TWI682008B - Solvent composition for electronic device manufacturing, printing ink for electronic device manufacturing, method for manufacturing the same, and use of solvent composition and printing ink - Google Patents

Abstract

The invention provides a solvent composition, which is a solvent composition used in printing ink for forming wiring or electrodes of an electronic device by a printing method, which can improve the printing accuracy of the printing ink, can be sintered at a low temperature, and can be suppressed The ash content produced after sintering makes the ash content extremely low.

The solvent composition for manufacturing electronic devices of the present invention is a solvent composition used in printing inks for manufacturing electronic devices by a printing method, which contains a solvent and a compound represented by the following formula (1). In the following formula, R represents an aliphatic hydrocarbon group having 1 or more carbon atoms. In addition, all four R systems in the formula are the same group or two different groups.

Description

Solvent composition for electronic device manufacturing, printing ink for electronic device manufacturing, method for manufacturing the same, and use of solvent composition and printing ink

The present invention relates to a solvent composition used in printing inks that use a printing method to form wiring or electrodes in the manufacture of electronic devices. This case claims the priority of Japanese Patent Application No. 2015-019637 filed in Japan on February 3, 2015 and the contents thereof are invoked here.

Electronic devices manufactured using the printing method include capacitors, inductors, varistors, thermal resistors, transistors, speakers, actuators, antennas, solid oxide fuel cells, etc.

For example, multilayer ceramic capacitors are usually manufactured through the following steps.

1. Form a slurry containing a binder powder of ceramic powder, polyvinyl acetal resin, etc., and a solvent into a thin sheet to obtain a green sheet.

2. The green sheet is coated with a material containing electrical properties (for example, nickel, palladium, etc.), a binder resin (for example, ethyl cellulose, etc.), and an organic solvent (for example, terpineol, etc.) by printing. Ink printing, forming conductive circuit wiring, electrodes, etc. (hereinafter sometimes referred to as "wiring etc.") (coating step).

3. Dry the coated ink (drying step).

4. Cut the green sheet on which wiring and the like are formed into a predetermined size, stack a plurality of sheets and press-fit.

5. Allow to sinter (sintering step).

The binder resin contained in the printing ink has the function of fixing the material imparting electrical characteristics to the green sheet, and has the function of imparting a moderate viscosity to form a fine print pattern. As the binder resin, ethyl cellulose has been mainly used so far. However, ethyl cellulose needs to be sintered at a high temperature due to its low thermal decomposition property. Since it is exposed to high temperature for a long time, a member having a coated surface (hereinafter sometimes referred to as "coated surface member") softens and deforms The problem of the situation is that the carbon component remains as ash after sintering, which causes the problem of reduced conductivity.

In order to solve the above problems, various improvements have been made to the improvement of the binder resin. For example, Patent Document 1 discloses that the substitution of polyvinyl acetal resin for ethyl cellulose can reduce the amount of ash produced. However, even with the use of polyvinyl acetal resin, it is still impossible to obtain sufficiently satisfactory results for these problems.

Prior technical literature Patent Literature

Patent Literature 1 Japanese Patent Laid-Open No. 2006-299030

Therefore, an object of the present invention is to provide a solvent composition for forming a solvent composition used in ink for wiring or electrodes of electronic devices by a printing method, which can improve the printing accuracy of the ink and can be sintered at a low temperature , Suppress the ash content generated after sintering to make the ash content extremely low.

Another object of the present invention is to provide an ink and a method for manufacturing the same, which is an ink for forming wiring or electrodes of an electronic device by a printing method, which has excellent printing accuracy, can be sintered at a low temperature, and is produced after sintering The ash component is very small.

The inventors have studied and solved the above-mentioned problems and found that the compound represented by the following formula (1) is self-organized when heated and dissolved in a solvent to form a rope-like assembly and produces a viscosity like a polymer compound. Compared with ethyl cellulose and other binder resins, it can be sintered at low temperature, and the ash content after sintering is very small.

Therefore, it was found that the ink obtained by the step of heating and dissolving the compound represented by the above formula (1) and the solvent has a viscosity suitable for forming wiring by the printing method, etc., so that dripping can be suppressed and high-precision wiring can be formed The pattern, in the sintering step, can be quickly and easily sintered at a lower temperature than in the case of printing ink containing binder resin such as ethyl cellulose, which can prevent the coated surface member from being exposed to high temperature for a long time. Softening and deformation can significantly reduce the amount of ash residue after sintering, and can suppress the reduction in electrical characteristics caused thereby. The present invention is based on these findings.

That is, the present invention provides a solvent composition for manufacturing an electronic device, which is a solvent composition used in an ink for manufacturing an electronic device by a printing method, which contains a solvent and a compound represented by the following formula (1) ,

(In the formula, R represents an aliphatic hydrocarbon group having 1 or more carbon atoms. In addition, all four R systems in the formula are the same group or two different groups).

The present invention also provides the aforementioned solvent composition for manufacturing an electronic device, wherein R in formula (1) is a linear or branched chain alkyl, alkenyl, or alkynyl group having 6 to 18 carbon atoms.

The present invention also provides the aforementioned solvent composition for manufacturing an electronic device, wherein the SP value [(cal/cm ³ ) ^0.5 ] of the solvent at 25° C. is 7.0 to 9.0.

The present invention also provides the aforementioned solvent composition for manufacturing electronic devices, wherein the solvent is selected from the group consisting of n-decane, n-dodecane, propylene glycol methyl-n-propyl ether, propylene glycol methyl-n-butyl ether, Dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl-n-butyl ether, dipropylene glycol methyl isoamyl ether, tripropylene glycol methyl-n-propyl ether, cyclic At least one of the group consisting of hexyl acetate, 2-methylcyclohexyl acetate, and 4-t-butyl cyclohexyl acetate.

The present invention also provides the aforementioned solvent composition for manufacturing an electronic device, wherein the content of the compound represented by formula (1) is 0.1 to 50 parts by weight relative to 100 parts by weight of the solvent.

The present invention also provides a method for manufacturing an ink for manufacturing an electronic device, which includes a step of heating and dissolving the solvent composition for manufacturing an electronic device at 30 to 90°C.

The invention also provides an ink for manufacturing electronic devices, which comprises a solvent and a compound represented by the following formula (1)

(In the formula, R represents an aliphatic hydrocarbon group having 1 or more carbon atoms. In addition, all four R systems in the formula are the same group or two different groups).

The present invention still further provides the printing ink for manufacturing electronic devices as described above, which includes a conductive metal material, a semiconductor material, a magnetic material, a dielectric material, or an insulating material.

The invention also provides the printing ink for manufacturing electronic devices as described above, wherein the binder resin content is 10% by weight or less.

That is, the present invention relates to the following:

[1] A solvent composition for manufacturing an electronic device, which is a solvent composition used in an ink for manufacturing an electronic device by a printing method, which contains a solvent and a compound represented by formula (1).

[2] The solvent composition for manufacturing an electronic device as described in [1], wherein R in formula (1) is a linear or branched chain alkyl, alkenyl, or alkynyl group having 6 to 18 carbon atoms .

[3] The solvent composition for manufacturing an electronic device according to [1] or [2], wherein the compound represented by formula (1) is selected from the compounds represented by formulas (1-2) to (1-5) Up to 1 compound.

[4] The solvent composition for manufacturing an electronic device according to [1] or [2], wherein the compound represented by formula (1) is a compound represented by formula (1-3) and/or formula (1-4) ).

[5] The solvent composition for manufacturing an electronic device according to any one of [1] to [4], wherein the evaporation temperature of the compound represented by formula (1) is 120 to 380°C.

[6] The solvent composition for manufacturing an electronic device according to any one of [1] to [5], wherein the SP value [(cal/cm ³ ) ^0.5 ] of the solvent at 25° C. is 7.0 to 9.0.

[7] The solvent composition for electronic device manufacturing as described in any one of [1] to [6], wherein the content of the solvent is 20.0 to 99.9% by weight of the total amount of the solvent composition for electronic device manufacturing.

[8] The solvent composition for manufacturing an electronic device according to any one of [1] to [7], wherein the solvent is selected from n-decane, n-dodecane, propylene glycol methyl-n-propyl Ether, propylene glycol methyl-n-butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl-n-butyl ether, dipropylene glycol methyl isoamyl ether, At least one of the group consisting of tripropylene glycol methyl-n-propyl ether, cyclohexyl acetate, 2-methylcyclohexyl acetate, and 4-t-butylcyclohexyl acetate.

[9] The solvent composition for manufacturing an electronic device according to any one of [1] to [8], wherein n-decane, n-dodecane, propylene glycol methyl-n-propyl ether, and propylene glycol methyl alcohol -N-butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl-n-butyl ether, dipropylene glycol methyl isoamyl ether, tripropylene glycol methyl -The content of solvents other than -n-propyl ether, cyclohexyl acetate, 2-methylcyclohexyl acetate, and 4-t-butyl cyclohexyl acetate is smaller than that of the solvent composition for the manufacture of electronic devices Contains 50% by weight of the total solvent.

[10] The solvent composition for manufacturing an electronic device according to any one of [1] to [9], wherein the content of the compound represented by formula (1) is 0.1 to 50 with respect to 100 parts by weight of the solvent Parts by weight.

[11] A method for manufacturing an ink for electronic device manufacturing, comprising the step of heating and dissolving the solvent composition for electronic device manufacturing as described in any one of [1] to [10] at 30 to 90°C.

[12] An ink for manufacturing an electronic device, which is obtained by the manufacturing method described in [11].

[13] An ink for manufacturing an electronic device, which contains the solvent composition for manufacturing an electronic device as described in any one of [1] to [10].

[14] An ink for manufacturing an electronic device, which contains a solvent and a compound represented by formula (1).

[15] The printing ink for manufacturing an electronic device as described in any one of [12] to [14], which further contains a material imparting electrical characteristics.

[16] The printing ink for manufacturing an electronic device according to [15], wherein the electrical property-imparting material is a conductive metal material, a semiconductor material, a magnetic material, a dielectric material, or an insulating material.

[17] The printing ink for manufacturing electronic devices as described in any one of [12] to [16], wherein the binder resin content is 10% by weight or less.

[18] The printing ink for electronic device manufacturing described in [17], wherein the binder resin is a polymer compound having a molecular weight of 10,000 or more.

[19] The printing ink for manufacturing electronic devices as described in [17] or [18], wherein the binder resin is selected from the group consisting of ethyl cellulose resin, alkyl cellulose resin, polyvinyl acetal resin, and acrylic resin At least one type of group.

[20] The printing ink for electronic device manufacturing as described in any one of [12] to [19] has a viscosity at 25°C [at a shear rate of 0.5 s ^-1 ] of 0.01 to 1000 Pa‧s.

[21] A method of manufacturing an electronic device, comprising a step of applying the printing ink for manufacturing an electronic device as described in any one of [12] to [20] by a printing method, and forming a wiring through a sintering step after drying .

[22] The method for manufacturing an electronic device as described in [21], wherein the sintering temperature is in the range of 100 to 350°C.

[23] The method for manufacturing an electronic device as described in [21] or [22], which forms wiring with a residual amount of ash of 4.5% by weight or less.

[24] The method for manufacturing an electronic device according to any one of [21] to [23], wherein the electronic device is a multilayer ceramic capacitor.

[25] An electronic device obtained by using the method for manufacturing an electronic device as described in any one of [21] to [24].

[26] The electronic device according to [25], which has wiring with a residual amount of ash of 4.5% by weight or less.

Since the solvent composition for manufacturing an electronic device of the present invention contains the compound represented by the above formula (1), the ink can be manufactured through the step of heating and dissolving, and the ink has a viscosity suitable for forming a wiring or the like by a printing method.

In addition, the ink system obtained by using the solvent composition for manufacturing an electronic device of the present invention is less prone to dripping, and a high-precision wiring pattern can be formed by a printing method. In addition, in the sintering step, sintering can be performed at a lower temperature, and the member to be coated surface can be prevented from softening and deforming by being exposed to high temperature for a long time. Furthermore, the residual amount of ash after sintering can be significantly reduced, and the reduction in electrical characteristics caused thereby can be suppressed.

Therefore, according to the solvent composition for manufacturing an electronic device of the present invention, it is possible to form a wiring and the like having excellent electrical characteristics by a printing method, and it is possible to efficiently manufacture an electronic device having a wiring and the like having excellent electrical characteristics.

Forms for carrying out the invention [Solvent composition for electronic device manufacturing]

The solvent composition for manufacturing electronic devices of the present invention (hereinafter sometimes referred to as "solvent composition") is a solvent composition for manufacturing printing inks for electronic devices using a printing method, which contains a solvent and the formula (1) Of compounds.

(Compound represented by formula (1))

The solvent composition of the present invention contains a compound represented by the following formula (1). In the formula, R represents an aliphatic hydrocarbon group having 1 or more carbon atoms. In addition, all four R systems in the formula are the same group or two different groups. The compound represented by the following formula (1) functions as a thickener.

In formula (1), R is an aliphatic hydrocarbon group having 1 or more carbon atoms, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, and octyl. , 2-ethylhexyl, decyl, dodecyl, tetradecyl, octadecyl, nonadecyl, etc., the carbon number is about 1~20 (compared Preferably 6 to 18) linear or branched chain alkyl; vinyl, 3-butenyl, 4-pentenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl , 5-hexenyl, 7-octenyl, 9-decenyl, 11-dodecenyl, octadecenyl, etc. have a carbon number of about 2 to 20 (preferably 6 to 18, particularly preferably 12 ~18) linear or branched chain alkenyl; butynyl, pentynyl, hexynyl, octynyl, decynyl, pentadecynyl, octadecynyl, etc. Linear or branched chain alkynyl groups of about 20 (preferably 6-18, particularly preferably 12-18).

Examples of the compound represented by formula (1) include compounds represented by the following formulas (1-1) to (1-5). In the following formulas, R ¹ and R ² represent aliphatic hydrocarbon groups having a carbon number of 1 or more different from each other, and the same examples as the above R can be given. In addition, when there is a plural R ¹ in the formula, these systems represent the same group. The same is true for R ² .

As the compound represented by the formula (1) in the present invention, the point where the viscosity can be increased by adding a small amount, the above formula (1-2) to (1-5) The compound shown is preferable, and particularly preferably the compound shown in the above formula (1-3) and/or the compound shown in the above formula (1-4).

As the compound represented by formula (1), the evaporation temperature is 120 to 380°C (preferably 150 to 330°C, further preferably 150 to 320°C, particularly preferably 150 to 315°C, and most preferably 170 to 315℃) is better, the evaporation temperature can be controlled by the type of side chain. If the evaporation temperature is higher than the above range, sintering at low temperature becomes difficult, and the member to be coated may be softened and deformed by being exposed to high temperature for a long time. On the other hand, when the evaporation temperature is lower than the above range, the composition may be vaporized during ink preparation or printing to change the composition, and it may become difficult to form wiring stably.

The compound represented by the formula (1) can be self-bonded by hydrogen bonding at the amide binding site, and can form a fibrous self-organizing body. Furthermore, since the R group has an affinity for the solvent, the solvent can be thickened by miscibility with the solvent, which can form a stable ink for electronic device manufacturing over time.

The content of the compound represented by formula (1) in the solvent composition of the present invention (total content when two or more kinds are contained) is, for example, about 0.1 to 50 parts by weight, preferably 0.5 to about 100 parts by weight of the solvent 30 parts by weight, particularly preferably 0.5 to 10 parts by weight. If the content of the compound represented by the formula (1) is lower than the above range, it becomes difficult to maintain the viscosity of the printing ink stably due to temperature changes, etc., and it is difficult to form a highly accurate wiring pattern due to dripping Situation. On the other hand, if the content of the compound represented by the formula (1) is higher than the above range, the viscosity of the printing ink becomes too high, and it may be difficult to form wiring or the like by the printing method.

The compound represented by formula (1) can be produced by, for example, the following method.

1. A method of reacting cyclohexane tetracarboxylic acid and thionyl chloride to obtain cyclohexane tetracarboxylic acid tetrachloride, and reacting the obtained cyclohexane tetracarboxylic acid tetrachloride with an amine.

2. A method of reacting cyclohexanetetracarboxylic dianhydride with amine (1) to obtain amide acid, and further condensing with amine (2) (which may be the same as or different from amine (1)) with a condensing agent.

As the cyclohexane tetracarboxylic acid used in the production method of the above 1, 1,2,4,5-cyclohexane tetracarboxylic acid can be suitably used.

Examples of the amine (R-NH ₂ : R is the same as described above) used in the production method of the above 1 include, for example, butylamine, pentylamine, isoamylamine, hexylamine, octylamine, 2-ethyl Hexylamine, decylamine, dodecylamine, tetradecylamine, octadecylamine, octadecylamine, etc. have a carbon number of 1 or more (preferably a carbon number of 6 to 20, particularly preferred It is an amine of an aliphatic hydrocarbon group having 6 to 18 carbon atoms (for example, a linear or branched chain alkyl group, alkenyl group, or alkynyl group).

In the production method of the above 1, the reaction of cyclohexanetetracarboxylic acid tetrachloride and amine can be performed, for example, by dropping cyclohexanetetracarboxylic acid tetrachloride in a system charged with amine. As the amine system, one kind may be used alone, or two different kinds of amines may be used.

The amount of amine used (the total amount when two different amines are used) is relative to 1 mole of cyclohexanetetracarboxylic acid tetrachloride, such as about 4 to 8 moles, preferably 4 to 6 moles.

烷、1,2-二甲氧基乙烷、環戊基甲基醚等之醚系溶媒；乙腈、苯甲腈等之腈系溶媒；二甲基碸等之碸系溶媒；環丁碸等之環丁碸系溶媒；二甲基甲醯胺等之醯胺系溶媒；聚矽氧油等之高沸點溶媒等。此等係可1種單獨使用、或組合2種以上使用。 The reaction system of cyclohexanetetracarboxylic acid tetrachloride and amine can be carried out in the presence or absence of a solvent. Examples of the aforementioned solvents include saturated or unsaturated hydrocarbon-based solvents such as pentane, hexane, heptane, octane, and petroleum ether; aromatic hydrocarbon-based solvents such as benzene, toluene, and xylene; and methylene chloride , Chloroform, 1,2-dichloroethane, chlorobenzene, bromobenzene and other halogenated hydrocarbon-based solvents; diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, di

Ether-based solvents such as alkane, 1,2-dimethoxyethane, cyclopentyl methyl ether, etc.; nitrile-based solvents such as acetonitrile, benzonitrile, etc.; benzene-based solvents such as dimethyl ash; ciclobutane, etc. The cyclic butadiene-based solvents; the amide-based solvents such as dimethylformamide; the high-boiling solvents such as silicone oil. These systems can be used alone or in combination of two or more.

The use amount of the aforementioned solvent is, for example, about 50 to 300% by weight relative to the total amount of cyclohexanetetracarboxylic acid tetrachloride and amine. If the use amount of the solvent is higher than the above range, the concentration of the reaction component decreases, and the reaction rate tends to decrease.

The reaction of cyclohexanetetracarboxylic acid tetrachloride and amine is usually carried out under normal pressure. The gas environment for the above reaction is not particularly limited as long as it does not hinder the reaction. For example, any one of an air gas environment, a nitrogen gas environment, and an argon gas environment may be used. The reaction temperature is, for example, about 30 to 60°C. The reaction time is, for example, about 0.5 to 20 hours. After the reaction is completed (=after the dropping is completed), the aging step can also be set. When the aging step is provided, the aging temperature is, for example, about 30 to 60° C., and the aging time is, for example, about 1 to 5 hours. In addition, the reaction can be carried out by any method such as batch type, semi-batch type, and continuous type.

After the reaction is completed, the resulting reaction product can be separated and purified by, for example, separation means such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, or a combination of these separation means .

In the production method of the above 2, for example, cyclohexanetetracarboxylic dianhydride and amine (1) and the following solvent can be charged into the system and matured to form an amidic acid, followed by charging amine (2) and a condensing agent (For example, carbodiimide or its salt, etc.) The compound represented by formula (1) is produced by aging.

As the cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid-1,2:4,5-dianhydride can be suitably used.

Examples of the amines (1) and (2) include the same amines that can be used in the production method of the above 1.

The amount of the amine (1) used is, for example, about 2 to 4 moles relative to 1 mole of cyclohexanetetracarboxylic dianhydride, preferably 2 to 3 moles. The amount of the amine (2) used is, for example, about 2 to 4 moles relative to 1 mole of cyclohexanetetracarboxylic dianhydride, preferably 2 to 3 moles.

The carbodiimide system is represented by the following formula.

R”-N=C=N-R’

In the above formula, examples of R′ and R” include, for example, a linear or branched chain alkyl group having 3 to 8 carbon atoms which may have a heteroatom-containing substituent, or a ring of 3 to 8 members Alkyl. R', R" may be the same or different. In addition, R'and R" may be combined with each other to form a ring together with the (-N=C=N-) group in the above formula.

Examples of the straight-chain or branched-chain alkyl groups having 3 to 8 carbon atoms include propyl, isopropyl, butyl, isobutyl, and s-butyl. Group, t-butyl, pentyl, isopentyl, s-pentyl, t-pentyl, hexyl, isohexyl, s-hexyl, t-hexyl and the like.

Examples of the aforementioned 3- to 8-membered cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

Examples of the aforementioned hetero atom-containing substituents include nitrogen atom-containing substituents such as bis(C _1-3 )alkylamine groups such as amine groups and dimethylamino groups.

Examples of the carbodiimide include diisopropylcarbodiimide, dicyclohexylcarbodiimide, and N-(3-dimethylaminopropyl)-N'-ethyl. Carbodiimide, etc. In addition, examples of the carbodiimide salt include hydrochloride (specifically, N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride Salt, etc.) etc. These systems can be used alone or in combination of two or more.

The amount of carbodiimide used is, for example, about 2 to 6 moles, preferably 2 to 4 moles, relative to 1 mole of cyclohexanetetracarboxylic dianhydride.

As the solvent, it is preferable to use a proton-accepting solvent (for example, pyridine, triethylamine, tributylamine, etc.) having excellent solubility in amide acid. These systems can be used alone or in combination of two or more.

The use amount of the aforementioned solvent is, for example, about 50 to 300% by weight, preferably 100 to 250% by weight, relative to the total amount of amide acid. If the use amount of the solvent is higher than the above range, the concentration of the reaction component decreases, and the reaction rate tends to decrease.

The above reaction is usually carried out under normal pressure. In addition, the gas environment of the above reaction is not particularly limited as long as it does not hinder the reaction. For example, any of an air gas environment, a nitrogen gas environment, an argon gas environment, etc. may be used. The aging temperature (reaction temperature) is, for example, about 30 to 70°C. The aging time of cyclohexanetetracarboxylic dianhydride and amine is, for example, about 0.5 to 5 hours, and the aging time of amide acid and amine is, for example, about 0.5 to 20 hours. In addition, the reaction can be carried out by any of batch method, semi-batch method, and continuous method.

After the reaction is completed, the resulting reaction product can be separated and purified by, for example, separation means such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, or a combination of these separation means .

(Solvent)

As the solvent contained in the solvent composition of the present invention, it is preferable to use a solvent having excellent solubility in the compound represented by the above formula (1).

As the aforementioned solvent, among them, the solubility in the compound represented by the above formula (1) is excellent, and the heating temperature at which the compound represented by the above formula (1) can be dissolved can be lowered, for example, suppressed to about 50 to 90°C. It is preferable to use one or two or more solvents at 25°C with an SP value [(cal/cm ³ ) ^0.5 : Fedors calculated value] in the range of 7.0 to 9.0 (preferably 7.5 to 9.0). Solvents with an SP value outside the above range have low solubility because of the compound represented by the above formula (1), and when dissolving the aforementioned compound, there is a tendency to heat at a higher temperature.

As the aforementioned solvent, for example, preferably selected from n-decane (SP value: 7.6), n-dodecane (SP value: 7.7), propylene glycol methyl-n-propyl ether (SP value: 8.1), Propylene glycol methyl-n-butyl ether (SP value: 8.1), dipropylene glycol dimethyl ether (SP value: 8.4), dipropylene glycol methyl-n-propyl ether (SP value: 8.2), dipropylene glycol methyl-n-butyl ether (SP value: 8.2), dipropylene glycol methyl isoamyl ether (SP value: 8.0), tripropylene glycol methyl-n-propyl ether ( SP value: 8.2), cyclohexyl acetate (SP value: 8.9), 2-methylcyclohexyl acetate (SP value: 8.5), and 4-t-butyl cyclohexyl acetate (SP value: 8.2) At least one of the groups formed.

The content of the solvent in the solvent composition of the present invention (the total content when two or more kinds are included) is, for example, 20.0 to 99.9% by weight, preferably 30.0 to 99.5% by weight, particularly preferably 40.0 to 99.5% by weight, and most preferably 50.0 to 99.5% by weight, particularly preferably 70.0 to 99.5% by weight. If the solvent content is lower than the above range, the viscosity of the printing ink becomes too high, and it may be difficult to form wiring or the like by the printing method. On the other hand, if the solvent content is higher than the above range, it becomes difficult to maintain the viscosity of the printing ink stably due to temperature change, etc., and it may be difficult to form a high-precision wiring pattern due to dripping or the like.

In addition, in the solvent composition of the present invention, as long as the effect is not impaired, it may be necessary to add a solvent other than the above-mentioned solvents (hereinafter sometimes referred to as "other solvents". Other solvents include well-known ones used in electronic device manufacturing applications Conventional solvent). The amount of other solvents added is, for example, less than 50% by weight of the total solvent (100% by weight) contained in the solvent composition of the present invention, preferably 30% by weight or less, particularly preferably 20% by weight or less, and most preferably 10% by weight or less.

[Ink for electronic device manufacturing, and manufacturing method thereof]

The ink for manufacturing electronic devices (hereinafter sometimes referred to as "ink") of the present invention is an ink for forming wiring or electrodes of an electronic device by coating using a printing method, and contains a solvent and the above formula (1) Of compounds.

The printing ink of the present invention can be dissolved by heating the solvent composition at 30 to 90°C (the upper limit is preferably 80°C, the lower limit is preferably 40°C, particularly preferably 50°C, and most preferably 70°C). And manufacture.

The manufacturing method of the printing ink of the present invention includes heating and dissolving the above solvent composition at 30 to 90°C (the upper limit is preferably 80°C, the lower limit is preferably 40°C, particularly preferably 50°C, and most preferably 70°C) step.

The time required for dissolution by heating is, for example, about 3 to 60 minutes (preferably 10 to 30 minutes).

After heating and dissolving, it is preferable to have a step of cooling to room temperature (for example, 1 to 30° C.) or less. The cooling system can be cooled slowly at room temperature, or by rapid cooling such as ice cooling.

In the printing ink of the present invention, it is preferable to further add at least one kind of electrical property-imparting material selected from the group consisting of conductive metal materials, semiconductor materials, magnetic materials, dielectric materials, and insulating materials. The content of the electrical property-imparting material (the total amount when two or more kinds are included) is, for example, about 0.1 to 90% by weight of the total amount of ink (100% by weight).

As the aforementioned conductive metal material and magnetic material, well-known ones can be used, and examples thereof include gold, silver, copper, nickel, palladium, aluminum, iron, platinum, molybdenum, tungsten, zinc, lead, cobalt, iron oxide, and oxide Chromium, ferrite iron, and these alloys. As the semiconductor material, well-known ones can be used, and examples thereof include fused pentabenzene, fullerene derivatives, polythiophene derivatives, metals (copper, indium, gallium, selenium, arsenic, cadmium, tellurium, and alloys thereof) , Silicon particles, etc. As the dielectric material and the insulating material, well-known ones can be used, and examples thereof include cycloolefin polymers, fluororesins, butyral resins, glass, paper, and Teflon (registered trademark).

The printing ink of the present invention obtained through the above steps contains the compound represented by the above formula (1), and the compound is self-organized in a solvent to form a rope-like assembly. Due to the viscosity of the polymer compound, Therefore, even if the binder resin is not blended, the wiring or electrode of the electronic device can be formed with high accuracy by the printing method, because it has moderate viscosity.

The printing ink of the present invention has moderate viscosity, and the viscosity at 25°C [shear speed 0.5s ^-1 ] is, for example, about 0.01 to 1000 Pa‧s, preferably 0.1 to 500 Pa‧s, particularly preferably 1 to 200Pa‧s.

Therefore, the printing ink of the present invention does not require the addition of binder resins (for example, ethyl cellulose resins, alkyl cellulose resins, polyvinyl acetal resins, acrylic resins, and other polymer compounds with a molecular weight of 10,000 or more), even if there are In the case of addition, the addition amount is, for example, 10% by weight or less, preferably 5% by weight or less, more preferably less than 5% by weight, particularly preferably 3% by weight or less, most preferably the total amount of ink (100%) 1% by weight or less. If the amount of the binder resin added is higher than the above range, the ash content from the binder resin due to sintering will cause a decrease in electrical characteristics, which is not good.

In addition, the rope assembly system composed of the compound represented by the formula (1) contained in the ink of the present invention is excellent in thermal decomposition and is easy to be reduced in molecular weight. Therefore, the printing ink of the present invention can be used at a low temperature (for example, 100-350°C, preferably 150-300°C, and particularly preferably 150-250, compared with inks that use ethyl cellulose or other binder resin to impart viscosity. ℃) Sintering can prevent softening and deformation of the coated surface member in the sintering step. Furthermore, the residual ash content after sintering can be reduced to a very low amount (the residual ash content is, for example, 4.5% by weight or less, preferably 4.0% by weight or less, particularly preferably 3.0% Less than 2.5% by weight, preferably 2.5% by weight or less), which can suppress the decrease in electrical characteristics due to ash.

According to the ink of the present invention, the electrical characteristics (for example, electrical conductivity or electrical conductivity) can be formed with high accuracy through the steps of applying to the member to be coated (eg, ceramic substrate, green sheet, etc.) by printing, drying, and sintering. Insulation) excellent wiring, etc. Therefore, the ink of the present invention is particularly useful as, for example, the manufacture of capacitors, inductors, varistors, thermal resistors, speakers, actuators, antennas, solid oxide fuel cells (SOFC), etc. (especially multilayer ceramic capacitors) Use ink.

Examples

The present invention will be described in more detail below based on examples, but the present invention is not limited in any way by these examples.

Preparation Example 1 [Synthesis of tackifier (1): 1,2,4,5-cyclohexanetetracarboxylic acid bis(2-ethylhexyl amide) bis(octadecenyl amide)]

A 100 mL 4-port separable flask equipped with a wearable condenser, nitrogen inlet, dropping funnel, and thermocouple was charged with 20 mL of pyridine, 1,2,4,5-cyclohexanetetracarboxylic acid-1,2:4 5,5-dianhydride 4.5g (0.02mol), octadecenylamine 10.6g (0.04mol), the temperature in the system was set to 50 ℃, aging for 3 hours.

Subsequently, 5.2 g (0.04 mol) of 2-ethylhexylamine and 5.5 g (0.044 mol) of diisopropylcarbodiimide were charged, and aging was further carried out for 8 hours.

Subsequently, the low boiling point component of the obtained crude liquid was removed with an evaporator and washed with methanol to obtain a pale yellow wet powder. The obtained wet powder was further recrystallized with CHCl ₃ /CH ₃ OH (70/30 (v/v)) to obtain 11.9 g of 1,2,4,5-cyclohexane tetracarboxylic acid bis(2-ethyl Hexyl amide) bis (octadecenyl amide) (1,2,4,5-cyclohexanetetracarboxylic acid-1,4-bis(2-ethylhexyl amide)-2,5-di( Octadecenylamide) and 1,2,4,5-cyclohexanetetracarboxylic acid-1,5-bis(2-ethylhexylamide)-2,4-bis(octadecenylamide) ) Mixture] (Yield: 61%). The structure of the reaction product was confirmed by ¹ H-NMR.

Preparation Example 2 [Synthesis of tackifier (2): 1,2,4,5-cyclohexanetetracarboxylic acid bis(2-ethylhexyl amide) bis(octadecyl amide)]

Except that octadecylamine 10.7 g (0.04 mol) was used instead of octadecenylamine, it was carried out in the same manner as in Preparation Example 1 to obtain 11.2 g of 1,2,4,5-cyclohexanetetracarboxylic acid di(2 -Ethylhexyl amide) bis(octadecyl amide) (1,2,4,5-cyclohexanetetracarboxylic acid-1,4-bis(2-ethylhexyl amide)-2,5 -Di(octadecylamide) and 1,2,4,5-cyclohexanetetracarboxylic acid-1,5-bis(2-ethylhexylamide)-2,4-di(octadecane Amidylamide)] (yield: 57%).

Preparation Example 3 [Synthesis of tackifier (3): 1,2,4,5-cyclohexanetetracarboxylic acid bis(octadecyl amide) bis(octadecenyl amide)]

Except that 10.7 g (0.04 mol) of octadecylamine was used instead of 2-ethylhexylamine, it was carried out in the same manner as in Preparation Example 1 to obtain 13.4 g of 1,2,4,5-cyclohexanetetracarboxylic acid di( Octadecyl amide) bis(octadecenyl amide) (1,2,4,5-cyclohexanetetracarboxylic acid-1,4-di(octadecyl amide)-2,5- Di(octadecenylamide) and 1,2,4,5-cyclohexanetetracarboxylic acid-1,5-bis(octadecylamide)-2,4-bis(octadecenylamide) Amine)] (yield: 53%).

Preparation Example 4 [Tackifier (4): Synthesis of 1,2,4,5-cyclohexanetetracarboxylic acid tetrakis(octadecenylamide)]

Except that 10.7 g (0.04 mol) of octadecenylamine was used instead of 2-ethylhexylamine, it was carried out in the same manner as in Preparation Example 1 to obtain 12.3 g of 1,2,4,5-cyclohexanetetracarboxylic acid tetrakis( Octadecenyl amide) (yield: 49%).

Example 1

The tackifier (1) obtained in Preparation Example 1 was added to n-decane (manufactured by Wako Pure Chemical Industries, Ltd.) as a solvent so that the concentration of the tackifier became 1% by weight to obtain a solvent composition (1).

The resultant solvent composition (1) was heated to a liquid temperature of 80 deg.] C to dissolve 0.5 hours, allowed to cool to room temperature (25 deg.] C), to obtain a paste ink (1) (viscosity at 25 deg.] C of [shear rate of 0.5s ^{- 1} time]: 6Pa‧s).

Examples 2 to 6, Comparative Example 1

The solvent composition was obtained like Example 1 except having changed to the composition (unit: weight%) described in Table 1 below, and the ink was obtained. Furthermore, ethyl cellulose (trade name "Ethocel STD200", manufactured by Nissin Kasei Co., Ltd.) was added to Comparative Example 1 to replace the thickener with a resin concentration of 5% by weight, and heated and dissolved at a liquid temperature of 80°C for 3 hours. , Let cool to room temperature (25 ℃) to obtain paste ink.

<evaluation>

The printing inks obtained in Examples and Comparative Examples were evaluated for residual ash content and coatability by the following method.

Residual ash content:

20 mg of each printing ink was measured by TG-DTA at 10° C./min from 20° C. to 400° C. The weight of each temperature was measured, and the residual ash content at 250° C. (the ratio of the residual ash content relative to the total printing ink) was evaluated. ).

Spreadability:

Using a screen printing machine (trade name "LS-150 TV screen printing machine", manufactured by Newlong Precision Industry Co., Ltd.), those who can be coated are marked as "○", and those who cannot be coated are marked as "×".

The results are summarized in the following table.

The abbreviations in Table 1 are shown below.

Tackifier

1: 1,2,4,5-cyclohexanetetracarboxylic acid bis(2-ethylhexyl amide) bis(octadecenyl amide)

2: 1,2,4,5-Cyclohexanetetracarboxylic acid bis(2-ethylhexyl amide) bis(octadecyl amide)

3: 1,2,4,5-Cyclohexanetetracarboxylic acid bis(octadecyl amide) bis(octadecenyl amide)

4: 1,2,4,5-cyclohexanetetracarboxylic acid tetra(octadecenylamide) resin

EC200: ethyl cellulose, trade name "Ethocel STD200", Nissin Chemicals Co., Ltd.

Solvent

Decane: n-decane (Wako Pure Chemical Industries, Ltd., SP value: 7.6)

DPMNP: dipropylene glycol methyl-n-propyl ether (made by Daicel, SP value: 8.2)

CHXA: cyclohexyl acetate (made by Daicel, SP value: 8.9)

Any of the printing inks obtained in the examples vaporizes at a lower temperature than the printing inks obtained in the comparative examples. Further, by heating at 250° C., the ash content of the ink obtained in the comparative example was 4.6% by weight of the entire ink, and the ash content of the ink obtained in the examples was 2.1% by weight or less of the ink.

[Possibility of industrial use]

The solvent composition for manufacturing an electronic device of the present invention can produce an ink having a viscosity suitable for forming wiring and the like by a printing method through a heating and dissolving step.

In addition, the ink system obtained by using the solvent composition for manufacturing an electronic device of the present invention is less prone to dripping, and a high-precision wiring pattern can be formed by a printing method. In addition, in the sintering step, it is possible to sinter at a lower temperature, and it is possible to prevent the member to be coated from being softened and deformed by being exposed to high temperature for a long time. In addition, the residual amount of ash after sintering can be significantly reduced, and the reduction in electrical characteristics caused thereby can be suppressed.

Therefore, if the solvent composition for manufacturing an electronic device of the present invention is used, a wiring or the like having excellent electrical characteristics can be formed by a printing method, and an electronic device having a wiring or the like having excellent electrical characteristics can be efficiently manufactured.

Claims (12)

A solvent composition for manufacturing an electronic device, which is a solvent composition used in an ink for manufacturing an electronic device by a printing method, which includes a solvent and a compound represented by the following formula (1),

(In the formula, R represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an alkynyl group having 2 to 20 carbon atoms. Furthermore, all four R series in the formula are the same group, or 2 Different bases). The solvent composition for manufacturing an electronic device according to claim 1, wherein R in formula (1) is a linear or branched chain alkyl, alkenyl, or alkynyl group having 6 to 18 carbon atoms. The solvent composition for manufacturing an electronic device according to claim 1, wherein at least one of R in formula (1) is octadecenyl. The solvent composition for manufacturing an electronic device according to any one of claims 1 to 3, wherein the SP value of the solvent at 25°C [(cal/cm ³ ) ^0.5 ] is 7.0 to 9.0. The solvent composition for manufacturing an electronic device according to any one of claims 1 to 3, wherein the solvent is selected from the group consisting of n-decane, n-dodecane, propylene glycol methyl-n-propyl ether, and propylene glycol methyl-n -Butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl-n-butyl ether, dipropylene glycol methyl isoamyl ether, tripropylene glycol methyl-n- At least one of the group consisting of propyl ether, cyclohexyl acetate, 2-methylcyclohexyl acetate, and 4-t-butyl cyclohexyl acetate. The solvent composition for manufacturing an electronic device according to any one of claims 1 to 3, wherein the content of the compound represented by formula (1) is relative to the solvent 100 The part by weight is 0.1 to 50 parts by weight. A manufacturing method of printing ink for electronic device manufacturing, which has a step of heating and dissolving the solvent composition for electronic device manufacturing according to any one of claims 1 to 6 at 30 to 90°C. An ink for manufacturing electronic devices, which contains a solvent and a compound represented by the following formula (1),

(In the formula, R represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an alkynyl group having 2 to 20 carbon atoms. Furthermore, all four R series in the formula are the same group, or 2 Different bases). The printing ink for manufacturing an electronic device according to claim 8 further contains conductive metal materials, semiconductor materials, magnetic materials, dielectric materials, or insulating materials. If the printing ink for electronic device manufacturing according to claim 8 or 9 does not contain the following binder resin, or even when it contains, the content of the following binder resin is 10% by weight or less, and the binder resin: molecular weight of 10,000 or more Polymer compound. Use of a solvent composition for manufacturing printing inks for electronic devices by a printing method, the solvent composition comprising a solvent and a compound represented by the following formula (1),

(In the formula, R represents an aliphatic hydrocarbon group having 1 or more carbon atoms, and all four R series in the formula are the same group or two different groups). An application of printing ink, which is used to manufacture electronic devices, the printing ink contains a solvent and a compound represented by the following formula (1),

(In the formula, R represents an aliphatic hydrocarbon group having 1 or more carbon atoms, and all four R series in the formula are the same group or two different groups).