Multiband photosensitive solder resist ink, preparation method and application thereof

Abstract

This invention discloses a multi-band photosensitive solder resist ink, its preparation method, and its application. The ink comprises the following components: epoxy acrylate resin; acrylate polymer solution; composite photosensitizer; multifunctional monomer resin; filler; and additives. The composite photosensitizer includes 2-methyl-1-(4-methylthiomethyl)-2-morpholine-1-propanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-isopropylthioxanthone, and tetraethylmienone-4,4-bis(diethylamino)benzophenone. Traditional photosensitive inks have limited applicability in LED exposure machines and LDI lithography machines, failing to meet the combined needs of multiple devices. The ink provided by this invention has broader applicability, enabling simultaneous use in both LED exposure machines and LDI lithography machines, thereby improving equipment flexibility and efficiency.

Description

Technical Field

[0001] This invention relates to the field of solder resist ink technology, and in particular to a multi-band photosensitive solder resist ink, its preparation method, and its application. Background Technology

[0002] In the production process of LEDs (light-emitting diodes), photosensitive solder resist ink is typically used to protect the conductive circuitry. This ink plays a crucial role in ensuring smooth circuit connection and soldering, laying the foundation for the efficient illumination and stable operation of LED lights.

[0003] Meanwhile, two main exposure technologies are typically used in LED manufacturing: LED exposure machines and LDI lithography machines. LED exposure machines primarily utilize wavelengths of 385, 395, and 405 nm, each with its own characteristics and specifically designed for different manufacturing processes. On the other hand, LDI lithography machines use wavelengths of 405, 415, and 425 nm. These wavelengths are used to create photosensitive plates for precise lithography in subsequent processes.

[0004] However, although both types of equipment play important roles in the LED manufacturing process, the different photosensitive solder resist inks they use prevent them from being used together on the same production line. This results in inefficiencies and increased costs in the production process. Summary of the Invention

[0005] The first technical problem to be solved by this invention is:

[0006] An ink is provided.

[0007] The second technical problem to be solved by this invention is:

[0008] A method for preparing the ink is provided.

[0009] The third technical problem to be solved by this invention is:

[0010] The application of the ink.

[0011] To solve the first technical problem, the technical solution adopted by the present invention is as follows:

[0012] An ink comprising the following components:

[0013] Epoxy acrylic resin;

[0014] Acrylic polymer solution;

[0015] Composite photosensitizer;

[0016] Multifunctional monomer resins;

[0017] Filler;

[0018] Additives;

[0019] The composite photosensitizer includes 2-methyl-1-(4-methylthiomethyl)-2-morpholino-1-propanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-isopropylthioxanthone, and tetraethylmielone-4,4-bis(diethylamino)benzophenone.

[0020] According to embodiments of the present invention, one of the technical solutions has at least one of the following advantages or beneficial effects:

[0021] 1. This invention pioneered the introduction of multi-wavelength (385-415nm) photosensitizers for the first time, changing the structural defect of traditional ink systems that only use photosensitizers such as 369, 907, and ITX, which cannot meet the requirements of deep curing.

[0022] 2. By adjusting the resin acid value and photosensitivity and combining photosensitizers of different wavelengths in the formulation, this invention enhances the deep curing effect of the ink, increasing the solder bridge fabrication capability of the photosensitive ink from 4mil to 2mil, and supporting secondary development. This not only meets market demands for photosensitive inks but also significantly reduces the difficulty of product manufacturing, thereby achieving the goal of producing high-precision circuit boards using photosensitive inks.

[0023] 3. This invention is the first to employ photosensitizers of multiple wavelengths. Without significantly altering material costs, it reduces the photosensitive speed of the product from the traditional ink (exposure energy 800-1000 MJ using an LED exposure machine, exposure time 15-20 seconds) to an exposure energy of 300-500 MJ and an exposure time of 5-8 seconds; simultaneously, it more than doubles the energy and time required for power performance. The solder bridge is increased from 5 mil to 2 mil; acid resistance is improved from 10% dilute sulfuric acid at 25 degrees Celsius for 30 minutes to 10% dilute sulfuric acid at 40 degrees Celsius for 30 minutes. The new ink product prepared by this invention features low energy consumption, fast photosensitive speed, and excellent heat resistance, chemical resistance, and weather resistance. It can simultaneously meet the requirements of various surface treatment processes such as lead-free tin plating, immersion gold, immersion tin, immersion silver, and OSP. This is the first time in the industry that photosensitive inks have been able to meet the surface treatment requirements of long-term high-temperature and high-acid immersion gold, immersion silver, and immersion tin processes, making photosensitive inks suitable for industries with high ink quality requirements, such as computer motherboards, mobile phone carrier boards, and various communication terminals.

[0024] According to one embodiment of the present invention, the ink comprises the following components in parts by weight:

[0025] Epoxy acrylic resin, 30-50 parts;

[0026] Acrylic polymer solution, 15-25 parts;

[0027] Composite photosensitizer, 12-19 parts;

[0028] Multifunctional monomer, 5-10 parts;

[0029] Filler, 45-80 parts;

[0030] Additives, 8-18 parts.

[0031] According to one embodiment of the present invention, the photosensitizer 907 is 2-methyl-1-(4-methylthiomethyl)-2-morpholino-1-propanone.

[0032] According to one embodiment of the present invention, the photosensitizer TPO is 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.

[0033] According to one embodiment of the present invention, the photosensitizer ITX is 2-isopropylthioxanthraquinone.

[0034] According to one embodiment of the present invention, the photosensitizer EMK is tetraethylmielone 4,4-bis(diethylamino)benzophenone.

[0035] According to one embodiment of the present invention, the acid value of the epoxy acrylate resin is 30-54 mgKOH / g. By adjusting the acid value, the reaction time between the resin and Na2CO3 or K2CO3 in the ink during the developing stage can be extended, thus avoiding a decrease in ink adhesion due to over-development.

[0036] According to one embodiment of the present invention, the acid value of the acrylate polymer solution is 28-34 mg KOH / g.

[0037] According to one embodiment of the present invention, the multifunctional monomer resin includes at least one of trifunctional acrylate, hexafunctional acrylate, and nonfunctional acrylate.

[0038] According to one embodiment of the present invention, the trifunctional acrylate includes trimethylolpropane triacrylate.

[0039] According to one embodiment of the present invention, the filler comprises at least one of precipitated barium sulfate and modified bentonite.

[0040] According to one embodiment of the present invention, the precipitated barium sulfate includes at least one of Jimei B35, Jimei B30, and Anyi JB61.

[0041] According to one embodiment of the present invention, the modified bentonite is bentonite activated by ethanol and N,N-diacetone formamide.

[0042] According to one embodiment of the present invention, the additive includes at least one of a polymerization inhibitor, a liquid hysteresis modifier, and an organosilicon defoamer.

[0043] According to one embodiment of the present invention, the polymerization inhibitor comprises 2,6-di-tert-butyl-4-methylphenol.

[0044] According to one embodiment of the present invention, the liquid rheology modifier comprises the rheology modifier BYK-R 605 unsaturated polyester.

[0045] According to one embodiment of the present invention, the silicone defoamer includes Jingyue KS66.

[0046] To solve the second technical problem, the technical solution adopted by the present invention is as follows:

[0047] A method for preparing the ink includes the following steps:

[0048] The ink is obtained by mixing epoxy acrylic resin, acrylate polymer solution, composite photosensitizer, multifunctional monomer resin, filler and additives, and stirring.

[0049] Another aspect of the present invention relates to the application of the ink in multi-band photosensitive solder resist inks shared by LED exposure machines and LDI lithography machines. This includes the inks described in the embodiments of the first aspect above. Since this application employs all the technical solutions of the aforementioned inks, it possesses at least all the beneficial effects brought about by the technical solutions of the above embodiments.

[0050] Other features and advantages of the invention will be set forth in the description which follows, and will be apparent in part from the description, or may be learned by practicing the invention. Detailed Implementation

[0051] The terms "preferred," "more preferably," etc., used in this invention refer to embodiments of the invention that provide certain beneficial effects under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of this invention.

[0052] When a numerical range is disclosed herein, the range is considered continuous and includes the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0053] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of the present invention.

[0054] Unless otherwise specified, the reagents, methods and equipment used in this invention are all conventional reagents, methods and equipment in this technical field.

[0055] In the examples, the epoxy acrylate resin is an epoxy acrylate resin obtained by reacting raw materials epoxy acrylate resin 202, epoxy acrylate resin 704 and acrylic acid.

[0056] In the embodiments, the multifunctional monomer is a trifunctional monomer, specifically, trimethylolpropane triacrylate.

[0057] In the examples, the raw materials and methods for preparing the acrylate polymer solution are shown in Table 1.

[0058] Table 1

[0059]

[0060]

[0061] Example 1

[0062] An ink comprising the following components in parts by weight:

[0063] 30 parts epoxy acrylic resin;

[0064] Acrylic polymer solution, 15 parts;

[0065] Photosensitizer 907, 3 parts;

[0066] Photosensitizer TPO, 6 parts;

[0067] Photosensitizer ITX, 2 parts;

[0068] 1 part of photosensitizer EMK;

[0069] Polymerization inhibitor 2,6-di-tert-butyl-4-methylphenol, 2 parts;

[0070] Multifunctional monomer, 5 portions;

[0071] Barium sulfate precipitate B30, 30 parts;

[0072] Rheology modifier BYK-R 605 unsaturated polyester, 1 part;

[0073] Modified bentonite, 15 parts;

[0074] 5 parts of silicone defoamer Jingyue KS66.

[0075] The preparation of the above ink includes the following steps:

[0076] The ink is obtained by mixing and stirring the components evenly. This ink is a multi-band photosensitive solder resist ink that can be used by both LED exposure machines and LDI lithography machines.

[0077] This invention is the first to introduce multiple types of photosensitizers and multifunctional monomeric resins, overcoming the structural defects of traditional ink systems that only use single photosensitizers such as 369 and 907 to meet the needs of a fixed wavelength range and lack deep curing. This invention enhances the deep curing effect of solder resist photosensitive inks, enabling them to absorb and be used in the ultraviolet light absorption wavelength range from 365 to 405 nm, achieving the goal of simultaneous use in LED and LDI devices.

[0078] Example 2

[0079] An ink comprising the following components in parts by weight:

[0080] Epoxy acrylic resin, 40 parts;

[0081] Acrylic polymer solution, 18 parts;

[0082] Photosensitizer 907, 4 parts;

[0083] Photosensitizer TPO, 6 parts;

[0084] Photosensitizer ITX, 4 parts;

[0085] Photosensitizer EMK, 1.5 parts;

[0086] Polymerization inhibitor 2,6-di-tert-butyl-4-methylphenol, 2 parts;

[0087] Multifunctional monomer, 7 samples;

[0088] Anyi JB61 precipitated barium sulfate, 38 parts;

[0089] Rheology modifier BYK-R 605 unsaturated polyester, 1 part;

[0090] Modified bentonite, 17 parts;

[0091] Six parts of silicone defoamer Jingyue KS66.

[0092] The preparation of the above ink includes the following steps:

[0093] The ink is obtained by mixing and stirring the components evenly. This ink is a multi-band photosensitive solder resist ink that can be used by both LED exposure machines and LDI lithography machines.

[0094] Example 3

[0095] An ink comprising the following components in parts by weight:

[0096] Epoxy acrylic resin, 45 parts;

[0097] Acrylic polymer solution, 20 parts;

[0098] Photosensitizer 907, 4 parts;

[0099] Photosensitizer TPO, 5.5 parts;

[0100] Photosensitizer ITX, 2.3 parts;

[0101] Photosensitizer EMK, 1.5 parts;

[0102] Polymerization inhibitor 2,6-di-tert-butyl-4-methylphenol, 2 parts;

[0103] Multifunctional monomer, 8 portions;

[0104] Barium sulfate precipitate B35, 42 parts;

[0105] Rheology modifier BYK-R 605 unsaturated polyester, 1.5 parts;

[0106] Modified bentonite, 20 parts;

[0107] 8 parts of silicone defoamer Jingyue KS66.

[0108] The preparation of the above ink includes the following steps:

[0109] The ink is obtained by mixing and stirring the components evenly. This ink is a multi-band photosensitive solder resist ink that can be used by both LED exposure machines and LDI lithography machines.

[0110] Example 4

[0111] An ink comprising the following components in parts by weight:

[0112] Epoxy acrylic resin, 50 parts;

[0113] Acrylic polymer solution, 25 parts;

[0114] Photosensitizer 907, 4 parts;

[0115] Photosensitizer TPO, 7 parts;

[0116] Photosensitizer ITX, 5 parts;

[0117] Photosensitizer EMK, 2 parts;

[0118] Polymerization inhibitor 2,6-di-tert-butyl-4-methylphenol, 2 parts;

[0119] DPHA monomer, 10 parts; (bis-pentaerythritol hexaacrylate)

[0120] Barium sulfate precipitate B35, 50 parts;

[0121] Rheology modifier BYK-R 605 unsaturated polyester, 2 parts;

[0122] Modified bentonite, 17 parts;

[0123] Six parts of silicone defoamer Jingyue KS66.

[0124] The preparation of the above ink includes the following steps:

[0125] The ink is obtained by mixing and stirring the components evenly. This ink is a multi-band photosensitive solder resist ink that can be used by both LED exposure machines and LDI lithography machines.

[0126] Comparative Example 1

[0127] The difference between Comparative Example 1 and Example 1 is that Comparative Example 1 uses conventional photosensitizers 907, 369, and ITX as photoinitiators, replacing one of the photosensitizers 907, TPO, ITX, EMK, BHT, and multifunctional monomers (bis-pentaerythritol hexaacrylate / trimethylolpropane trimethacrylate) in Example 1.

[0128] Comparative Example 2

[0129] The difference between Comparative Example 2 and Example 2 is that Comparative Example 2 uses conventional photosensitizers such as 907 (3.5% absorption wavelength 231-307nm), 369 (1% absorption wavelength 232-323nm), and ITX (0.6-0.8% absorption wavelength 258-382nm) as photoinitiators, respectively replacing one of the following monomers in Example 2: 907 (absorption wavelength 231-307nm), TPO (absorption wavelength 299-366nm), ITX (absorption wavelength 258-382nm), EMK (absorption wavelength 248-375nm), BHT (absorption wavelength 248-375nm), and multifunctional monomers (bis-pentaerythritol hexaacrylate / trimethylolpropane trimethacrylate).

[0130] Performance testing:

[0131] The inks of Examples 1-4 and Comparative Examples 1-2 were tested as follows, and the test results are shown in Table 2.

[0132] Table 2

[0133]

[0134]

[0135] As can be seen from Table 1, using different proportions of epoxy resin, along with photosensitizers and monomers, can increase the curing of the green layer, reduce lateral corrosion, and also provide excellent heat resistance and adhesion.

[0136] This invention solves at least the following problems:

[0137] 1. Traditional photosensitive solder resist inks have limited applicability in LED exposure machines and LDI lithography machines, failing to meet the needs of multiple devices operating simultaneously. The multi-band photosensitive solder resist ink provided by this invention has broader applicability, enabling simultaneous use in both LED exposure machines and LDI lithography machines, thereby improving equipment flexibility and efficiency.

[0138] 2. Traditional methods for preparing photosensitive solder resist inks suffer from complex processes and high costs, failing to meet the demands of modern manufacturing. This invention provides a preparation method that simplifies the process, reduces costs, and improves production efficiency.

[0139] 3. Traditional photosensitive solder resist inks are prone to compatibility issues when used in different devices, leading to unstable product quality. The multi-band photosensitive solder resist ink provided by this invention, through adjustments to the formula and process, can achieve good compatibility across different devices, ensuring stable and consistent product quality.

[0140] The above are merely embodiments of the present invention and do not limit the patent scope of the present invention. Any equivalent modifications made based on the content of the present invention specification, or direct or indirect applications in related technical fields, are similarly included within the patent protection scope of the present invention.

Claims

1. An ink, characterized by: It consists of the following components in parts by weight: Epoxy acrylic resin, 30-50 parts; Acrylic polymer solution, 15-25 parts; Composite photosensitizer, 12-19 parts; Multifunctional monomer resin, 5-10 parts; Filler, 45-80 parts; Additives, 8-18 parts; The composite photosensitizer is composed of 2-methyl-1-(4-methylthiomethyl)-2-morpholino-1-propanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-isopropylthioxanthone, and tetraethylmielone-4,4-bis(diethylamino)benzophenone. The acid value of the epoxy acrylate resin is 48-54 mgKOH / g; The multifunctional monomer resin is trimethylolpropane triacrylate; The acid value of the acrylate polymer solution is 28-34 mg KOH / g; The ink is a multi-band photosensitive solder resist ink.

2. The ink of claim 1, wherein: The filler material includes at least one of precipitated barium sulfate and modified bentonite.

3. The ink according to claim 1, characterized in that: The additives include at least one of polymerization inhibitors, liquid modifiers, and silicone defoamers.

4. The ink of claim 3, wherein: The polymerization inhibitor includes 2,6-di-tert-butyl-4-methylphenol.

5. A method for preparing an ink as described in any one of claims 1 to 4, characterized in that: Includes the following steps: The ink is obtained by mixing epoxy acrylic resin, acrylate polymer solution, composite photosensitizer, multifunctional monomer, filler and additives, and stirring.

Images