JP2006232654A - Glass paste composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a glass paste composition exhibiting improved flocculation stability and sedimentation stability when it is stored in comparison with conventional ones. <P>SOLUTION: The glass paste composition contains one or more kinds of acyl compounds each having two or more groups of each of acyl group and hydrophilic group. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a glass paste composition used for electronic use such as a ceramic package of a semiconductor circuit, an automobile and the like.

  In recent years, glass paste compositions have been used for printing, electronics, automobiles, etc., and the composition is mainly composed of glass frit, a solvent, and an organic binder, and if necessary, pigments, photosensitive agents, plasticizers Etc. are added. The glass paste composition is printed and applied onto a substrate, and becomes a product through drying and baking processes. In particular, in glass pastes for printing such as semiconductor integrated circuits, in order to form a dense glass film, a glass powder having a smaller particle size is used. There was a problem that glass particles easily aggregated and settled and had to be redispersed when used.

Patent Document 1 discloses a technology for suppressing sedimentation of particles and bubbles during storage using a glass paste comprising a glass powder, a vehicle using a polar organic solvent, and a polycarboxylic acid type anionic surfactant. However, the effect is still inadequate in the region of a fine particle size such that the glass particle size is 10 μm or less.
JP-A-53-94181

  An object of this invention is to provide the glass paste composition which can improve the aggregation and sedimentation stability at the time of preservation | save of a glass paste composition compared with the past.

  As a result of intensive studies to solve the above problems, the present inventors have obtained one or more kinds of specific compounds, that is, compounds having two or more acyl groups and hydrophilic groups in the molecule (acyl compounds). By using the glass paste composition contained, it was found that a glass paste composition capable of improving the sedimentation stability during storage as compared with the conventional one can be obtained, and the present invention has been completed.

That is, the present invention is as follows.
1. A glass paste composition comprising one or more acyl compounds each having two or more acyl groups and hydrophilic groups in the molecule.
2. At least one of the acyl compounds has an amino acid residue in the molecule. The glass paste composition described in 1.
3. At least one of the acyl compounds is a compound represented by the following general formula (1): Or 2. The glass paste composition according to any one of the above.

（上記一般式（１）において、Ｘはｍ個の官能基、およびそれ以外の置換基を有していてもよい分子量１００万以下の直鎖または分枝鎖または環状鎖または芳香族炭化水素鎖であるスペーサーであり、Ｘに結合しているｎ（ｍ≧ｎ）個のＱは、下記一般式（２）で表される置換基で、それぞれ互いに同一でも異なっていてもよい。下記一般式（２）において、ＺはＸの有する官能基に由来する結合部であり、Ｒ¹ＣＯは炭素原子数２〜２０の飽和または不飽和の脂肪酸から誘導されるアシル基を示し、Ｒ²は水素であるか、またはヒドロキシル基またはカルボキシル基が置換していてもよい炭素原子数１〜３の低級アルキル基を示し、Ｙはカルボキシル基、スルホン酸基、硫酸エステル基、リン酸エステル基またはそれらの塩を示し、ｊ、ｋはそれぞれ独立に０，１，２のいずれかであり、かつｊ、ｋは同時に０ではない。ｎは２〜２０の整数を示す。）

(In the above general formula (1), X is a linear, branched, cyclic or aromatic hydrocarbon chain having a molecular weight of 1,000,000 or less, which may have m functional groups and other substituents. N (m ≧ n) Q bonded to X are substituents represented by the following general formula (2), which may be the same as or different from each other. In (2), Z is a bond derived from a functional group of X, R ¹ CO represents an acyl group derived from a saturated or unsaturated fatty acid having 2 to 20 carbon atoms, and R ² represents hydrogen Or a lower alkyl group having 1 to 3 carbon atoms which may be substituted by a hydroxyl group or a carboxyl group, and Y represents a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group or a group thereof. Indicate salt, j, k They are either each independently 0, 1, 2, and j, k are not 0 at the same time .n represents an integer of 2 to 20.)

４．さらに有機バインダーと溶媒を含むガラスペーストであることを特徴とする前記１．〜３．のいずれかに記載のガラスペースト組成物。

4). The glass paste further comprises an organic binder and a solvent. ~ 3. The glass paste composition according to any one of the above.

  The glass paste composition of the present invention has high aggregation / sedimentation stability during storage, that is, good dispersibility, and can maintain a uniform state without aggregation / sedimentation for a long period of time.

  Hereinafter, the present invention will be specifically described with a focus on preferred embodiments.

  The glass paste composition referred to in the present invention is a paste obtained by dispersing one or more types of glass powder in a solvent, and includes at least one type of acyl compound having a specific structure in the composition. It is the composition which becomes. The acyl compound here is a compound having a structure having at least two acyl groups and two hydrophilic groups in the molecule.

  Two or more acyl groups may be independently different or the same. Each acyl group is preferably derived from a saturated or unsaturated fatty acid having 2 to 20 carbon atoms, and may be linear, branched or cyclic. However, the carboxyl group is not included.

  Examples of the acyl group include acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, Linear fatty acids such as margaric acid, stearic acid, nonadecanoic acid, arachidic acid;

  2-butyl-5-methylpentanoic acid, 2-isobutyl-5-methylpentanoic acid, dimethyloctanoic acid, dimethylnonanoic acid, 2-butyl-5-methylhexanoic acid, methylundecanoic acid, dimethyldecanoic acid, 2-ethyl- 3-methylnonanoic acid, 2,2-dimethyl-4-ethyloctanoic acid, methyldocosanoic acid, 2-propyl-3-methylnonanoic acid, methyltridecanoic acid, dimethyldodecanoic acid, 2-butyl-3-methylnonanoic acid, methyltetradecanoic acid , Ethyltridecanoic acid, propyldodecanoic acid, butylundecanoic acid, pentyldecanoic acid, hexylnonanoic acid, 2- (3-methylbutyl) -3-methylnonanoic acid, 2- (2-methylbutyl) -3-methylnonanoic acid, butylethylnonane Acid, methylpentadecanoic acid, ethyltetradecanoic acid, propyltri Canic acid, butyldodecanoic acid, pentylundecanoic acid, hexyldecanoic acid, heptylnonanoic acid, dimethyltetradecanoic acid, butylpentylheptanoic acid, trimethyltridecanoic acid, methylhexadecanoic acid, ethylpentadecanoic acid, propyltetradecanoic acid, butyltridecanoic acid, pentyldodecane Acid, hexylundecanoic acid, heptyldecanoic acid, methylheptylnonanoic acid, dipentylheptanoic acid, methylheptadecanoic acid, ethylhexadecanoic acid, ethylhexadecanoic acid, propylpentadecanoic acid, butyltetradecanoic acid, pentyltridecanoic acid, hexyldodecanoic acid, heptyl Undecanoic acid, octyldecanoic acid, dimethylhexadecanoic acid, methyloctylnonanoic acid, methyloctadecanoic acid, ethylheptadecanoic acid, dimethylheptadecanoic acid, Octyl decanoic acid, Mechirunonadekan acid, Mechirunonadekan acid, dimethyl octadecanoic acid, branched fatty acids such as butyl heptyl nonanoic acid;

  Octenoic acid, nonenoic acid, decenoic acid, caproleic acid, undecylenic acid, Lindellic acid, touric acid, lauroleic acid, tridecenoic acid, tuzuic acid, myristoleic acid, pentadecenoic acid, hexedenoic acid, palmitoleic acid, heptadecenoic acid, octadecenoic acid, Linear monoenoic acids such as oleic acid, nonadecenoic acid, gondoic acid;

  Such as methylheptenoic acid, methylnonenoic acid, methylundecenoic acid, dimethyldecenoic acid, methyldodecenoic acid, methyltridecenoic acid, dimethyldodecenoic acid, dimethyltridecenoic acid, methyloctadecenoic acid, dimethylheptadecenoic acid, ethyloctadecenoic acid Branched monoenoic acid;

  Di- or trienoic acids such as linoleic acid, linoelaidic acid, eleostearic acid, linolenic acid, linolenic elaidic acid, pseudoeleostearic acid, parinalic acid, arachidonic acid;

  Acetylene acids such as octinoic acid, nonic acid, decinic acid, undecinic acid, dodecinic acid, tridecic acid, tetradecic acid, pentadecinic acid, heptadecinic acid, octadecinic acid, nonadesinic acid, dimethyloctadesinic acid;

Of methyleneoctadecenoic acid, methyleneoctadecanoic acid, aleprolic acid, alepresinic acid, allepuric acid, alepuric acid, hydnocarpic acid, shoulmuric acid, gorulic acid, α-cyclopentylic acid, α-cyclohexylic acid, α-cyclopentylethylic acid Cyclic acids such as;
Are derived from

  The acyl group may be a fatty acid-derived acyl group obtained from natural fats and oils, and is preferably a mixed fatty acid-derived acyl group containing 80% or more of the above saturated or unsaturated fatty acid having 2 to 20 carbon atoms. For example, acyl groups derived from palm oil fatty acid, palm oil fatty acid, linseed oil fatty acid, sunflower oil fatty acid, soybean oil fatty acid, sesame oil fatty acid, castor oil fatty acid, olive oil fatty acid, camellia oil fatty acid, rapeseed oil fatty acid, palm kernel oil fatty acid, etc. Etc. Two or more of these acyl compounds having an acyl group may be used in combination. The number of carbon atoms of the acyl group is preferably 8 to 20 from the viewpoint of enhancing the dispersibility.

  Two or more hydrophilic groups contained in the acyl compound may be independently different or the same. Examples of the hydrophilic group include a carboxyl group, a sulfonic acid group, a sulfuric acid residue, a phosphoric acid residue or a salt thereof, an oxyalkylene group, a polyethylene glycol group, or the like, or an amino group, a quaternary ammonium group, a pyridinium group, a sulfonium group. Or the salt etc. are raised. The hydrophilic group is preferably a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group or a salt thereof.

  The number of acyl groups or hydrophilic groups contained in the acyl compound is preferably 2 or more and 60 or less, more preferably 2 or more and 40 or less. Further, it is particularly preferably 2 or more and 20 or less.

  When the acyl compound is used as a salt, for example, an alkali metal salt, an alkaline earth metal salt, an ammonium salt, an organic amine salt, a basic amino acid salt and the like are preferable. Specifically, sodium, potassium, lithium and the like Alkali metals, alkaline earth metals such as calcium and magnesium, metals such as aluminum and zinc, organic amines such as ammonia, monoethanolamine, diethanolamine, triethanolamine and triisopropanolamine, basic amino acids such as arginine and lysine It is more preferable to use a salt with one kind or two or more kinds selected arbitrarily. Among these, sodium salts, potassium salts, organic amine salts, and basic amino acid salts are particularly preferable. Moreover, when manufacturing an electrically conductive paste using an aqueous slurry, it is preferable to set it as an organic amine salt, a basic amino acid salt, etc.

  In the glass paste composition, it is preferable that at least one acyl compound contained in the glass paste composition is an acyl compound represented by the general formulas (1) and (2).

  The acyl compound here is structurally linked with a compound having at least one acyl group and a hydrophilic group in the molecule with an appropriate spacer as shown in the general formulas (1) and (2). Of structure.

In the general formula (2), the acyl groups represented by R ¹ CO may be independently, that is, may be different or the same, and are derived from a saturated or unsaturated fatty acid having 2 to 20 carbon atoms as described above. Any material can be used as long as it is linear, branched or cyclic.

In general formula (2), the acyl group represented by R ¹ CO is preferably derived from a saturated or unsaturated fatty acid having 8 to 20 carbon atoms.

In general formula (2), R ² is hydrogen, or the number of carbon atoms that may be substituted by a hydroxyl group, a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group, or a salt thereof. 1 to 3 lower alkyl groups, and examples of the lower alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a hydroxymethyl group, a hydroxyethyl group, a hydroxy (iso) propyl group, and a dihydroxy (iso) propyl group. Group, carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group and the like.

  In the general formula (1), n substituents Q (formula (2)) bonded to X may be different from each other or the same. Moreover, Formula (2) shows what is called an acidic amino acid N-acylated, and it does not ask | require whether they are optical isomers, for example, D-form, L-form, and a racemate.

  The acidic amino acid is a monoaminodicarboxylic acid having 2 and 1 carboxyl groups and 1 amino group, respectively, in the molecule, and the amino group may be an N-methyl group or an N-ethyl group. It does not matter whether it is an optical isomer, for example, a D-form, an L-form, or a racemate. Examples of acidic amino acids include glutamic acid, aspartic acid, lanthionine, β-methyllanthionine, cystathionine, diencholic acid, ferrinin, aminomalonic acid, β-oxyaspartic acid, α-amino-α-methylsuccinic acid, β-oxyglutamic acid. , Γ-oxyglutamic acid, γ-methylglutamic acid, γ-methyleneglutamic acid, γ-methyl-γ-oxyglutamic acid, α-aminoadipic acid, α-amino-γ-oxyadipic acid, α-aminopimelic acid, α-amino- Examples thereof include γ-oxypimelic acid, β-aminopimelic acid, α-aminosuberic acid, α-aminosebacic acid, pantothenic acid and the like.

  The n substituents (formula (2)) attached to X are preferable because the acidic amino acid is an L-acidic amino acid molecule because it is excellent in biodegradability.

In the general formula (2), Z is a bonding part (—O) derived from m functional groups (hydroxyl group, amino group, thiol group) substituted with X (m ≧ n and an integer of 2 to 20). -, -NR < ³ >-, -S-). Here, R ³ is hydrogen, or an alkyl group, alkenyl group, aryl group, or alkylaryl group having 1 to 10 carbon atoms.

  In general formula (1), X is a linear or branched or cyclic chain having a molecular weight of 1 million or less and having m functional groups consisting of one or more selected from a hydroxyl group, an amino group and a thiol group. It is a spacer which is an aromatic hydrocarbon chain, and X may have a substituent other than the hydroxyl group, amino group and thiol group.

  In the general formula (1), X is preferably a residue of an m-valent compound having a molecular weight of 1 million or less and having m functional groups of one kind or two or more kinds selected from a hydroxyl group, an amino group and a thiol group. , A compound residue that may have a substituent other than a hydroxyl group, an amino group, or a thiol group. Here, the m-valent compound means that a bond derived from m functional groups can be formed. It does not matter whether they are optical isomers such as D-form, L-form, and racemate.

  Examples of such m-valent compounds include amino acids such as serine, threonine, cysteine, cystine, cystine disulfoxide, cystathionine, methionine, arginine, lysine, tyrosine, histidine, tryptophan, and oxyproline;

  Aminoethanol, aminopropanol, aminobutanol, aminopentanol, aminohexanol, aminopropanediol, aminoethylethanolamine, aminoethylaminoethanol, aminocresol, aminonaphthol, aminonaphtholsulfonic acid, aminohydroxybenzoic acid, aminohydroxybutanoic acid Compounds having an amino group and a hydroxyl group in the molecule such as aminophenol, aminophenethyl alcohol, glucosamine;

  Compounds having a thiol group and a hydroxyl group in the molecule such as mercaptoethanol, mercaptophenol, mercaptopropanediol, glucothiose;

Compounds having a thiol group and an amino group in the molecule such as aminothiophenol and aminotriazole thiol;
Is mentioned. Further, proteins, peptides, etc., or those obtained by hydrolyzing them may be used.

  In the general formula (1), X is preferably an m-valent (m ≧ n) polyhydroxyl compound residue having a molecular weight of 1,000,000 or less, which may have a substituent other than a hydroxyl group. Here, the m-valent polyhydroxyl compound means that m ester bonds can be formed. It does not matter whether they are optical isomers such as D-form, L-form, and racemate.

  Examples of such m-valent polyhydroxyl compounds include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol. , Pentanediol, 1,6-hexanediol, cyclohexanediol, dimethylolcyclohexane, neopentyl glycol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, isoprene glycol, 3-methyl -1,5-pentanediol, sorbite, catechol, resorcin, hydroquinone, bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, dimer diol, dimethylolpropionic acid, dimethylolbutanoic acid, tartaric acid, dihydro Shi tartaric, mevalonate, 3,4-dihydroxy cinnamic acid, 3,4-dihydroxy-hydro cinnamic acid, hydroxy benzoic acid, dihydroxy stearic acid, dihydroxyphenylalanine, and the like, and divalent hydroxyl compounds such as isomers thereof;

  Glycerin, trioxyisobutane, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2-methyl-1,2,3-propanetriol, 2-methyl-2,3,4-butanetriol, 2-ethyl-1,2,3-butanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-3,4,5-heptanetriol, 2,4-dimethyl- Trivalent poly, such as 2,3,4-pentanetriol, 1,2,4-butanetriol, 1,2,4-pentanetriol, trimethylolethane, trimethylolpropane, diethanolamine, triethanolamine, trihydroxystearic acid Hydroxyl compounds;

  Pentaerythritol, erythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5-pentanetetrol, 1,3,4,5-hexane Tetravalent polyhydroxyl compounds such as tetrol, diglycerin and sorbitan;

  Pentavalent polyhydroxyl compounds such as adonitol, arabitol, xylitol, triglycerin;

Hexavalent polyhydroxyl compounds such as dipentaerythritol, sorbitol, mannitol, iditol, inositol, dulcitol, talose, allose;
Or these dehydration condensates, polyglycerol, etc. are mentioned.

  Sugars such as tetroses such as erythrose, sreose, erythrulose;

  Pentose such as ribose, arabinose, xylose, lyxose, xylulose, ribulose; monosaccharides such as hexose such as allose, altrose, glucose, mannose, guylose, idose, galactose, talose, fructose, sorbose, psicose, tagatose;

  And oligosaccharides such as maltose, isomaltose, cellobiose, gentiobiose, melibiose, lactose, tulanose, trehalose, saccharose, mannitolose, cellotriose, gentianose, raffinose, meletitose, cellotetorose, stachyose and the like.

  In addition, other saccharides such as heptose, deoxy sugar, amino sugar, thio sugar, seleno sugar, aldone sugar, uronic acid, sugar acid, ketoaldonic acid, anhydro sugar, unsaturated sugar, sugar ester, sugar ether, glycoside, etc. It may be a group, and may be a polysaccharide such as starch, glycogen, cellulose, chitin, chitosan or the like, or a hydrolyzed product thereof.

  In general formula (2), X is preferably an m-valent polyamino compound residue having a molecular weight of 1,000,000 or less, which may have a substituent other than an amino group. Here, the m-valent polyamino compound means that m acid amide bonds can be formed. It does not matter whether they are optical isomers such as D-form, L-form, and racemate.

  Examples of such m-valent polyamino compounds include N, N′-dimethylhydrazine, ethylenediamine, N, N′-dimethylethylenediamine, diaminopropane, diaminobutane, diaminopentane, diaminohexane, diaminoheptane, diaminooctane, diaminononane, Aliphatic diamines such as diaminodecane, diaminododecane, diaminoadipic acid, diaminopropanoic acid, diaminobutanoic acid and their isomers;

  Diethylenetriamine, triaminohexane, triaminododecane, 1,8-diamino-4-aminomethyl-octane, 2,6-diaminocapric acid-2-aminoethyl ester, 1,3,6-triaminohexane, 1,6 , 11-triaminoundecane, aliphatic triamines such as di (aminoethyl) amine and isomers thereof;

  Alicyclic polyamines such as diaminocyclobutane, diaminocyclohexane, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, triaminocyclohexane;

  Aromatic polyamines such as diaminobenzene, diaminotoluene, diaminobenzoic acid, diaminoanthraquinone, diaminobenzenesulfonic acid, diaminobenzoic acid, and their respective isomers;

  Araliphatic polyamines such as diaminoxylene, di (aminomethyl) benzene, di (aminomethyl) pyridine, di (aminomethyl) naphthalene, and their isomers;

  And polyamines substituted with hydroxyl groups such as diaminohydroxypropane and isomers thereof.

  In the general formula (1), X is preferably an m-valent polythiol compound residue having a molecular weight of 1,000,000 or less, which may have a substituent other than a thiol group. Here, the m-valent polythiol compound means that m thioester bonds can be formed. It does not matter whether they are optical isomers such as D-form, L-form, and racemate.

  Examples of such m-valent polythiol compounds include dithiol compounds such as dithioethylene glycol, dithioerythritol, and dithiothreitol.

  X is preferably a group having 1 to 40 carbon atoms among the residues of the compounds listed above, and more preferably X has 1 to 20 carbon atoms. X is preferably a naturally occurring type from the viewpoint of excellent biodegradability.

  In general formula (2), the carboxyl group, sulfonic acid group, sulfate ester group, phosphate ester group represented by Y and the carboxyl group, sulfonate group, sulfate ester group, phosphate ester group, etc. that can be contained in X are: As described above, salts can be formed with various basic substances.

  As a method for producing such acyl compounds represented by the general formulas (1) and (2), an N-acyl acidic amino acid anhydride represented by the general formula (3), a hydroxyl group, an amino group, a thiol in the molecule By reacting a compound having one or more m functional groups selected from a group in water and / or a mixed solvent of water and an organic solvent, or tetrahydrofuran, benzene, toluene, xylene, It can be obtained by reacting by using an inert solvent such as carbon tetrachloride, chloroform, acetone or the like, or by mixing at -5 ° C. to 200 ° C. at a temperature higher than any melting point without solvent.

  Alternatively, the acyl compounds represented by the general formulas (1) and (2) are an N-acyl acidic amino acid mono-lower ester (for example, methyl ester, ethyl ester) and a polyhydroxyl compound, a polyamino compound, a polythiol compound, or a hydroxyl group in the molecule. A compound having any two or three of a group, an amino group and a thiol group is dissolved in a suitable solvent such as dimethylformamide, a catalyst such as potassium carbonate is added, and -5 ° C to 250 ° C under reduced pressure. It can obtain by removing reaction solvent after making it heat-react with. Alternatively, the acyl compound can be obtained by melting with heating without a solvent, adding a catalyst such as sodium hydroxide, and performing a transesterification reaction at room temperature to 250 ° C.

  In the glass paste composition, the acyl compound is preferably 0.001 to 10 parts by mass of the acyl compound with respect to 100 parts by mass of the glass paste composition. When the ratio of the acyl compound is 0.001 part by mass or more, a dispersion effect is obtained, and when it is 10 parts by mass or less, the remaining amount to the glass film and the generation of pinholes hardly occur. More preferably, the acyl compound is 0.1 to 5 parts by mass with respect to 100 parts by mass of the glass paste composition.

  The glass powder in the glass paste composition is not particularly limited, but examples thereof include glass powders of lead silicate type, lead borosilicate type, etc., having an average particle diameter of 0.1 to 30 μm. The thickness is preferably 0.1 to 10 μm. The content of the glass powder in the glass paste composition is not particularly limited, and can be appropriately prepared according to the use, purpose and the like. Furthermore, the softening temperature, thermal expansion coefficient, specific surface area, and average particle diameter of the glass powder can be appropriately selected as necessary.

  In a preferred embodiment of the glass paste composition, the stability can be further improved by using an organic binder. Here, it is necessary that the organic binder does not remain after firing. For example, methyl (meth) acrylate, ethyl (meth) acrylate, normerbutyl (meth) acrylate, isobutyl me (meth) acrylate, isopropyl (meth) acrylate, 2-ethyl Acrylic resins such as methyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate, polyvinyl non-curable resins such as polyvinyl butyral resin and polyvinyl alcohol, phenol resins, alkyd resins, rosin esters, ethyl cellulose, methyl cellulose, nitrocellulose In general, various cellulose derivatives such as cellulose acetate, cellulose propionate, and cellulose butyrate can be used in general glass paste compositions. In particular, but are not limited to. 1-20 mass% is preferable and, as for binder content in a glass paste composition, 1-15 mass% is more preferable.

  In a preferred embodiment of the glass paste composition, the solvent is preferably a good solvent for the binder, and an alcohol-based, hydrocarbon-based, ether-based, ester-based organic solvent or water, or a mixed solvent thereof is used. it can. Examples include terpineol, butyl carbitol, carbitol acetate, tetralin, kerosene, decyl alcohol, decane and the like.

  In the glass paste composition, if necessary, other than the above, as commonly used in conventional glass paste compositions, high melting point glass, alumina, magnesia, calcia, cordierite, silica, mullite, zircon, zirconia, etc. Fillers such as ceramic powder, glycerin, ethyl oleate, glyceryl monooleate, higher fatty acid, higher fatty acid ester, phosphate ester, sulfate ester, polyacrylic acid or salt thereof, vinyl-maleic acid copolymer or salt thereof, Formalin condensate of naphthalene sulfonic acid or salt thereof, acylamino acid or salt thereof, nonyl phenyl ether type, octyl phenyl ether type, alkyl allyl ether type, polymeric ether type, dispersing agent or surfactant such as fatty acid ethanolamide, Also conductive metal Chelate compounds such as ethylenediamine and ethylenediaminetetraacetic acid or their salts that can form a chelate complex with the powder, polyethylene glycols, phthalic acid esters, sebacic acid esters, adipic acid esters, glycolic acid esters, citric acid Plasticizers such as esters, antifoaming agents, thickeners, black or white pigments, antioxidants, polymerization inhibitors, and the like can be appropriately used.

  The glass paste composition of this invention can be manufactured by a well-known method, for example, can be manufactured by the following methods.

  The glass powder, the organic binder, the solvent, the acyl compound, and other components as described above can be produced using a stirrer, a kneader such as a ball mill, a triple roll, or a kneader, a crusher, or the like.

  Hereinafter, the present invention will be described more specifically with reference to examples and the like. However, the present invention is not limited to specific modes such as these examples.

Means for evaluating various physical properties are as follows.
(Evaluation of paste stability)

The presence or absence of settling for a long time of the glass paste composition left still at room temperature (25 degreeC) was confirmed.
Evaluation criteria No sedimentation confirmed for more than 1 month
Sedimentation was confirmed in one week or more and less than one month ・ ・ ・ △
Sedimentation confirmed in less than one week ・ ・ ・ ×
(Evaluation of paste cohesiveness)

The glass paste composition that was allowed to stand at room temperature for 1 week was thinly spread on a glass plate, and the presence or absence of aggregates was confirmed.
Evaluation criteria Aggregate not confirmed ・ ・ ・ ○
Obviously agglomerates are confirmed ... ×
(Production Example 1 of acyl compound)

  9.1 g (0.05 mol) of L-lysine hydrochloride was mixed with 57 g of water. While this solution was adjusted to a pH range of 10 to 11 with a 25% aqueous sodium hydroxide solution and the reaction temperature was maintained at 5 ° C., 31.1 g of N-lauroyl-L-glutamic anhydride (0. 1 mol) was added over 2 hours to carry out the reaction. After stirring for another 30 minutes, tertiary butanol was added to a concentration of 20% by mass in the liquid, 75% sulfuric acid was added dropwise to bring the pH value of the liquid to 2, and the liquid temperature to 65 ° C. It was adjusted. After completion of the dropwise addition, stirring was stopped, and the mixture was allowed to stand at 65 ° C. for 20 minutes. Tertiary butanol and water were added to the separated organic layer, the temperature was raised to 65 ° C., and the mixture was stirred for 20 minutes. After the stirring was stopped, the mixture was allowed to stand to separate into an organic layer and an aqueous layer. After repeating the same water washing operation with respect to the obtained organic layer, the solvent was removed from the obtained organic layer, and this was dried to obtain a composition containing an acyl compound represented by the formula (4).

（アシル化合物の製造例２）

(Production Example 2 of acyl compound)

The composition containing an acyl compound was carried out under the same conditions as in Production Example 1 except that 31.1 g of N-lauroyl-L-glutamic anhydride was changed to N-cocoyl-L-glutamic anhydride in Production Example 1. I got a thing.
(Acyl Compound Production Example 3)

In Production Example 1, the same conditions as in Production Example 1 except that 31.1 g of N-lauroyl-L-glutamic anhydride was changed to 39.5 g of N-stearoyl-L-glutamic anhydride and the reaction temperature was 20 ° C. To obtain a composition containing an acyl compound.
[Example 1]

75 parts by weight of glass powder (PbO—B ₂ O ₃ system, average particle diameter 5 μm), 20 parts by weight of terpineol, 10 parts by weight of ethyl cellulose, and 0.5 part by weight of the acyl compound of Production Example 1 are used as a dispersant. A glass paste composition was prepared by kneading with a roll mill. The evaluation results are shown in Table 1.
[Example 2]

In Example 1, it implemented on the same conditions as the method of Example 1 except the amount of ethyl cellulose having been 5 mass parts and the acyl compound of manufacture example 1 having been 5 mass parts of acyl compounds of manufacture example 2. The evaluation results are shown in Table 1.
[Example 3]

In Example 2, it implemented on the same conditions as Example 1 except the amount of ethyl cellulose having been 7 mass parts and the acyl compound of manufacture example 1 having been 2 mass parts of acyl compounds of manufacture example 3. The evaluation results are shown in Table 1.
[Comparative Example 1]

In Example 1, it implemented on the same conditions as Example 1 except not having added the acyl compound of manufacture example 1. FIG. The evaluation results are shown in Table 1.
[Comparative Example 2]

  In Example 1, it carried out on the same conditions as Example 1 except having made the acyl compound of a manufacture example into the polycarboxylic acid type surfactant (trademark "homogenol L-18"). The evaluation results are shown in Table 1.

Claims (4)

  A glass paste composition comprising one or more acyl compounds each having two or more acyl groups and hydrophilic groups in the molecule.   The glass paste composition according to claim 1, wherein at least one of the acyl compounds has an amino acid residue in the molecule. The glass paste composition according to claim 1, wherein at least one of the acyl compounds is a compound represented by the following general formula (1).

(In the above general formula (1), X is a linear, branched, cyclic or aromatic hydrocarbon chain having a molecular weight of 1,000,000 or less, which may have m functional groups and other substituents. N (m ≧ n) Q bonded to X are substituents represented by the following general formula (2), which may be the same as or different from each other. In (2), Z is a bond derived from a functional group of X, R ¹ CO represents an acyl group derived from a saturated or unsaturated fatty acid having 2 to 20 carbon atoms, and R ² represents hydrogen Or a lower alkyl group having 1 to 3 carbon atoms which may be substituted by a hydroxyl group or a carboxyl group, and Y represents a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group or a group thereof. Indicate salt, j, k They are either each independently 0, 1, 2, and j, k are not 0 at the same time .n represents an integer of 2 to 20.)

Furthermore, an organic binder and a solvent are included, The glass paste composition in any one of Claims 1-3 characterized by the above-mentioned.