阅读说明：本技术 具有高附着力的pcb板制程用uv固化喷墨打印油墨 (UV curing ink-jet printing ink with high adhesive force for PCB (printed circuit board) manufacturing process ) 是由 黄时雨 陆晓健 张燕红 朱坤 陆兰 顾群艳 向文胜 赵建龙 张兵 于 2020-12-17 设计创作，主要内容包括：本发明公开了一种具有高附着力的PCB板制程用UV固化喷墨打印油墨,其包括胺改性聚醚丙烯酸酯齐聚物5-30份、光活性稀释单体20-50份、功能性单体5-35份、光引发剂1-20份、助剂1-10份、颜料5-20份；所述光活性稀释单体为含有烷氧基的单官能丙烯酸酯、烷氧基的双官能丙烯酸酯、或烷氧基的三官能丙烯酸酯中的一种或多种的丙烯酸酯化合物；所述功能性单体为含有氨基的单官能或多官能丙烯酸酯。本发明油墨室温粘度在10-50mPa·s之间,室温表面张力在20-30mN/m之间,在具有优良的喷印性能的同时,还对基材具有优异的附着力性能以及耐热冲击性能。(The invention discloses UV curing ink-jet printing ink with high adhesive force for PCB (printed circuit board) manufacturing process, which comprises 5-30 parts of amine modified polyether acrylate oligomer, 20-50 parts of photoactive diluent monomer, 5-35 parts of functional monomer, 1-20 parts of photoinitiator, 1-10 parts of auxiliary agent and 5-20 parts of pigment; the photoactive dilution monomer is an acrylate compound containing one or more of monofunctional acrylate containing alkoxy, difunctional acrylate containing alkoxy, or trifunctional acrylate containing alkoxy; the functional monomer is a monofunctional or multifunctional acrylate containing an amino group. The ink has the room temperature viscosity of 10-50 mPa.s and the room temperature surface tension of 20-30mN/m, has excellent jet printing performance, and also has excellent adhesive force performance and thermal shock resistance to a base material.)

1. The UV curing ink-jet printing ink with high adhesive force for the PCB manufacturing process is characterized in that: the paint comprises 5-30 parts of amine modified polyether acrylate oligomer, 20-50 parts of optical activity diluent monomer, 5-35 parts of functional monomer, 1-20 parts of photoinitiator, 1-10 parts of auxiliary agent and 5-20 parts of pigment; the photoactive dilution monomer is an acrylate compound containing one or more of monofunctional acrylate containing alkoxy, difunctional acrylate containing alkoxy, or trifunctional acrylate containing alkoxy; the functional monomer is a monofunctional or multifunctional acrylate containing an amino group.

2. The high adhesion UV curable inkjet printing ink for PCB processing according to claim 1, wherein: the number of acrylate functional groups contained in each molecule of the amine modified polyether acrylate oligomer is 2-6, and the room-temperature viscosity is 20-10000mPa & s.

3. The high adhesion UV curable inkjet printing ink for PCB processing according to claim 1, wherein: the viscosity of the alkoxy-containing monofunctional acrylate at room temperature is 10-1000mPa & s, and the surface tension is 20-30 mN/m.

4. The high adhesion UV curable inkjet printing ink for PCB processing according to claim 1, wherein: the photoactive dilution monomer is selected from one or more of trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, 2-trimethylolpropane tetraacrylate, hydroxybutyl acrylate, hydroxyethyl acrylate, trimethylolpropane diacrylate, hydroxystyrene acrylate and hydroxypropyl methacrylate.

5. The high adhesion UV curable inkjet printing ink for PCB processing according to claim 1, wherein: the functional monomer is selected from one or more of dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, carbamate acrylate, carbamate methacrylate, polyurethane methacrylate, tert-butylaminoethyl acrylate and tert-butylaminoethyl methacrylate.

6. The high adhesion UV curable inkjet printing ink for PCB processing according to claim 1, wherein: the photoinitiator is one or more of benzoin and derivatives thereof, alkyl phenones and derivatives thereof, acyl phosphorus oxides and derivatives thereof, anthrone and derivatives thereof.

7. The high adhesion UV curable inkjet printing ink for PCB processing according to claim 1, wherein: the auxiliary agent is one or more of a flatting agent, a defoaming agent and a film-forming auxiliary agent.

8. The high adhesion UV curable inkjet printing ink for PCB processing according to claim 1, wherein: the pigment is selected from one or more of red, yellow, blue, white, black, purple pigment, dye and pigment.

[ technical field ] A method for producing a semiconductor device

The invention belongs to the technical field of PCB printing ink, and particularly relates to UV curing ink-jet printing ink with high adhesive force for PCB manufacturing process.

[ background of the invention ]

Digital Printing Inkjet Technology (Digital Printing Inkjet Technology) was expected to be popularized and applied in PCB production as early as 1990 and will likely become the mainstream Technology for PCB production. The advantages of digital ink jet printing technology, both fast and low cost, are now gradually recognized and understood, and are particularly desirable for the production of multi-variety and low volume PCB products.

The PCB needs to spray a layer of printing ink on the surface of the PCB to play a role in protection in the manufacturing process of the PCB, and the printing ink cannot crack, discolor, separate and the like in the manufacturing process of the PCB due to the complexity and the particularity of the manufacturing process of the PCB, so that the printing ink used for ink-jet printing of the PCB has excellent properties such as good adhesive force, insulativity, heat resistance, acid and alkali resistance, solvent resistance and the like. In order to increase the adhesion of the UV curable inkjet printing ink for PCB manufacturing process in the prior art, compounds such as high molecular weight and high viscosity polyurethane are often added, and the color block of the ink printed character with the high viscosity polyurethane compounds may change color and fall off in the processes of soldering tin, gold melting, etc.

Therefore, it is required to provide a new UV curable inkjet printing ink for PCB manufacturing process with high adhesion to solve the above problems.

[ summary of the invention ]

The invention mainly aims to provide the UV curing ink-jet printing ink with high adhesion for the PCB manufacturing process, wherein the room-temperature viscosity is 10-50mPa & s, and the room-temperature surface tension is 20-30mN/m, so that the enhanced adhesion is greatly improved, and the thermal shock resistance can be enhanced.

The invention realizes the purpose through the following technical scheme: the UV curing ink-jet printing ink with high adhesive force for the PCB manufacturing process comprises 5-30 parts of amine modified polyether acrylate oligomer, 20-50 parts of photoactive dilution monomer, 5-35 parts of functional monomer, 1-20 parts of photoinitiator, 1-10 parts of auxiliary agent and 5-20 parts of pigment; the photoactive dilution monomer is an acrylate compound containing one or more of monofunctional acrylate containing alkoxy, difunctional acrylate containing alkoxy, or trifunctional acrylate containing alkoxy; the functional monomer is a monofunctional or multifunctional acrylate containing an amino group.

Furthermore, the number of acrylate functional groups contained in each molecule of the amine modified polyether acrylate oligomer is 2-6, and the room-temperature viscosity is 20-10000mPa & s.

Further, the viscosity of the monofunctional acrylate having an alkoxy group at room temperature is 10 to 1000 mPas, and the surface tension is 20 to 30 mN/m.

Further, the optically active dilution monomer is selected from one or more of trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, 2-trimethylolpropane tetraacrylate, hydroxybutyl acrylate, hydroxyethyl acrylate, trimethylolpropane diacrylate, hydroxystyrene acrylate, hydroxypropyl methacrylate, and the like.

Further, the functional monomer is selected from one or more of dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, urethane acrylate, urethane methacrylate, tert-butylaminoethyl acrylate and tert-butylaminoethyl methacrylate.

Further, the photoinitiator is one or more of benzoin and derivatives thereof, alkyl phenones and derivatives thereof, acyl phosphorus oxides and derivatives thereof, anthrone and derivatives thereof.

Further, the auxiliary agent is one or more of a flatting agent, a defoaming agent and a film-forming auxiliary agent.

Further, the pigment is selected from one or more of red, yellow, blue, white, black, purple pigment, dye and pigment.

Compared with the prior art, the UV curing ink-jet printing ink with high adhesive force for the PCB manufacturing process has the beneficial effects that: the greenhouse viscosity of the ink-jet printing ink prepared by the scheme is 25-35mPa & s, the room-temperature surface tension is 22-26mN/m, the ink-jet printing ink has excellent printing performance and excellent adhesive force and thermal shock resistance, can completely meet the requirements of PCB (printed circuit board) manufacturing procedures, and can effectively prevent the ink from cracking, discoloring, separating and the like. Before photocuring and non-baking of the printing ink in the current market, oil is scraped and dropped between the PCB plates due to human factors and the like in the transportation process, the adhesion force of the printing ink before baking is greatly increased, and the oil dropping phenomenon of the PCB plates due to scraping can be effectively avoided; in the later-stage processing of the PCB, the processes of tin soldering, gold melting and the like, particularly the tin soldering process, the character printing ink is easy to drop characters due to high temperature, and the printing ink prepared by the scheme has higher heat resistance and can effectively avoid the phenomenon of character dropping due to high temperature.

[ detailed description ] embodiments

Example (b):

the embodiment is a high-adhesion UV curing ink-jet printing ink for PCB manufacturing process, which comprises the following components: amine modified polyether acrylate A, an optically active diluent monomer B, a functional monomer C, a photoinitiator D, an auxiliary agent E and a pigment F.

The preparation method comprises the following steps: the raw materials are uniformly mixed according to the formula proportion, the raw materials are stirred for 1-2h by a dispersion machine at the rotating speed of 500-₅₀The ink of the scheme is obtained by filtering the mixture by a 1 mu filter at a temperature of between 100 and 300 nm.

The present invention will be described in further detail with reference to specific examples and comparative examples. The materials were mixed uniformly in the proportions shown in Table 1, and ink-jet printing inks of examples 1 to 3 and comparative examples 1 to 6 were prepared according to the above-mentioned procedures.

TABLE 1 ingredients and proportions in examples 1-3 and comparative examples 1-6

Ingredient brand description: component A is amine modified polyether acrylate oligomer (IGM company), component B is alkoxylated tetrahydrofuran acrylate (sartomer), component C is dimethylaminoethyl acrylate (sartomer), component D is 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide (Sigma-Aldrich), component E is BYK-306 (Pico chemical), and component F is titanium dioxide R-706 (DuPont).

And (3) performance testing:

the ink-jet printing inks of examples 1 to 3 and comparative examples 1 to 6 prepared above were injected into the ink sac of an ink-jet printer using a 395nm LED lamp with an exposure lamp energy set at 300-²The temperature of the spray head is set to be 45-55 ℃, the substrate can adopt ceramics/glass/FCCL/FR-4 and the like, a specific spray printing mode program is started for carrying out ink-jet printing, a sample plate is prepared, and then the performance evaluation is carried out on the ink coating, wherein the spray printing process and the performance evaluation method are as follows:

(1) finger touch dryness test

The ink coating obtained immediately after the ink jet printing was touched with a finger, and then the degree of drying and the surface condition thereof were visually observed.

The finger-touch dryness test criteria are as follows:

o: the ink has good ink jet instant curability and no fingerprint printing;

x: the ink had poor ink jet instant curability and was marked on finger touch.

(2) Adhesion test

And (3) placing the sample plate in a drying oven at 150 ℃ for baking for 1h, testing the adhesive force of the sample plate by adopting a one-hundred-grid method, cutting the ink-jet ink coating to the surface of the base material to form grid-shaped scratches, sticking and tearing the scratches by using a 3M adhesive tape, observing the shedding condition of the coating, and then evaluating.

The adhesion test criteria are as follows:

o: no drop trace exists;

and (delta): slight corner drop but no flaking off;

x: large area of the film is peeled off.

(3) Insulation reliability test

DC 100V bias voltage is applied to an IPC-B comb-shaped electrode on the sample plate, the sample plate is placed in a constant temperature and humidity tank with the temperature of 90 percent R.H for one week under the condition of temperature cycle of 25 to 65 ℃, then the sample plate is treated for one minute under the conditions of room temperature and DC 500V, and resistance value measurement and optical microscope observation are carried out by a multimeter.

The insulation reliability test criteria are as follows:

o: the insulation property is hardly decreased, and no surface change is observed;

and (delta): the insulativity is slightly reduced, or a small amount of copper ions are migrated;

x: the insulation property is obviously reduced, or the copper ions are greatly transferred.

(4) Solder thermal shock resistance test

The panels were placed in a tin furnace at 288 ℃ and immersed in the tin furnace for 10s and then removed and cooled to room temperature for a total of three times.

The solder heat shock resistance test standard is as follows:

o: no discoloration, peeling and bulging;

and (delta): color change, but no drop and protrusion;

x: the appearance has obvious color change, falling and protrusion.

(5) Acid resistance test

The panels were soaked in 10% volume fraction H₂SO₄After taking out the mixture from the water solution for 30 minutes, washing the mixture with deionized water, drying the mixture in the air and observing the mixture.

The evaluation criteria for the acid resistance test are as follows:

o: no discoloration, peeling and bulging;

and (delta): color change, but no drop and protrusion;

x: the appearance has obvious color change, falling and protrusion.

(6) Alkali resistance test

And soaking the sample plate in 10% NaOH aqueous solution by volume fraction for 30 minutes, taking out, washing with deionized water, air-drying, and observing.

The evaluation criteria for the acid resistance test are as follows:

o: no discoloration, peeling and bulging;

and (delta): color change, but no drop and protrusion;

x: the appearance has obvious color change, falling and protrusion.

(7) Solvent resistance test

The sample was immersed in a PMA (propylene glycol methyl ether acetate) solution for 30 minutes, taken out, washed with deionized water, air-dried, and observed.

The evaluation criteria for the acid resistance test are as follows:

o: no discoloration, peeling and bulging;

and (delta): color change, but no drop and protrusion;

x: the appearance has obvious color change, falling and protrusion.

The results of the above test tests conducted for examples 1 to 3 and comparative examples 1 to 6 are shown in Table 2.

TABLE 2 results of performance test of inks prepared in examples 1 to 3 and comparative examples 1 to 6

As can be seen from the test results in Table 2, the inks prepared in the embodiments 1-3 have the best performance, especially adhesion and thermal shock resistance, and meet the performance requirements of PCB process for printing ink.

What has been described above are merely some embodiments of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the inventive concept thereof, and these changes and modifications can be made without departing from the spirit and scope of the invention.