JP2007281306A - Screen-print paste for multilayer ceramic electronic component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a screen-print paste for a multilayer ceramic electronic components that is used to manufacture the multilayer ceramic electronic components. <P>SOLUTION: The screen-print paste for the multilayer ceramic electronic components contains a binder resin, an organic solvent, and an inorganic powder. In the organic solvent, when rising temperature at a programming rate from 25 to 10°C/min, the temperature that becomes 10 wt.% of the initial weight is 110-185°C. Meanwhile, the binder resin is a polymer in which: it consists of repeating unit (1) and repeating unit (2); the mole ratio of repeating unit (1) is 0.5-0.99, and the mole ratio of repeating unit (2) is 0.01-0.5; and the weight average molecular weight measured by gel permeation chromatography (GPC) is 10,000-1,000,000. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a screen printing paste for a multilayer ceramic electronic component used for manufacturing a multilayer ceramic electronic component, and more particularly, it has excellent thermal decomposability and has high coatability and printability, and ceramic green. The present invention relates to a screen-printing paste for multilayer ceramic electronic components having a small sheet attack when applied on a sheet.

  In recent years, in various fields, a paste obtained by dispersing an inorganic powder such as conductive powder, ceramic powder, and glass powder in a binder resin is applied to a carrier film made of polyethylene terephthalate using a doctor blade method and dried. In addition, a precise conductive film, ceramic film, and glass film are produced by firing. A multilayer electronic component such as a multilayer ceramic capacitor is generally manufactured in the following manner.

  First, a ceramic slurry obtained by uniformly mixing a binder resin such as a butyral resin or a (meth) acrylic acid ester resin, a ceramic raw material powder, a plasticizer, and a dispersant is used as a polyethylene terephthalate film or a stainless steel plate. A ceramic green sheet is manufactured by casting from the release treatment surface of the support plate and then peeling from the support plate.

  Next, a conductive paste made by dispersing conductive powder such as palladium or nickel is applied to each of a plurality of ceramic green sheets by screen printing, etc., and then the plurality of ceramic green sheets are stacked on top of each other and thermocompression bonded. To produce a laminate. Then, the laminated body is degreased and fired to produce a fired ceramic product, and an external electrode is sintered on the end face of the fired ceramic product to produce a laminated ceramic capacitor.

  In the production process of the multilayer ceramic capacitor, as described above, the ceramic green sheet coated with the conductive paste is laminated. At this time, the portion coated with the conductive paste (conductive paste layer) is applied on the ceramic green sheet. And a portion where the conductive paste is not applied, the ceramic green sheet and the conductive paste layer are delaminated due to the step when the ceramic green sheets are laminated. In other words, so-called delamination occurs or the dielectric layer or the conductive layer is deformed at the end of the multilayer ceramic capacitor. In particular, in recent years, multilayer ceramic capacitors have been required to have higher capacities, and further multilayering and thinning have been demanded. Therefore, the effect of the step on the surface of the ceramic green sheet caused by the application of the conductive paste is noticeable. There was a fear.

  Therefore, Patent Document 1 discloses a method of eliminating the step on the ceramic green sheet by applying the ceramic paste to the portion where the conductive paste is not applied on the ceramic green sheet using screen printing or the like. .

  And as binder resin used for conductive paste and ceramic paste, it is excellent in coating properties, and can be suitably applied to coating methods such as screen printing to easily form a precise-shaped coating film. Therefore, ethyl cellulose resin is often used.

  However, since ethyl cellulose resin is inferior in thermal decomposability, the carbon component remains after firing the laminated body, and the electrical characteristics of the obtained multilayer ceramic capacitor are deteriorated even when degreasing is performed. .

  In addition, as described above, since there is a demand for higher capacity of the multilayer ceramic capacitor, the ceramic green sheet is also thinned. When a conductive paste is applied to such a ceramic green sheet by screen printing, the conductive paste This causes a so-called sheet attack that dissolves the ceramic green sheet. As a result, after firing, the dielectric layer and the conductive layer are delaminated, so-called delamination and short-circuiting occur.

JP 2002-280250 A

  The present invention is used for manufacturing a multilayer ceramic electronic component, has excellent thermal decomposability, has high coatability and printability, and has less sheet attack when applied on a ceramic green sheet. Provided is a screen printing paste for a multilayer ceramic electronic component capable of obtaining a multilayer ceramic electronic component having excellent characteristics.

  The screen printing paste for multilayer ceramic electronic components of the present invention is a screen printing paste for multilayer ceramic electronic components containing a binder resin, an organic solvent and an inorganic powder, and the organic solvent is heated from 25 ° C. to 10 ° C./min. While the temperature that becomes 10% by weight of the initial weight when heated at a temperature rate is 110 to 185 ° C., the binder resin is a repeating unit (1) represented by Formula 1 and a repeat represented by Formula 2. And the molar ratio of the repeating unit (1) is 0.5 to 0.99, the molar ratio of the repeating unit (2) is 0.01 to 0.5, and gel permeation It is a polymer having a weight average molecular weight of 10,000 to 1,000,000 as measured by chromatography (GPC).

但し、Ａは、HO-A-OHが少なくとも両末端に水酸基を有し且つ数平均分子量が４００〜１０００００のポリエチレングリコール（化合物Ａ）である２価基であり、Ｂは、OCN-B-NCOが鎖状脂肪族ジイソシアナート又は環状脂肪族ジイソシアナート(化合物Ｂ)である２価基であり、Ｄが、HO-D-OHが式３、式４又は式５で表される櫛形疎水性ジオール（化合物Ｄ）であることを特徴とする積層セラミック電子部品用スクリーン印刷ペースト。

However, A is a divalent group of polyethylene glycol (compound A) having hydroxyl groups at both ends of HO-A-OH and having a number average molecular weight of 400 to 100,000, and B is OCN-B-NCO. Is a divalent group which is a chain aliphatic diisocyanate or a cycloaliphatic diisocyanate (Compound B), and D is a comb-shaped hydrophobic group in which HO-D-OH is represented by Formula 3, Formula 4 or Formula 5. A screen printing paste for multilayer ceramic electronic parts, characterized in that it is a functional diol (compound D).

（但し、Ｒ¹は、炭素数が１〜２０の炭化水素基である。Ｒ²及びＲ³は、炭素数が４〜２１の炭化水素基である。炭化水素基Ｒ¹、Ｒ²及びＲ³中の水素の一部又は全部がフッ素、塩素、臭素又は沃素で置換されていてもよく、Ｒ²とＲ³とは同一であっても異なっていてもよい。ＹおよびＹ’は、水素、メチル基又はCH₂Cl基であり、ＹとＹ’とは同一であっても異なっていてもよい。Ｚ及びＺ’は酸素、硫黄又はCH₂基であり、ＺとＺ’とは同一であっても異なっていてもよい。ｎは、Ｚが酸素の場合は０〜１５の整数であり、Ｚ’が硫黄又はCH₂基の場合は０であり、ｎとｎ’は同じでも異なっていてもよい）

(However, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms. R ² and R ³ are hydrocarbon groups having 4 to 21 carbon atoms. Hydrocarbon groups R ¹ , R ² and R A part or all of hydrogen in ³ may be substituted with fluorine, chlorine, bromine or iodine, and R ² and R ³ may be the same or different. , Methyl group or CH ₂ Cl group, and Y and Y ′ may be the same or different. Z and Z ′ are oxygen, sulfur or CH ₂ group, and Z and Z ′ are the same. N is an integer of 0 to 15 when Z is oxygen, 0 when Z ′ is sulfur or CH ₂ , and n and n ′ are the same or different. May be)

（但し、Ｒ⁴は、炭素数が１〜２０の炭化水素基である。Ｒ⁵及びＲ⁶は、炭素数が４〜２１の炭化水素基である。Ｒ⁴、Ｒ⁵及びＲ⁶中の水素の一部又は全部はフッ素、塩素、臭素又は沃素で置換されていてもよく、Ｒ⁵とＲ⁶とは同一であっても異なっていてもよい。Ｙ、Ｙ’及びＹ”は、水素、メチル基又はCH₂Cl基であり、ＹとＹ’は同一であっても異なっていてもよい。Ｒ⁷は炭素数が２〜４のアルキレン基であり、ｋは０〜１５の整数である。また、ｎは、Ｚが酸素の場合は０〜１５の整数であり、Ｚが硫黄又はCH₂基の場合は０である。ｎ’は、Ｚ’が酸素の場合は０〜１５の整数であり、Ｚ’が硫黄又はCH₂基の場合は０であり、ｎとｎ’は同一であっても異なっていてもよい）

(However, R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms. R ⁵ and R ⁶ are hydrocarbon groups having ⁴ to 21 carbon atoms. In R ⁴ , R ⁵ and R ⁶ , Part or all of hydrogen may be substituted with fluorine, chlorine, bromine or iodine, and R ⁵ and R ⁶ may be the same or different. Y, Y ′ and Y ″ are hydrogen , Methyl group or CH ₂ Cl group, Y and Y ′ may be the same or different, R ⁷ is an alkylene group having 2 to 4 carbon atoms, and k is an integer of 0 to 15. N is an integer of 0 to 15 when Z is oxygen, and 0 when Z is sulfur or a CH ₂ group, and n ′ is 0 to 15 when Z ′ is oxygen. An integer, 0 when Z ′ is sulfur or CH ₂ , and n and n ′ may be the same or different)

（但し、Ｒ⁸及びＲ⁹は、Ｒ⁸とＲ⁹の炭素数の合計が２〜２０の炭化水素基である。Ｒ¹⁰及びＲ¹¹は、炭素数が４〜２１の炭化水素基である。Ｒ⁸、Ｒ⁹、Ｒ¹⁰及びＲ¹¹の水素の一部又は全部がフッ素、塩素、臭素又は沃素で置換されていてもよい。Ｒ⁸とＲ⁹とは同一であっても異なっていてもよい。Ｒ¹⁰とＲ¹¹とは同一であっても異なっていてもよい。Ｒ¹²は、炭素数が２〜７のアルキレン基である。またＹおよびＹ’は、水素、メチル基又はCH₂Cl基であり、ＹとＹ’とは、同一であっても異なっていてもよい。Ｚ及びＺ’は、酸素、硫黄、又はCH₂基であり、ＺとＺ’とは同一であっても異なっていてもよい。ｎは、Ｚが酸素の場合は０〜１５の整数であり、Ｚが，硫黄又はCH₂基の場合は０である。ｎ’は、Ｚ’が酸素の場合は０〜１５の整数であり、Ｚ’が硫黄又はCH₂基の場合は０であり、ｎとｎ’とは同一であっても異なっていてもよい）

(However, R ⁸ and R ⁹ are hydrocarbon groups having a total of 2 to 20 carbon atoms in R ⁸ and R ^9. R ¹⁰ and R ¹¹ are hydrocarbon groups having 4 to 21 carbon atoms. R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ may be partially or fully substituted with fluorine, chlorine, bromine or iodine, and R ⁸ and R ⁹ may be the same or different. R ¹⁰ and R ¹¹ may be the same or different, and R ¹² is an alkylene group having 2 to 7 carbon atoms, and Y and Y ′ are hydrogen, methyl group or CH _{2 is a} Cl group, and Y and Y ′ may be the same or different, Z and Z ′ are oxygen, sulfur, or CH ₂ groups, and Z and Z ′ are the same. N is an integer from 0 to 15 when Z is oxygen, and 0 when Z is sulfur or a CH ₂ group, and n ′ is when Z ′ is oxygen. Is an integer from 0 to 15 Ri, Z 'when the sulfur or a CH ₂ group is 0, n and n' may be the same or different and)

  The binder resin constituting the screen printing paste for multilayer ceramic electronic parts is a polyurethane having comb-type hydrophobic groups obtained by connecting polyethylene glycol and comb-type hydrophobic diols with polyisocyanate.

  400-100000 are preferable and, as for the number average molecular weight of the polyethyleneglycol (compound A) used by this invention, 1000-20000 are more preferable. This is because when the number average molecular weight of polyethylene glycol is less than 400, it is easy to obtain a product having low adhesiveness and poor dispersibility of inorganic powder, and is unsuitable for use as a binder. On the other hand, the number of polyethylene glycol (compound A) This is because if the average molecular weight is larger than 100,000, a product with low solubility is easily obtained.

  In addition, as the compound B, a chain aliphatic diisocyanate or a cyclic aliphatic diisocyanate is used because of excellent solubility of the product and a low residual carbon ratio at the time of degreasing and an excellent binder resin. A chain aliphatic diisocyanate is preferred. And since the solubility of a polyurethane will fall easily when the total carbon number of the compound B is large, 3-18 are preferable.

  The chain aliphatic diisocyanate is a diisocyanate compound having a structure in which NCO groups are connected by a linear or branched alkylene group, specifically, methylene diisocyanate, ethylene diisocyanate, Trimethylene diisocyanate, 1-methylethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, 2-methylbutane-1,4-diisocyanate, hexamethylene diisocyanate (HDI), heptamethylene di Isocyanate, 2-2′-dimethylpentane-1,5-diisocyanate, lysine diisocyanate methyl ester (LDI), octamethylene diisocyanate, 2,5-dimethylhexane-1,6-diisocyanate, 2,2,4-trimethylpentane-1,5-diisosilane Narate, nonamethyl diisocyanate, 2,4,4-trimethylhexane-1,6-diisocyanate, decamethylene diisocyanate, tridecamethylene diisocyanate, tetradecamethylene diisocyanate, pentadecamethylene diisocyanate Hexadecamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc., and hexamethylene diisocyanate is preferred.

  Cycloaliphatic diisocyanate is a diisocyanate compound in which an alkylene group connecting NCO groups has a cyclic structure. Specific examples include cyclohexane-1,2-diisocyanate, cyclohexane-1,3. -Diisocyanate, cyclohexane-1,4-diisocyanate, 1-methylcyclohexane-2,4-diisocyanate, 1-methylcyclohexane-2,6-diisocyanate, 1-ethylcyclohexane-2,4- Diisocyanate, 4,5-dimethylcyclohexane-1,3-diisocyanate, 1,2-dimethylcyclohexane-ω, ω′-diisocyanate, 1,4-dimethylcyclohexane-ω, ω′-diisocyanate , Isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate Narate, dicyclohexylmethylmethane-4,4′-diisocyanate, dicyclohexyldimethylmethane-4,4′-diisocyanate, 2,2′-dimethyldicyclohexylmethane-4,4′-diisocyanate, 3,3 ′ -Dimethyldicyclohexylmethane-4,4'-diisocyanate, 4,4'-methylene-bis (isocyanatocyclohexane), isopropylidenebis (4-cyclohexylisocyanate) (IPCI), 1,3-bis (isocyanato) Methyl) cyclohexane, hydrogenated tolylene diisocyanate (HTDI), hydrogenated 4,4′-diphenylmethane diisocyanate (HMDI), hydrogenated xylylene diisocyanate (HXDI), norbornene diisocyanate (NBDI) and the like. , Isophoronzi Cyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, norbornene diisocyanate are preferred.

  The comb-type hydrophobic diol (compound D) used in the present invention is represented by the above formula 3, formula 4 or formula 5, and has 2 secondary hydroxyl groups in the molecule and 3 or more hydrophobic chains in the molecule. It has hydrophobic diols.

  These hydrophobic diols can be obtained by adding various oxirane compounds (compounds having an oxirane ring) to primary amines. The addition reaction between the amino group of amines and the oxirane compound is highly active, and the reaction proceeds sufficiently even without catalyst.

  Specifically, the primary amines include primary chain or cyclic alkylamines, primary chain or cyclic alkenylamines, primary aralkylamines, primary dialkylaminoalkylamines. Primary N-benzylaminopyrrolidines, primary N-aminoalkylmorpholines, primary arylamines, primary aminopyridines, primary aminoalkylpyridines, primary alkyloxyalkylamines And primary alkenyloxyalkylamines, primary aryloxyalkylamines, primary aralkyloxyalkylamines, and the like.

  First, examples of primary chain alkylamines include methylamine, ethylamine, n-butylamine, ter-butylamine, sec-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, 2-aminoheptane. , N-octylamine, isooctylamine, 2-aminooctane, 2-ethylhexylamine, 2-amino-6-methylheptane, nonylamine, isononylamine, 1,4-dimethylheptylamine, 3-aminononane, 2-amino -6-ethylheptane, n-decylamine, n-undecylamine, 2-aminoundecane, 6-aminoundecane, n-dodecylamine, n-tridecylamine, 2-aminotridecane, n-tetradecylamine, 2 -Aminotetradecane, n-pentadecylamine, - amino pentadecane, n- hexadecylamine, n- heptadecyl amine, n- octadecylamine, n- nonadecylamine, such as 2-amino-nona decane.

  Examples of primary chain alkenylamines include allylamine and oleylamine. Examples of primary cyclic alkylamines include cyclohexylamine, cycloheptylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, aminomethylcyclohexane, cyclooctylamine, 2,3-dimethylcyclohexyl. Amine, 3,3,5-trimethylcyclohexylamine, 4-ter-butylcyclohexylamine, 1-cyclopentyl-2-aminopropane, 1-aminoindane, cyclododecylamine, o-aminobicyclohexyl, 3-aminospiro [5 5] Undecane, bornylamine, 1-adamantanamine, 2-aminonorbornane, 1-adamantanemethylamine and the like.

  Examples of the primary cyclic alkenylamines include dihydroabiethylamine and 2- (1-cyclohexenyl) ethylamine. Examples of primary aralkylamines include benzylamine, phenethylamine, p-methoxyphenethylamine, α-phenylethylamine, 1-methoxy-3-phenylpropylamine, N-aminopropylaniline and the like.

  Examples of primary dialkylaminoalkylamines include N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-diisopropylethylenediamine, N, N-dimethyl-1,3-propanediamine, and diethylaminopropyldiamine. , Dibutylaminopropylamine, 1-dimethylamino-2-propylamine, N2, N2-dimethyl-1,2-propanediamine, 4-dimethylaminobutylamine, 1-dimethylaminoethyl-2-aminopropane, N, N- Dimethyl neopentanediamine, 1-diethylamino-2-propylamine, 6-dimethylaminohexylamine, 2-di-n-propylaminoethylamine, N-ethyl-N-butylethylenediamine, 7-diethylaminoheptylamine, N1 N1-di-n-propyl-1,2-propanediamine, N ′, N′-di-n-propanediamine, 5-diethylaminopentylamine, 2-amino-5-diethylaminopentane, N, N-di-n -Butylethylenediamine, N, N-di-tert-butylethylenediamine, 2-diisobutylaminoethylamine, 4-diisopropylamine, 7-diethylaminoheptylamine, 3- (di-n-butylamino) propylamine, N, N-diisobutyl -1,6-hexanediamine, 3-dioctylaminopropylamine, 3-didecylaminopropylamine 1- (2-aminoethyl) piperidine, 3-piperidinopropylamine, 4-pyrrolidinobutylamine, N-aminoethyl -4-pipecoline, 3-aminotropane, 5-pyrrolidi Amylamine, N-aminopropyl-4-pipecoline, 1- (3-aminopropyl) -2-pipecoline, 1-aza-bicyclo [2,2,2] oct-3-ylamine, 1-benzyl-3-aminopyrrolidine, N1-ethyl-N1-phenylpropane-1,3-diamine and the like can be mentioned.

  Examples of primary arylamines include aniline, 2-chloroaniline, 2,3-dichloroaniline, 2,4-dibromoaniline, 2,4,6-tribromoaniline, o-toluidine, 2- Chloro-4-methylaniline, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2-ethylaniline, 2-isopropylaniline, 4-tert-butylaniline, p-decylaniline, Examples include p-dodecylaniline, p-tetradecylaniline, 4-cyclohexylaniline, 2-aminobiphenyl, 1-naphthylamine, 5-aminoindane, 1-aminonaphthacene, 6-aminochrysene, and 1-aminopyrene.

  Examples of primary aminopyridines include 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-6-methylpyridine, 2-amino-4-ethylpyridine, -Amino-4-propylpyridine, 2-amino-4,6-dimethylpyridine, 2-amino-3-nitropyridine and the like.

  Furthermore, examples of primary aminoalkylpyridines include 2-aminomethylpyridine, 3-aminomethylpyridine, 4-aminomethylpyridine, 3-aminomethyl-6-chloropyridine and the like.

  Alkyloxyalkylamines include 2-alkoxyethylamines, 3-alkoxypropylamines, 4-alkoxybutylamines, alkenyloxyalkylamines, aralkyloxyalkylamines, aryloxyalkylamines, alcohol-alkylenes. Examples include oxide-loaded aminoalkyl ethers, phenol / alkyl-substituted phenol-alkylene oxide loaded aminoalkyl ethers, and the like.

  Examples of 2-alkoxyethylamines include 2-methoxyethylamine, 2-ethoxyethylamine, 2-propoxyethylamine, 2-isopropoxyethylamine, 2-butoxyethylamine, 2- (isobutoxy) ethylamine, 2- (ter- Butoxy) ethylamine, 2-pentyloxyethylamine, 2-hexyloxyethylamine, 2-heptyloxyethylamine, 2-octyloxyethylamine, 2- (2-ethylhexyloxy) ethylamine, 2- (α-butyloctyloxy) ethylamine, 2 -Decyloxyethylamine, 2-dodecyloxyethylamine, 2-tetradecyloxyethylamine, 2-pentadecyloxyethylamine, 2-hexadecyloxyethylamine 2-heptadecyl Oxy ethylamine, 2-octadecyloxy-ethyl amine, 2-nonadecyl-ethylamine, 2-eicosyl ethylamine and the like.

  Moreover, as 3-alkoxypropylamines, for example, 3-methoxypropylamine, 3-ethoxypropylamine, 3- (isobutoxy) propylamine, 3- (ter-butoxy) propylamine, 3-pentyloxypropylamine, 3-hexyloxypropylamine, 3-heptyloxypropylamine, 3-octyloxypropylamine, 3- (2-ethylhexyloxy) propylamine, 3- (α-butyloctyloxy) propylamine, 3-decyloxypropylamine 3-dodecyloxypropylamine, 3-, 3-tetradecyloxypropylamine, 3-pentadecyloxypropylamine, 3-hexadecyloxypropylamine, 3-heptadecyloxypropylamine, 3-octadecyloxypro Triethanolamine, 3-nonadecyl propylamine, 3-eicosyl propylamine and the like.

  Furthermore, as 4-alkoxybutylamines, 4-methoxybutylamine, 4-ethoxybutylamine, 4-propoxybutylamine, 4-isopropoxybutylamine, 4-butoxybutylamine, 4- (isobutoxy) butylamine, 4- (ter-butoxy) Butylamine, 4-pentyloxybutylamine, 4-hexyloxybutylamine, 4-heptyloxybutylamine, 4-octyloxybutylamine, 4- (2-ethylhexyloxy) butylamine, 4- (α-butyloctyloxy) butylamine, 4-decyl Oxybutylamine, 4-dodecyloxybutylamine, 4-tetradecyloxybutylamine, 4-pentadecyloxybutylamine, 4-hexadecyloxybutylamine, 4-heptadecyloxy Ethylamine, 4-octadecyloxy-butyl amine, 4-nonadecyl tributylamine, 4-eicosyl tributylamine, and 4 (2,4-di -ter- amylphenoxy) butylamine.

  Examples of the primary alkenyloxyalkylamines include 2-allyloxyethylamine and 3-oleyloxypropylamine. Examples of aralkyloxyalkylamines include 2-benzyloxyethylamine and 3-phenethyloxypropylamine. Examples of aryloxyalkylamines include 2-phenyloxyethylamine and 3- (p-nonylphenyloxy) propylamine.

  Examples of the other amines include aminoalkanol ethers of alkylene oxide adducts such as alcohols and phenols (ethylene oxide adducts, propylene oxide adducts, epichlorohydrin adducts, etc.). Examples of the aminoalkanol ether of the alcohol-ethylene oxide adduct include 2- [2- (dodecyloxy) ethoxy] ethylamine, 3,6,9-trioxapentadecylamine, and the like.

  Similarly, it is also possible to use aminoalkanol ethers of propylene oxide adducts of alcohols and phenols, propylene oxide / ethylene oxide adducts, and epichlorohydrin adducts. The addition number k is suitably about 1 to 15. If the additional number exceeds 15, stickiness tends to occur and stringing occurs during printing.

  Examples of other primary amines include pyrazines such as 2-aminomethylpyrazine, 2-aminopyrazine, and sulfalene.

  Further, as the oxirane compound, various glycidyl ethers, 1,2-epoxyalkanes, 1,2-epoxyalkenes, glycidyl sulfides and the like can be used.

  First, examples of glycidyl ethers include alkyl glycidyl ethers, alkenyl glycidyl ethers, aralkyl glycidyl ethers, and aryl glycidyl ethers.

  Examples of alkyl glycidyl ethers include n-butyl glycidyl ether, se-butyl glycidyl ether, ter-butyl glycidyl ether, glycidyl pentyl ether, glycidyl hexyl ether, glycidyl octyl ether, 2-ethylhexyl glycidyl ether, 2-methyl Octyl glycidyl ether, glycidyl nonyl ether, decyl glycidyl ether, dodecyl glycidyl ether, glycidyl lauryl ether, glycidyl tridecyl ether, glycidyl tetradecyl ether, glycidyl pentadecyl ether, glycidyl hexadecyl ether, glycidyl stearyl ether, 3- (2- ( Perfluorohexyl) ethoxy) -1,2-epoxypropane, 3- (3-perfluoro Octyl-2-Iodopuropokishi) -1,2-epoxy propane.

  Examples of alkenyl glycidyl ethers include allyl glycidyl ether and oleyl glycidyl ether. Examples of aralkyl glycidyl ethers include benzyl glycidyl ether and phenethyl glycidyl ether. As aryl glycidyl ethers, for example, phenyl glycidyl ether, 4-ter-butylphenyl glycidyl ether, 2-ethylphenyl glycidyl ether, 4-ethylphenyl glycidyl ether, 2-methylphenyl glycidyl ether, glycidyl-4-nonylphenyl ether Glycidyl-3- (pentadecadienyl) phenyl ether, 2-bisphenyl glycidyl ether, α-naphthyl glycidyl ether, dibromophenyl glycidyl ether, and the like.

  Examples of the other glycidyl ethers include glycidyl ethers of alkylene oxide adducts such as alcohols and phenols (ethylene oxide adducts, propylene oxide adducts, epichlorohydrin adducts, etc.).

  Examples of the glycidyl ether of the ethylene oxide adduct include, for example, glycidyl ether of 2-ethylhexyl alcohol-ethylene oxide adduct, glycidyl ether of lauryl alcohol-ethylene oxide adduct, glycidyl ether of 4-ter-butylphenol-ethylene oxide adduct, Examples thereof include glycidyl ethers of nonylphenol-ethylene oxide adducts.

  Similarly, it is also possible to use glycidyl ethers of propylene oxide adducts of alcohols and phenols, propylene oxide / ethylene oxide adducts, and epichlorohydrin adducts.

  The glycidyl ethers of industrial chemicals usually contain glycidyl ethers of epichlorohydrin adducts as by-products, but such low-purity raw materials can also be used. The addition number n is suitably about 1 to 15. If the addition number exceeds 15, the solution viscosity of the polyurethane tends to decrease.

  Examples of 1,2-epoxyalkanes and 1,2-epoxyalkenes include, for example, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 1,2-epoxy. Nonane, 1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane, 1,2-epoxyeicosane, 1,2-epoxy -7-octene, 1,2-epoxy-9-decene and the like.

  Other oxirane compounds include alkyl glycidyl thioethers (alkyl glycidyl sulfide) such as 2-ethylhexyl glycidyl sulfide and decyl glycidyl sulfide, and aryl glycidyl thioethers (aryl glycidyl sulfide) such as p-nonylphenyl glycidyl sulfide.

  Compound D can be obtained by reacting the above amines and oxirane compounds with one molecule of amines at a ratio of two molecules of oxirane compound. Formula 6 represents the reaction formula.

（但し、Ｒ^ａ、Ｒ^ｂ、Ｒ^ｃは式３〜５の各置換基に対応する。）

(However, R ^a , R ^b , and R ^c correspond to each substituent of Formulas 3 to 5.)

  The reaction is easier when glycidyl ethers are used than when 1,2-epoxyalkanes, 1,2-epoxyalkenes, and glycidyl sulfides are used as oxirane compounds. This is probably because the reactivity between glycidyl ethers and amines is high.

Compound D has 3 to 4 hydrophobic chains (R ¹ , R ² and R ³ in Formula ³ , R ⁴ , R ⁵ and R ⁶ in Formula ⁴ , R ⁸ and R ^{9 in} Formula 5 in the molecule). , R ¹⁰ and R ¹¹ ), but these hydrophobic chains are close to each other, thereby providing an effect of imparting appropriate hydrophobicity to the polyurethane. It is presumed that it is this moderate hydrophobicity that gives the paste an appropriate plasticity and caking property when used as a binder. The number of carbon atoms in each hydrophobic chain needs to be long enough to give polyurethane an appropriate hydrophobicity.

The number of carbon atoms in the hydrophobic chain of amines is preferably 1-20. When an amine having a carbon number of the substituent R ¹ or R ⁴ exceeding 20 is used, the solubility of the polyurethane is lowered. Similarly, when an amine having a total of more than 20 carbon atoms in the substituents R ⁸ and R ⁹ is used, the solubility of the polyurethane is lowered.

The number of carbon atoms of the hydrophobic chain of glycidyl ethers (R ² and R ³ in formula ³ , R ⁵ and R ⁶ in formula 4, R ¹⁰ and R ^{11 in} formula 5) is limited to 4-21. When glycidyl ether having less than 4 carbon atoms is used, the solubility of polyurethane is lowered. More preferably, an alkyl glycidyl ether having a linear or branched alkyl group having 4 to 18 carbon atoms as a hydrophobic group, or an aromatic or alkyl-substituted aromatic having 6 to 18 carbon atoms as a hydrophobic group Aryl glycidyl ethers.

For the same reason, 1,2-epoxyalkane, 1,2-epoxyalkene, alkyl glycidyl thioether, hydrophobic group of aryl glycidyl thioether (R ² and R ³ in formula ³ , R ⁵ and R ⁶ in formula 4, The number of carbon atoms of R ¹⁰ and R ¹¹ ) in formula 5 is limited to 4-21.

  The above binder resins may be used alone or in combination of two or more thereof, and further synthetic resins widely used as binder resins such as cellulose resins and butyral resins may be mixed.

  Next, the manufacturing method of a comb-shaped hydrophobic diol is demonstrated. The method for synthesizing the comb-shaped hydrophobic diol used in the present invention is not limited to this example.

  Raw material amines and oxirane compounds are supplied to a reaction vessel having a stirrer, a raw material introduction mechanism, and a temperature control mechanism, and reacted while stirring at a predetermined reaction temperature. The reaction can be carried out without solvent, but a common solvent such as dimethylformamide (DMF) may be used. The supply of the raw materials to the reaction vessel may be performed by supplying amines and oxirane compounds all at once to the reaction vessel, or after supplying any one of amines or oxirane compounds to the reaction vessel, the other The reaction vessel may be supplied continuously or stepwise.

  The reaction temperature is about room temperature to 160 ° C, more preferably 60 to 120 ° C. The reaction time is preferably 0.5 to 10 hours, although it depends on the reaction temperature and the like. Further, the OH value can be obtained by a conventional method.

  As shown in Formula 7, the soluble polyurethane having a comb-shaped hydrophobic group includes two hydroxyl groups of polyethylene glycol (Compound A) and a comb-shaped hydrophobic diol (Compound D) and two of a diisocyanate (Compound B). Synthesized by reaction of NCO group. The soluble polyurethane in which the molar ratio of the repeating unit (1) is (1-x) and the molar ratio of the repeating unit (2) is x, the molar ratio of the compound A and the compound D is (1-x): x ratio It is obtained by reacting with

  Hereinafter, the production method of the soluble polyurethane will be described by way of example, but the present invention is not limited to the following production method. After the inside of the reaction vessel having a stirrer, a raw material introduction mechanism and a temperature control mechanism is replaced with an inert gas, polyethylene glycol is supplied to the reaction vessel together with a solvent as necessary.

  The catalyst is added while controlling the reaction vessel to a set reaction temperature, and then the diisocyanate compound and the comb-shaped hydrophobic diol are supplied to the reaction vessel while stirring the vessel. In addition, the supply method to the reaction vessel of the diisocyanate and the comb-shaped hydrophobic diol is not particularly limited, and may be supplied continuously or intermittently.

  In addition, the diisocyanate and the comb-shaped hydrophobic diol may be supplied into the reaction vessel at the same time, or the di-isocyanate compound may be fed after the diisocyanate compound is fed, or the diisocyanate compound may be fed after the comb-shaped hydrophobic diol is fed. May be supplied.

  It is not always necessary to add the catalyst to the polyethylene glycol before the reaction, and it is also possible to start the reaction by adding the catalyst after adding the diisocyanate or the comb-shaped hydrophobic diol to the polyethylene glycol. Alternatively, a catalyst may be added in advance to diisocyanate or comb-shaped hydrophobic diol, and these may be added to polyethylene glycol and reacted.

  The catalyst used for the reaction is not particularly limited, and known catalysts generally used for the reaction of isocyanates and polyols such as organometallic compounds, metal salts, tertiary amines, other basic catalysts and acid catalysts are used. Can be used. Examples of such catalysts include dibutyltin dilaurate (hereinafter abbreviated as DBTDL), dibutyltin di (dodecylthiolate), stannous octanoate, phenylmercuric acetate, zinc octoate, lead octoate, zinc naphthenate, lead naphthenate, triethylamine. (TEA), tetramethylbutanediamine (TMBDA), N-ethylmorpholine (NEM), 1,4-diaza [2.2.2] bicyclooctane (DABCO), 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), N, N'-dimethyl-1,4-diazacyclohexane (DMP) and the like.

  The amount of the catalyst used for the reaction varies depending on the reaction temperature and the type of the catalyst and is not particularly limited, but is preferably 0.0001 to 0.1 mol per mol of polyethylene glycol, 0.001 to 0.00. 1 mole is more preferred.

  The reaction can be carried out without a solvent, but can also be carried out using a solvent in order to lower the melt viscosity of the product. Examples of such solvents include halogen solvents such as carbon tetrachloride, dichloromethane, chloroform, and trichrene, aromatic solvents such as xylene, toluene, and benzene, decane, octane, heptane, hexane, cyclohexane, pentane, and the like. Saturated hydrocarbon solvents, ether solvents such as dioxane, tetrahydrofuran, diethyl ether, dimethyl ether, and ethylene glycol dimethyl ether; ketone solvents such as diethyl ketone, methyl ethyl ketone, and dimethyl ketone; and ester solvents such as ethyl acetate and methyl acetate A solvent having no active hydrogen such as a solvent is effectively used. In addition, it is preferable not to use a solvent because the process of removing the solvent is unnecessary, which is advantageous in terms of manufacturing cost and less likely to cause environmental pollution.

  The amount of diisocyanate used in the reaction is 0.7 to 1.3 mol of the diisocyanate compound (NCO / OH) with respect to 1 mol in total of polyethylene glycol and comb hydrophobic diol. Is preferable, and it is more preferable that it is 0.8-1.2 mol. This is because if the number of moles of the diisocyanate compound is less than 0.7 or exceeds 1.3, the average molecular weight of the product is small, and the ability as a binder may be insufficient.

  However, when water is contained in polyethylene glycol or comb-shaped hydrophobic diol, the amount of the above-mentioned diisocyanate needs to be used in excess as much as the diisocyanate is decomposed by moisture. Therefore, it is preferable to use a sufficiently dried raw material. The moisture contained in the raw material is preferably 5000 ppm or less, more preferably 1000 ppm or less, and particularly preferably 200 ppm or less.

  The amount of the comb-shaped hydrophobic diol used in the reaction varies depending on the molecular weight of polyethylene glycol and the number of carbon atoms of the hydrophobic group of the comb-shaped hydrophobic diol, but the number of moles of the comb-shaped hydrophobic diol is 0.01 to 1 per mole of polyethylene glycol. Mole (x is 0.01 to 0.5) is appropriate. When the number of moles of the comb-shaped hydrophobic diol is less than 0.01 mole, a sufficient hydrophobic effect may not be exhibited. On the other hand, when the number of moles of the comb-shaped hydrophobic diol exceeds 1 mole, the solubility is lowered. Since it may be made, it is not preferable. In addition, the numerical value in () represents the value of x in Equation 7.

  The reaction temperature varies depending on the type and amount of the catalyst used, but is preferably 50 to 180 ° C, more preferably 60 to 150 ° C, and particularly preferably 80 to 120 ° C. This is because if the reaction temperature is less than 50 ° C, the reaction rate is slow and not economical, while if it exceeds 180 ° C, the product may be thermally decomposed. The reaction time varies depending on the type and amount of the catalyst used and the reaction temperature, and is not particularly limited, but is preferably 1 minute to 10 hours. The reaction pressure is not particularly limited, and the reaction can be carried out at normal pressure, reduced pressure or increased pressure, but it is preferable to react at normal pressure or slightly increased pressure.

  Furthermore, the screen printing paste for multilayer ceramic electronic components of the present invention contains an inorganic powder. Examples of such inorganic powders include conductive powders such as nickel, palladium, silver, and copper, and ceramic powders such as barium titanate. These may be used alone or in combination of two or more.

  By using a conductive powder as the inorganic powder, the screen printing paste for multilayer ceramic electronic parts of the present invention can be used as a conductive paste.

  When the conductive powder is used as the inorganic powder, if the content of the binder resin in the screen printing paste for multilayer ceramic electronic parts is small, the film forming performance of the conductive paste may be deteriorated. Since the carbon component tends to remain, the amount is preferably 3 to 25 parts by weight, more preferably 5 to 15 parts by weight with respect to 100 parts by weight of the conductive powder.

  When ceramic powder is used as the inorganic powder, the screen printing paste for multilayer ceramic electronic components of the present invention can be used as the above-described step absorbing ceramic paste. The ceramic powder is preferably composed of the same components as the ceramic powder contained in the ceramic green sheet.

  When ceramic powder is used as the inorganic powder, if the content of the binder resin in the screen print paste for multilayer ceramic electronic components is small, the film forming performance of the screen print paste for multilayer ceramic electronic components may be reduced. If the amount is too large, the carbon component tends to remain after degreasing and firing.

  Furthermore, the screen printing paste for a multilayer ceramic electronic component of the present invention has a temperature of 110 to 185 ° C. that is 10% by weight of the initial weight when the temperature is increased from 25 ° C. at a rate of temperature increase of 10 ° C./min. Contains organic solvents (called volatile conditions).

  Here, the temperature which becomes 10% by weight of the initial weight when the organic solvent is heated from 25 ° C. at a rate of 10 ° C./min is commercially available from TAinstruments under the trade name “SDT2960 (DSC-TGA)”. The temperature is obtained by performing measurement under the conditions of a sample volume of 30 mg and an Air flow rate of 100 ml / min using a 70 μl alumina pan as a sample pan.

  In this way, by using an organic solvent that satisfies the volatility condition, the organic solvent is rapidly volatilized after the screen printing paste for multilayer ceramic electronic components is applied onto the ceramic green sheet, and the ceramic green sheet is dissolved by the organic solvent. Can be prevented to prevent sheet attack, and delamination and short-circuiting after firing can be prevented.

  In an organic solvent, if the temperature that is 10% by weight of the initial weight when the temperature is raised from 25 ° C. at a rate of 10 ° C./min, the screen printing paste for multilayer ceramic electronic components is printed using a screen printer. In this case, clogging of the plate and applicability on the ceramic green sheet are deteriorated. On the other hand, if it is high, sheet attack is generated, so that the temperature is limited to 110 to 185 ° C.

  Examples of the organic solvent include carboxylic acids such as acetic acid, octylic acid, and trimethylhexanoic acid; ketones such as acetone, methyl ethyl ketone, dipropyl ketone, and diisobutyl ketone; methanol, ethanol, isopropanol, butanol, α-terpineol, Alcohols such as dihydroterpineol; aromatic hydrocarbons such as toluene and xylene; methyl propionate, ethyl propionate, butyl propionate, methyl butanoate, ethyl butanoate, butyl butanoate, methyl pentanoate, ethyl pentanoate, Butyl pentanoate, methyl hexanoate, ethyl hexanoate, butyl hexanoate, 2-ethylhexyl acetate, 2-ethylhexyl butyrate, methylcellosolve, ethylcellosolve, butylcellosolve, butylcellosol Examples include esters such as acetate, butyl carbitol acetate, terpineol acetate, dihydroterpineol acetate, and contain at least one organic compound selected from the group consisting of carboxylic acids, alcohols, ketones, and esters. Preferred is a mixed organic solvent comprising at least one organic compound selected from the group consisting of carboxylic acids, alcohols, ketones and esters, and an organic solvent other than this organic compound, more preferably terpineol and other A mixed organic solvent comprising an organic solvent is particularly preferred, and a mixed organic solvent comprising α-terpineol and another organic solvent is most preferred.

  When a butyral resin is used as the binder resin constituting the ceramic green sheet, as the organic solvent, at least one or more of carboxylic acids, alcohols, ketones or esters that are relatively difficult to dissolve the butyral resin is used. When used, the organic solvent dissolves and swells the ceramic green sheet when the screen printing paste for multilayer ceramic electronic components is applied onto the ceramic green sheet, in combination with the fact that the organic solvent satisfies the volatile conditions. Before, the organic solvent can be volatilized and removed smoothly, and the occurrence of sheet attack can be prevented.

  In addition, the organic solvent may be used alone or in combination of two or more, but in the case of using two or more organic solvents in combination, two or more organic solvents are mixed. It is only necessary that the obtained mixed organic solvent satisfies the volatile conditions.

  If the content of the organic solvent in the screen print paste for multilayer ceramic electronic components is small, the coatability of the screen print paste for multilayer ceramic electronic components may be deteriorated. Since a sheet attack may occur when the screen printing paste is applied onto the ceramic green sheet, the amount is preferably 50 to 200 parts by weight with respect to 100 parts by weight of the inorganic powder.

  Further, the organic solvent may be diluted with a diluting solvent. Such a diluting solvent is not particularly limited, and for example, n-pentane, isopentane, n-hexane, n-heptane, n-octane, isooctane, n -Hydrocarbon solvents such as paraffin, isoparaffin, benzene, solvent naphtha, cyclohexane, methylcyclohexane, ethylcyclohexane, liquid paraffin, tetrahydronaphthalene, decahydronaphthalene, isohexane, isoheptane, ligroin and the like.

  Further, a dispersant may be contained in the screen printing paste for multilayer ceramic electronic components. Such a dispersant is not particularly limited, and fatty acids, aliphatic amines, alkanolamides, and phosphate esters are preferable. The fatty acid is not particularly limited, and examples thereof include saturated fatty acids such as behenic acid, stearic acid, palmitic acid, myristic acid, lauric acid, capric acid, caprylic acid, and coconut fatty acid; oleic acid, linoleic acid, linolenic acid, sorbine Examples thereof include unsaturated fatty acids such as acids, beef tallow fatty acids and castor hardened fatty acids, and lauric acid, stearic acid, oleic acid and the like are preferable.

  The aliphatic amine is not particularly limited. For example, laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, alkyl (coconut) amine, alkyl (cured beef tallow) amine, alkyl (beef tallow) amine, alkyl (soybean) An amine etc. are mentioned.

  The alkanolamide is not particularly limited, and examples thereof include coconut fatty acid diethanolamide, beef tallow fatty acid diethanolamide, lauric acid diethanolamide, and oleic acid diethanolamide. Furthermore, it does not specifically limit as said phosphate ester, For example, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene alkyl allyl ether phosphate ester, etc. are mentioned.

  In addition, the screen printing paste for multilayer ceramic electronic components of the present invention may contain conventionally known additives such as plasticizers, lubricants, antistatic agents and the like within a range that does not impair their physical properties.

  Next, the manufacturing method of the screen printing paste for multilayer ceramic electronic components is demonstrated. The manufacturing method of the screen printing paste for multilayer ceramic electronic components is not particularly limited. For example, a binder resin, an organic solvent that satisfies the volatility condition, and an inorganic powder are supplied to a general-purpose mixer such as a blender mill or a three roll. The manufacturing method to mix is mentioned.

  The screen printing paste for multilayer ceramic electronic components is applied and used on a ceramic green sheet using a general-purpose printing method such as screen printing, and has an extremely precise shape containing inorganic powder on the ceramic green sheet. A coating film can be formed.

  Then, a plurality of ceramic green sheets on which a coating film containing an inorganic powder is formed are stacked on each other and heat-pressed to produce a laminate, and the laminate is degreased and fired to fire the ceramic. A multilayer ceramic capacitor can be manufactured by manufacturing a product and sintering external electrodes on the end face of the ceramic fired product.

  Here, a butyral resin is preferable as the binder resin constituting the ceramic green sheet to which the screen printing paste for multilayer ceramic electronic components is applied. If the calculated molecular weight of the butyral resin is high, the degree of freedom of molecular motion of the butyral resin is large, so the dissolution time in an organic solvent is shortened and sheet attack is likely to occur, so the calculated molecular weight is 20000 or more. Is preferable, and 50000 or more is more preferable. The calculated molecular weight of the butyral resin was determined by dissolving the butyral resin in DMSO-d6 (dimethyl sulfoxide), measuring the degree of butyral using 13C-NMR (nuclear magnetic resonance spectrum), and polymerizing the starting polyvinyl alcohol. It is calculated together with the degree of polymerization, and is substantially dependent on the degree of polymerization of polyvinyl alcohol used for the synthesis of butyral resin.

  In addition, if the hydroxyl group content of the butyral resin is low, the polarity of the butyral resin becomes low, and the affinity for an organic solvent increases, so that sheet attack is likely to occur. Therefore, it is preferably 20 mol% or more, more preferably 22 mol% or more. . The hydroxyl group content of the butyral resin refers to a value obtained by dissolving the butyral resin in DMSO-d6 (dimethyl sulfoxide) and using 13C-NMR (nuclear magnetic resonance spectrum), and is used for synthesizing the butyral resin. Increasing the amount of butyraldehyde added decreases the amount of hydroxyl groups in the butyral resin, while decreasing the amount of butyraldehyde used in the synthesis of the butyral resin increases the amount of hydroxyl groups in the butyral resin.

  The screen printing paste for multilayer ceramic electronic components of the present invention is a screen printing paste for multilayer ceramic electronic components containing a binder resin, an organic solvent and an inorganic powder, and the organic solvent is heated from 25 ° C. to 10 ° C./min. While the temperature at 10% by weight of the initial weight when the temperature is raised at a temperature rate is 110 to 185 ° C., the binder resin is represented by the repeating unit (1) represented by the above formula 1 and the above formula 2. And the repeating unit (1) has a molar ratio of 0.5 to 0.99 and the repeating unit (2) has a molar ratio of 0.01 to 0.5. It is a polymer having a weight average molecular weight of 10,000 to 1,000,000 measured by permeation chromatography (GPC), and the binder resin is excellent in thermal decomposability. Residue less after cage firing, it is possible to obtain a multilayer ceramic electronic device having excellent electrical characteristics.

  The screen printing paste for multilayer ceramic electronic components according to the present invention uses an organic solvent with excellent volatility that satisfies a predetermined condition as the organic solvent, and is therefore suitable when applied on a ceramic green sheet. However, it does not cause a so-called sheet attack phenomenon that quickly volatilizes and dissolves and swells the ceramic green sheet.

  Furthermore, since the screen printing paste for multilayer ceramic electronic components of the present invention has excellent coating properties, in particular, excellent screen printing properties, it can be accurately applied on a ceramic green sheet, A coating film having a precise shape can be accurately formed on the ceramic green sheet.

(Manufacture of polyurethane)
A magnetic stirrer, a thermometer, and a dropping funnel were installed in a 1500 ml round bottom flask, and 64.6 parts by weight of 2-ethylhexylamine was supplied into the round bottom flask, and the inside of the flask was replaced with nitrogen.

  The inside of the round bottom flask was stirred while heating the round bottom flask to 60 ° C. using an oil bath, and 2-ethylhexyl glycidyl ether (trade name “Denacol EX” manufactured by Nagase Chemical Industries, Ltd.) was added into the round bottom flask using a dropping funnel. -121 ", epoxy value 188) and 188.0 parts by weight were added dropwise over 40 minutes. After completion of the dropping, the temperature of the oil bath was raised to 80 ° C., and the round bottom flask was heated for 10 hours.

  Subsequently, the temperature of the oil bath was raised to 120 ° C., and a small amount of unreacted substances was distilled off under reduced pressure using a vacuum pump with the inside of the round bottom flask set to a vacuum degree of 399 Pa. A comb-shaped hydrophobic diol (average molecular weight 490 based on OH value) (formula 8) in which 2-ethylhexyl glycidyl ether was added at a ratio of 2 mol to 1 mol of 2-ethylhexylamine was obtained in a yield of 98%.

  After supplying 100 parts by weight of polyethylene glycol (trade name “PEG # 6000” manufactured by Junsei Chemical Co., Ltd., number average molecular weight: 8700) from an OH value to a 500 ml stainless steel separable flask, nitrogen was added to the separable flask. After the replacement, the inside of the separable flask was heated to 150 ° C. to melt the polyethylene glycol.

  Next, the polyethylene glycol was dried for 3 hours while reducing the pressure inside the separable flask to 399 Pa while stirring the inside of the separable flask. The water remaining in the polyethylene glycol was 200 ppm with respect to its total weight.

  Subsequently, the temperature in the separable flask was lowered to 80 ° C., and 1 part by weight of the above comb-type hydrophobic diol and 2.28 parts by weight of hexamethylene diisocyanate (Tokyo Kasei) were separated while the inside of the separable flask was stirred. It was fed into a bull flask.

  Furthermore, when 0.01 part by weight of dibutyltin dilaurate was supplied as a catalyst into the separable flask, the viscosity rapidly increased in about 10 minutes. Stirring was stopped and the reaction was continued for another 2 hours. After completion of the reaction, the polyurethane was taken out from the separable flask, cut into small pieces, and allowed to cool. Next, the product cut into small pieces was further cooled with liquid nitrogen, and then pulverized using an electric mill so that the particle size became 1 mm or less to obtain polyurethane powder.

  In the obtained polyurethane, the molar ratio of the repeating unit (1) represented by the formula 1 was 0.88, and the molar ratio of the repeating unit (2) represented by the formula 2 was 0.12. The weight average molecular weight measured by GPC in the polyurethane was 500,000.

(Example 1, Comparative Examples 1-5)
Mixing of 7 parts by weight of the binder resin shown in Table 1 in the polyurethane or ethyl cellulose obtained above (trade name “STD45 type”), 95% by weight of 2-ethylhexyl acetate and 5% by weight of α-terpineol. Organic solvent A, 50% by weight of α-terpineol and 50% by weight of 3,5,5-trimethylhexanoic acid Mixed organic solvent B, 60 parts by weight of organic solvent shown in Table 1 among α-terpineol or 2-ethylhexyl acetate And 100 parts by weight of nickel fine particles (trade name “2020SS” manufactured by Mitsui Kinzoku Co., Ltd.) are mixed with a three-roll roll with an optical microscope until there are no aggregates (uncrushed materials). Screen printing paste for multilayer ceramic electronic components (Conductive paste) was obtained. In addition, about each organic solvent, the temperature used as 10 weight% of initial weight when it heats up from 25 degreeC with the temperature increase rate of 10 degree-C / min was shown in the column of "volatile temperature" of Table 1.

  The printability, thermal decomposability and sheet attack property of the obtained conductive paste were measured as follows, and the results are shown in Table 1.

(Printability)
A 300 mesh polyester plate was used to continuously print 20 straight lines per 1 cm width, and the printability was evaluated according to the following criteria.
○: No problem occurred during printing.
X: A problem occurred during printing.

(Pyrolytic)
10 parts by weight of butyral resin is added to a mixed solvent of 30 parts by weight of toluene and 15 parts by weight of ethanol and stirred and dissolved. Further, 3 parts by weight of dibutyl phthalate as a plasticizer is added and stirred and dissolved to obtain a resin solution. It was.

  In addition, in Example 1 and Comparative Examples 1-3 and 5 as butyral resin, butyral resin marketed by Sekisui Chemical Co., Ltd. under the trade name “ESREC B“ BM-S ”” is used. A butyral resin commercially available from Chemical Industries under the trade name “ESREC B“ BL-1 ”” was used.

  100 parts by weight of barium titanate (trade name “BT-01 (average particle size: 0.3 μm)” manufactured by Sakai Chemical Industry Co., Ltd.) as ceramic powder was added to the obtained resin solution, and the mixture was used for 48 hours using a ball mill. The ceramic slurry composition was obtained by mixing.

  The obtained ceramic slurry composition was coated on a polyester film whose one surface was subjected to a release treatment so that the thickness after drying was about 5 μm, and then air-dried at room temperature for 1 hour. It was supplied and dried at 80 ° C. for 3 hours and then at 120 ° C. for 2 hours to obtain a ceramic green sheet.

The ceramic green sheet was cut into a flat square shape with a side of 5 cm to produce 100 green sheet pieces. A conductive paste is applied to one surface of each green sheet piece by screen printing, and 100 green sheet pieces are overlapped with each other in the thickness direction, and then 1.47 × 10 ⁷ Pa in the thickness direction at a temperature of 70 ° C. The green sheet pieces adjacent to each other were integrated by compressing for 10 minutes with a pressure of 1 to obtain a ceramic green sheet laminate.

The obtained ceramic green sheet laminate was heated to 450 ° C. at a temperature rising rate of 3 ° C./min in a nitrogen atmosphere, held for 5 hours, and further to 1350 ° C. at a temperature rising rate of 5 ° C./min. The temperature was raised and held for 10 hours to obtain a ceramic sintered body. The obtained ceramic sintered body was visually observed, and the thermal decomposability was evaluated according to the following criteria.
○: Sintered uniformly, and nothing other than ceramic powder was observed.
X: A black dot-like thing was rarely confirmed in the dielectric layer.

(Sheet attack)
The cross section of the ceramic green sheet laminate was observed with a microscope, and the sheet attack property was evaluated according to the following criteria.
○: No through holes or wrinkles were observed on the green sheet piece.
X: A through-hole and a wrinkle were confirmed in the green sheet piece.

(Example 2, Comparative Examples 6 to 10)
Mixing of 7 parts by weight of the binder resin shown in Table 1 in the polyurethane or ethyl cellulose obtained above (trade name “STD45 type”), 95% by weight of 2-ethylhexyl acetate and 5% by weight of α-terpineol. Organic solvent A, 50% by weight of α-terpineol and 50% by weight of 3,5,5-trimethylhexanoic acid Mixed organic solvent B, 60 parts by weight of organic solvent shown in Table 1 among α-terpineol or 2-ethylhexyl acetate Then, 100 parts by weight of barium titanate (trade name “BT-03” manufactured by Sakai Chemical Industry Co., Ltd.) was kneaded for 48 hours using a ball mill to obtain a screen printing paste (ceramic paste) for multilayer ceramic electronic components. .

  The printability, thermal decomposability and sheet attack property of the obtained ceramic paste were measured as follows, and the results are shown in Table 1.

(Printability)
10 parts by weight of butyral resin (Sekisui Chemical Co., Ltd., trade name “ESREC B“ BM-S ”, polymerization degree: 800)” was added to a mixed solvent of 30 parts by weight of toluene and 15 parts by weight of ethanol, and stirred and dissolved. Further, 3 parts by weight of dibutyl phthalate was added as a plasticizer and stirred and dissolved to obtain a resin solution.

  In addition, in Example 2 and Comparative Examples 6 to 8 and 10, as the butyral resin, butyral resin commercially available from Sekisui Chemical Co., Ltd. under the trade name “ESREC B“ BM-S ”” is used. A butyral resin commercially available from Chemical Industries under the trade name “ESREC B“ BL-1 ”” was used.

  To the obtained resin solution, 100 parts by weight of barium titanate (“BT-03 (average particle size: 0.3 μm)” manufactured by Sakai Chemical Industry Co., Ltd.) as ceramic powder was added and mixed with a ball mill for 48 hours to produce ceramics. A rally composition was obtained.

  The obtained slurry composition was coated on a polyester film whose one surface was release-treated so that the thickness after drying was about 10 μm, and then air-dried at room temperature for 1 hour, and further a hot-air dryer Was dried at 80 ° C. for 3 hours and then at 120 ° C. for 2 hours to obtain a ceramic green sheet.

Using a screen printing machine (trade name “Minomat Y-3540” manufactured by Mino Group) and a screen plate (trade name “SX300B” manufactured by Mino Group), a ceramic paste is screen-printed on a ceramic green sheet. The printed surface during sheet printing was observed visually or with a magnifying microscope, and the printability was evaluated according to the following criteria.
A: No blur or thread-like ceramic paste was observed on the printed surface.
X: Scratch or thread-like ceramic paste was observed on the printed surface.

(Pyrolytic)
The ceramic green sheet produced at the time of measuring the printability was cut into a flat square shape with a side of 5 cm to produce 100 green sheet pieces. After applying a ceramic paste to one side of each green sheet piece by screen printing, 100 pieces of green sheet pieces were superposed on each other in the thickness direction and then 1.47 × 10 ⁷ Pa in the thickness direction at a temperature of 70 ° C. The green sheet pieces adjacent to each other were integrated by compressing for 10 minutes with a pressure of 1 to obtain a ceramic green sheet laminate.

The obtained ceramic green sheet laminate was heated to 450 ° C. at a temperature rising rate of 3 ° C./min in a nitrogen atmosphere, held for 5 hours, and further to 1350 ° C. at a temperature rising rate of 5 ° C./min. The temperature was raised and held for 10 hours to obtain a ceramic sintered body. The obtained ceramic sintered body was visually observed, and the thermal decomposability was evaluated according to the following criteria.
○: Sintered uniformly, and nothing other than ceramic powder was observed.
X: A large number of black dots on the green sheet were confirmed.

(Sheet attack)
The cross section of the ceramic green sheet laminate was observed with a microscope, and the sheet attack property was evaluated according to the following criteria.
○: No through holes or wrinkles were observed on the green sheet piece.
X: A through-hole and a wrinkle were confirmed in the green sheet piece.

Claims (6)

A screen printing paste for a multilayer ceramic electronic component containing a binder resin, an organic solvent and an inorganic powder, wherein the organic solvent is 10% by weight of the initial weight when the temperature is increased from 25 ° C. at a rate of 10 ° C./min The binder resin is composed of the repeating unit (1) represented by the formula 1 and the repeating unit (2) represented by the formula 2, and the repeating unit (1). The molar ratio of the repeating unit (2) is 0.01 to 0.5, and the weight average molecular weight measured by gel permeation chromatography (GPC) is 10,000. A screen printing paste for multilayer ceramic electronic components, characterized in that the polymer is a polymer of ˜1000000.

However, A is a divalent group of polyethylene glycol (compound A) having hydroxyl groups at both ends of HO-A-OH and having a number average molecular weight of 400 to 100,000, and B is OCN-B-NCO. Is a divalent group which is a chain aliphatic diisocyanate or a cycloaliphatic diisocyanate (Compound B), and D is a comb-shaped hydrophobic group in which HO-D-OH is represented by Formula 3, Formula 4 or Formula 5. A screen printing paste for multilayer ceramic electronic parts, characterized in that it is a functional diol (compound D).

(However, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms. R ² and R ³ are hydrocarbon groups having 4 to 21 carbon atoms. Hydrocarbon groups R ¹ , R ² and R A part or all of hydrogen in ³ may be substituted with fluorine, chlorine, bromine or iodine, and R ² and R ³ may be the same or different. , Methyl group or CH ₂ Cl group, and Y and Y ′ may be the same or different. Z and Z ′ are oxygen, sulfur or CH ₂ group, and Z and Z ′ are the same. N is an integer of 0 to 15 when Z is oxygen, 0 when Z ′ is sulfur or CH ₂ , and n and n ′ are the same or different. May be)

(However, R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms. R ⁵ and R ⁶ are hydrocarbon groups having ⁴ to 21 carbon atoms. In R ⁴ , R ⁵ and R ⁶ , Part or all of hydrogen may be substituted with fluorine, chlorine, bromine or iodine, and R ⁵ and R ⁶ may be the same or different. Y, Y ′ and Y ″ are hydrogen , Methyl group or CH ₂ Cl group, Y and Y ′ may be the same or different, R ⁷ is an alkylene group having 2 to 4 carbon atoms, and k is an integer of 0 to 15. N is an integer of 0 to 15 when Z is oxygen, and 0 when Z is sulfur or a CH ₂ group, and n ′ is 0 to 15 when Z ′ is oxygen. An integer, 0 when Z ′ is sulfur or CH ₂ , and n and n ′ may be the same or different)

(However, R ⁸ and R ⁹ are hydrocarbon groups having a total of 2 to 20 carbon atoms in R ⁸ and R ^9. R ¹⁰ and R ¹¹ are hydrocarbon groups having 4 to 21 carbon atoms. R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ may be partially or fully substituted with fluorine, chlorine, bromine or iodine, and R ⁸ and R ⁹ may be the same or different. R ¹⁰ and R ¹¹ may be the same or different, and R ¹² is an alkylene group having 2 to 7 carbon atoms, and Y and Y ′ are hydrogen, methyl group or CH _{2 is a} Cl group, and Y and Y ′ may be the same or different, Z and Z ′ are oxygen, sulfur, or CH ₂ groups, and Z and Z ′ are the same. N is an integer from 0 to 15 when Z is oxygen, and 0 when Z is sulfur or a CH ₂ group, and n ′ is when Z ′ is oxygen. Is an integer from 0 to 15 Ri, Z 'when the sulfur or a CH ₂ group is 0, n and n' may be the same or different and) 2. The screen printing paste for multilayer ceramic electronic components according to claim 1, wherein the inorganic powder is at least one inorganic compound selected from the group consisting of nickel, palladium, silver, copper and barium titanate. The organic solvent is a mixed organic solvent containing at least one organic compound selected from the group consisting of carboxylic acids, alcohols, ketones, and esters. Screen printing paste for multilayer ceramic electronic components. The screen printing paste for multilayer ceramic electronic components according to any one of claims 1 to 3, wherein the screen printing paste is used for coating on a ceramic green sheet containing butyral resin as a binder resin. The screen printing paste for multilayer ceramic electronic components according to claim 4, wherein the butyral resin has a calculated molecular weight of 20000 or more. The screen printing paste for multilayer ceramic electronic components according to claim 4 or 5, wherein the butyral resin has a hydroxyl group content of 20 mol% or more.