CN102985453B - Calcining resin glue and manufacture method, paste composition and inorganic sintered body - Google Patents

Calcining resin glue and manufacture method, paste composition and inorganic sintered body Download PDF

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CN102985453B
CN102985453B CN201180030809.3A CN201180030809A CN102985453B CN 102985453 B CN102985453 B CN 102985453B CN 201180030809 A CN201180030809 A CN 201180030809A CN 102985453 B CN102985453 B CN 102985453B
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mass
monomer
composition
monomer mixture
resin glue
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CN102985453A (en
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佐藤阳
佐伯慎二
渡边富二男
藤田沙纪
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Mitsubishi Kasei Corp
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Mitsubishi Rayon Co Ltd
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Abstract

The present invention provides a kind of calcining resin glue, monomer mixture (A) copolymerization is obtained by it, described monomer mixture (A) (methyl) alkyl acrylate (A-1) containing 60～99.8 mass %, the compound (A-2) with more than 2 unsaturated double-bonds of the energy radical polymerization of 0.1～5 mass %, the water-soluble unsaturated monomer (A-3) of 0.1～30 mass %, and 0～39.8 other of mass % can the monomer (A-4) of copolymerization, wherein said water-soluble unsaturated monomer (A-3) is the monomer except the compound (A-2) with more than 2 unsaturated double-bonds except the radical polymerization of above-mentioned energy, the 15 mass % solution that described resin is dissolved in the above-mentioned resin obtained in terpineol meet the following conditions: η1/η10Less than 2.5, and η1/η5000It is more than 5.

Description

Calcining resin glue and manufacture method, paste composition and inorganic sintered body
Technical field
The present invention relates to the manufacture method of the calcining resin glue of use and the resin glue thus obtained and paste composition when the inorganic powders such as metal dust, metal oxide powder, fluorescent powder, glass dust (glassfrit) are carried out figuration.
The application is based on the May 6th, 2010 of the Patent 2010-106439 CLAIM OF PRIORITY in Japanese publication, and its content is incorporated herein.
Background technology
In the fields such as electronic material, the molded body that sometimes uses inorganic matter, the pattern (such as Wiring pattern, insulating pattern etc.) formed by this molded body. As the method forming such molded body, pattern, known following method: the inorganic powders such as metal dust, metal oxide powder, fluorescent powder, glass dust are mixed with resin glue, prepare paste composition, after forming the shape of regulation, pattern with this paste composition, calcine, by resin glue thermal cracking.
The resin glue now used plays the role that processability when improving processing and forming, will not bond inorganic powder in time moving in the way of damaging. This resin glue is removed by thermal cracking when making inorganic powder sinter before becoming final products, therefore it is required that thermal cracking is high, it is excellent respectively to add the workability in man-hour.
Processing method as paste composition, it is known that carry out the method for silk screen printing, utilize scraper etc. to be shaped to the method for lamellar, infusion process, dotting glue method (dispensemethod) etc.
Wherein, when applying silk screen print method, paste composition is more high in the thixotropy of high-shear region, and printing is more high. Additionally, levelability aspect after printing, the thixotropy in low sheraing region is more low more good. Therefore, when carrying out silk screen printing, as paste composition, it is desirable to thixotropy is low in low sheraing region at high-shear region height.
For this requirement, patent documentation 1 proposes a kind of resin glue, its be polymerization (methyl) alkyl acrylate, can the compound with more than 2 unsaturated double-bonds of radical polymerization and (methyl) acrylate containing hydroxyl.
In addition, patent documentation 2 proposes a kind of resin glue, its essential component is: alkyl methacrylate monomer 90～99 weight % at least of more than two kinds, at least one 0.1～5 weight % in unsaturated carboxylic acid monomer, (methyl) alkyl acrylate monomer containing amino, (methyl) alkyl acrylate monomer containing hydroxyl, and multi-functional (methyl) alkyl acrylate monomer 0.001～0.1 weight %.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2003-183331 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2004-217686 publication
Summary of the invention
But, even with the paste composition of the resin glue recorded in patent documentation 1, it is also difficult to make levelability all attain full and complete satisfaction with the printing in silk screen printing.
Additionally, the thixotropic of paste composition employing the resin glue recorded in patent documentation 2 presents less, it is unsuitable for silk screen printing.
The present invention makes in view of the foregoing, its object is to provide paste composition that the printing in levelability and silk screen printing is all excellent, for being readily derived the calcining resin glue of this paste composition and manufacture method thereof and the inorganic sintered body calcined this paste composition and obtain.
[1] a kind of calcining resin glue, is calcining resin glue monomer mixture (A) copolymerization obtained, and described monomer mixture (A) contains:
(methyl) alkyl acrylate (A-1) of 60～99.8 mass %,
The compound (A-2) with more than 2 unsaturated double-bonds of the energy radical polymerization of 0.1～5 mass %,
The water-soluble unsaturated monomer (A-3) of 0.1～30 mass % (but, be except described can monomer except the compound (A-2) with more than 2 unsaturated double-bonds of radical polymerization), and
The monomer (A-4) of other energy copolymerization of 0～39.8 mass %;
The 15 mass % solution that described resin is dissolved in the described resin obtained in terpineol meet the following conditions:
η1/η10Less than 2.5,
η1/η5000It is more than 5,
Wherein, η1、η10And η5000Use determination of viscoelasticity device (Anton-Paar company system, " PhyscaMCR300 "), cone angle be 0.5 °, flat board radius be 25mm, to measure temperature be 23 DEG C when the viscosity of resin solution that measures, η1Be shear rate be 1(1/s) time viscosity, η10Be shear rate be 10(1/s) time viscosity, η5000Be shear rate be 5000(1/s) time viscosity.
[2] a kind of calcining resin glue, the 2nd polymer obtained containing making monomer mixture (2) carry out radical polymerization under the 1st polymer existent condition, described 1st polymer makes monomer mixture (1) carry out radical polymerization and obtain;
Described monomer mixture (1) contains:
(methyl) alkyl acrylate (a-1) of 35～99.7 mass %,
The compound (a-2) with more than 2 unsaturated double-bonds of the energy radical polymerization of 0.3～5 mass %,
The water-soluble unsaturated monomer (a-3) of 0～40 mass % (but, be except described can monomer except the compound (a-2) with more than 2 unsaturated double-bonds of radical polymerization), and
Other monomer (a-4) of 0～64.7 mass %;
Described monomer mixture (2) contains:
(methyl) alkyl acrylate (b-1) of 35～99.9 mass %,
The compound (b-2) with more than 2 unsaturated double-bonds of the energy radical polymerization of 0～1 mass %,
The water-soluble unsaturated monomer (b-3) of 0.1～30 mass % (but, be except described can monomer except the compound (b-2) with more than 2 unsaturated double-bonds of radical polymerization), and
Other monomer (b-4) of 0～64.9 mass %.
[3] according to the resin described in [1] or [2], wherein, calcining resin glue is volume average particle size is the particle of less than 100 μm.
[4] a kind of paste composition, containing the calcining resin glue described in [1] or [2], inorganic powder and organic solvent.
[5] a kind of inorganic sintered body, is undertaken calcining by the paste composition described in [4] and obtain.
[6] a kind of manufacture method calcining use resin glue, including following operation:
1st polymerization process, makes monomer mixture (1) carry out radical polymerization and obtain the 1st polymer, and
2nd polymerization process, under described 1st polymer existent condition, makes monomer mixture (2) carry out radical polymerization and obtain the 2nd polymer;
Wherein, described monomer mixture (1) contains:
(methyl) alkyl acrylate (a-1) of 35～99.7 mass %,
The compound (a-2) with more than 2 unsaturated double-bonds of the energy radical polymerization of 0.3～5 mass %,
The water-soluble unsaturated monomer (a-3) of 0～40 mass % (but, be except described can monomer except the compound (a-2) with more than 2 unsaturated double-bonds of radical polymerization), and
Other monomer (a-4) of 0～64.7 mass %;
Described monomer mixture (2) contains:
(methyl) alkyl acrylate (b-1) of 35～99.9 mass %,
The compound (b-2) with more than 2 unsaturated double-bonds of the energy radical polymerization of 0～1 mass %,
The water-soluble unsaturated monomer (b-3) of 0.1～30 mass % (but, be except described can monomer except the compound (b-2) with more than 2 unsaturated double-bonds of radical polymerization), and
Other monomer (b-4) of 0～64.9 mass %.
If using the calcining resin glue of the present invention, then can be readily derived the paste composition that levelability is all excellent with the printing in silk screen printing.
Additionally, the manufacture method of the calcining resin glue according to the present invention, the calcining resin glue that can be readily derived the levelability paste composition all excellent with the printing in silk screen printing can be manufactured.
Additionally, the levelability of the paste composition of the present invention is all excellent with the printing in silk screen printing.
Detailed description of the invention
Hereinafter, the present invention is explained.
Should illustrating, in this manual, (methyl) acrylate represents acrylate and methacrylate, and (methyl) acrylic acid represents acrylic acid and methacrylic acid.
(calcining resin glue and manufacture method thereof)
Monomer mixture (A) copolymerization is manufactured by the calcining resin glue of the present invention, described monomer mixture (A) (methyl) alkyl acrylate (A-1) containing 60～99.8 mass % is (following, it is called " (A-1) composition "), the compound (A-2) with more than 2 unsaturated double-bonds of the energy radical polymerization of 0.1～5 mass % is (following, it is called " (A-2) composition "), the water-soluble unsaturated monomer (A-3) of 0.1～30 mass % is (following, it is called " (A-3) composition "), and 0～39.8 mass % other can the monomer (A-4) of copolymerization (following, it is called " (A-4) composition "). as preferred manufacture method, following methods can be enumerated.
A kind of manufacture method calcining use resin glue, including following operation:
1st polymerization process, makes monomer mixture (1) carry out radical polymerization and obtain the 1st polymer, and
2nd polymerization process, under above-mentioned 1st polymer existent condition, makes monomer mixture (2) carry out radical polymerization and obtain the 2nd polymer,
Wherein, described monomer mixture (1) (methyl) alkyl acrylate (a-1) containing 35～99.7 mass % is (following, it is called " (a-1) composition "), the compound (a-2) with more than 2 unsaturated double-bonds of the energy radical polymerization of 0.3～5 mass % is (following, it is called " (a-2) composition "), the water-soluble unsaturated monomer (a-3) of 0～40 mass % (but, it is the monomer except the compound (a-2) with more than 2 unsaturated double-bonds except the radical polymerization of above-mentioned energy) (following, it is called " (a-3) composition "), and 0～64.7 other monomer (a-4) of mass % (following, it is called " (a-4) composition "),
Described monomer mixture (2) (methyl) alkyl acrylate (b-1) containing 35～99.9 mass % is (following, it is called " (b-1) composition "), the compound (b-2) with more than 2 unsaturated double-bonds of the energy radical polymerization of 0～1 mass % is (following, it is called " (b-2) composition "), the water-soluble unsaturated monomer (b-3) of 0.1～30 mass % (but, it is the monomer except the compound (b-2) with more than 2 unsaturated double-bonds except the radical polymerization of above-mentioned energy) (following, it is called " (b-3) composition "), and 0～64.9 other monomer (b-4) of mass % (following, it is called " (b-4) composition ").
<monomer mixture (A)>
Monomer mixture (A) is containing (A-1) composition, (A-2) composition and (A-3) composition.
(A-1) composition is (methyl) alkyl acrylate. As (A-1) composition, the carbon number of preferred alkyl is (methyl) alkyl acrylate of 1～8, specifically, (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) butyl acrylate can be enumerated, single (methyl) acrylate such as (methyl) 2-EHA etc. (A-1) composition can be used alone a kind, it is possible to and use two or more.
The quality ratio of (A-1) composition in monomer mixture (A) is 60～99.8 mass % when monomer mixture (A) is set to 100 mass %. It is 60～99.8 mass % by the ratio of (A-1) composition, excellent calcining can be given to obtained calcining resin glue, calcined materials can be suitable as. (A-1) lower limit of the ratio of composition preferably more than 65 mass %, more preferably more than 70 mass %.
(A-2) composition is the compound with more than 2 unsaturated double-bonds of energy radical polymerization. as (A-2) composition, such as can enumerate two (methyl) acrylic acid glycol ester, two (methyl) polyalkylene glycol acrylate ester, two (methyl) acrylic acid 1, 3-butanediol ester, two (methyl) acrylic acid 1, 4-butanediol ester, two (methyl) acrylic acid 1, 6-hexanediol ester, two (methyl) acrylic acid DOPCP, 3-hydroxypivalic acid neopentyl glycol two (methyl) acrylate, two (methyl) acrylic acid polypropylene glycol ester, two (methyl) acrylic acid polybutadiene alcohol ester, trimethylolpropane tris (methyl) acrylate, ethoxylated trimethylolpropane three (methyl) acrylate, propoxylation trimethylolpropane tris (methyl) acrylate, glycerol three (methyl) acrylate, ethoxylated glycerol three (methyl) acrylate, dipentaerythritol six (methyl) acrylate. these compounds due to the balancing good of viscosity-increasing effect Yu thermal cracking, even and if become high viscosity also be difficult to occur wire drawing, therefore particularly preferably. (A-2) composition can be used alone a kind, it is possible to and use two or more.
The quality ratio of (A-2) composition in monomer mixture (A) is 0.1～5 mass % when monomer mixture (A) is set to 100 mass %. It is 0.1～5 mass % by the ratio of (A-2) composition, thus the viscosity of the paste composition containing obtained calcining resin glue can be made to improve and improve printing, additionally, calcined materials can be suitable as.
(A-2) lower limit of the ratio of composition preferably more than 0.5 mass %. If (A-2) ratio of composition is more than 0.5 mass %, then viscosity-increasing effect improves with the balance of thermal cracking, and can give the printing in the silk screen printing of excellence. On the other hand, from deliquescent aspect in organic solvent, the higher limit of the ratio of (A-2) composition preferably below 3 mass %.
(A-3) composition is the water-soluble unsaturated monomer except (A-2) composition. As (A-3) composition, can enumerate and there is unsaturated bond and the dissolubility in water is the compound of more than 10%, specifically, (methyl) acrylic acid, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) Hydroxypropyl acrylate, acrylic acid 4-hydroxy butyl ester, acrylamide, maleic acid, fumaric acid etc. can be enumerated. (A-3) composition can be used alone a kind, it is possible to and use two or more.
The quality ratio of (A-3) composition in monomer mixture (A) is 0.1～30 mass % when monomer mixture (A) is set to 100 mass %. It is more than 0.1 mass % by the ratio of (A-3) composition, thus the viscosity of the paste composition containing obtained calcining resin glue can be made to improve and improve printing, and the levelability of excellence can be given. Additionally, when making paste composition, the dispersion stabilization of inorganic powder can be made to improve. It is below 30 mass % by the ratio of (A-3) composition, the calcining of calcining resin glue can be made to improve.
In monomer mixture (A), except above-mentioned (A-1) composition, (A-2) composition and (A-3) composition, also can contain (A-4) composition.
As (A-4) composition, for instance styrene, α-methyl styrene, acrylonitrile, diethylaminoethyl methacrylate, vinyl acetate etc. can be enumerated. The kind of these free radical polymerization monomers suitably can select according to the kind of the inorganic powder being coupled in calcining resin glue, organic solvent etc.
The quality ratio of (A-4) composition in monomer mixture (A) is 0～39.8 mass % when monomer mixture (A) is set to 100 mass %, it is preferred to below 30 mass %. Particularly, by being set to below 30 mass %, efficiency calcining resin glue can be manufactured well. (A-4) ratio of composition more preferably below 20 mass %.
<monomer mixture (1)>
Monomer mixture (1) is containing (a-1) composition and (a-2) composition.
(a-1) composition is (methyl) alkyl acrylate, identical with above-mentioned (A-1) composition. (a-1) quality ratio of composition is 35～99.7 mass % when monomer mixture (1) is set to 100 mass %. It is 35～99.7 mass % by the ratio of (a-1) composition, excellent calcining can be given to obtained calcining resin glue, calcined materials can be suitable as. (a-1) lower limit of the ratio of composition preferably more than 50 mass %, more preferably more than 70 mass %.
(a-2) composition is the compound with more than 2 unsaturated double-bonds of energy radical polymerization, identical with above-mentioned (A-2) composition. (a-2) quality ratio of composition is 0.3～5 mass % when monomer mixture (1) is set to 100 mass %. It is 0.3～5 mass % by the ratio of (a-2) composition, the viscosity of the paste composition containing obtained calcining resin glue can be made to improve and improve printing, additionally, calcined materials can be suitable as. (a-2) lower limit of the ratio of composition preferably more than 0.5 mass %. Being more than 0.5 mass % by the ratio of (a-2) composition, the balance of viscosity-increasing effect and thermal cracking improves, and can give the printing of excellence in silk screen printing. On the other hand, from deliquescent aspect in organic solvent, the higher limit of the ratio of (a-2) composition preferably below 3 mass %.
Monomer mixture (1) can contain (a-3) composition. (a-3) composition is water-soluble unsaturated monomer, identical with above-mentioned (A-3) composition. (a-3) quality ratio of composition is 0～40 mass % when monomer mixture (1) is set to 100 mass %. (a-3) higher limit of composition preferably below 30 mass %. This is because, by being set to below 30 mass %, the calcining of calcining resin glue can be improved.
In monomer mixture (1), except above-mentioned (a-1) composition, (a-2) composition and (a-3) composition, also can contain (a-4) composition.(a-4) composition is identical with above-mentioned (A-4) composition. (a-4) quality ratio of composition is 0～64.7 mass % when monomer mixture (1) is set to 100 mass %, it is preferred to below 40 mass %. This is because, by being set to below 40 mass %, efficiency calcining resin glue can be manufactured well. (a-4) ratio of composition more preferably below 30 mass %.
<monomer mixture (2)>
Monomer mixture (2) is containing (b-1) composition and (b-3) composition.
(b-1) composition is (methyl) alkyl acrylate, identical with above-mentioned (A-1) composition. As (b-1) composition, it is preferably (methyl) alkyl acrylate with the alkyl that atomic number of alkyl carbon is 2～8, specifically, (methyl) esters of acrylic acids such as (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) cyclohexyl acrylate can be enumerated. (methyl) alkyl acrylate with the alkyl that atomic number of alkyl carbon is 2～8 can be preferably used the calcining resin glue of favorable solubility in organic solvent. (b-1) composition and (a-1) composition can be identical, it is also possible to different. (b-1) composition can be used alone a kind, it is possible to and use two or more.
The quality ratio of (b-1) composition in monomer mixture (2) is 35～99.9 mass % when monomer mixture (2) is set to 100 mass %. Being 35～99.9 mass % by the ratio of (b-1) composition, obtained calcining resin glue is swelling in organic solvent, it is possible to present good printing. (b-1) lower limit of the ratio of composition preferably more than 50 mass %, more preferably more than 70 mass %.
Monomer mixture (2) can contain (b-2) composition. (b-2) composition is the compound with more than 2 unsaturated double-bonds of energy radical polymerization, identical with above-mentioned (A-2) composition. (b-2) composition and (a-2) composition can be identical, it is also possible to different. (b-2) quality ratio of composition is 0～1 mass % when monomer mixture (2) is set to 100 mass %. This is because, by being set to below 1 mass %, obtained calcining resin glue swellbility in organic solvent becomes big, and printing is prone to present. Quality ratio preferably below the 0.5 mass % of (b-2) composition in monomer mixture (2).
(b-3) composition is water-soluble unsaturated monomer, identical with above-mentioned (A-3) composition. (b-3) composition and (a-3) composition can be identical, it is also possible to different. (b-3) composition can be used alone a kind, it is possible to and use two or more.
The quality ratio of (b-3) composition in monomer mixture (2) is 0.1～30 mass % when monomer mixture (2) is set to 100 mass %. It is more than 0.1 mass % by the ratio of (b-3) composition, the viscosity of the paste composition containing obtained calcining resin glue can be made to improve and improve printing, and the levelability of excellence can be given. Additionally, when making paste composition, the dispersion stabilization of inorganic powder can be made to improve. Additionally, be below 30 mass % by the ratio of (b-3) composition, the calcining of calcining resin glue can be made to improve.
In monomer mixture (2), also can contain (b-4) composition except above-mentioned (b-1) composition, (b-2) composition and (b-3) composition. (b-4) composition is identical with above-mentioned (A-4) composition. (b-4) composition and (a-4) composition can be identical, it is also possible to different.(b-4) quality ratio of composition is 0～64.9 mass when monomer mixture (2) is set to 100 mass %, it is preferred to below 30 mass %. This is because, by being set to below 30 mass %, efficiency calcining resin glue can be manufactured well.
The manufacture method of the calcining resin glue of the present invention can radical polymerization is incompatible to be manufactured by making monomer mixture (2) carry out under the polymer existent condition making monomer mixture (1) carry out radical polymerization and to obtain.
The quality ratio of monomer mixture (1) is preferably 20～80 mass % when total monomer mixture is set to 100 mass %. Being 20～80 mass % by the ratio of monomer mixture (1), present the thixotropy of paste composition, printing becomes good.
On the other hand, the quality ratio of monomer mixture (2) is when being set to 100 mass % by total monomer mixture, it is preferred to 20～80 mass %. Being 20～80 mass % by the ratio of monomer mixture (2), the viscosity of paste composition becomes appropriateness, can prevent sagging etc.
Should illustrate, in the present invention, when manufacturing calcining resin glue, make the operation that other monomer mixture (0) beyond demonomerization mixture (1), (2) carries out radical polymerization before making monomer mixture (1) carry out the 1st polymerization process of radical polymerization and/or make monomer mixture (2) carry out after carrying out the 2nd polymerization process of radical polymerization, or can carry out between these operations. Should illustrating, before making monomer mixture (1) carry out radical polymerization so that it is when its monomer mixture (0) carries out radical polymerization, the polymer of other monomer mixture (0) plays the effect of seed particles (seedparticle).
Other monomer mixture (0) contains the one kind or two or more monomer of energy radical polymerization, its kind is not particularly limited, but the timing control according to other monomer mixture (0), it is preferable that containing at least one in above-mentioned (a-1)～(a-4), (b-1)～(b-4) composition. Additionally, other monomer mixture (0) can be the composition identical with monomer mixture (1) or (2), it is also possible to be different compositions.
The quality ratio of other monomer mixture (0) is preferably smaller than 50 mass % when total monomer mixture is set to 100 mass %. This is because, by being set to, less than 50 mass %, can easily control the particle diameter of obtained calcining resin glue. The higher limit of the ratio of other monomer mixture (0) is more preferably less than 30 mass %. Particularly, when making other monomer mixture (0) only first be polymerized than monomer mixture (1), the ratio of other monomer mixing (0) is preferably smaller than 20 mass %.
Polymerization when carrying out radical polymerization as making each monomer mixture, the known methods such as suspension polymerization, emulsion polymerization method, solution polymerization process can be enumerated, wherein, from the view point of the particle diameter of easily controllable obtained calcining resin glue, it is preferable that emulsion polymerization method.
For emulsion polymerization method, specifically, water adds monomer mixture (1) and emulsifying agent and polymerization initiator, is heated and is polymerized. Then, this reaction system is added monomer mixture (2) to be polymerized.
As emulsifying agent, for instance anionic emulsifier (dodecylbenzene sodium sulfonate, dodecyl sodium sulfate, sodium lauryl sulfate etc.) can be used, containing the reactive emulsifier etc. in the anionic emulsifier of polyoxyethylene groups, non-ionic emulsifier (ethylene nonyl phenyl ether, polyoxyethylene lauryl ether etc.), molecule with vinyl polymerized double bond.
As polymerization initiator, for instance the peroxide such as benzoyl peroxide, hydrogen phosphide cumene, hydrogen peroxide can be used; The azo-compounds such as azodiisobutyronitrile; The persulfate compounds such as Ammonium persulfate., potassium peroxydisulfate; The oxidoreduction series initiators etc. formed by the combination crossing chloric acid compound, perboric acid compound or peroxide and reproducibility sulfenyl comcoune.
Additionally, in emulsion polymerization, as chain-transferring agent, the thio-alcohols etc. such as n-dodecyl mercaptan, tertiary lauryl mercaptan, n octylmercaptan, n-tetradecane base mercaptan, n-hexyl mercaptan can be used.
When carrying out emulsion polymerization, it is preferred to use seeding polymerization, i.e. a small amount of other monomer mixture (0) is polymerized in the lump and makes seed particles, then by monomer mixture dropping polymerization. This is because, by using seeding polymerization, it is easier to control the particle diameter of obtained calcining resin glue. When making seed particles, the quality ratio of other monomer mixture (0) is preferably 1～10 mass % when total monomer mixture is set to 100 mass %.
Should illustrate, when forming seed particles, a part for monomer mixture (1) can be used to be used as other monomer mixture (0).
The calcining resin glue like this obtained, its particle diameter becomes more little, and dissolubility in organic solvent is more high. Therefore, the volume average particle size of calcining resin glue is preferably less than 100 μm, more preferably less than 50 μm. More preferably less than 5 μm. If the volume average particle size of calcining resin glue is less than 100 μm, then can fully improve calcining resin glue dissolubility in organic solvent.
At this, volume average particle size is the value measured with light scattering photometer. Should illustrate, 1 particle diameter when the particle diameter in the present invention is to utilize radical polymerization to manufacture, different from 2 particle diameters of particle diameter when carrying out granulating etc. after radical polymerization.
The present inventor etc. have investigated, and result specify that by using the calcining resin glue obtained by the present invention, can be readily derived the paste composition that levelability is all excellent with the printing in silk screen printing. Consider this be due to, monomer mixture (2) is made to carry out the incompatible manufacture calcining resin glue of radical polymerization as described above under the polymer existent condition of monomer mixture (1), thus the thixotropy development brought by structural viscosity improves with the mobility in paste.
Consider that the calcining resin glue obtained by above-mentioned manufacture method has following nucleocapsid structure: so that the polymer that monomer mixture (1) carries out radical polymerization and obtains is as core, so that the polymer that monomer mixture (2) carries out radical polymerization and obtains is as shell, estimates this structure and contribute to thixotropy and mobility.
The calcining resin glue of the present invention is preferably dissolved in 15 mass % solution of the above-mentioned resin obtained in terpineol and meets the following conditions.
η1/η10Less than 2.5
η1/η5000It is more than 5
This, η1、η10And η5000Use determination of viscoelasticity device (Anton-Paar company system, " PhyscaMCR300 "), cone angle be 0.5 °, flat board radius be 25mm, measure temperature 23 DEG C when the viscosity of resin solution that measures, η1For shear rate 1(1/s) time viscosity, η10For shear rate 10(1/s) time viscosity, η5000For shear rate 5000(1/s) time viscosity. Should illustrate, the mixture that terpineol is alpha-terpineol, β-terpineol and γ-terpineol used during viscosimetric analysis, for " terpineol (trade name) " of spice medicine Co., Ltd. of Japan.
(paste composition)
The paste composition of the present invention contains above-mentioned calcining resin glue, inorganic powder and organic solvent.
Additionally, paste composition can contain plasticizer, dispersing aid, defoamer etc. as required.
As long as inorganic powder is dispersed in the inorganic powder in calcining resin glue, just it is not particularly limited.
Concrete example as inorganic powder, for instance the oxides such as aluminium oxide, zirconium oxide, titanium oxide, Barium metatitanate. can be enumerated; The nitride such as aluminum oxynitride, silicon nitride, boron nitride; The metals such as copper, silver, nickel; The silica-based powder body such as glass powder with low melting point; Various fluorophor etc.
Calcining resin glue is different and different according to the proportion of inorganic powder from the preferred mass ratio of inorganic powder, but such as preferably with respect to inorganic powder 100 mass parts, the solid constituent of calcining resin glue is 3～30 mass parts. If the solid constituent of calcining resin glue is more than 3 mass parts, then easily by inorganic powder molding, if below 30 mass parts, then can reliably obtain target molded body, pattern after firing.
Organic solvent uses the organic solvent that can dissolve calcining resin glue.
As organic solvent, it is preferable that boiling point is more than 100 DEG C, more preferably boiling point is more than 120 DEG C. If boiling point is more than 100 DEG C, then organic solvent is difficult to evaporate, therefore obtained paste composition printing or coating time workability good. Should illustrating, in the present invention, " boiling point " is the boiling point under 1 air pressure (1013hPa).
As the organic solvent that boiling point is more than 100 DEG C, such as can enumerate α, β, γ-terpineol, propylene glycol monomethyl ether, ethyl-3-ethoxy-c acid esters, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetic acid ester, ethylene glycol monobutyl ether acetas, TC, TC acetas, diethylene glycol monobutyl ether acetas, 2, 2, 4-trimethyl-1, 3-pentanediol list isobutyl ester, isophorone, 3-methoxybutyl acetas, benzylalcohol, 1-capryl alcohol, 1 nonyl alcohol, 2-ethyl-1-hexanol, 1-decanol, 1-undecyl alcohol, 1, 2-ethylene glycol, 1, 2-propylene glycol, 1, ammediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, toluene, dimethyl sulfoxide, dimethylformamide, dimethyl acetylamide, N-Methyl pyrrolidone etc. organic solvent can be used alone a kind, it is possible to and use two or more.
In above-mentioned organic solvent, from dissolubility excellence aspect, it is preferable that α, beta, gamma-terpineol, propylene glycol monomethyl ether.
In order to make silk screen printing, dip coated become possible to, in order to improve the viscosity of paste composition, it is preferable that contain the α of more than 50 mass %, beta, gamma-terpineol in organic solvent, more preferably contain more than 70 mass %.
The content of the organic solvent in paste composition is preferably in being 5～70 mass % when paste composition is set to 100 mass %. If the content of organic solvent is more than 5 mass %, then can give mobility to paste, if below 70 mass %, then present high printing.
Aforesaid paste compositions is due to the calcining resin glue containing the present invention, and therefore levelability is all excellent with the printing in silk screen printing.
This paste composition printing in silk screen printing is excellent, when therefore forming pattern on base material, it is preferable that application silk screen printing, but also can apply the method except silk screen printing. When paste composition viscosity is high, Dipcoat method, some glue rubbing method can be applied, when viscosity is low, scraper for coating method, cast coating method can be applied.
Base material as printing or coating paste composition, for instance ceramic substrate, capacitor etc. can be enumerated.
(inorganic sintered body)
The inorganic sintered body of the present invention is the inorganic sintered body that calcining aforesaid paste compositions obtains. As method for calcinating, can enumerate printing or be coated with the base material configuration of aforesaid paste compositions method in high temperature environments, but being not limited to this. In calcination process, the organic substance comprising calcining resin glue contained by paste composition is decomposed and removed, and inorganic powder is melted, sintering, thus obtaining inorganic sintered body. As calcining heat, can suitably determine according to the kind of organic substance contained in the melt temperature of substrate, inorganic powder, paste composition etc., be generally 200～1500 DEG C, it is preferred to 300～1000 DEG C.
Embodiment
Hereinafter, for the present invention, embodiment and comparative example is utilized to illustrate. Should illustrating, " part " in following example refers to " mass parts ", and " % " refers to " quality % ".
Mensuration and the manufacture method of evaluation methodology and calcining resin glue in following example are as described below.
<measuring and evaluation methodology>
(mensuration of volume average particle size)
The volume average particle size of the particle of calcining resin glue is measured with light scattering photometer (big Electronics Co., Ltd system, " FPAR-1000 type ").
(evaluation of levelability)
With determination of viscoelasticity device (Anton-Paar company system, " PhyscaMCR300 ") cone angle be 0.5 °, flat board radius be 25mm, measure temperature 23 DEG C when measure the viscosity of calcining resin glue solution. Obtain shear rate 1(1/s) time viscosity be set to η1, shear rate 10(1/s) time viscosity be set to η10Time η1/η10Value. Then, levelability is evaluated according to following metewand. Should illustrate, η1/η10Being worth more little, levelability is more excellent.
◎: η1/η10Less than 2.0.
Zero: η1/η10It is 2.0 less than 2.5.
×: η1/η10It is more than 2.5.
(evaluation of printing)
Measure viscosity in the same manner as the evaluation of levelability, obtain shear rate 1(1/s) time viscosity be set to η1, shear rate 5000(1/s) time viscosity be set to η5000Time η1/η5000Value. Then, printing is evaluated according to following metewand. Should illustrate, η1/η5000Being worth more big, printing is more excellent.
◎: η1/η5000It is more than 10.
Zero: η1/η5000It is 5 less than 10.
×: η1/η5000Less than 5.
(evaluation of thermal weight loss rate)
Use differential thermobalance TG-DTA(Co., Ltd. Rigaku system, trade name: ThermoplusEVO), obtain according to the following formula by measure 5mg sample in atmosphere with the speed of 15 DEG C/min from (starting temperature) 30 DEG C be warmed up to 500 DEG C time 450 DEG C thermal weight loss rate (%).
Thermal weight loss rate (%)=(quality (mg) of sampling quality (mg)-residue)/sampling quality (mg)
<manufacture method of calcining resin glue>
(manufacturing example 1～9)
In the polyplant that can heat and cool down, add 100 parts of water, as the dialkyl sodium sulfosuccinate (Kao Corp's system, " PelexOTP ") of the amount of Table 1 of emulsifying agent and the potassium peroxydisulfate 0.05 part as polymerization initiator. And then, in this polyplant, add isobutyl methacrylate 4 parts, in nitrogen environment, heat 0.5 hour at 80 DEG C while stir limit with the rotating speed of 150rpm, so as to be polymerized, obtain the emulsion containing seed particles.
Contain in the emulsion of seed particles at this, using deionized water 25 parts, as dialkyl sodium sulfosuccinate (Kao Corp's system of emulsifying agent, " PelexOTP ") monomer mixture (1) 48 part of quality ratio (coordinating composition) shown in 1 part and table 1,2 carries out emulsifying, after 2 hours drip, heat 0.5 hour at 80 DEG C, so as to be polymerized.
Then, using deionized water 25 parts, as dialkyl sodium sulfosuccinate (Kao Corp's system of emulsifying agent, " PelexOTP ") monomer mixture (2) 48 parts of quality ratio shown in 1 part and table 1,2 carries out emulsifying, after 2 hours are added drop-wise in reaction solution, keep 1 hour at 80 DEG C, obtain the emulsion of calcining resin glue.
By emulsion spray-drying installation (Ohkawara Kakohki Co., Ltd.'s system of obtained calcining resin glue, " L-8 type ") carry out spray drying when chamber ingress temperature 150 DEG C, chamber outlet temperature 55 DEG C, atomizer rotational speed 20000rpm, obtain the particle (A1～A9) of calcining resin glue.
The measurement result of the volume average particle size of obtained calcining resin glue is shown in Table 1.
(manufacturing example 10)
Operate in the same manner as manufacturing example 1～9, the preparation emulsion containing seed particles.
In the emulsion containing this seed particles, using deionized water 15 parts, as dialkyl sodium sulfosuccinate (Kao Corp's system of emulsifying agent, " PelexOTP ") monomer mixture (1) 30 part of quality ratio shown in 0.5 part and table 2 carries out emulsifying, after 1.5 hours drip, heat 0.5 hour at 80 DEG C, so as to be polymerized.
Then, using deionized water 35 parts, as dialkyl sodium sulfosuccinate (Kao Corp's system of emulsifying agent, " PelexOTP ") monomer mixture (2) 66 parts of quality ratio shown in 1.5 parts and table 2 carries out emulsifying, it was added drop-wise in reaction solution through 2.5 hours, keep 1 hour at 80 DEG C, obtain the emulsion of calcining resin glue.
The emulsion of obtained calcining resin glue is carried out spray drying in the same manner as manufacturing example 1～9, obtains calcining resin glue (A10).
The measurement result of the volume average particle size of obtained calcining resin glue is shown in Table 1.
(manufacturing example 11)
In the polyplant that can heat and cool down, put into 100 parts of water and the potassium peroxydisulfate 0.05 part as polymerization initiator. In nitrogen environment, while stir with the rotating speed of 150rpm, while be heated to 80 DEG C.
At this, using deionized water 35 parts, as dialkyl sodium sulfosuccinate (Kao Corp's system of emulsifying agent, " PelexOTP ") monomer mixture (1) 75 part of quality ratio shown in 1.5 parts and table 2 carries out emulsifying, after 2.5 hours drip, heat 0.5 hour at 80 DEG C, so as to be polymerized.
Then, using deionized water 15 parts, as dialkyl sodium sulfosuccinate (Kao Corp's system of emulsifying agent, " PelexOTP ") monomer mixture (2) 25 parts of quality ratio shown in 0.5 part and table 2 carries out emulsifying, after 1.5 hours are added drop-wise in reaction solution, keep 1 hour at 80 DEG C, obtain the emulsion of calcining resin glue.
The emulsion of obtained calcining resin glue is carried out spray drying in the same manner as manufacturing example 1～9, obtains calcining resin glue (A11).
The measurement result of the volume average particle size of obtained calcining resin glue is shown in Table 1.
(comparing manufacture example 1)
2L(liter heating up, cool down) four-hole boiling flask in, put into make polyvinyl alcohol 7.5 parts be dissolved in pure water 1000 parts the solution obtained. At this, put into further containing isobutyl methacrylate 225 parts, 2-Ethylhexyl Methacrylate 269.75 parts, methacrylic acid 5 parts, dipentaerythritol acrylate (Nippon Kayaku K. K's system, " KAYARADDPHA ") monomer mixture (1) of the 0.25 part lauroyl peroxide with 2.5 parts, it is stirred vigorously with 300rpm, form suspended state, it is warming up to 80 DEG C, so as to react 5 hours, terminates polymerization.
Obtained float is carried out, dehydration, dry, obtain calcining resin glue (A12).
When monomer mixture (1) is set to 100 mass %, the measurement result of the mean diameter of the quality ratio of each monomer component and obtained calcining resin glue is shown in Table 2.
(comparing manufacture example 2)
In the polyplant that can heat and cool down, put into 100 parts of water, as the dialkyl sodium sulfosuccinate (Kao Corp's system, " PelexOTP ") of the amount of Table 2 of emulsifying agent and the potassium peroxydisulfate 0.05 part as polymerization initiator. And then, in this polyplant, adding methyl methacrylate 2 parts and isobutyl methacrylate 2 parts, in nitrogen environment, stir with the rotating speed of 150rpm, while heating 0.5 hour at 80 DEG C, so as to be polymerized, obtaining the emulsion containing seed particles.
Contain in the emulsion of seed particles at this, using deionized water 50 parts, as dialkyl sodium sulfosuccinate (Kao Corp's system of emulsifying agent, " PelexOTP ") monomer mixture (1) 96 part of quality ratio (coordinating composition) shown in 2 parts and table 2 carries out emulsifying, after 4 hours drip, heat 1 hour at 80 DEG C, obtain the emulsion of calcining resin glue.
By emulsion spray-drying installation (Ohkawara Kakohki Co., Ltd.'s system of obtained calcining resin glue, " L-8 type ") carry out spray drying when chamber ingress temperature 150 DEG C, chamber outlet temperature 55 DEG C, atomizer rotational speed 20000rpm, obtain calcining resin glue (A13).
The measurement result of the volume average particle size of obtained calcining resin glue is shown in Table 2.
[embodiment 1～11, comparative example 1～2]
The calcining of kind shown in table 1 and 2 is put in the there-necked flask of 2L with resin glue (A1～A13) 150 parts, and then, this there-necked flask puts into terpineol (α-, β-, the mixture of γ-terpineol, Japan's spice medicine Co., Ltd.'s system (trade name)) 850 parts. Then, it is warming up to 80 DEG C, so as to dissolve dissolving in 3 hours, obtains calcining resin glue solution.
For obtained calcining resin glue solution, carry out the evaluation of levelability and printing. The results are shown in table 1.
[embodiment 12,13]
Calcining resin glue A1 and A4 is carried out the evaluation of thermal weight loss rate. The results are shown in table 3.
[reference example]
For ethyl cellulose (Nisshin Kasei Co. Ltd's system, trade name: STD100), carry out the evaluation of thermal weight loss rate. The results are shown in table 3.
[table 2]
[table 3]
Resin glue A1 is used in calcining Resin glue A4 is used in calcining Ethyl cellulose
Thermal weight loss rate (%) 98.5 97.8 92.0
Symbol in table 1,2 is as described below. Should illustrate, the quality ratio when amount of each monomer is that monomer mixture (0)～(2) are set to 100 mass % respectively in monomer mixture (0)～(2) shown in table 1,2. Additionally, the seed (0) in table 1,2 represents the implication identical with other monomer mixture (0).
IBMA: isobutyl methacrylate
NBMA: n-BMA
MMA: methyl methacrylate
EHMA: 2-Ethylhexyl Methacrylate
EDMA: Ethylene glycol dimethacrylate
DPHA: dipentaerythritol acrylate
HEMA: 2-hydroxyethyl methacrylate
MAA: methacrylic acid
AA: acrylic acid
By table 1,2 it can be seen that the calcining resin glue solution obtained in each embodiment to be all levelability all good with printing.
Additionally, as shown in Table 3, calcining is more excellent than the thermal cracking of ethyl cellulose with resin glue A1 and A4.
Industrial applicability
The calcining resin glue of the present invention is useful as the composition of levelability with all paste compositions of excellence of the printing in silk screen printing. Additionally, manufacturing method according to the invention, owing to such calcining resin glue can be readily derived, therefore it is useful.

Claims (5)

1. a resin glue solution is used in calcining, and containing resin and organic solvent, monomer mixture (A) copolymerization is obtained by described resin, and described monomer mixture (A) contains:
(methyl) alkyl acrylate (A-1) of 60～99.8 mass %,
The compound (A-2) with more than 2 unsaturated double-bonds of the energy radical polymerization of 0.1～5 mass %,
The water-soluble unsaturated monomer (A-3) of 0.1～30 mass %, it is the monomer except the compound (A-2) with more than 2 unsaturated double-bonds except the radical polymerization of described energy, and
The monomer (A-4) of other energy copolymerization of 0～39.8 mass %;
Described organic solvent contains terpineol;
The 15 mass % solution that described resin is dissolved in the described resin obtained in terpineol meet the following conditions:
η1/η10Less than 2.5,
η1/η5000It is more than 5,
Wherein, η1、η10And η5000Use determination of viscoelasticity device, cone angle be 0.5 °, flat board radius be 25mm, to measure temperature be 23 DEG C when the viscosity of resin solution that measures, η1Be shear rate it is viscosity when 1, η10Be shear rate it is viscosity when 10, η5000Be shear rate being viscosity when 5000, described determination of viscoelasticity device is the device that model is " PhyscaMCR300 " that Anton-Paar company manufactures, and the unit of described shear rate is 1/s.
2. resin glue solution is used in a calcining, containing resin and organic solvent, described resin contains the 2nd polymer making monomer mixture (2) carry out radical polymerization under the 1st polymer existent condition and to obtain, described 1st polymer makes monomer mixture (1) carry out radical polymerization and obtain
Described monomer mixture (1) contains:
(methyl) alkyl acrylate (a-1) of 50～99.7 mass %,
The compound (a-2) with more than 2 unsaturated double-bonds of the energy radical polymerization of 0.5～5 mass %,
The water-soluble unsaturated monomer (a-3) of 0～40 mass %, it is the monomer except the compound (a-2) with more than 2 unsaturated double-bonds except the radical polymerization of described energy, and
Other monomer (a-4) of 0～64.7 mass %,
Described monomer mixture (2) contains:
(methyl) alkyl acrylate (b-1) of 35～99.9 mass %,
The compound (b-2) with more than 2 unsaturated double-bonds of the energy radical polymerization of 0～1 mass %,
The water-soluble unsaturated monomer (b-3) of 0.1～30 mass %, it is the monomer except the compound (b-2) with more than 2 unsaturated double-bonds except the radical polymerization of described energy, and
Other monomer (b-4) of 0～64.9 mass %;
Described organic solvent contains terpineol.
3. calcining resin glue solution according to claim 1 and 2, wherein, described resin is volume average particle size is the particle of less than 100 μm.
4. a paste composition, containing the calcining described in claim 1 or 2 with resin glue solution and inorganic powder.
5. an inorganic sintered body, is undertaken calcining by the paste composition described in claim 4 and obtain.
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