CN114360903A - Roll printing paste binder for MLCC gravure printing and preparation method thereof - Google Patents

Abstract

The invention provides a roll printing paste binder for MLCC gravure printing and a preparation method thereof. The roll printing slurry binder comprises the following raw materials in percentage by mass: 4-8% of resin A; 2-4% of resin B; 80-95% of a solvent; 0.5-3% of wetting dispersant; 0.5-3% of a stabilizer; 0.5 to 5 percent of anti-settling agent. Meanwhile, the invention also discloses a preparation method of the adhesive. The invention mainly improves the composition and preparation process of the binder system, so that the viscosity and the dispersibility of the binder system are both suitable for the technical requirements of roll printing slurry, and the binder system has the advantages of cracking resistance, stable dispersibility, no carbon residue in slurry sintering and the like.

Description

Roll printing paste binder for MLCC gravure printing and preparation method thereof

Technical Field

The invention relates to the technical field of MLCC (multilayer ceramic capacitor), in particular to a roll printing paste binder for MLCC intaglio printing and a preparation method thereof.

Background

The Ceramic capacitor occupies more than 60% of the capacitance market due to the advantages of small volume, high capacity and low cost, while the shipment volume of the chip-type multilayer Ceramic capacitor (MLCC) accounts for more than 90% of the whole Ceramic capacitor, and the annual capacity is kept at the growth rate of 20-30% since 2018. With the increasing demand of MLCC, the search for high-efficiency MLCC production process is also becoming a new direction for people to explore. Printing, as a key process of the MLCC production process, has been a major breakthrough in the optimization and upgrading of the process. The traditional MLCC printing mode adopts screen printing, the screen printing is not influenced by printing stocks, the process is simple, and the advantages of microminiature and high-precision printing and the like can be carried out, so that the traditional MLCC printing mode has the leading position in the early MLCC printing mode, but the defects of the screen printing are also remarkable: due to the limitation of the screen printing plate and the printing mode, the screen printing efficiency is low, and the printing link becomes one of the bottlenecks of the expansion of the productivity of the MLCC. In recent years, with the spread of gravure printing (roll printing) in the MLCC process, it is considered that such a printing method having extremely high efficiency is becoming the main printing method of MLCC instead of screen printing.

The main difference between roll printing and silk printing is a feeding mode and a printing mode, the roll printing is dipped with proper slurry through a printing plate, and then the ceramic belt is driven by a transmission device to perform high-speed printing, the adverse factor of limiting the printing speed in the silk printing process is fundamentally solved by the printing mode, but higher technical requirements are provided for the slurry: firstly, the viscosity of the slurry is required not to be too high, and secondly, the dispersion performance of the slurry is required to be good; the low viscosity is beneficial to material taking and printing of a roller plate in the roller printing process, and the high dispersibility is beneficial to ensuring that the electrical property of a product reaches the standard. The adhesive is used as a main component playing a dispersing role in the slurry, the viscosity of the adhesive is generally in direct proportion to the dispersing performance, and the higher the viscosity is, the better the dispersing performance on the powder is; the lower the viscosity, the poorer the dispersibility in the powder.

As described above, the low viscosity and high powder dispersion required for MLCC roll marking pastes appear to be relatively contradictory; most of roll printing slurry which is mainstream at present adopts low molecular weight ethyl cellulose, polyvinyl butyral ester and the like, and forms a low-concentration single-system binder through a relevant solvent. The adhesive can meet gravure printing at high speed, but has defects in the storage of slurry, such as easy delamination of the slurry and pretreatment before use, mainly because the adhesive has small molecular weight and cannot form a good three-dimensional network structure, so that a stable dispersion system cannot be formed for a long time on powder; chinese patent CN113436886 mentions a preparation process of water-based roll printing slurry, but the binder is still a single resin system and has limited dispersion effect, the slurry of the type still has the phenomenon that powder is easy to precipitate and delaminate, and the pre-dispersion must be carried out by slow rolls or centrifugal deaeration before use, so that the complexity of the use process is increased.

Therefore, in order to solve such a phenomenon, it is urgently required to develop a binder system having a good dispersion characteristic and a viscosity satisfying the requirement of gravure printing.

Disclosure of Invention

According to the technical problem of poor dispersibility of an adhesive system in the existing roll printing paste, the roll printing paste adhesive for MLCC gravure printing and the preparation method thereof are provided, wherein the adhesive has good dispersibility and proper viscosity. The invention mainly improves the composition and preparation process of the binder system, and ensures that the viscosity and the dispersibility of the binder system are both suitable for the technical requirements of roll printing slurry.

The technical means adopted by the invention are as follows:

a roll printing paste binder for MLCC gravure printing, comprising: the material is composed of the following raw materials by mass percent:

4-8% of resin A;

2-4% of resin B;

80-95% of a solvent;

0.5-3% of wetting dispersant;

0.5-3% of a stabilizer;

0.5 to 5 percent of anti-settling agent.

Further, the resin A comprises one or more of methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose phthalate, microcrystalline cellulose ether and polyvinyl butyral, preferably ethyl cellulose.

Further, the resin B comprises one or more of rosin, vinyl chloride-vinyl acetate resin, furan resin, phenolic resin, epoxy resin and shellac, preferably vinyl chloride-vinyl acetate resin.

Further, the solvent comprises one or more of ethylene glycol monoethyl ether, terpineol, propylene glycol monomethyl ether, propylene glycol propyl ether, ethylene glycol butyl ether acetate, propylene glycol monomethyl ether and diethylene glycol ethyl ether acetate, and is preferably propylene glycol propyl ether.

Further, the wetting and dispersing agent comprises one or more of perfluoroalkyl betaine, alkyl ammonium salt, nonylphenol polyoxyethylene ether, phenethyl phenol polyoxyethylene ether, stearamide, heneicosanoic acid, ethyl palmitate and menthyl lactate, and preferably the nonylphenol polyoxyethylene ether.

Further, the stabilizer comprises one or more of castor oil derivatives, castor oil hydrides, organic bentonite, lecithin compounds and polyvinyl alcohol, and is preferably polyvinyl alcohol.

Further, the anti-settling agent comprises one or more than one of terephthalic acid esters, epoxidized alkyl ester and saturated fatty acid alkyl ester (C8-C10), preferably epoxidized alkyl ester.

The invention also discloses a preparation method of the gravure printing paste adhesive, which is characterized by comprising the following steps of,

step one, weighing a certain amount of solvent, placing the solvent in a stirring kettle, setting the temperature to be 40-60 ℃, setting the rotating speed to be 40-50RPM/min, and mixing and stirring for 5-10 min;

step two, adding a wetting dispersant, a stabilizer and an anti-settling agent into the stirring kettle according to a preset proportion, setting the temperature to be 40-60 ℃, setting the rotating speed to be 40-50RPM/min, and mixing and stirring for 5-10 min;

step three, adding the resin A and the resin B into the stirring kettle according to a preset proportion, setting the temperature to be 70-90 ℃, setting the rotating speed to be 500-700RPM/min, and mixing and stirring for 4-6 h;

step four, filtering the reacted binder by using a 3-micron filter element;

and step five, dispersing the filtered adhesive by using a three-roll mill, setting the pressure of the three-roll mill to be 5-10, setting the roll interval to be 5-15 units, and setting the rolling times to be 1-3.

And (3) taking a small amount of the binder after dispersion, preparing a sample by a tabletting method, and observing the resin dispersion degree by using a metallographic microscope, wherein if no obvious agglomeration phenomenon is observed under the microscope visual field, the binder dispersion degree is good.

The special adhesive for the MLCC roll printing paste is prepared from the low molecular weight resin, so that the requirement on viscosity in the printing process can be effectively met; the wetting dispersant, the stabilizer, the anti-settling agent and other auxiliaries are added into the system, so that on one hand, a cross-linking structure can be formed with resin, the system is changed into a three-dimensional network structure from a single chain structure, and the dispersing capacity of the binder is further improved; on the other hand, a binder composed of a plurality of components can obtain appropriate thixotropy by finely adjusting the ratio of the components.

Compared with the conventional roll printing paste binder system, the invention has the following advantages:

1. the binder system adopted by the invention has low resin content, and can reduce the cracking risk caused by too high resin volatilization speed in the glue discharging process of the slurry;

2. the binder system adopted by the invention is a double-resin crosslinking system, the dispersing performance is greatly improved compared with a single binder system, the dispersing performance is more stable, the long storage time of the slurry can be ensured, and the slurry is not easy to delaminate;

3. all the auxiliary agents in the binder system adopted by the invention have boiling points lower than the binder removal temperature of the slurry, and can be completely volatilized in the binder removal process, so that no carbon residue is left in the slurry sintering process, and the subsequent product production is not influenced;

4. the binder system adopted by the invention has a targeted dispersion process after high-temperature stirring, so that the formation of a resin agglomeration state can be further avoided;

5. the thixotropy adjusting window of the binder system adopted by the invention is large.

For the above reasons, the present invention can be widely applied to the field of roll printing paste manufacturing.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.

Fig. 1 is a microscope photograph showing the effect of dispersing metal powder using the binder of the present invention.

FIG. 2 is a graph showing the effect of the binder of the present invention (left) on the dispersion of powder compared to a conventional single component binder (right) (after standing for one month); the two are different only in the binder system, and the other components are consistent.

FIG. 3 is a graph showing the effect of a binder obtained in examples 1 to 5 (examples 1, 2, 3, 4 and 5 in the order from left to right) on powder dispersion in accordance with the present invention (after standing for one month).

Detailed Description

It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.

Example 1

The roll printing paste binder for MLCC gravure printing comprises the following substances in percentage by mass:

6% of ethyl cellulose;

2 percent of vinyl chloride-vinyl acetate copolymer

90% of terpineol;

0.5 percent of nonylphenol polyoxyethylene ether;

0.5 percent of polyvinyl alcohol;

epoxidized alkyl ester 1%

The invention also provides a preparation method of the adhesive, which comprises the following steps:

step one, weighing a certain amount of solvent into a stirring kettle, setting the mixing temperature at 40 ℃, setting the mixing rotation speed at 40RPM/min, and mixing and stirring for 5 min;

step two, adding a dispersing agent, a stabilizing agent and an anti-settling agent into the stirring kettle in proportion, setting the mixing temperature to be 40 ℃, setting the mixing rotating speed to be 40RPM/min, and mixing and stirring for 5 min;

adding a proper amount of resin into the stirring kettle in proportion, setting the reaction temperature to be 70 ℃, setting the reaction rotating speed to be 500RPM/min, and reacting for 4 hours;

step four, filtering the reacted binder by using a 3-micron filter element;

and step five, dispersing the filtered adhesive by using a three-roll mill, and setting the pressure of the three-roll mill to be 5, GAP to be 5 and the rolling frequency to be 3.

As shown in fig. 1, it can be seen that the binder provided by the present invention has a good effect of dispersing metal powder. As shown in FIG. 2, it can be seen that the powder dispersion effect of the binder of the present invention (left) is better than that of the common single-component binder (right) (after being left for one month), the two binder systems are different, and the other components are consistent.

Example 2

The roll printing paste binder for MLCC gravure printing comprises the following substances in percentage by mass:

8% of ethyl cellulose;

90% of terpineol;

0.5 percent of nonylphenol polyoxyethylene ether;

0.5 percent of polyvinyl alcohol;

epoxidized alkyl ester 1%

The invention also provides a preparation method of the adhesive, which comprises the following steps:

step one, weighing a certain amount of solvent into a stirring kettle, setting the mixing temperature at 50 ℃, setting the mixing rotation speed at 50RPM/min, and mixing and stirring for 5 min;

step two, adding a dispersing agent, a stabilizing agent and an anti-settling agent into the stirring kettle in proportion, setting the mixing temperature at 50 ℃, setting the mixing rotating speed at 50RPM/min, and mixing and stirring for 5 min;

adding a proper amount of resin into the stirring kettle in proportion, setting the reaction temperature to be 80 ℃, setting the reaction rotating speed to be 600RPM/min, and reacting for 5 hours;

step four, filtering the reacted binder by using a 3-micron filter element;

and step five, dispersing the filtered adhesive by using a three-roll mill, and setting the pressure of the three-roll mill to be 5, GAP to be 5 and the rolling frequency to be 2.

Example 3

The roll printing paste binder for MLCC gravure printing comprises the following substances in percentage by mass:

6% of ethyl cellulose;

2% of vinyl chloride-vinyl acetate copolymer;

90% of terpineol;

0.5% of heneicosanoic acid;

0.5 percent of polyvinyl alcohol;

epoxidized alkyl ester 1%.

The invention also provides a preparation method of the adhesive, which comprises the following steps:

step one, weighing a certain amount of solvent into a stirring kettle, setting the mixing temperature at 60 ℃, setting the mixing rotation speed at 45RPM/min, and mixing and stirring for 10 min;

step two, adding a dispersing agent, a stabilizing agent and an anti-settling agent into the stirring kettle in proportion, setting the mixing temperature to be 60 ℃, setting the mixing rotating speed to be 45RPM/min, and mixing and stirring for 10 min;

adding a proper amount of resin into the stirring kettle in proportion, setting the reaction temperature to be 85 ℃, setting the reaction rotating speed to be 600RPM/min, and reacting for 5 hours;

step four, filtering the reacted binder by using a 3-micron filter element;

and step five, dispersing the filtered adhesive by using a three-roll mill, and setting the pressure of the three-roll mill to be 5, GAP to be 5 and the rolling frequency to be 2.

Example 4

The roll printing paste binder for MLCC gravure printing comprises the following substances in percentage by mass:

6% of ethyl cellulose;

2 percent of vinyl chloride-vinyl acetate copolymer

90% of terpineol;

0.5 percent of nonylphenol polyoxyethylene ether;

lecithin compound 0.5%;

epoxidized alkyl ester 1%

The invention also provides a preparation method of the adhesive, which comprises the following steps:

step one, weighing a certain amount of solvent into a stirring kettle, setting the mixing temperature at 40 ℃, setting the mixing rotation speed at 50RPM/min, and mixing and stirring for 8 min;

step two, adding a dispersing agent, a stabilizing agent and an anti-settling agent into the stirring kettle in proportion, setting the mixing temperature to be 40 ℃, setting the mixing rotating speed to be 50RPM/min, and mixing and stirring for 8 min;

adding a proper amount of resin into the stirring kettle in proportion, setting the reaction temperature to be 90 ℃, setting the reaction rotating speed to be 700RPM/min, and reacting for 6 hours;

step four, filtering the reacted binder by using a 3-micron filter element;

and step five, dispersing the filtered adhesive by using a three-roll mill, setting the pressure of the three-roll mill to be 10, setting the GAP to be 5, and setting the rolling frequency to be 3.

Example 5

The roll printing paste binder for MLCC gravure printing comprises the following substances in percentage by mass:

6% of ethyl cellulose;

2% of vinyl chloride-vinyl acetate copolymer;

90% of terpineol;

0.5 percent of nonylphenol polyoxyethylene ether;

0.5 percent of polyvinyl alcohol;

1% of terephthalic acid ester.

The invention also provides a preparation method of the adhesive, which comprises the following steps:

step one, weighing a certain amount of solvent into a stirring kettle, setting the mixing temperature at 60 ℃, setting the mixing rotation speed at 50RPM/min, and mixing and stirring for 5 min;

step two, adding a dispersing agent, a stabilizing agent and an anti-settling agent into the stirring kettle in proportion, setting the mixing temperature to be 60 ℃, setting the mixing rotating speed to be 50RPM/min, and mixing and stirring for 5 min;

adding a proper amount of resin into the stirring kettle in proportion, setting the reaction temperature to be 80 ℃, setting the reaction rotating speed to be 600RPM/min, and reacting for 5 hours;

step four, filtering the reacted binder by using a 3-micron filter element;

and step five, dispersing the filtered adhesive by using a three-roll mill, and setting the pressure of the three-roll mill to be 5, GAP to be 5 and the rolling frequency to be 2.

In summary, as shown in fig. 3, the binder obtained in examples 1 to 5 of the present invention (examples 1, 2, 3, 4 and 5 in the order from left to right) is a comparative graph showing the effect of dispersing powder (after standing for one month). Compared with the prior art, the adhesive has more stable dispersion performance, can ensure that the slurry has longer storage time and is not easy to delaminate.

Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (8)

1. A roll printing paste binder for MLCC gravure printing, comprising: the material is composed of the following raw materials by mass percent:

4-8% of resin A;

2-4% of resin B;

80-95% of a solvent;

0.5-3% of wetting dispersant;

0.5-3% of a stabilizer;

0.5 to 5 percent of anti-settling agent.

2. The roll print paste binder for MLCC gravure printing according to claim 1 wherein the resin a comprises one or a mixture of more than one of methylcellulose, ethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose phthalate, microcrystalline cellulose ether, polyvinyl butyral.

3. The roll printing paste binder for MLCC intaglio printing according to claim 1 wherein the resin B comprises one or a mixture of more than one of rosin, vinyl chloride, furan, phenolic, epoxy, shellac.

4. The roll printing paste binder for MLCC gravure printing according to claim 1, wherein the solvent comprises one or a mixture of more than one of ethylene glycol monoethyl ether, terpineol, propylene glycol monomethyl ether, propylene glycol propyl ether, ethylene glycol butyl ether acetate, propylene glycol monomethyl ether, diethylene glycol ethyl ether acetate.

5. The roll printing paste binder for MLCC gravure printing according to claim 1, wherein the wetting dispersant comprises one or a mixture of more than one of perfluoroalkyl betaine, alkyl ammonium salt, nonylphenol polyoxyethylene ether, phenethyl phenol polyoxyethylene ether, stearamide, heneicosanoic acid, ethyl palmitate, menthyl lactate.

6. The roll printing paste binder for MLCC gravure printing according to claim 1, wherein the stabilizer comprises one or a mixture of more than one of castor oil derivatives, castor oil hydrides, organic bentonites, lecithin compounds, polyvinyl alcohol.

7. The roll print paste binder for MLCC gravure printing according to claim 1, wherein the anti-settling agent comprises one or a mixture of more than one of terephthalate, epoxidized alkyl ester, saturated fatty acid alkyl ester (C8-C10).

8. A method for preparing the roll printing paste binder for MLCC gravure printing according to any of claims 1 to 7, characterized by comprising the steps of,

step one, weighing a certain amount of solvent, placing the solvent in a stirring kettle, setting the temperature to be 40-60 ℃, setting the rotating speed to be 40-50RPM/min, and mixing and stirring for 5-10 min;

step two, adding a wetting dispersant, a stabilizer and an anti-settling agent into the stirring kettle according to a preset proportion, setting the temperature to be 40-60 ℃, setting the rotating speed to be 40-50RPM/min, and mixing and stirring for 5-10 min;

step three, adding the resin A and the resin B into the stirring kettle according to a preset proportion, setting the temperature to be 70-90 ℃, setting the rotating speed to be 500-700RPM/min, and mixing and stirring for 4-6 h;

step four, filtering the reacted binder by using a 3-micron filter element;

and step five, dispersing the filtered adhesive by using a three-roll mill, setting the pressure of the three-roll mill to be 5-10, setting the roll interval to be 5-15 units, and setting the rolling times to be 1-3.

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