1-octylthiol (NOM) were added; the preparation method was the same as in Synthesis Example 1, and an alkali-soluble polymer (A12) with 40 wt% non-volatile matter was obtained.

[0078] Comparative Synthesis Example 3 This comparative synthesis example is based on the above synthesis example 1, and is the same as the above synthesis example 1, so it will not be repeated here; In this comparative synthesis example, LA-87 was not added, but 40 parts by mass of MMA and 20 parts by mass of St were added; the preparation method was the same as in Synthesis Example 1, and an alkali-soluble polymer (A13) with 40 wt% non-volatile matter was obtained.

[0079] The components and amounts added to the reaction systems of the above synthetic examples 1-10 and comparative synthetic examples 1-3 are shown in Table 1 below (by weight).

[0080] Table 1

[0081] The detection results of the alkali-soluble polymers prepared from the reaction systems of the above-mentioned synthetic examples 1-10 and comparative synthetic examples 1-3 are shown in Table 2 below.

[0082] Table 2

[0083] Example 1 This embodiment provides a photosensitive paste composition, the preparation method of which includes the following steps: 12 parts by mass of alkali-soluble polymer (A1), 100 parts by mass of silver particles with an average particle size of 2.5 μm as inorganic particles (B), 1 part by mass of photoradical initiator IrgacureOXE01 as curing catalyst (C), 6 parts by mass of curable resin (D) THEICTA, and 20 parts by mass of solvent (E) DPM were placed in a rotary mixer (ARE-310, manufactured by Shinki Corporation, Japan) and mixed at a rotation speed of 2000 rpm for 2 minutes to obtain the photosensitive paste composition.

[0084] Example 2 This embodiment provides a photosensitive paste composition. This embodiment is based on the above embodiment 1, and the similarities with the above embodiment will not be repeated.

[0085] In this example, 12 parts by weight of alkali-soluble polymer (A2) are used.

[0086] Example 3 This embodiment provides a photosensitive paste composition. This embodiment is based on the above embodiment 1, and the similarities with the above embodiment will not be repeated.

[0087] In this example, 12 parts by weight of alkali-soluble polymer (A3) are used.

[0088] Example 4 This embodiment provides a photosensitive paste composition. This embodiment is based on the above embodiment 1, and the similarities with the above embodiment will not be repeated.

[0089] In this example, 12 parts by weight of alkali-soluble polymer (A4) are used.

[0090] Example 5 This embodiment provides a photosensitive paste composition. This embodiment is based on the above embodiment 1, and the similarities with the above embodiment will not be repeated.

[0091] In this embodiment, 12 parts by weight of alkali-soluble polymer (A5) are used.

[0092] Example 6 This embodiment provides a photosensitive paste composition. This embodiment is based on the above embodiment 1, and the similarities with the above embodiment will not be repeated.

[0093] In this embodiment, 12 parts by weight of alkali-soluble polymer (A6) are used.

[0094] Example 7 This embodiment provides a photosensitive paste composition. This embodiment is based on the above embodiment 1, and the similarities with the above embodiment will not be repeated.

[0095] In this embodiment, 12 parts by weight of alkali-soluble polymer (A7) are used.

[0096] Example 8 This embodiment provides a photosensitive paste composition. This embodiment is based on the above embodiment 1, and the similarities with the above embodiment will not be repeated.

[0097] In this embodiment, 12 parts by weight of alkali-soluble polymer (A8) are used.

[0098] Example 9 This embodiment provides a photosensitive paste composition. This embodiment is based on the above embodiment 1, and the similarities with the above embodiment will not be repeated.

[0099] In this embodiment, 12 parts by weight of alkali-soluble polymer (A9) are used.

[0100] Example 10 This embodiment provides a photosensitive paste composition. This embodiment is based on the above embodiment 1, and the similarities with the above embodiment will not be repeated.

[0101] In this embodiment, 12 parts by weight of alkali-soluble polymer (A10) are used.

[0102] Comparative Example 1 This comparative example provides a photosensitive paste composition, which is based on Example 1 above, and the similarities with the above examples will not be repeated.

[0103] In this embodiment, 12 parts by weight of alkali-soluble polymer (A11) are used.

[0104] Comparative Example 2 This comparative example provides a photosensitive paste composition, which is based on Example 1 above, and the similarities with the above examples will not be repeated.

[0105] In this embodiment, 12 parts by weight of alkali-soluble polymer (A12) are used.

[0106] Comparative Example 3 This comparative example provides a photosensitive paste composition, which is based on Example 1 above, and the similarities with the above examples will not be repeated.

[0107] In this example, 12 parts by weight of alkali-soluble polymer (A13) are used.

[0108] The components and addition amounts of the photosensitive paste compositions of the above embodiments and comparative examples are shown in Table 3 below (by weight).

[0109] Table 3

[0110] The photosensitive paste compositions prepared in the above examples and comparative examples were screen-coated onto a glass substrate at a speed of 30 cm / s with a film thickness of 10 μm and a coating area of ​​2 cm × 2 cm. The substrates were then dried in a drying oven at 100°C for 10 minutes. The exposure was 250 mJ / cm². 2 Under certain conditions, striped wiring patterns with an L / S ratio of 20 μm / 20 μm were exposed and developed with 0.4% sodium carbonate aqueous solution at a jet pressure of 0.2 MPa and a temperature of 30°C to obtain linear patterns. Various evaluations were then performed on these linear patterns.

[0111] The test results of the above-described embodiments and comparative examples of photosensitive paste compositions are shown in Table 4.

[0112] Table 4

[0113] The evaluation methods for the test results in Table 4 are as follows: (a) Surface roughness: The surface roughness of the screen-coated surface after drying is measured using a surface roughness meter (to evaluate the coated surface after exposure); A (excellent): X < 2.5 micrometers; B (good): 2.5 micrometers ≤ X < 3.5 micrometers; C (poor): X ≥ 3.5 micrometers; (ii) Adhesion: The time for pattern peeling is evaluated by extending the alkaline development time; A: X≥5; B: 2≤X<5; C: X<2; (III) Line shape: The line pattern is evaluated after observation using an optical microscope; A (Excellent): No defects or skewness and clear; B (Good): Some defects or skewness are present; C (Poor): Overall defects or skewness are present; (iv) Line width: Measure the width of the linear pattern; A (excellent): 20 micrometers ≤ X < 21 micrometers; B (good): 21 micrometers ≤ X < 25 micrometers; C (poor): X ≥ 25 micrometers.

[0114] By comparing and verifying multiple embodiments and comparative examples of the photosensitive paste composition of the present invention, the crucial role of each component and its content ratio in the final performance is fully demonstrated.

[0115] The results show that when the ratio of the alkali-soluble polymer, inorganic material, and curing catalyst is within the preferred range defined by this invention, the prepared slurry exhibits the best overall performance in terms of pattern forming accuracy, substrate adhesion, and slurry storage stability. Specifically, under this optimized ratio, the photosensitive slurry can form fine patterns with clear edges and precise line widths, while exhibiting extremely strong adhesion to the substrate. Furthermore, the slurry itself has good dispersion stability, with no sedimentation or agglomeration. Conversely, in the comparative examples, obvious performance defects were observed when the content of each component deviated from the preferred range.

[0116] In summary, this invention can form high-precision, controllable linewidth micro-patterns. The high content of aromatic groups in the alkali-soluble polymer effectively absorbs and suppresses the scattering and random reflection of irradiated light caused by inorganic particles during exposure, thereby significantly reducing abnormal pattern expansion. This ensures that the final circuit accurately conforms to the preset dimensions, meeting the stringent requirements for miniaturization in high-performance electronic components. The composition of this invention exhibits excellent substrate adhesion. The functional groups at the ends of the alkali-soluble polymer molecules (such as carboxyl, hydroxyl, or amino groups) play a crucial role. These terminal functional groups act as "anchors," forming strong physical adsorption with the substrate surface, effectively overcoming the previous defects of sacrificing adhesion in pursuit of pattern precision. This ensures that the cured pattern will not peel off or crack from the substrate during subsequent processing and use, greatly improving product reliability. This invention also ensures excellent performance of the slurry system. Dispersibility and stability; a specific molecular weight range gives the adhesive moderate rheological properties, while various functional groups (such as carboxyl groups, phenolic hydroxyl groups, etc.) on the molecular side chains can effectively prevent the aggregation and sedimentation of inorganic metal particles in the slurry through steric hindrance or electrostatic interaction, resulting in uniform slurry composition, stable storage, and the formation of a smooth, defect-free coating during processes such as screen printing; this invention also provides high formulation flexibility and performance adjustability; by further limiting the glass transition temperature of the alkali-soluble polymer, the precise ratio of each component, the particle size of the inorganic material, and the type of curing catalyst, the film-forming properties, curing speed, conductivity, and other properties of the slurry can be precisely optimized for different application scenarios (such as forming thick or thin film electrodes, resistors, etc.); and electronic components made from this photosensitive slurry composition have outstanding advantages such as fine structure, stable performance, and high reliability.

[0117] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A photosensitive paste composition, characterized in that, It contains alkali-soluble polymers (A), inorganic substances (B), and curing catalysts (C); The alkali-soluble polymer (A) comprises more than 35 parts by mass of a polymeric monomer having aromatic groups, with a weight average molecular weight of 1,000 to 100,000, and functional groups at the molecular ends.

2. The photosensitive paste composition as described in claim 1, characterized in that, The functional groups at the molecular ends of the alkali-soluble polymer (A) are selected from one or more of carboxyl groups, hydroxyl groups, or amino groups.

3. The photosensitive paste composition as described in claim 1, characterized in that, The molecular side chains of the alkali-soluble polymer (A) have one or more functional groups selected from carboxyl groups and phenolic hydroxyl groups.

4. The photosensitive paste composition as described in claim 3, characterized in that, The glass transition temperature of the alkali-soluble polymer (A) is 0–150 °C.

5. The photosensitive paste composition according to claim 3, characterized in that, Relative to 100 parts by weight of inorganic matter (B), the composition contains 1 to 100 parts by weight of alkali-soluble polymer (A) and 0.1 to 10 parts by weight of curing catalyst (C).

6. The photosensitive paste composition according to claim 3, characterized in that, The inorganic material (B) has an average particle size of 0.01 to 10 μm.

7. The photosensitive paste composition according to claim 3, characterized in that, The curing catalyst (C) is selected from either the group composed of cationic curing catalysts or the group composed of free radical curing catalysts.

8. The photosensitive paste composition according to claim 3, characterized in that, The composition contains 1 to 100 parts by weight of curable resin (D) relative to 100 parts by weight of inorganic matter (B).

9. The photosensitive paste composition according to claim 3, characterized in that, The composition contains 1 to 100 parts by mass of solvent (E) relative to 100 parts by mass of inorganic matter (B).

10. An electronic component made from the photosensitive paste composition as described in claims 3 to 9.

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