CN114058209B - Light-cured solder resist ink suitable for high-frequency communication and preparation method thereof - Google Patents
Light-cured solder resist ink suitable for high-frequency communication and preparation method thereof Download PDFInfo
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- CN114058209B CN114058209B CN202111520440.6A CN202111520440A CN114058209B CN 114058209 B CN114058209 B CN 114058209B CN 202111520440 A CN202111520440 A CN 202111520440A CN 114058209 B CN114058209 B CN 114058209B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
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- C09D11/00—Inks
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- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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Abstract
The invention provides a photocuring solder resist ink suitable for high-frequency communication and a preparation method thereof, wherein the photocuring solder resist ink mainly comprises cholic acid modified alkali-soluble photocuring epoxy resin and a photoinitiator, wherein the cholic acid modified alkali-soluble photocuring epoxy resin is obtained by carrying out ring-opening reaction on epoxy resin and cholic acid, then carrying out esterification reaction on the epoxy resin and cholic acid, and finally carrying out esterification reaction on a monomer which contains an active group capable of reacting with carboxyl and has unsaturated double bonds in a molecular structure. The photocuring solder resist ink with high glass transition temperature and low dielectric constant is prepared by cholic acid graft modification of epoxy resin, and is suitable for the field of high-frequency communication.
Description
Technical Field
The invention belongs to the technical field of light-cured solder resist ink, and particularly relates to light-cured solder resist ink suitable for high-frequency communication and a preparation method thereof.
Background
Printed Circuit Boards (PCBs) are substrates for mounting and connecting components of modern electrical devices, and are important basic assemblies in the electronic industry.
The photo-curing solder resist ink is one of key materials of a Printed Circuit Board (PCB), and is a protective coating covering a copper wire of the printed circuit, and is used for preventing a circuit from being corroded and broken, preventing short circuit between wires caused by many welding points, adjusting the adhesion amount of soldering tin, reducing the dissolved pollution of copper in the welding line, saving the soldering tin, reducing the weight of an instrument, increasing the high density of wiring, avoiding false soldering and improving the inspection speed.
The traditional photo-curing solder resist ink generally comprises components such as a polymerization monomer, a photoinitiator, a polymerization inhibitor and the like. Currently, most of the photo-curable solder resist inks used in solder resists generally include a combination of a photo-polymerization initiator and a photo-curable and thermosetting resin containing a carboxyl group. Among them, the photocurable and thermosetting resin is generally epoxy acrylic resin, which has the advantages of good photocurability, developability, mechanical properties and the like, but the heat resistance of the cured film after curing is not high enough, and the cured film is easy to blister or oil drop during soldering, and cannot meet the requirements on high-requirement electric circuit boards.
At present, methods for improving the poor heat resistance of the carboxylated epoxy acrylate have two approaches of physical modification and chemical modification. The physical modification is mainly the addition of some organic and inorganic fillers, as disclosed in patent CN109073969A, a method for improving the heat resistance of products by adding silica fillers, but the method of physical blending is easy to generate interface effect to influence the basic performance of resin-filler composite materials. The chemical modification is mainly to select epoxy resin with higher functionality, so that the cured product has higher crosslinking degree, and thus has better heat resistance, such as phenolic epoxy resin and the like; for example, in patent CN110527350A, a method for modifying novolac epoxy resin by carboxylic acid with polyhydroxy group is disclosed, which can effectively increase the glass transition temperature of the resin.
Although the heat resistance of the system can be effectively improved using the above method, there are some problems. For example, the physical modification does not fundamentally change the heat resistance of the system, and there are cases where the system is unevenly dispersed during use, phase separation occurs upon long-term storage, and uniform film formation is difficult upon coating. The chemical modification method mainly introduces some rigid heat-resistant chain segments on the main chain structure of the carboxylic epoxy acrylate, but most of the modified resins used at present are difficult to increase the glass transition temperature only from the side chain modification.
With the arrival of high-frequency communication, the PCB substrate is also developing towards high density and refinement, and the performance requirement for the solder resist coating is higher and higher. In general, a lead soldering process is performed at a temperature of 260 ℃ or higher in a process of processing a high-precision PCB substrate suitable for high-frequency communication, and thus a photocurable solder resist ink corresponding thereto is required to have high resistance to heat soldering treatment. In addition, since a substrate having a low dielectric constant is required for high-speed information processing in high-frequency communication, a cured solder resist ink must have not only high electrical insulation properties but also both a high glass transition temperature and a low dielectric constant.
The traditional light-cured solder resist ink has poor heat resistance and high dielectric constant, is not suitable for manufacturing high-precision circuit boards, and is not beneficial to development and application of the solder resist ink in high-frequency communication.
In order to reduce the dielectric constant of the photo-curing solder resist ink, in the report of the prior art, mainly a filler with a low dielectric constant is added into the photo-curing solder resist ink, for example, the modified POSS is introduced into a polyimide resin system in the chinese patent application "POSS modified photo-sensitive solder resist ink with a low dielectric constant and its preparation method" (CN202010017355.7), so that a dielectric confinement effect can be generated, that is, a strong self-polarization induction effect is generated at a contacted heterogeneous medium, so that the electron cloud of a polymer contacted with the self-polarization induction effect is radially localized, and the electron cloud polarization of the polymer is limited, thereby further reducing the dielectric constant of the polymer material.
However, in order to significantly reduce the dielectric constant of the ink, the proportion of the filler with a low dielectric constant added must be high, and the compatibility of the component system must be poor, for example, in the above patent application, in order to further solve the problem of poor compatibility of POSS, POSS is modified first, and polyimide resin is particularly limited to solve the problem of poor compatibility. However, it should be noted that although the above technical solution improves the disadvantage of poor compatibility of the low-k filler with other components to some extent, the interfacial effect between the filler and the resin cannot be completely solved, and the addition of the filler in the subsequent ink product manufacturing process is affected. And the limitation of the resin matrix also greatly limits the application range thereof. In addition, the introduction of the filler with high addition amount and low dielectric constant in the photo-curing solder resist ink can cause the components of the photo-curing solder resist ink to be complicated, influence the elongation at break, alkali developability and the like of the photo-curing solder resist ink, lead the preparation process to be complicated and improve the cost.
Therefore, if the photo-curing solder resist ink has the advantages of simple preparation process, no compatibility problem, high heat resistance and low dielectric constant, the application and the development of the PCB substrate in the field of high-frequency communication are greatly facilitated.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the photocuring solder resist ink suitable for high-frequency communication and the preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme formed by the following technical measures.
The light-cured solder resist ink suitable for high-frequency communication mainly comprises the following raw materials in parts by weight:
100 parts of cholic acid modified alkali-soluble photocuring epoxy resin,
1-10 parts of a photoinitiator;
the cholic acid modified alkali-soluble photocuring epoxy resin is obtained by carrying out a ring-opening reaction on epoxy resin and cholic acid, then carrying out an esterification reaction on the epoxy resin and cholic acid, and finally carrying out an esterification reaction on the epoxy resin and unsaturated anhydride, wherein the molecular structure of the epoxy resin contains an active group capable of reacting with carboxyl and a monomer with an unsaturated double bond; the cholic acid is added in a molar ratio of (1-1.2) to an epoxy group of the epoxy resin: 1, and the unsaturated acid anhydride is added in a molar ratio of (1-4) to the epoxy group of the epoxy resin: 1, wherein the monomer having an active group capable of reacting with a carboxyl group and an unsaturated double bond in a molecular structure is added in a molar ratio of (1-4): 1 was added.
Wherein the epoxy resin has a viscosity of 700 to 20000mPa s at 25 ℃ and an epoxy equivalent of 180 to 280 g/eq.
Preferably, the epoxy resin is selected from any one of bisphenol A epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin, p-tert-butyl phenol novolac epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, diglycidyl phthalate, diglycidyl tetrahydrophthalate, triglycidyl isocyanurate and dicycladiene epoxy.
Generally, the unsaturated acid anhydride is preferably a monobasic acid anhydride for the purpose of reducing steric hindrance and improving reaction efficiency, and those skilled in the art can directly refer to and use the monobasic acid anhydride selected in the prior art of epoxy-based photo-curing solder resist inks. To better illustrate the present invention and to provide a reference for the anhydride option, it is further preferred that the monobasic anhydride option comprises at least one of tetrahydrophthalic anhydride, itaconic anhydride, maleic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride.
It should be noted that, because the spatial conformation of the cholic acid modified alkali-soluble photocuring epoxy resin defined in the present invention is complex, in order to prevent the system from generating gel during the grafting of the unsaturated anhydride, the unsaturated anhydride is preferably tetrahydrophthalic anhydride, because the unsaturated double bond of the tetrahydrophthalic anhydride has lower activity than other unsaturated anhydrides during the reaction process, and is not easy to generate a crosslinking reaction.
The molecular structure of the monomer contains a monomer which contains an active group capable of reacting with carboxyl and has an unsaturated double bond, the active group capable of reacting with the carboxyl comprises any one of epoxy, hydroxyl and amino, and the number of the active groups capable of reacting with the carboxyl in the monomer is 1.
Further, the molecular structure of the monomer contains an active group capable of reacting with carboxyl and has unsaturated double bonds, and the number of the unsaturated double bonds is 1-2, and is preferably 1.
It is to be noted that the monomer having an unsaturated double bond and an active group capable of reacting with a carboxyl group in the molecular structure is preferably a monomer having not more than 10 carbon atoms due to the effect of steric hindrance. In order to better illustrate the present invention and provide several alternative technical solutions, preferably, the monomer having an unsaturated double bond and containing a reactive group capable of reacting with a carboxyl group in the molecular structure is selected from at least one of hydroxyethyl methacrylate, glycidyl methacrylate and glycidyl acrylate.
Typically, the photoinitiator is a photoinitiator conventionally used in the art for photocuring solder resist inks.
Further, the preparation method of the cholic acid modified alkali-soluble photocuring epoxy resin comprises the following steps:
(1) preheating a solvent to 70-90 ℃ under the nitrogen atmosphere, adding and dissolving epoxy resin, cooling to 50-60 ℃, adding cholic acid, heating to 70-80 ℃, adding a cyclic ester ring-opening polymerization catalyst, stirring and reacting for 1-2 hours at 95-110 ℃, then adjusting the temperature to 100-125 ℃, stirring and reacting for 12-24 hours until the acid value of the reaction solution is less than 10mgKOH/g, and obtaining an epoxy resin solution containing a cholic acid group;
(2) cooling the epoxy resin solution containing the cholic acid group obtained in the step (1) to 70-80 ℃, then adding unsaturated anhydride and a polymerization inhibitor for mixing, continuing to stir at 90-100 ℃ for 3-9 hours, cooling the reaction system to 70-80 ℃ after the reaction time is up, then adding a monomer which contains an active group capable of reacting with carboxyl and has an unsaturated double bond in a molecular structure and a polymerization inhibitor for mixing, continuing to stir at 100-110 ℃ for 3-6 hours, and obtaining cholic acid modified alkali-soluble photocuring epoxy resin after the reaction time is up; wherein the addition amount of the polymerization inhibitor is 0.4-2.5 wt% of the epoxy resin in the step (1).
Generally, the cyclic ester ring-opening polymerization catalyst in the step (1) is a cyclic ester ring-opening polymerization catalyst generally used in the field of epoxy resin ring-opening polymerization, and a person skilled in the art can select a suitable cyclic ester ring-opening polymerization catalyst according to actual needs. For more convenient illustration of the present invention, preferably, the cyclic ester ring-opening polymerization catalyst in step (1) is one of triethylamine, triethanolamine, 4-dimethylaminopyridine, tetrabutylammonium bromide, tetramethylammonium chloride, N-dimethylbenzylamine and triphenylphosphine; the addition amount of the cyclic ester ring-opening polymerization catalyst is 0.2-1 wt% of the epoxy resin.
Generally, the solvent used in the epoxy resin preparation in the technical field is selected from the solvents commonly used in the technical field for preparing epoxy resin solutions, and one skilled in the art can select a suitable solvent according to the selection and actual requirements of the epoxy resin. In order to more conveniently explain the invention, the solvent in the step (1) is at least one of dibasic ester high-boiling-point environment-friendly solvent, ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, propylene glycol methyl ether propionate, dipropylene glycol methyl ether, propylene glycol methyl ether, trimethylbenzene and tetramethylbenzene; in the step (1), the mass of the solvent is as follows: the mass of the epoxy resin is (0.5-1.5): 1.
in order to improve the reaction efficiency and reduce the loss caused by the solid reactant adhering to the wall of the reaction container, the cholic acid is usually dissolved in a proper amount of solvent and then added; the solvent may be the same solvent as described above for dissolving the epoxy resin.
Wherein, in the step (1), the cyclic ester ring-opening polymerization catalyst is added, and in order to improve the reaction efficiency and reduce the loss caused by the adhesion of the solid reactant and the wall of the reaction vessel, the cyclic ester ring-opening polymerization catalyst is usually dissolved in a proper amount of solvent and then added; the solvent may be the same solvent as described above for dissolving the epoxy resin.
In order to improve the reaction efficiency and reduce the loss caused by the adhesion of the solid reactant and the wall of the reaction vessel, the unsaturated anhydride is usually dissolved in a proper amount of solvent and then added; the solvent may be the same solvent as described above for dissolving the epoxy resin.
Wherein, the polymerization inhibitor in the step (2) is selected from the polymerization inhibitors commonly used in the technical field for the conventional use of the photo-curing solder resist ink, and the technical personnel can select the proper polymerization inhibitor according to the selection of the epoxy resin and the actual requirement. For the convenience of describing the present invention, the polymerization inhibitor in the step (2) is selected from at least one of hydroquinone, o-methyl hydroquinone, p-hydroxyanisole, p-benzoquinone and 2, 6-di-tert-butyl-4-methylphenol. Preferably, the two added polymerization inhibitors are the same polymerization inhibitor.
Generally, the stirring reaction in steps (1) and (2) is a stirring reaction conventionally used in the art, including magnetic stirring or mechanical stirring, and a person skilled in the art can select a suitable stirring reaction mode according to the production scale or the current state of the process conditions. In order to better illustrate the invention and provide a process scheme suitable for a laboratory operation environment, the stirring reaction can be carried out at a stirring speed of 100-300 rpm.
The finally prepared photocuring solder resist ink suitable for high-frequency communication has the dielectric constant as low as 2.51, the glass transition temperature as high as 144.3 ℃, the weight loss temperature of five percent heat of 250.5 ℃ and the residual weight of 21% at 700 ℃.
The main principle of the invention is to substitute cholic acid for carboxylic acid components such as acrylic acid and the like which are conventionally used in the light-cured solder resist ink, so that a large amount of cyclic structures which are special for the cholic acid are introduced into the epoxy resin. It is worth to be noted that cholic acid itself is not a low dielectric constant monomer, but the photo-curable solder resist ink finally prepared by the present invention does have the technical effect of significantly reducing the dielectric constant.
The molecular structural formula of cholic acid is as above, and the inventor speculates that the finally prepared photocuring solder resist ink has low dielectric constant performance, probably because when the density of double bonds in a cholic acid modified alkali-soluble photocuring epoxy resin system reaches a certain specific value or range, the spatial structure of cholic acid after photocuring can just form a three-dimensional network structure with certain regularity with a network formed after cross-linking of the double bonds, and the internal voids not only reduce the dielectric constant of the system, but also can reduce the density of polar groups in the system, thereby further reducing the dielectric constant. It should be noted that since cholic acid itself does not have a low dielectric constant, the technical effect achieved by the present invention is based on the fact that it is not obvious whether other carboxylic acids similar to cholic acid structure have the same contribution, and the principle of reducing the dielectric constant is only inferred.
To better illustrate the principle of the present invention, one of the technical solutions is described as an example:
when the unsaturated anhydride is selected as tetrahydrophthalic anhydride and the monomer which contains an active group capable of reacting with carboxyl in the molecular structure and has an unsaturated double bond is selected as glycidyl methacrylate, the reaction route of the cholic acid modified alkali-soluble photocuring epoxy resin is as follows:
through the reaction route, it can be obviously seen that each mole of epoxy group can correspond to one mole of cholic acid through a ring-opening reaction, each branched chain of the obtained product has 4 hydroxyl groups, 1-4 moles of unsaturated anhydride (especially monobasic anhydride) can be corresponding through an esterification reaction, at the moment, each branched chain of the obtained product has 4 carboxyl groups, but at the moment, the obtained product does not have an unsaturated double bond and has no photocuring characteristic, so that the unsaturated double bond is introduced through the esterification reaction again, namely, a monomer which contains an active group capable of reacting with the carboxyl group in a molecular structure of 1-4 moles and has the unsaturated double bond can be corresponding through the esterification reaction, and the cholic acid modified alkali-soluble photocuring epoxy resin is obtained.
It should be noted that, the unsaturated double bond is introduced through the two-step esterification reaction, rather than directly introduced through the unsaturated anhydride, because the double bond reactivity of the unsaturated anhydride is low, the higher double bond conversion rate cannot be achieved after photocuring, and the crosslinking density in the system cannot meet the standards of various performances, the unsaturated double bond with high reactivity, that is, the unsaturated double bond in the structure of the methacrylic or the propylene, needs to be continuously introduced into the system, so that the system has higher photosensitivity.
Note that, although one mole of cholic acid can be reacted by ring-opening reaction per one mole of epoxy group, because cholic acid has a special molecular configuration, although its cyclic molecular structure is compact, the phenomenon of steric hindrance of the reaction is not known for the moment, and therefore, in order to satisfy the principle of sufficient reaction as much as possible, the cholic acid is added in a molar ratio of (1 to 1.2) to the epoxy group of the epoxy resin: addition was carried out in the manner of 1.
Preferably, in order to further reduce the dielectric constant of the light-curable solder resist ink suitable for high-frequency communication, the molar amount of epoxy groups in the epoxy resin is: the molar weight of the monomer having an unsaturated double bond and containing an active group capable of reacting with a carboxyl group in the molecular structure is 1 (1.0 to 1.1) or 1 (2.9 to 3.1), and more preferably 1:1 or 1: 3.
it should be noted that the above preferred range is not a continuous range, because it is actually found by comparative experiments that it is probably because when the density of double bonds in the cholic acid modified alkali-soluble photocuring epoxy resin system reaches a certain value or range, that is, when the density of double bonds is within the range of 1 (1.0-1.1) or 1 (2.9-3.1), the steric structure of cholic acid after photocuring can be exactly in a three-dimensional network structure with a certain regularity with the network composition formed after double bonds are crosslinked, thereby further reducing the dielectric constant.
Further, the light-cured solder resist ink suitable for high-frequency communication mainly comprises the following raw materials in parts by weight:
among them, a reactive diluent, preferably one having an ethylenically unsaturated group in the molecule, may be added for adjusting the viscosity of the system and facilitating coating. Such a reactive diluent having an ethylenically unsaturated group in the molecule is photo-cured by irradiation with an active energy ray, making the solder resist ink of the present invention insoluble in an aqueous alkali solution or contributing to insolubilization. At least one of polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, and hydroxyalkyl acrylate-based reactive diluents is preferable.
In order to improve the physical strength of a coating film after the solder resist ink is used, the solder resist ink component comprises a filler, wherein the filler is a known and conventional inorganic or organic filler, preferably one or more of titanium dioxide, bentonite, barium sulfate, spherical silica, nano calcium carbonate and talc, and further preferably a known and conventional metal oxide is simultaneously used as the filler and the pigment.
The additive is one or a combination of a plurality of pigments, a thermal polymerization inhibitor, a tackifier, a defoaming agent, a flatting agent, a coupling agent, an antioxidant and an antirust agent. Conventionally, the above pigments, thermal polymerization inhibitors, tackifiers, defoamers, leveling agents, coupling agents, antioxidants and rust inhibitors are known and conventionally used.
The light-cured solder resist ink suitable for high-frequency communication can be prepared by mixing all the components according to the prior art. For example, the components are preliminarily mixed in a mixer, and then kneaded by a three-roll mill to obtain the photocurable solder resist ink suitable for high-frequency communication.
When the above-mentioned solder resist ink is used, it is applied to a substrate, dried appropriately (about 60 to 120 ℃), exposed to light through a pattern film or the like to obtain a cured coating film, and the unexposed portion is developed. In the development, solvent development may be carried out using the above-mentioned solvent or a known and conventional halogen-based solvent such as trichloroethylene, but alkali development is preferably carried out because a carboxyl group is introduced into the cholic acid-modified alkali-soluble photocurable epoxy resin and an unexposed portion is dissolved in an alkali aqueous solution. The alkaline solvent development can be selected from alkali metal compounds, such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, etc.; alkaline earth metal compounds such as calcium hydroxide, etc. can also be selected; alkaline solution ammonia water can also be selected; water-soluble organic amines such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dipropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, dimethylaminoethyl methacrylate, polyethyleneimine and the like can also be selected.
In general, the above-mentioned photo-curable solder resist ink suitable for high-frequency communication can be used in a state of having a dry film of a solder resist layer formed by coating and drying a thin film of PET or the like in advance, in addition to a method of directly coating the ink in a liquid state on a substrate.
The invention has the following beneficial effects:
1. according to the invention, the cholic acid is used for grafting and modifying the epoxy resin, so that the dielectric constant of the prepared photocuring solder resist ink is greatly reduced, the high glass transition temperature is given to the photocuring solder resist ink, and the photocuring solder resist ink is completely suitable for production and manufacturing of PCB substrates for high-frequency communication.
2. According to the invention, cholic acid is used for grafting and modifying epoxy resin, unsaturated double bonds are introduced through two-step esterification reaction, and a contrast experiment shows that when the unsaturated double bonds in a system reach a certain specific value or range, the space structure of cholic acid after photocuring can be just crosslinked with the double bonds to form a network to form a three-dimensional network structure with certain regularity, so that the dielectric constant is further reduced.
3. The preparation method is simple, the influence caused by the steric hindrance effect is reduced in the preferred technical scheme, the reaction degree of each step is very high, and the influence of related side reactions is very small, so that the overall quality of the product is improved.
4. The photo-curing solder resist ink in the preferred scheme provided by the invention has excellent characteristics in the aspects of mechanical property, soldering heat resistance, solvent resistance, chemical resistance, electroless gold plating resistance, electroless tin plating resistance and electrical characteristics after being tested.
Drawings
FIG. 1 is a photograph showing a modified cholic acid-soluble photocurable epoxy resin prepared in Synthesis example 1 of the present invention.
FIG. 2 is a photograph showing a film obtained by photocuring the photo-curable solder resist ink of example 1 of the present invention.
FIG. 3 is an IR spectrum of an intermediate product of the cholic acid-modified alkali-soluble photocured epoxy resin preparation process of Synthesis example 1. The ECTG is the infrared spectrum of the product obtained by esterification reaction of the ECTG and a monomer which contains an active group capable of reacting with carboxyl and has unsaturated double bonds in a molecular structure.
FIG. 4 is a graph showing a thermogravimetric analysis of a coating film obtained by photocuring the photo-curable solder resist ink of examples 1-4 of the present invention.
FIG. 5 is a loss tangent spectrum of a coating film obtained by photocuring the photocurable solder resist ink of examples 1-4 of the present invention.
FIG. 6 is a spectrum of dielectric constant of a coating film obtained by photocuring the photocurable solder resist ink of examples 1-4 of the present invention.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the accompanying drawings. It should be noted that the examples given are not to be construed as limiting the scope of the invention, and that those skilled in the art, on the basis of the teachings of the present invention, will be able to make numerous insubstantial modifications and adaptations of the invention without departing from its scope.
Reagents and equipment used in the following examples:
epoxy cresol novolac (EOCN, epoxy equivalent 200-.
Cholic Acid (CA), Glycidyl Methacrylate (GMA), catalyst 4-Dimethylaminopyridine (DMAP), polymer inhibitor Hydroquinone (HQ), 2-methyl-4' - (methylthio) -2-morpholinophenylpropiophenone (photoinitiator 907), and 4-isopropyl-9-thioxanthone (ITX) for photopolymerization were all available from Kyowa Chemicals, Inc.
The reactive diluents 1, 6-hexanediol diacrylate (HDDA), ethanol and ethyl 2- (2-ethoxyethoxy) acetate (DCAC) were supplied as solvents from Dow chemical engineering laboratories.
1,2,5, 6-tetrahydrophthalic anhydride (THPA) was supplied by Dodbett reagent, Inc.
Fourier transform Infrared Spectroscopy (FT-IR) measured using a Nicolet 560 Fourier transform Infrared spectrometer; the thermal stability of the samples was determined by TG 209F1 thermogravimetric analyzer (Netzsch, germany); dynamic Mechanical Analysis (DMA) scanning using a TA Q850(TA instruments, usa) dynamic mechanical analyzer; the dielectric constant was measured with Concept-50(Novocontrol GmbH, Germany).
The infrared test method comprises the following steps: coating the resin on the surface of the potassium bromide flaky crystal, and testing by adopting a transmission method;
the thermal weight loss test method comprises the following steps: weighing 3-8 mg of a cured film sample, and heating to 700 ℃ from 25 ℃ per minute at 10 ℃ under the protection of nitrogen;
the DMA test method comprises the following steps: preparing the cured film into a sample strip with the thickness of about 15-25 um, the width of 8mm and the length of 10-12 mm, and testing at 5 ℃ and every minute at the frequency of 1Hz and the temperature of 25-200 ℃;
and (3) dielectric test: preparing the cured film into a square sample with the thickness of about 15-25 um and the length and width of more than 9mm, and testing at room temperature for 10-10 mm7Dielectric constant in the Hz frequency range.
Synthesis example 1
The preparation method of the cholic acid modified alkali-soluble photocuring epoxy resin comprises the following steps:
(1) adding 80.0g of diethylene glycol ethyl ether acetate (DCAC) into a 1L three-neck flask with a stirrer in nitrogen atmosphere, heating to 90 ℃, adding 88.8g of epoxy resin NPCN-704, keeping the temperature for one hour to fully dissolve the epoxy resin NPCN-704, cooling to 60 ℃, adding 168.2g of Cholic Acid (CA) dissolved in 120g of diethylene glycol ethyl ether acetate (DCAC) (the molar ratio of epoxy group to cholic acid is 1:1), heating to 70 ℃, adding 2.5g of catalyst 4-dimethylaminopyridine dissolved in 3.3g of diethylene glycol ethyl ether acetate, stirring and reacting at the constant temperature of 105 ℃ for 1 hour, heating to 115 ℃, stirring and reacting at the constant temperature for 12 hours until the acid value of the reaction solution is less than 10mgKOH/g, and obtaining the epoxy resin solution containing the cholic acid group;
(2) cooling the epoxy resin containing the cholic acid group obtained in the step (1) to 80 ℃, adding 127.5g of tetrahydrophthalic anhydride (THPA) (the molar ratio of epoxy group to anhydride is 1:4) and 0.5g of hydroquinone serving as a polymerization inhibitor dissolved in 120g of diethylene glycol ethyl ether acetate, heating to 95 ℃, and stirring for reaction for 7 hours. And finally, cooling the reaction system to 80 ℃, adding 44.5g of glycidyl methacrylate (the molar ratio of epoxy group to monomer is 1:1) and 0.5g of hydroquinone serving as a polymerization inhibitor dissolved in 30g of diethylene glycol ethyl ether acetate, heating to 110 ℃, stirring and reacting for 3 hours, and obtaining the cholic acid modified alkali-soluble photocuring epoxy resin after the reaction time is up.
The cholic acid-modified alkali-soluble photocurable epoxy resin obtained in this synthetic example was designated as ECTG 1.
Synthesis example 2
The cholic acid modified alkali-soluble photocuring epoxy resin of the synthesis example has the preparation method comprising the following steps of:
(1) adding 80.0g of diethylene glycol ethyl ether acetate (DCAC) into a 1L three-neck flask with a stirrer in nitrogen atmosphere, heating to 90 ℃, adding 88.8g of epoxy resin NPCN-704, keeping the temperature for one hour to fully dissolve the epoxy resin NPCN-704, cooling to 60 ℃, adding 168.2g of Cholic Acid (CA) dissolved in 120g of diethylene glycol ethyl ether acetate (DCAC) (the molar ratio of epoxy group to cholic acid is 1:1), heating to 70 ℃, adding 2.5g of catalyst 4-dimethylaminopyridine dissolved in 3.3g of diethylene glycol ethyl ether acetate, stirring and reacting at the constant temperature of 105 ℃ for 1 hour, heating to 115 ℃, stirring and reacting at the constant temperature for 12 hours until the acid value of the reaction solution is less than 10mgKOH/g, and obtaining the epoxy resin solution containing the cholic acid group;
(2) cooling the epoxy resin containing the cholic acid group obtained in the step (1) to 80 ℃, adding 127.5g of tetrahydrophthalic anhydride (THPA) (the molar ratio of epoxy group to anhydride is 1:4) and 0.5g of hydroquinone serving as a polymerization inhibitor dissolved in 120g of diethylene glycol ethyl ether acetate, heating to 95 ℃, and stirring for reaction for 7 hours. And finally, cooling the reaction system to 80 ℃, adding 89.0g of glycidyl methacrylate (the molar ratio of epoxy group to monomer is 1:2) and 1.0g of hydroquinone serving as a polymerization inhibitor dissolved in 60g of diethylene glycol ethyl ether acetate, heating to 110 ℃, stirring and reacting for 3 hours, and obtaining the cholic acid modified alkali-soluble photocuring epoxy resin after the reaction time is up.
The cholic acid-modified alkali-soluble photocurable epoxy resin obtained in this synthetic example was designated as ECTG 2.
Synthesis example 3
The cholic acid modified alkali-soluble photocuring epoxy resin of the synthesis example has the preparation method comprising the following steps of:
(1) adding 80.0g of diethylene glycol ethyl ether acetate (DCAC) into a 1L three-neck flask with a stirrer in nitrogen atmosphere, heating to 90 ℃, adding 88.8g of epoxy resin NPCN-704, keeping the temperature for one hour to fully dissolve the epoxy resin NPCN-704, cooling to 60 ℃, adding 168.2g of Cholic Acid (CA) dissolved in 120g of diethylene glycol ethyl ether acetate (DCAC) (the molar ratio of epoxy group to cholic acid is 1:1), heating to 70 ℃, adding 2.5g of catalyst 4-dimethylaminopyridine dissolved in 3.3g of diethylene glycol ethyl ether acetate, stirring and reacting at the constant temperature of 105 ℃ for 1 hour, heating to 115 ℃ and stirring and reacting at the constant temperature for 12 hours until the acid value of the reaction solution is less than 10mgKOH/g to obtain an epoxy resin solution containing a cholic acid group;
(2) cooling the epoxy resin containing the cholic acid group obtained in the step (1) to 80 ℃, adding 127.5g of tetrahydrophthalic anhydride (THPA) (the molar ratio of epoxy group to anhydride is 1:4) and 0.5g of hydroquinone serving as a polymerization inhibitor dissolved in 120g of diethylene glycol ethyl ether acetate, heating to 95 ℃, and stirring for reaction for 7 hours. And finally, cooling the reaction system to 80 ℃, adding 133.5g of glycidyl methacrylate (the molar ratio of epoxy group to monomer is 1:3) and 1.5g of hydroquinone serving as a polymerization inhibitor dissolved in 90g of diethylene glycol ethyl ether acetate, heating to 110 ℃, stirring and reacting for 3 hours, and obtaining the cholic acid modified alkali-soluble photocuring epoxy resin after the reaction time is up.
The cholic acid-modified alkali-soluble photocurable epoxy resin obtained in this synthesis example was designated as ECTG 3.
Synthesis example 4
The preparation method of the cholic acid modified alkali-soluble photocuring epoxy resin comprises the following steps:
(1) adding 80.0g of diethylene glycol ethyl ether acetate (DCAC) into a 1L three-neck flask with a stirrer in nitrogen atmosphere, heating to 90 ℃, adding 88.8g of epoxy resin NPCN-704, keeping the temperature for one hour to fully dissolve the epoxy resin NPCN-704, cooling to 60 ℃, adding 168.2g of Cholic Acid (CA) dissolved in 120g of diethylene glycol ethyl ether acetate (DCAC) (the molar ratio of epoxy group to cholic acid is 1:1), heating to 70 ℃, adding 2.5g of catalyst 4-dimethylaminopyridine dissolved in 3.3g of diethylene glycol ethyl ether acetate, stirring and reacting at the constant temperature of 105 ℃ for 1 hour, heating to 115 ℃, stirring and reacting at the constant temperature for 12 hours until the acid value of the reaction solution is less than 10mgKOH/g, and obtaining the epoxy resin solution containing the cholic acid group;
(2) cooling the epoxy resin containing the cholic acid group obtained in the step (1) to 80 ℃, adding 127.5g of tetrahydrophthalic anhydride (THPA) (the molar ratio of epoxy group to anhydride is 1:4) and 0.5g of hydroquinone serving as a polymerization inhibitor dissolved in 120g of diethylene glycol ethyl ether acetate, heating to 95 ℃, and stirring for reaction for 7 hours. And finally, cooling the reaction system to 80 ℃, adding 178.0g of glycidyl methacrylate (the molar ratio of the epoxy group to the monomer is 1:4) and 2.0g of hydroquinone serving as a polymerization inhibitor dissolved in 120g of diethylene glycol ethyl ether acetate, heating to 110 ℃, stirring and reacting for 3 hours, and obtaining the cholic acid modified alkali-soluble photocuring epoxy resin after the reaction time is up.
The cholic acid-modified alkali-soluble photocurable epoxy resin obtained in this synthesis example was designated as ECTG 4.
Synthesis example 5
The preparation method of the cholic acid modified alkali-soluble photocuring epoxy resin comprises the following steps:
(1) preheating a propylene glycol methyl ether solvent to 80 ℃ in the nitrogen atmosphere, adding bisphenol A type epoxy resin for dissolving, cooling to 50 ℃, adding cholic acid, heating to 80 ℃, adding a triethanolamine catalyst, stirring and reacting at 100 ℃ for 1.5 hours, then adjusting the temperature to 110 ℃, stirring and reacting for 18 hours until the acid value of the reaction solution is less than 10mgKOH/g, and obtaining epoxy resin solution containing the cholic acid group; wherein, the cholic acid is added in a molar ratio of 1.1: 1, solvent mass: epoxy resin mass 1.2: 1, the addition amount of the cyclic ester ring-opening polymerization catalyst is 0.5 wt% of the epoxy resin.
(2) Cooling the epoxy resin solution containing the cholic acid group obtained in the step (1) to 70 ℃, then adding itaconic anhydride and p-hydroxyanisole for mixing, continuing to stir at 90 ℃ for reaction for 8 hours, cooling the reaction system to 70 ℃ after the reaction time is up, then adding hydroxyethyl methacrylate and p-hydroxyanisole for mixing, continuing to stir at 100 ℃ for reaction for 5 hours, and obtaining the cholic acid modified alkali-soluble photocuring epoxy resin after the reaction time is up; wherein, the unsaturated acid anhydride is added in a molar ratio of 3: 1, the addition of hydroxyethyl methacrylate is carried out in such a way that the molar ratio of hydroxyethyl methacrylate to the epoxy group of the epoxy resin is 1.5: 1, and the addition amount of the polymerization inhibitor is 1 wt% of the epoxy resin in the step (1).
Synthesis example 6
The preparation method of the cholic acid modified alkali-soluble photocuring epoxy resin comprises the following steps:
(1) preheating a glycol ethyl ether acetate solvent to 70 ℃ in a nitrogen atmosphere, adding diglycidyl phthalate for dissolving, cooling to 55 ℃, adding cholic acid, heating to 80 ℃, adding an N, N-dimethylbenzylamine catalyst, stirring for reaction at 95 ℃ for 2 hours, then adjusting the temperature to 100 ℃, stirring for reaction for 24 hours, and obtaining an epoxy resin solution containing a cholic acid group when the acid value of the reaction solution is less than 10 mgKOH/g; wherein, the cholic acid is added in a molar ratio of 1.2: 1, and the mass of the solvent is as follows: epoxy resin mass ═ 0.8: 1, the addition amount of the cyclic ester ring-opening polymerization catalyst is 0.8 wt% of the epoxy resin.
(2) Cooling the epoxy resin solution containing the cholic acid group obtained in the step (1) to 80 ℃, then adding hexahydrophthalic anhydride and 2, 6-di-tert-butyl-4-methylphenol for mixing, continuing to stir at 100 ℃ for 5 hours for reaction, cooling the reaction system to 80 ℃ after the reaction time is up, then adding glycidyl acrylate and 2, 6-di-tert-butyl-4-methylphenol for mixing, continuing to stir at 110 ℃ for reaction for 4 hours, and obtaining the cholic acid modified alkali-soluble photocuring epoxy resin after the reaction time is up; wherein, the unsaturated acid anhydride is added in a molar ratio of 2: 1, and the addition of the glycidyl acrylate is carried out in a molar ratio of 1:1, and the addition amount of the polymerization inhibitor is 1.5 wt% of the epoxy resin in the step (1).
Example 1
The embodiment of the photo-curing solder resist ink suitable for high-frequency communication mainly comprises the following raw materials in parts by weight:
the above-mentioned components and the component ratios (parts by weight) were mixed and preliminarily mixed in a mixer, and then kneaded by a three-roll mill to prepare an alkali-developable photocurable solder resist ink.
The dielectric constant of the material is 3.25 (10)6Hz), the glass transition temperature is 141.47 ℃, the five percent thermal weight loss temperature is 242.89 ℃, and the residual weight at 700 ℃ is 9.09%.
Example 2
The embodiment of the photo-curing solder resist ink suitable for high-frequency communication mainly comprises the following raw materials in parts by weight:
the above-mentioned components and the component ratios (parts by weight) were mixed and preliminarily mixed in a mixer, and then kneaded by a three-roll mill to prepare an alkali-developable photocurable solder resist ink.
The dielectric constant of the material is 4.75 (10)6Hz), the glass transition temperature is 134.12 ℃, the five percent thermal weight loss temperature is 227.13 ℃, and the residual weight at 700 ℃ is 3.92%.
Example 3
The embodiment of the photo-curing solder resist ink suitable for high-frequency communication mainly comprises the following raw materials in parts by weight:
the above-mentioned components and the component ratios (parts by weight) were mixed and preliminarily mixed in a mixer, and then kneaded by a three-roll mill to prepare an alkali-developable photocurable solder resist ink.
The dielectric constant of the dielectric ceramic is 2.63 (10)6Hz), the glass transition temperature is 144.32 ℃, the five percent thermal weight loss temperature is 250.56 ℃, and the residual weight at 700 ℃ is 21.01 percent.
Example 4
The embodiment of the photo-curing solder resist ink suitable for high-frequency communication mainly comprises the following raw materials in parts by weight:
the above-mentioned components and the component ratios (parts by weight) were mixed and preliminarily mixed in a mixer, and then kneaded by a three-roll mill to prepare an alkali-developable photocurable solder resist ink.
The dielectric constant of the material is 5.20 (10)6Hz), the glass transition temperature is 137.58 ℃, the five percent thermal weight loss temperature is 240.32 ℃, and the residual weight at 700 ℃ is 4.77%.
It is noted that the selection and the proportion of the components in the above embodiments are only for convenience to illustrate the technical effects of the present invention, and those skilled in the art will understand that, on the premise that the cholic acid modified alkali-soluble photocurable epoxy resin is determined, the components other than the cholic acid modified alkali-soluble photocurable epoxy resin are arbitrarily selected and adjusted according to the related art of photocurable solder resist ink, and therefore, the technical effects of the present invention are achieved.
Claims (9)
1. The light-cured solder resist ink suitable for high-frequency communication is characterized by mainly comprising the following raw materials in parts by weight:
100 parts of cholic acid modified alkali-soluble photocuring epoxy resin,
1-10 parts of a photoinitiator;
the cholic acid modified alkali-soluble photocuring epoxy resin is obtained by carrying out a ring-opening reaction on epoxy resin and cholic acid, then carrying out an esterification reaction on the epoxy resin and cholic acid, and finally carrying out an esterification reaction on the epoxy resin and unsaturated anhydride, wherein the molecular structure of the epoxy resin contains an active group capable of reacting with carboxyl and a monomer with an unsaturated double bond; the cholic acid is added in a molar ratio of (1-1.2) to an epoxy group of the epoxy resin: 1, and the unsaturated acid anhydride is added in a molar ratio of (1-4) to the epoxy group of the epoxy resin: 1, wherein the monomer containing an active group capable of reacting with a carboxyl group and having an unsaturated double bond in a molecular structure is added in a molar ratio of (1.0 to 1.1): 1 or (2.9-3.1): addition was carried out in the manner of 1.
2. The light-curable solder resist ink according to claim 1, characterized in that: the epoxy resin is selected from those having a viscosity of 700 to 20000mPa s at 25 ℃ and an epoxy equivalent of 180 to 280 g/eq.
3. The light-curable solder resist ink according to claim 1, characterized in that: the epoxy resin is selected from any one of bisphenol A type epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin, p-tert-butyl phenol novolac epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, diglycidyl phthalate, diglycidyl tetrahydrophthalate, triglycidyl isocyanurate and dicyclodiene epoxide.
4. The light-curable solder resist ink according to claim 1, characterized in that: the unsaturated anhydride is a monobasic anhydride.
5. The light-curable solder resist ink according to claim 1, characterized in that: the molecular structure contains a monomer which contains an active group capable of reacting with carboxyl and has an unsaturated double bond, the active group capable of reacting with the carboxyl comprises any one of epoxy, hydroxyl and amino, and the number of the active groups capable of reacting with the carboxyl in the monomer is 1.
6. The light-curable solder resist ink according to claim 1, characterized in that: the molecular structure contains an active group capable of reacting with carboxyl and a monomer with unsaturated double bonds, and the number of the unsaturated double bonds is 1-2.
7. The light-curable solder resist ink according to claim 1, wherein the cholic acid-modified alkali-soluble light-curable epoxy resin is prepared by a method comprising the steps of:
(1) preheating a solvent to 70-90 ℃ under the nitrogen atmosphere, adding and dissolving epoxy resin, cooling to 50-60 ℃, adding cholic acid, heating to 70-80 ℃, adding a cyclic ester ring-opening polymerization catalyst, stirring and reacting for 1-2 hours at 95-110 ℃, then adjusting the temperature to 100-125 ℃, stirring and reacting for 12-24 hours until the acid value of the reaction solution is less than 10mgKOH/g, and obtaining an epoxy resin solution containing a cholic acid group;
(2) cooling the epoxy resin solution containing the cholic acid group obtained in the step (1) to 70-80 ℃, then adding unsaturated anhydride and a polymerization inhibitor for mixing, continuing to stir at 90-100 ℃ for 3-9 hours, cooling the reaction system to 70-80 ℃ after the reaction time is up, then adding a monomer which contains an active group capable of reacting with carboxyl and has an unsaturated double bond in a molecular structure and a polymerization inhibitor for mixing, continuing to stir at 100-110 ℃ for 3-6 hours, and obtaining cholic acid modified alkali-soluble photocuring epoxy resin after the reaction time is up; wherein the addition amount of the polymerization inhibitor is 0.4-2.5 wt% of the epoxy resin in the step (1).
8. The light-curable solder resist ink according to claim 1, wherein the light-curable solder resist ink suitable for high-frequency communication mainly comprises the following raw materials in parts by weight:
100 parts of cholic acid modified alkali-soluble photocuring epoxy resin;
3-5 parts of a photoinitiator;
20-50 parts of a filler;
5-30 parts of a reactive diluent;
1-25 parts of an additive.
9. The light-curable solder resist ink according to any one of claims 1 to 8, which is applied to a high-frequency communication PCB substrate.
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| CN116463006B (en) * | 2023-03-02 | 2023-12-08 | 广东炎墨方案科技有限公司 | Low-cost photo-curing solder resist ink suitable for high-frequency communication and preparation method thereof |
| CN117186361B (en) * | 2023-08-08 | 2024-05-17 | 广东炎墨方案科技有限公司 | Adamantane modified high-heat-resistance photo-curing solder resist ink and preparation method thereof |
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Denomination of invention: A UV curable solder resist ink suitable for high-frequency communication and its preparation method Effective date of registration: 20230605 Granted publication date: 20220617 Pledgee: Guangdong Development Bank Co.,Ltd. Heshan Sub branch Pledgor: HESHAN YANMO TECHNOLOGY Co.,Ltd. Registration number: Y2023980042831 |