Photosensitive resin composition containing photobleached aminomethyl anthracene photosensitizer and application thereof

Abstract

The invention provides a photosensitive resin composition containing a photobleaching aminomethyl anthracene photosensitizer and application thereof.The structural main body anthracene ring of the photosensitizer introduces an aminomethyl functional group to the 9th and / or 10th site: through introduction of the aminomethyl functional group, while the electron cloud density of polycyclic aromatic hydrocarbon is maintained, the maximum absorption wavelength is subjected to red shift, and the photosensitive resin composition is especially suitable for a 405nm illumination system; the initiation efficiency is obviously improved; the exposure energy is reduced; compared with an existing DBA type photoinitiator, the problem of alkoxy carbon-oxygen bond breakage caused by p-pi conjugation of DBA is avoided, generation of small molecule fragments is effectively inhibited, defects are reduced, and the yield is increased. In addition, compared with DPHA and DAcOA, the photosensitizer also shows better solubility and formula compatibility. The preparation method has the characteristics of simple preparation process and low cost, and can be widely applied to the photocuring fields of dry films, paints, coatings, printing inks, forming materials and the like.

Description

Technical Field

[0001] The present invention belongs to the field of photopolymerizable materials, and particularly relates to a photosensitive resin composition containing a photo - bleachable aminomethylanthracene photosensitizer and its application. Background Art

[0002] Photosensitive resin compositions are widely used as key pattern transfer materials in the fields of printed circuit board (PCB), lead frame (LF), and semiconductor package (IC) substrate printed circuit board manufacturing. Among them, the photosensitive resin composition is usually coated on the surface of a PET support film, and after drying, a protective layer, such as a polyethylene film (PE) protective layer, is closely attached to its surface to form a photosensitive dry film (or dry film resist). When realizing the pattern transfer process, first, the dry film resist is attached to the copper substrate, a mask with a certain pattern is covered on the dry film resist, and graphic exposure is carried out; then, a weakly alkaline aqueous solution is used as the developer to remove the unexposed parts, and then etching or electroplating treatment is carried out to form a pattern; finally, the cured part of the dry film is stripped off with a stripping solution, thus realizing the pattern transfer.

[0003] With the development of electronic devices towards miniaturization and high density, the requirement for the fineness of circuits is continuously increasing. In order to meet the needs of fine circuit manufacturing, the photosensitive resin composition needs to have higher resolution. To improve the resolution, an appropriate sensitizer needs to be added to the photosensitive resin composition. For the photosensitive resin composition, a suitable photo - initiation system has a direct impact on photosensitivity, resolution, and production yield.

[0004] Currently, small - molecule anthracene derivatives represented by 9,10 - dibutoxyanthracene (DBA), 9,10 - diacyloxyanthracene (DAcOA), and 9,10 - diphenylanthracene (DPHA) are widely used as photosensitizers. Generally, to obtain higher photosensitive performance and resolution, such photosensitizers need to be used in combination with 2,4,5 - triaryl imidazole dimer (HABI) (such as patent CN101568883B); however, such a photosensitizer / photo - initiator combination system usually faces the following problems:

[0005] (1) Short - chain alkoxy anthracene derivatives with solubility advantages (similar to DBA), due to their initiation mechanism, the fragments after initiation are prone to migrate in the dry film and penetrate to the surface of the polyethylene (PE) protective film to form crystals, thus causing defects such as short - circuit and open - circuit of the resist pattern, or the risk of decreased photosensitivity due to the penetration of the photosensitizer from the photosensitive layer;

[0006] (2) 9,10-diacyloxyanthracene photosensitizer (DAcOA) has an increased electron cloud density of the 9,10 anthracene ring due to the electron-pulling induction effect of the acyl group. As a result, the efficiency of this type of photosensitizer in catalyzing the curing reaction is reduced. The verticality of the sidewalls of the cured photosensitive resin composition is poor, and the length difference between the top and bottom lines is large, forming an "inverted trapezoid" problem. In addition, the energy required for exposure of this type of photoinitiator is increased, and the photobleaching efficiency is reduced.

[0007] (3) Although DPHA has the advantage of high photon yield, it is easy to aggregate in the developer during the development process to produce precipitate garbage due to its large conjugated system, high molecular rigidity and poor solubility. It is easy to adhere to the surface of the copper plate, causing problems such as residual copper or short circuit, affecting the product yield.

[0008] Therefore, developing a new photoinitiator system with good solubility, high photoquantum yield, low migration characteristics and excellent development compatibility, and constructing a high-performance photocurable resin composition based on it has become a technical problem to be solved urgently in this field. Summary of the invention

[0009] Therefore, the purpose of the present invention is to overcome the above-mentioned defects of the prior art and provide an anthracene photosensitizer, a photosensitive resin composition and its application which have low electroplating pollution, high photoinitiation efficiency, simple process and low cost.

[0010] After extensive literature research and experimental studies, the present invention has found the following problems and proposed innovative improvement plans: Anthracene compounds or anthracene derivatives can undergo dimerization under light due to their unique structure, thereby being photobleached. This characteristic effectively avoids the problem of excessive energy absorption by the upper photosensitizer during exposure, and enables the bottom layer photosensitive resin composition to receive light more fully, so that the photosensitive resin composition can be uniformly cured during exposure and achieve better resolution. For example, patent CN101218538B discloses 9,10-dialkoxy anthracene photosensitizers, CN110446976B discloses alkoxy anthracene or phenyl anthracene photosensitizers, and CN116300313A discloses 9,10-diacyloxy anthracene or 9,10-diphenyloxy anthracene photosensitizers. The above anthracene photosensitizers all have good resolution and adhesion.

[0011] However, the present invention discovers that during the exposure of 9,10-dialkoxyanthracene photosensitizers, the C-O bonds at the 9,10 positions will break, the anthracene ring will dimerize, and at the same time, small molecule alkoxy fragments will be released. These small molecule fragments will migrate from the cured photosensitive resin composition to the electroplating solution during the subsequent electroplating process, causing pollution and affecting the life of the plating solution and the electroplating effect; due to the electron-withdrawing inductive effect of the acyloxy group, 9,10-diacyloxyanthracene photosensitizers (DAcOA) result in an increase in the electron cloud density at the 9,10 positions of the anthracene ring. Therefore, the efficiency of such photosensitizers in the catalytic curing reaction decreases, the sidewall perpendicularity of the cured photosensitive resin composition is poor, and there is a large difference in the line lengths at the top and bottom, forming a "reverse trapezoid" problem. Moreover, the energy required for the exposure of such photoinitiators increases, and the photo-bleaching efficiency decreases; for 9,10-diarylanthracene photosensitizers, due to their rigid molecular structure, the solubility is greatly reduced, which has a great impact on the uniformity and consistency of the product.

[0012] Based on the above findings, the present invention proposes a photosensitizer based on 9-aminomethylanthracene or 9,10-diaminomethylanthracene, as well as a corresponding initiation system and photosensitive resin composition, which can reduce the problem of photosensitizer migration existing in existing dry film products, thereby reducing developing waste, improving the photo-quantum yield of the photoinitiator, and reducing the exposure energy.

[0013] (I) Photosensitive resin composition

[0014] The first aspect of the present invention provides a photosensitive resin composition. Based on 100 parts by mass of the photosensitive resin composition, it contains the following components: 50 - 65 parts of alkali-soluble resin A; 35 - 50 parts of photopolymerizable monomer B, which is selected from olefinically unsaturated carboxylic acids and / or olefinically unsaturated carboxylic acid esters; 2 - 5 parts of photoinitiator C, which is selected from bisimidazole compounds; and 0.1 - 1 part of photosensitizer D, wherein the photosensitizer D is a 9,10-diaminomethylanthracene compound having the structure of formula (I) or a 9-aminomethylanthracene compound having the structure of formula (II):

[0015]

[0016] Wherein, R 1 、R 2 、R 3 and R 4 each independently selected from hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 unsaturated hydrocarbon group, C6-C12 aryl or C3-C12 heteroaryl, C6-C12 aryl or C3-C12 heteroaryl substituted by one or more C1-C6 alkyl groups, C6-C12 aryl or C3-C12 heteroaryl substituted by one or more C1-C6 alkoxy groups; wherein the group in the formula (I) or formula (II) compound of R 1 、R2 Optionally forms a 3- to 8-membered ring with N; R in the group 3 , R 4 Optionally forms a 3- to 8-membered ring with N,

[0017] Wherein, the photosensitive resin composition is photocured through the following photoinduced free radical polymerization reaction mechanism: the aminomethylanthracene compound is excited by visible light to generate anthracene radicals, which initiate the homolysis of the bisimidazole compound to generate imidazole radicals, and the imidazole radicals activate the ethylenically unsaturated carboxylic acid and / or ethylenically unsaturated carboxylic acid ester to undergo crosslinking curing.

[0018] Specifically, the photocuring process follows the mechanism of photoinduced free radical polymerization: the first step is that the aminomethylanthracene compound as a photosensitizer is excited to generate anthracene radicals after absorbing photons; the second step is that the anthracene radicals cause the homolysis of the bisimidazole compound as a photoinitiator to generate imidazole radicals; the third step, namely the curing stage: the imidazole radicals act on the ethylenically unsaturated carboxylic acid and / or ethylenically unsaturated carboxylic acid ester, open the unsaturated bonds of the activated monomers, and undergo a crosslinking reaction to form a 3D network structure, and the material is rapidly cured and hardened.

[0019] The compound structure involved in the present invention follows the general representation rules in the field of organic chemistry. When the end of the chemical bond in the substituent is presented in a wavy line form, it indicates that the substituent is connected to the parent nucleus structure through the wavy line end point.

[0020] Base-soluble resin A

[0021] According to the photosensitive resin composition provided by the present invention, wherein the base-soluble resin A is an acrylate copolymer containing an aromatic group. From the perspective of improving the product resolution and chemical resistance, preferably, based on the total mass of the comonomers in the copolymerization process, the copolymerization ratio of the comonomer having an aromatic group is 50-70%.

[0022] In some embodiments of the present invention, the alkali-soluble resin A is obtained by copolymerizing one or more of (meth)acrylic acid, (meth)acrylic acid alkyl ester, benzyl (meth)acrylate, benzyl (meth)acrylate derivative, phenyl (meth)acrylate, styrene, and styrene derivative. In some embodiments of the present invention, the alkali-soluble resin A is copolymerized from (meth)acrylic acid and copolymerization units selected from one or more of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and styrene. In some specific embodiments of the present invention, the copolymerization monomers of the alkali-soluble resin A include methacrylic acid, methyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, and styrene.

[0023] Furthermore, the weight-average molecular weight of the alkali-soluble resin A is 20,000 - 60,000, the resin acid value is 160 - 220 mg KOH / g, and the molecular weight distribution index is 1.0 - 3.0. In the embodiments of the present invention, the content of the alkali-soluble resin A is 50 - 65 parts by mass, preferably 55 - 60 parts by mass. If the content is less than 50 parts by mass, there is a tendency for the resist layer to flow, and if the content exceeds 65 parts by mass, there is a tendency for the resolution to decrease.

[0024] Photopolymerizable monomer B

[0025] According to the photosensitive resin composition provided by the present invention, wherein the photopolymerizable monomer B is a monomer having an ethylenically unsaturated double bond, preferably selected from (meth)acrylate monomers. In a preferred embodiment of the present invention, the photopolymerizable monomer B is selected from one or more of methoxypolyethylene glycol monoacrylate, ethoxy(propoxy)nonylphenol acrylate, ethoxy(propoxy)bisphenol A di(meth)acrylate, ethoxy(propoxy)di(meth)acrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, ethoxy(propoxy)trimethylolpropane tri(meth)acrylate, di(trimethylolpropane) tetraacrylate, ethoxy(propoxy)pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

[0026] In the embodiments of the present invention, the content of the photopolymerizable monomer B is 35 - 50 parts by mass, preferably 40 - 50 parts by mass, and more preferably 45 - 50 parts by mass. If the content is less than 35 parts by mass, there is a tendency for the sensitivity and chemical resistance of the resist to decrease, and if the content exceeds 50 parts by mass, there is a tendency for the photosensitive resin composition to be difficult to form a thin film and for the resist layer to flow.

[0027] Photoinitiator C

[0028] The photosensitive resin composition provided by the present invention, wherein the photoinitiator C is a bisimidazole compound, for example, it can be 2,4,5-triaryl imidazole dimer. Typical bisimidazole compounds, such as hexaaryl bisimidazole (HABI): As a representative of bisimidazole photoinitiators, its maximum absorption peak is located at 255-275 nm and is insensitive to long-wave ultraviolet light (such as 365 nm) and visible light; another example is 2-(2-hydroxyphenyl) benzimidazole which has absorption at 320-380 nm and can match with a UV-A light source (such as a 365 nm LED), but is insensitive in the visible light region of 405 nm. The present invention successfully adjusts the working wavelength of the bisimidazole photoinitiator to about 405 nm by using an aminomethyl anthracene photosensitizer that can be excited under 405 nm light illumination conditions.

[0029] In a preferred embodiment of the present invention, the photoinitiator C is selected from one or more of 2-(2-chlorophenyl)-4,5-diphenyl imidazole dimer, 2-(2-chlorophenyl)-4,5-bis(methoxyphenyl) imidazole dimer, 2-(2-fluorophenyl)-4,5-diphenyl imidazole dimer, 2-(2-methoxyphenyl)-4,5-diphenyl imidazole dimer, 2-(4-methoxyphenyl)-4,5-diphenyl imidazole dimer, 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole.

[0030] In an embodiment of the present invention, the content of the photoinitiator C is 2-5 parts by mass, preferably 2-4 parts by mass, and more preferably 2.5-3.5 parts by mass. If the content is less than 2 parts by mass, there is a tendency for the sensitivity and resolution of the resist to decrease; if the content exceeds 5 parts by mass, there is a tendency for an increase in development waste.

[0031] Photosensitizer D

[0032] The photosensitive resin composition provided by the present invention uses an aminomethyl anthracene compound of formula (I) with an aminomethyl functional group introduced at the 9 and / or 10 positions as the photosensitizer D, which has significant advantages compared with existing DBA photosensitizers: By introducing the aminomethyl group, while maintaining the electron cloud density of the polycyclic aromatic hydrocarbon, the maximum absorption wavelength is redshifted, especially suitable for a 405 nm light illumination system, significantly improving the initiation efficiency and reducing the exposure energy; at the same time, it avoids the problem of the cleavage of the alkoxy carbon-oxygen bond caused by p-π conjugation in DBA, effectively inhibiting the generation of small molecule fragments, reducing defects and improving the yield. Compared with 9,10-diaryl anthracene (DPHA) and 9,10-diacyloxy anthracene (DAcOA), this photosensitizer also exhibits better solubility and formulation compatibility. The present invention has the characteristics of simple preparation process and low cost, and can be widely applied to the field of photocuring such as dry film, paint, coating, ink and molding materials.

[0033] In a preferred embodiment of the present invention, the photosensitizer D is selected from one or more of the compounds TM1-TM13 shown below:

[0034]

[0035] .

[0036] The chemical names of the above compounds TM1 to TM13 can be successively called: anthracene-9,10-dimethylamine, N,N'-[anthracene-9,10-diylbis(methylene)]bis(prop-1-amine), N,N'-[anthracene-9,10-diylbis(methylene)]bis(pent-4-en-1-amine), N,N'-[anthracene-9,10-diylbis(methylene)]diphenylamine, N,N'-[anthracene-9,10-diylbis(methylene)]bis(4-methylaniline), N,N'-[anthracene-9,10-diylbis(methylene)]bis(4-methoxyaniline), 1,1'-(anthracene-9,10-diyl)bis(N,N-dimethylmethanamine), N,N'-[anthracene-9,10-diylbis(methylene)]bis(N-ethylethanamine), N,N'-[anthracene-9,10-diyl(methylene)]bis(N-methylprop-2-en-1-amine), N,N'-[anthracene-9,10-diyl(methylene)]bis(N-allylprop-2-en-1-amine), 9,10-bis(piperidin-1-ylmethyl)anthracene, anthracene-9-ylmethanamine, N,N-dimethyl-anthracene-9-ylmethanamine.

[0037] In the embodiment of the present invention, the content of the photosensitizer D is 0.1-1 part by mass, preferably 0.1-0.8 part by mass, and more preferably 0.2-0.5 part by mass. If the content is less than 0.1 part by mass, the sensitivity of the resist tends to decrease. If the content exceeds 1 part by mass, there is a tendency that the bottom layer of the resist is not completely cured, resulting in a "reverse trapezoid" cross-sectional shape of the resist and poor resolution.

[0038] The preparation strategy of the aminomethylanthracene photosensitizer shown in formula (I) of the present invention can be generally deduced through the typical synthesis routes of the examples. Those skilled in the art can clarify the general preparation logic of the aminomethylanthracene photosensitizer based on the conventional principles of organic synthesis and the specific operations for preparing compounds TM1 to TM13 in the examples. For example, the nucleophilic substitution reaction of 9,10-dichloromethylanthracene with different amines adopted in the preparation routes of compounds TM1 to TM13 described in the examples, by adjusting the structure of the amine (aliphatic amine / aromatic amine / unsaturated amine / cyclic amine), reaction conditions (temperature / solvent / protection measures) and post-treatment methods, covers R 1 , R 2 , R 3 and R4 The need for diverse preparation of groups. Those skilled in the art can derive the preparation methods of all aminomethylanthracene photosensitizers of formula (I) by replacing amine reagents and optimizing reaction parameters.

[0039] Other additive E

[0040] In various embodiments of the present invention, as needed, the photosensitive resin composition may further comprise one or more additives E selected from dyes, photochromic agents, plasticizers, adhesion promoters, polymerization inhibitors, defoaming agents, and coating aids. Preferably, the total amount of the additive E is 0.5 - 5.0 parts by mass.

[0041] (II) Photosensitive dry film

[0042] The second aspect of the present invention provides a photosensitive dry film, which comprises, from bottom to top: a support layer; a photosensitive resist layer attached to the surface of the support layer; and a protective layer attached to the surface of the photosensitive resist layer, wherein the photosensitive resist layer is formed by using the photosensitive resin composition provided in the first aspect of the present invention.

[0043] In some preferred embodiments of the present invention, the photosensitive dry film comprises, from bottom to top: a PET support layer, a photosensitive resist layer formed by coating and drying the photosensitive resin composition provided in the first aspect of the present invention on the surface of the PET support layer, and a PE protective layer.

[0044] (III) Applications of the photosensitive dry film

[0045] The third aspect of the present invention provides the applications of the above-mentioned photosensitive dry film in printed circuit boards, lead frames, semiconductor packaging substrates, solar cells, and photocurable inks, etc.

[0046] The present invention has the following beneficial effects: Using the aminomethylanthracene compound of formula (I) with 9 and / or 10 positions introducing aminomethyl functional groups as a photosensitizer has significant advantages compared with the existing DBA photosensitizers: By introducing the aminomethyl group, while maintaining the electron cloud density of the polycyclic aromatic hydrocarbon, the maximum absorption wavelength is redshifted, especially suitable for the 405 nm light illumination system, significantly improving the initiation efficiency and reducing the exposure energy; at the same time, it avoids the problem of the cleavage of the alkoxy carbon-oxygen bond caused by p-π conjugation in DBA, effectively inhibiting the generation of small molecule fragments, reducing defects and increasing the yield. Compared with 9,10-diarylanthracene (DPHA) and 9,10-diacyloxyanthracene (DAcOA), this photosensitizer also exhibits better solubility and formulation compatibility. The present invention has the characteristics of simple preparation process and low cost, and can be widely applied to the photocuring fields such as dry film, paint, coating, ink and molding materials. At the same time, on the basis of maintaining or exceeding the high resolution level of the commercially available anthracene photosensitizers, the present invention can fully meet the requirements of high-precision circuit manufacturing, making the pattern clearer and sharper, and is suitable for the production of miniaturized and high-density electronic devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Hereinafter, the embodiments of the present invention will be described in detail with reference to the drawings, wherein:

[0048] Figure 1 are the 1 H-NMR and 13 C-NMR spectra of the photosensitizer TM1 in Example 1 of the present invention;

[0049] Figure 2 are the 1 H-NMR and 13 C-NMR spectra of the photosensitizer TM2 in Example 2 of the present invention;

[0050] Figure 3 are the 1 H-NMR and 13 C-NMR spectra of the photosensitizer TM3 in Example 3 of the present invention;

[0051] Figure 4 are the 1 H-NMR and 13 C-NMR spectra of the photosensitizer TM4 in Example 4 of the present invention;

[0052] Figure 5 are the 1 H-NMR and 13 C-NMR spectra of the photosensitizer TM5 in Example 5 of the present invention;

[0053] Figure 6 are the 1 H-NMR and 13 C-NMR spectra of the photosensitizer TM6 in Example 6 of the present invention;

[0054] Figure 7 are the 1 H-NMR and 13 C-NMR spectra of photosensitizer TM7 of Example 7 of the present invention;

[0055] Figure 8 are the 1 H-NMR and 13 C-NMR spectra of photosensitizer TM8 of Example 8 of the present invention;

[0056] Figure 9 are the 1 H-NMR and 13 C-NMR spectra of photosensitizer TM9 of Example 9 of the present invention;

[0057] Figure 10 are the 1 H-NMR and 13 C-NMR spectra of photosensitizer TM10 of Example 10 of the present invention;

[0058] Figure 11 are the 1 H-NMR and 13 C-NMR spectra of photosensitizer TM11 of Example 11 of the present invention;

[0059] Figure 12 are the 1 H-NMR and 13 C-NMR spectra of photosensitizer TM12 of Example 12 of the present invention;

[0060] Figure 13 are the 1 H-NMR and 13 C-NMR spectra of photosensitizer TM13 of Example 13 of the present invention;

[0061] Figure 14 are the ultraviolet absorption spectra of photosensitizers TM1, TM2, TM3 and TM4;

[0062] Figure 15 are the ultraviolet absorption spectra of photosensitizers TM5, TM6, TM7 and TM8;

[0063] Figure 16 are the ultraviolet absorption spectra of photosensitizers TM9, TM10 and TM11;

[0064] Figure 17 are the ultraviolet absorption spectrum of photosensitizer TM12;

[0065] Figure 18 are the ultraviolet absorption spectrum of photosensitizer TM13;

[0066] Figure 19 is the UV absorption spectrum of DBA;

[0067] Figure 20 is the UV absorption spectrum of photosensitizer TM1 under 405 nm light irradiation for different irradiation times;

[0068] Figure 21 is the UV absorption spectrum of photosensitizer TM2 under 405 nm light irradiation for different irradiation times;

[0069] Figure 22 is the UV absorption spectrum of photosensitizer TM4 under 405 nm light irradiation for different irradiation times;

[0070] Figure 23 is the UV absorption spectrum of photosensitizer TM7 under 405 nm light irradiation for different irradiation times;

[0071] Figure 24 is the UV absorption spectrum of photosensitizer TM10 under 405 nm light irradiation for different irradiation times;

[0072] Figure 25 is the UV absorption spectrum of photosensitizer TM11 under 405 nm light irradiation for different irradiation times;

[0073] Figure 26 is the UV absorption spectrum of photosensitizer TM12 under 405 nm light irradiation for different irradiation times. Detailed Embodiments

[0074] The present invention will be further described in detail below in conjunction with the detailed embodiments. The examples given are only for clarifying the present invention and not for limiting the scope of the present invention.

[0075] Example 1: Preparation of Photosensitizer TM1

[0076]

[0077] Add 9,10-(bis(chloromethyl))anthracene (1 eq, 1 mmol, 275 mg) and hexamethylenetetramine (2 eq, 2 mmol, 280 mg) to a 50 mL three-necked flask equipped with a magnetic stirrer and a serpentine condenser, and perform nitrogen displacement 3 times. Add 50 ml of chloroform, start stirring, and heat to reflux for reaction. During this period, samples are taken for TLC monitoring. When the raw materials are basically completely reacted and a yellow precipitate appears in the reaction solution, filter by suction to obtain a yellow solid and wash it 3 times with chloroform. Add the crude product to a mixed solution (5 ml of concentrated HCl and 40 ml of ethanol) and heat to reflux for 24 h. After cooling to 0 °C, filter the solid precipitate, and use 10% Na2 CO 3 The product was washed with 20 mL of solution and dried in vacuo to obtain 142 mg of yellow solid TM1 with a yield of 60%. (In the reaction formula, "reflux" represents reflux.)

[0078] Figure 1 is that of photosensitizer TM1 1 1H-NMR spectrum and 13 13C-NMR spectrum.

[0079] 1 1H NMR (400 MHz, CDCl 3 ): δ 8.41 (d, J = 10.20 Hz, 4H), 7.57 (d, J =10.16 Hz, 4H), 4.84 (s, 4H), 1.64 (s, 4H).

[0080] 13 13C NMR (100 MHz, CDCl3): δ 134.9, 129.5, 125.9, 124.8, 38.6.

[0081] Example 2: Preparation of photosensitizer TM2

[0082]

[0083] 9,10-(Bis(chloromethyl))anthracene (1 eq, 1 mmol, 275 mg) and tetrabutylammonium bromide (0.1 eq, 0.1 mmol, 32 mg) were added to a 50 mL single-necked flask equipped with a magnetic stir bar, and the system was purged with nitrogen three times. 5 mL of toluene was added, and the mixture was stirred. Aqueous sodium hydroxide solution (30%, 3 eq, 3 mmol, 120 mg) was added dropwise, followed by n-propylamine (5 eq, 5 mmol, 296 mg). The reaction mixture was heated to 60 °C and monitored by TLC during the reaction. When the raw materials were almost completely reacted, the reaction mixture was cooled to room temperature, transferred to a separatory funnel, and extracted three times with DCM. The organic phase was dried over anhydrous Na 2 SO 4 and the solvent was removed by distillation under reduced pressure. The crude product was separated by column chromatography to obtain 256 mg of yellow solid TM2 with a yield of 80%.

[0084] 1 1H NMR (400 MHz, CDCl 3): δ 8.39 (d, J = 10.19 Hz, 4H), 7.54 (d, J =10.17 Hz, 4H), 4.72 (s, 4H), 2.86 (t, J = 7.25 Hz, 4H), 1.67 – 1.56 (m, 6H),0.97 (t, J = 7.38 Hz, 6H).

[0085] 13 C NMR (100 MHz, CDCl 3 ): δ 132.3, 130.2, 125.7, 125.0, 52.7, 46.1,23.4, 12.0.

[0086] Example 3: Preparation of Photosensitizer TM3

[0087]

[0088] Add 9,10-(bis(chloromethyl))anthracene (1 eq, 1 mmol, 275 mg) and tetrabutylammonium bromide (0.1 eq, 0.1 mmol, 32 mg) into a 50 mL single-necked flask equipped with a magnetic stir bar, and conduct nitrogen displacement three times. Add 5 ml of toluene, start stirring, and dropwise add 30% aqueous sodium hydroxide solution (3 eq, 3 mmol, 120 mg). Then dropwise add 4-penten-1-amine (5 eq, 5 mmol, 426 mg). Keep it in the dark and heat up to 60 °C for reaction. During the reaction, take samples for TLC monitoring. After the raw materials have basically reacted completely, cool the reaction solution back to room temperature, transfer the reaction solution to a separatory funnel and extract it three times with DCM. The organic phase is dried with anhydrous Na 2 SO 4 and dried, and the solvent is removed by distillation under reduced pressure. The crude product is separated by column chromatography to obtain 279 mg of yellow solid TM3 with a yield of 75%.

[0089] 1 H NMR (400 MHz, CDCl 3): δ 8.38 (d, J = 10.18 Hz, 4H), 7.54 (d, J =10.14 Hz, 4H), 5.83 (ddt, J = 16.93, 10.12, 6.68 Hz, 2H), 5.02 (dd, J =17.09, 1.85 Hz, 2H), 4.96 (dd, J = 10.15, 1.90 Hz, 2H), 4.71 (s, 4H), 3.69(q, J = 7.01 Hz, 2H), 2.90 (t, J = 7.20 Hz, 4H), 2.14 (q, J = 7.18 Hz, 4H),1.70 (p, J = 7.33 Hz, 4H).

[0090] 13 C NMR (100 MHz, CDCl 3 ): δ 138.6, 132.2, 130.2, 125.8, 125.0, 114.9,50.1, 46.1, 31.7, 29.3.

[0091] Example 4: Preparation of Photosensitizer TM4

[0092] Add 9,10-bis(chloromethyl)anthracene (1 eq, 1 mmol, 275 mg) and tetrabutylammonium bromide (0.1 eq, 0.1 mmol, 32 mg) to a 50 mL single-necked flask equipped with a magnetic stir bar, and perform nitrogen displacement 3 times. Add 5 ml of toluene, start stirring, and dropwise add 30% aqueous sodium hydroxide solution (3 eq, 3 mmol, 120 mg). Then dropwise add aniline (3 eq, 3 mmol, 279 mg), and raise the temperature to 60 °C for reaction. During the reaction, take samples for TLC monitoring. After the raw materials have basically reacted completely, cool the reaction solution to room temperature, transfer the reaction solution to a separatory funnel, and extract it 3 times with DCM. The organic phase is dried with anhydrous Na 2 SO 4 and dried, and the solvent is removed by distillation under reduced pressure. The crude product is separated by column chromatography to obtain 280 mg of yellow solid TM4 with a yield of 72%.

[0093] 1 H NMR (400 MHz, CDCl 3): δ 8.35 (d, J = 10.12 Hz, 4H), 7.54 (d, J = 10.12 Hz, 4H), 7.31 (t, J = 7.16 Hz, 4H), 6.86 - 6.82 (m, 6H), 5.19 (s, 4H), 3.88 (s, 2H).

[0094] 13 C NMR (100 MHz, CDCl 3 ): δ 148.5, 130.8, 130.4, 129.6, 126.4, 125.0, 118.0, 112.8, 41.2.

[0095] Example 5: Preparation of Photosensitizer TM5

[0096]

[0097] Add 9,10 - (bis(chloromethyl))anthracene (1 eq, 1 mmol, 275 mg), tetrabutylammonium bromide (0.1 eq, 0.1 mmol, 32 mg), and p - toluidine (3 eq, 3 mmol, 321 mg) into a 50 mL single - necked flask equipped with a magnetic stir bar. Replace the air with nitrogen three times. Add 5 ml of toluene, start stirring, and dropwise add 30% aqueous sodium hydroxide solution (3 eq, 3 mmol, 120 mg). Heat the reaction mixture to 60 °C for reaction, and monitor the reaction by TLC during the process. After the raw materials are basically completely reacted, cool the reaction solution to room temperature, transfer the reaction solution to a separatory funnel, and extract it with DCM three times. The organic phase is dried with anhydrous Na 2 SO 4 and the solvent is removed by distillation under reduced pressure. The crude product is separated by column chromatography to obtain 300 mg of yellow solid TM5 with a yield of 72%.

[0098] 1 1H NMR (400 MHz, CDCl 3 ): δ 8.34 (d, J = 10.12, 4H), 7.53 (d, J = 10.12 Hz, 4H), 6.91 (d, J = 8.88 Hz, 4H), 6.79 (d, J = 8.88 Hz, 4H), 5.12 (s, 4H), 3.83 (s, 6H), 3.64 (s, 2H).

[0099] 13 C NMR (100 MHz, CDCl 3): δ 152.5, 142.3, 131.5, 130.4, 128.0, 125.1, 117.8, 113.4, 60.1, 42.7.

[0100] Example 6: Preparation of Photosensitizer TM6

[0101]

[0102] Add 9,10-(bis(chloromethyl)anthracene) (1 eq, 1 mmol, 275 mg), tetrabutylammonium bromide (0.1 eq, 0.1 mmol, 32 mg), and p-methoxyaniline (3 eq, 3 mmol, 369 mg) to a 50 mL single-necked flask equipped with a magnetic stir bar. Replace the air with nitrogen three times. Add 5 mL of toluene, start stirring, and slowly add 30% aqueous sodium hydroxide solution (3 eq, 3 mmol, 120 mg). Heat the reaction mixture to 60 °C and monitor the reaction progress by TLC. After the reaction is complete, let the reaction mixture cool to room temperature, transfer it to a separatory funnel, and extract it three times with DCM. Dry the organic phase with anhydrous Na 2 SO 4 and remove the solvent by rotary evaporation under reduced pressure. The crude product is purified by column chromatography to obtain 313 mg of a yellowish-brown solid TM6 with a yield of 70%.

[0103] 1 H NMR (400 MHz, (CD 3 ) 2 SO): δ 8.34 (d, J = 10.44 Hz, 4H), 7.57 (d, J = 10.44 Hz, 4H), 6.82 (s, 8H), 5.43 (t, J = 5.00 Hz, 2H), 5.03 (s, 4H), 3.69 (s, 6H).

[0104] 13 C NMR (100 MHz, (CD 3 ) 2 SO): δ 151.0, 143.6, 131.0, 129.9, 125.8, 125.2, 114.6, 113.2, 55.4, 40.9.

[0105] Example 7: Preparation of Photosensitizer TM7

[0106]

[0107] Add 9,10-(bis(chloromethyl))anthracene (1 eq, 1 mmol, 275 mg), tetrabutylammonium bromide (0.1 eq, 0.1 mmol, 32 mg) to a 50 mL single-necked flask equipped with a magnetic stir bar, and perform nitrogen displacement three times. Add 5 mL of toluene, start stirring, and dropwise add 30% aqueous sodium hydroxide solution (3 eq, 3 mmol, 120 mg), then dropwise add dimethylamine solution (5 eq, 5 mmol, 225 mg). Heat the mixture to 60 °C for reaction, and monitor the reaction by TLC sampling during the process. After the raw materials have basically reacted completely, let the reaction solution return to room temperature, transfer the reaction solution to a separatory funnel, and extract it three times with DCM. The organic phase is dried with anhydrous Na 2 SO 4 and the solvent is removed by distillation under reduced pressure. The crude product is separated by column chromatography to obtain 248 mg of yellow solid TM7 with a yield of 85%.

[0108] 1 H NMR (400 MHz, CDCl 3 ): δ 8.52 (d, J = 10.27 Hz, 4H), 7.52 (d, J =10.20 Hz, 4H), 4.40 (s, 4H), 2.39 (s, 12H).

[0109] 13 C NMR (100 MHz, CDCl 3 ): δ 130.9, 130.8, 125.4, 125.2, 55.4, 45.7.

[0110] Example 8: Preparation of photosensitizer TM8

[0111]

[0112] Add 9,10-(bis(chloromethyl))anthracene (1 eq, 1 mmol, 275 mg), tetrabutylammonium bromide (0.1 eq, 0.1 mmol, 32 mg) to a 50 mL single-necked flask equipped with a magnetic stir bar, and perform nitrogen displacement three times. Add 5 mL of toluene, start stirring, and dropwise add 30% aqueous sodium hydroxide solution (3 eq, 3 mmol, 120 mg), then dropwise add diethylamine solution (5 eq, 5 mmol, 366 mg). Heat the mixture to 60 °C for reaction, and monitor the reaction by TLC sampling during the process. After the raw materials have basically reacted completely, let the reaction solution return to room temperature, transfer the reaction solution to a separatory funnel, and extract it three times with DCM. The organic phase is dried with anhydrous Na 2 SO 4Dry it, and remove the solvent by distillation under reduced pressure. The crude product was separated by column chromatography to obtain 293 mg of yellow solid TM8 with a yield of 84%.

[0113] 1 H NMR (400 MHz, CDCl 3 ): δ 8.61 (d, J = 10.45 Hz, 4H), 7.51 (d, J =10.43 Hz, 4H), 4.55 (s, 4H), 2.68 (q, J = 6.79 Hz, 8H), 1.12 (t, J = 7.11 Hz,12H).

[0114] 13 C NMR (100 MHz, CDCl 3 ): δ 131.2(bs), 125.7, 124.9, 50.4, 46.6, 11.8.

[0115] Example 9: Preparation of photosensitizer TM9

[0116]

[0117] Add 9,10-(bis(chloromethyl))anthracene (1 eq, 1 mmol, 275 mg) and tetrabutylammonium bromide (0.1 eq, 0.1 mmol, 32 mg) to a 50 mL single-necked flask equipped with a magnetic stir bar, and displace with nitrogen three times. Add 5 ml of toluene, start stirring, and dropwise add 30% aqueous sodium hydroxide solution (3 eq, 3 mmol, 120 mg). Then dropwise add N-methylallylamine (5 eq, 5 mmol, 356 mg). Keep it in the dark and heat to 60 °C for reaction, and monitor the reaction by TLC during the process. When the raw materials are basically completely reacted, cool the reaction solution to room temperature, transfer the reaction solution to a separatory funnel and extract it three times with DCM. The organic phase was dried with anhydrous Na 2 SO 4 Dry it, and remove the solvent by distillation under reduced pressure. The crude product was separated by column chromatography to obtain 248 mg of yellow solid TM9 with a yield of 72%.

[0118] 1 H NMR (400 MHz, ( CDCl 3): δ 8.56 (d, J = 10.24 Hz, 4H), 7.57 (d, J =10.24 Hz, 4H), 6.05(ddt, J = 16.81, 10.13, 6.58 Hz, 2H), 5.30 (dd, J = 17.18,1.77 Hz, 2H), 5.22 (dd, J = 10.14, 2.00 Hz, 2H), 4.47 (s, 4H), 3.27 (d, J =6.63 Hz, 4H), 2.27 (s, 6H).

[0119] 13 C NMR (100 MHz, ( CDCl 3 ): δ 136.1, 131.1, 131.0, 125.6, 125.2,117.9, 61.5, 53.3, 42.2.

[0120] Example 10: Preparation of Photosensitizer TM10

[0121]

[0122] Add 9,10-bis(chloromethyl)anthracene (1 eq, 1 mmol, 275 mg) and tetrabutylammonium bromide (0.1 eq, 0.1 mmol, 32 mg) to a 50 mL single-necked flask equipped with a magnetic stir bar, and replace the nitrogen 3 times. Add 5 ml of toluene, start stirring, and dropwise add 30% aqueous sodium hydroxide solution (3 eq, 3 mmol, 120 mg). Then dropwise add diallylamine (4 eq, 4 mmol, 389 mg), keep it in the dark, heat up to 60 °C for reaction, and take samples for TLC monitoring during the reaction. After the raw materials are basically completely reacted, cool the reaction solution to room temperature, transfer the reaction solution to a separatory funnel and extract it with DCM 3 times. The organic phase is dried with anhydrous Na 2 SO 4 and dried, and the solvent is removed by distillation under reduced pressure. The crude product is separated by column chromatography to obtain 293 mg of yellow solid TM10 with a yield of 74%.

[0123] 1 H NMR (400 MHz, CDCl 3): δ 8.59 (d, J = 10.28 Hz, 4H), 7.53 (d, J =10.21 Hz, 4H), 5.96 (ddt, J = 16.82, 10.19, 6.53 Hz, 4H), 5.22 (dd, J =17.15, 1.82 Hz, 4H), 5.16 (dd, J = 10.14, 1.98 Hz, 4H), 4.54 (s, 4H), 3.21(d, J = 6.76 Hz, 8H).

[0124] 13 C NMR (100 MHz, CDCl 3 ): δ 136.3, 131.3, 131.1, 125.8, 125.0, 117.8,57.0, 50.5.

[0125] Example 11: Preparation of Photosensitizer TM11

[0126]

[0127] Add 9,10-bis(chloromethyl)anthracene (1 eq, 1 mmol, 275 mg) and tetrabutylammonium bromide (0.1 eq, 0.1 mmol, 32 mg) to a 50 mL single-necked flask equipped with a magnetic stir bar, and perform three nitrogen displacements. Add 5 mL of toluene, start stirring, and dropwise add 30% aqueous sodium hydroxide solution (3 eq, 3 mmol, 120 mg). Then dropwise add piperidine (4 eq, 4 mmol, 341 mg), and raise the temperature to 60 °C for reaction. During the reaction, samples are taken for TLC monitoring. After the raw materials have basically reacted completely, cool the reaction solution to room temperature, transfer the reaction solution to a separatory funnel, and extract it three times with DCM. The organic phase is dried with anhydrous Na 2 SO 4 and the solvent is removed by distillation under reduced pressure. The crude product is separated by column chromatography to obtain 279 mg of yellow solid TM11 with a yield of 75%.

[0128] 1 H NMR (400 MHz, CDCl 3 ): δ 8.57 (d, J = 10.28 Hz, 4H), 7.49 (d, J =10.26 Hz, 4H), 4.38 (s, 4H), 2.58 (t, J = 5.11 Hz, 8H), 1.56 – 1.43 (m, 10H).

[0129] 1313C NMR (100 MHz, CDCl 3 ): δ 131.3, 130.9, 125.9, 124.9, 55.4, 54.9, 26.3, 24.7.

[0130] Example 12: Photosensitizer TM12

[0131]

[0132] This product can be directly purchased. CAS No.: 18004 - 58 - 5, brand Leyan, purity 98%, product number 1824286.

[0133] 1 1H NMR (400 MHz, CDCl 3 ): δ 8.40 (s, 1H), 8.34 (d, J = 7.51 Hz, 2H), 8.02 (d, J = 8.17 Hz, 2H), 7.55 (t, J = 8.00 Hz, 2H), 7.48 (t, J = 7.80 Hz, 2H), 4.83 (s, 2H), 1.68 (s, 2H).

[0134] 13 13C NMR (100 MHz, CDCl 3 ): δ δ 134.8, 131.8, 129.5, 129.4, 127.0, 126.3, 125.1, 123.9, 38.4.

[0135] Example 13: Preparation of Photosensitizer TM13

[0136]

[0137] Add 9 - chloromethylanthracene (1 eq, 1 mmol, 226 mg) and tetrabutylammonium bromide (0.1 eq, 0.1 mmol, 32 mg) to a 50 mL single - necked flask equipped with a magnetic stir bar, and conduct nitrogen displacement 3 times. Add 5 ml of toluene, start stirring, and dropwise add 30% aqueous sodium hydroxide solution (2 eq, 2 mmol, 80 mg), then dropwise add dimethylamine solution (2.5 eq, 2.5 mmol, 102 mg). Heat the mixture to 60 °C for reaction, and monitor the reaction by TLC during the process. After the raw materials have basically reacted completely, cool the reaction solution to room temperature, transfer the reaction solution to a separatory funnel, and extract it with DCM 3 times. The organic phase is dried with anhydrous Na 2 SO 4Dry under reduced pressure to distill off the solvent. The crude product was separated by column chromatography to obtain 202 mg of yellow solid TM13 with a yield of 86%.

[0138] 1 H NMR (400 MHz, CDCl 3 ): δ 8.48 (d, J = 8.95 Hz, 2H), 8.43 (s, 1H), 8.02 (d, J = 8.33 Hz, 2H), 7.54 (t, J = 8.00 Hz, 2H), 7.47 (t, J = 8.12 Hz, 2H), 4.39 (s, 2H), 2.40 (s, 6H).

[0139] 13 C NMR (100 MHz, CDCl 3 ): δ 131.6, 131.4, 130.5, 129.1, 127.6, 125.9, 124.9(bs), 55.5, 45.8.

[0140] Figure 1-13 Successively are the 1 H-NMR spectra and 13 C-NMR spectra of photosensitizers TM1 - TM13.

[0141] Example 14: UV-Visible Absorption Spectroscopy (UV-vis) Measurement and Photobleaching Experiment

[0142] The UV-visible absorption spectrum (UV-vis) was measured on a Shimadzu UV-1900 UV-visible spectrophotometer using toluene as the solvent at a concentration of 4×10 -5 mol / L.

[0143] According to the Lambert-Beer law, the molar extinction coefficient ε = A bn / c, where A bn is the absorbance of the UV-visible absorption spectrum and c is the concentration.

[0144] Photobleaching experiment: Using toluene as the solvent, under a 450 nm LED, the change in the UV-visible absorption spectrum of the sample solution was measured with a Shimadzu UV-1900 UV-visible spectrophotometer.

[0145] Figure 14 are the UV absorption spectra of TM1, TM2, TM3, TM4; Figure 15 are the UV absorption spectra of TM5, TM6, TM7, TM8; Figure 16 are the UV absorption spectra of TM9, TM10, TM11. Figure 17It is the ultraviolet absorption spectrum of TM12; Figure 18 It is the ultraviolet absorption spectrum of TM13; Figure 19 It is the ultraviolet absorption spectrum of DBA; Figure 20-26 They are the ultraviolet absorption spectra of the photosensitizers TM1, TM2, TM4, TM7, TM10, TM12, TM13 of the present invention after different illumination times under the illumination condition of 405 nm. The molar extinction coefficient results of the photosensitizers TM1-TM13 and DBA are shown in Table 1 below:

[0146]

[0147] It can be seen from the comparison of the ultraviolet absorption spectra in Table 1 that the photosensitizers of the present invention generally have higher molar extinction coefficients compared with DBA, and even some are more than 50% higher;

[0148] Through Figure 14-26 It can be seen from the comparison of the ultraviolet absorption spectra that the photosensitizers of the present invention have very good photobleaching performance and can be completely photobleached within 90 minutes.

[0149] III. Solubility Test

[0150] Taking acetone, toluene and methanol as solvent representatives, the solubility of the photosensitizers TM1-TM13 of Examples 1-13 and DBA, DPHA and DAcOA in the solvents was tested. The solute was added to the solvent according to the ratio of 0.1 g solute / 1 g solvent (10% w / w), and the dissolution situation was recorded according to the following classification criteria. The test results are shown in Table 2:

[0151] A (rapid dissolution): A clear, transparent and uniform solution can be formed within 1 minute at room temperature and under stirring conditions;

[0152] B (slow dissolution): A clear, transparent and uniform solution can be formed after more than 5 minutes at room temperature and under stirring conditions; or it cannot be completely dissolved at room temperature, but a clear, transparent and uniform solution can be formed when heated to 50-60 °C, and there is no obvious turbidity after returning to room temperature;

[0153] C (partial dissolution): It cannot be completely dissolved after more than 5 minutes at room temperature and under stirring conditions; or it can be completely dissolved when heated to 50-60 °C, but it becomes significantly turbid after returning to room temperature.

[0154]

[0155] It can be seen from the data in Table 2 that compared with the conventional photosensitizers DBA, DPHA and DAcOA in the prior art, the photosensitizers TM1-TM13 of the present invention mostly show better solubility in various common solvents.

[0156] Example 15: Preparation of Photosensitive Resin Composition

[0157] According to the formulation shown in Table 3, each component was uniformly mixed to prepare a photosensitive resin composition.

[0158]

[0159] Note: The weights in Table 3 are calculated based on the solid content and do not include the solvent component.

[0160] The component descriptions of each component code in Table 3 are as follows:

[0161] Alkali-soluble resin A: Acrylate copolymer, solution polymerization method, polymerized according to the mass ratio of methacrylic acid / butyl methacrylate / benzyl methacrylate = 25 / 10 / 65; the solvent is acetone, the solid content is 46%, the weight average molecular weight is 40,000, the dispersity is 2.1, and the acid value is 163 mgKOH / g. (Hunan Chuyuan New Materials Co., Ltd.)

[0162] The photoinitiator monomer B consists of the following components (purchased from Sartomer Guangzhou Chemical Co., Ltd.): 5 g of methoxypolyethylene glycol (350) monomethacrylate, 20 g of 10 (ethoxy) bisphenol A dimethacrylate, 5 g of 6 (propoxy) bisphenol A dimethacrylate, 10 g of 3(ethoxy) trimethylolpropane triacrylate, 4 g of bis (trimethylolpropane) tetraacrylate

[0163] Photoinitiator C: 2,2’-bis(2-chlorophenyl)-4,4’,5,5’-tetraphenyl-1H-imidazole (BCIM)

[0164] Additive E consists of the following components (purchased from Energy Chemical): 0.5 g of leuco crystal violet, 0.05 g of malachite green, 0.8 g of p-toluenesulfonamide, 0.03 g of 2,6-di-tert-butyl-4-methylphenol

[0165] The solvent consists of the following components: 8% acetone, 10% toluene, 5% methanol

[0166] Example 16: Preparation of Photosensitive Dry Film

[0167] The photosensitive resin composition listed in Table 3 of Example 15 was used to prepare a photosensitive dry film, including the following steps:

[0168] Using experimental equipment (model: AB4220, TQC, Netherlands), the photosensitive composition slurry prepared according to Table 3 was respectively coated on a 15 μm thick polyethylene terephthalate (PET) support film; baked at 80 °C for 10 min to remove the solvent, and the thickness of the photosensitive layer after baking was controlled at 30 μm, and then covered with a polyethylene film (PE) for protection to obtain a photosensitive dry film.

[0169] Example 17: Preparation of Substrate with Resist Pattern

[0170] A substrate with a resist pattern was prepared using the photosensitive compositions of Samples 1-9 of the examples and Comparative Samples 1-3 of the present invention shown in Table 3. The procedures are as follows:

[0171] (1) Photosensitive layer formation step: A photosensitive layer was formed on the substrate using the photosensitive composition.

[0172] (2) Exposure step: A part of the above photosensitive layer was irradiated with actinic rays to photocure the above area to form a cured area.

[0173] (3) Development step: The part of the above photosensitive layer other than the cured area was removed from the substrate to form a resist pattern on the substrate.

[0174] Hereinafter, the operating conditions of each step will be specifically described.

[0175] Photosensitive layer formation step: A copper-clad laminate with a 35-μm-thick rolled 1.2-mm-thick copper foil was used. After surface conditioning and preheating to 80 °C, while peeling off the PE protective film of the photosensitive dry film obtained from each example or comparative example, the above photosensitive resin composition layer was laminated on the copper-clad laminate using a hot roll laminator (Zisheng Technology Co., Ltd., CSL-M25E) under the conditions of a roll temperature of 110 °C, an air pressure of 0.35 MPa, and a lamination speed of 1.5 m / min to obtain a test substrate.

[0176] Exposure step: Exposure was performed using a direct drawing exposure machine (Xinqi Micro, main wavelength 405 nm). A Stouffer 41-step exposure scale was used for the sensitivity test, and the exposure grid count was controlled within 14-18 grids.

[0177] Development step: After exposure, the PET support film was peeled off. A caustic developer (manufactured by Guangzhou Julong Printed Circuit Board Equipment Co., Ltd., a developer for dry film) was used to spray a 1 wt% Na 2 CO 3 aqueous solution at 30 °C for twice the minimum development time to dissolve and remove the unexposed part of the photosensitive resin layer. After development, washing was performed with pure water for 1.5 times the development time, and water removal treatment was performed using an air knife, followed by warm air drying to obtain a substrate with a cured film for evaluation. The shortest time required for complete dissolution of the unexposed part of the photosensitive resin layer was defined as the minimum development time.

[0178] Evaluation Items

[0179] 1. Sensitivity Evaluation

[0180] On the above-mentioned test substrate after film lamination, a Stouffer 41-step exposure ruler was placed for sensitivity testing. After the exposure process, the test substrate was left standing for more than 20 minutes, and then the PET film layer was peeled off. A 1.0 wt% sodium carbonate aqueous solution was sprayed at 30 °C to remove the unexposed resist layer, and the development time was 2.0 times the minimum development time. After the above operations, a cured film obtained by curing the photosensitive resin composition was formed on the substrate surface. The exposure energy (mJ / cm 2 ), when the number of remaining segments of the step exposure ruler obtained through the cured film was 16 segments, was used to evaluate the sensitivity of the photosensitive resin composition. The smaller this value, the better the sensitivity.

[0181] 2. Adhesion evaluation

[0182] On the above-mentioned test substrate after film lamination, using photomask data with a line width / spacing width of n:400 (unit: μm) wiring pattern, exposure was carried out with an energy that made the number of remaining step levels after developing the Stouffer 41-step exposure ruler reach 16. After the development process, an optical microscope was used to observe the resist pattern, and the value of the minimum line width where a complete cured resist line was formed was used as the value of adhesion to evaluate adhesion (μm). The smaller this value, the better the adhesion.

[0183] 3. Resolution evaluation

[0184] On the above-mentioned test substrate after film lamination, using photomask data with a line width / spacing width of n:n (unit: μm) wiring pattern, exposure was carried out with an energy that made the number of remaining step levels after developing the Stouffer 41-step exposure ruler reach 16. After the development process, an optical microscope was used to observe the resist pattern, and the value of the minimum line width where a complete cured resist line was formed was used as the value of adhesion to evaluate adhesion (μm). The smaller this value, the better the resolution.

[0185] 4. Resist shape evaluation

[0186] In the resist pattern used for the above resolution evaluation, the best resolution part was observed with a SU1000 type scanning electron microscope (manufactured by Hitachi). Evaluation was carried out according to the following evaluation criteria:

[0187] ■: The difference between the top and bottom widths at the front cross-section of the resist is less than or equal to 0.8 μm, and basically no inverted trapezoid can be observed;

[0188] ○: The difference between the top and bottom widths at the front cross-section of the resist is greater than 0.8 μm and less than 1.2 μm, and the cross-section is slightly inverted trapezoidal;

[0189] ×: The width difference between the top and bottom at the front cross-section of the resist is greater than or equal to 1.2 μm, and the cross-section is an obvious inverted trapezoid.

[0190] The test results of evaluation items 1-4 are summarized in Table 4 below.

[0191]

[0192] The results in Table 4 show that, in terms of exposure energy, the samples of the present invention are slightly higher than DPHA, equal to DBA, and lower than DAcOA; under the condition of ensuring the same resolution, the samples of the present invention have obvious advantages in adhesion and developed images, and solve the problem that the resist formed by the curing of photosensitizers DBA, DPHA and DAcOA is prone to form an inverted trapezoid. In addition, the experimental data of Examples 6-9 show that as the amount of photosensitizer added gradually decreases to 0.28 g (70% of the parallel experiment reference amount), the photosensitive performance equivalent to the reference amount can still be maintained, and the photosensitive performance is insufficient until the amount is reduced to 0.24 g (60% of the parallel experiment reference amount), indicating that the photosensitizer of the present invention has high photosensitive efficiency and a wide process application window, can maintain the stability of the system performance while reducing the usage amount and production cost, and demonstrates excellent formulation adaptability.

[0193] The above content is only the preferred embodiment of the present invention and is not used to limit the present invention. Those skilled in the art can make various modifications and changes under the spirit and principle of the present invention. Any modification, equivalent substitution or improvement within this scope shall be regarded as covered by the protection scope of the present invention.

Claims

1. A photosensitive resin composition, characterized in that: Based on 100 parts by mass of the photosensitive resin composition, it comprises the following components: 50-65 parts of an alkali-soluble resin A; 35-50 parts of a photopolymerizable monomer B selected from ethylenically unsaturated carboxylic acids and / or ethylenically unsaturated carboxylic acid esters; 2-5 parts of a photoinitiator C selected from bisimidazole compounds; and 0.1-1 part of photosensitizer D, Wherein, the photosensitizer D is a 9,10-diaminomethylanthracene compound having a structure of formula (I) or a 9-aminomethylanthracene compound having a structure of formula (II): wherein R1, R2, R3 and R4 are each independently selected from hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 unsaturated hydrocarbon, C6-C12 aryl or C3-C12 heteroaryl, C6-C12 aryl or C3-C12 heteroaryl substituted by one or more C1-C6 alkyl, C6-C12 aryl or C3-C12 heteroaryl substituted by one or more C1-C6 alkoxy; wherein the compound of formula (I) or formula (II) R1, R2 and N in the group optionally form a 3-8 membered ring; R3, R4 and N in the group optionally form a 3-8 membered ring, The photosensitive resin composition is photocured through the following photoinduced free radical polymerization reaction mechanism: the aminomethylanthracene compound is excited by visible light to generate anthracene free radicals, which trigger the homolysis of the biimidazole compound to generate imidazole free radicals, and the imidazole free radicals activate the ethylenically unsaturated carboxylic acid and / or ethylenically unsaturated carboxylic acid ester to cause cross-linking and curing.

2. The photosensitive resin composition according to claim 1, characterized in that: The photosensitizer D is selected from one or more of the following compounds TM1-TM13: 。 3. The photosensitive resin composition according to claim 1, characterized in that: The content of the photosensitizer D is 0.1-0.8 parts by mass, preferably 0.2-0.5 parts by mass.

4. The photosensitive resin composition according to claim 1, characterized in that: The alkali-soluble resin A is an acrylate copolymer containing an aromatic group; preferably, the copolymerization ratio of the copolymer having an aromatic group is 50-70% based on the total mass of the copolymerized monomers during the copolymerization process; preferably, the alkali-soluble resin A is copolymerized with (meth)acrylic acid and a copolymerization unit, and the copolymerization unit is selected from one or more of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, hydroxyethyl (meth)acrylate, and styrene; preferably, the weight average molecular weight of the alkali-soluble resin A is 20,000-60,000, the resin acid value is 160-220 mg KOH / g, and the molecular weight distribution index is 1.0-3.

0.

5. The photosensitive resin composition according to claim 1, characterized in that: The photopolymerizable monomer B is a (meth)acrylate monomer; preferably, the photopolymerizable monomer B is selected from one or more of methoxy polyethylene glycol monoacrylate, ethoxy (propoxy) nonylphenol acrylate, ethoxy (propoxy) bisphenol A di(meth)acrylate, ethoxy (propoxy) di(meth)acrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, ethoxy (propoxy) trimethylolpropane tri(meth)acrylate, di(trimethylolpropane) tetraacrylate, ethoxy (propoxy) pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate; preferably, the content of the photopolymerizable monomer B is 40-50 parts by mass, more preferably 45-50 parts by mass.

6. The photosensitive resin composition according to claim 1, characterized in that: The photoinitiator C is a 2,4,5-triaryl imidazole dimer; preferably, the photoinitiator C is selected from one or more of 2-(2-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(2-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(4-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,2',4-tri(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole; preferably, the content of the photoinitiator C is 2-4 parts by mass, more preferably 2.5-3.5 parts by mass.

7. The photosensitive resin composition according to claim 1, characterized in that: The photosensitive resin composition further comprises one or more additives E selected from dyes, photochromic agents, plasticizers, adhesion promoters, polymerization inhibitors, defoaming agents, and coating aids; preferably, the total amount of the additives E is 0.5-5.0 parts by weight.

8. A photosensitive dry film, comprising from bottom to top: Support layer; a photosensitive resist layer attached to the surface of the support layer; and a protective layer attached to the surface of the photoresist layer, It is characterized in that the photosensitive resist layer is formed by using the photosensitive resin composition according to any one of claims 1 to 7.

9. The photosensitive dry film according to claim 8, characterized in that: The support layer material is PET, and the protection layer material is PE.

10. Use of the photosensitive dry film according to claim 8 or 9 in printed circuit boards, lead frames, semiconductor packaging substrates, solar cells and photocurable inks.

Images