WO2012128028A1 - 金属ペースト組成物 - Google Patents
金属ペースト組成物 Download PDFInfo
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- WO2012128028A1 WO2012128028A1 PCT/JP2012/055706 JP2012055706W WO2012128028A1 WO 2012128028 A1 WO2012128028 A1 WO 2012128028A1 JP 2012055706 W JP2012055706 W JP 2012055706W WO 2012128028 A1 WO2012128028 A1 WO 2012128028A1
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- Prior art keywords
- paste composition
- metal paste
- metal
- mass
- parts
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/109—Esters; Ether-esters of carbonic acid, e.g. R-O-C(=O)-O-R
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
- H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
Definitions
- the present invention relates to a metal paste composition.
- a wiring board is manufactured by creating a wiring pattern using a metal paste composition on an insulating substrate and baking it at a high temperature.
- Various studies have been made on the metal paste composition.
- a metal paste composition in which ethyl cellulose is blended with metal see Patent Document 1
- a metal paste in which an acrylic resin is blended with metal see Patent Document 2
- the metal paste composition described in the prior art document has a problem that the fired body (wiring) after firing has a high volume resistivity.
- the objective of this invention is providing the metal paste composition from which the sintered body of a low volume resistivity is obtained in the wiring board after baking.
- the present invention relates to a metal paste composition as shown below. That is, Item 1. A metal paste composition comprising a metal, an aliphatic polycarbonate, and an organic solvent; Item 2. Item 2. The metal paste composition according to Item 1, wherein the aliphatic polycarbonate is an aliphatic polycarbonate obtained by polymerizing epoxide and carbon dioxide. Item 3. Item 3. The metal paste composition according to Item 1 or 2, wherein the aliphatic polycarbonate is at least one selected from the group consisting of polyethylene carbonate and polypropylene carbonate, Item 4. Item 4.
- Item 5. The metal paste composition according to any one of Items 1 to 4, wherein the metal is at least one selected from the group consisting of gold, silver, platinum, and alloys thereof.
- Item 6. Item 6.
- the metal paste composition according to the present invention is a metal paste composition containing a metal, an aliphatic polycarbonate, and an organic solvent.
- the metal used in the metal paste composition according to the present invention is not particularly limited, and examples thereof include gold, silver, copper, nickel, platinum, palladium, lead, titanium, barium, boron, and alloys thereof. . Among these metals, it is excellent in heat resistance and is not easily oxidized in the air. When the resulting metal paste composition is fired, the aliphatic polycarbonate is uniformly decomposed and low volume because it can be fired in the presence of oxygen. From the viewpoint of obtaining a fired body having a resistivity, gold, silver, platinum, and alloys thereof are preferably used. Note that these metals may be used alone or in combination of two or more.
- the shape of the metal is not particularly limited, it is preferably a powder from the viewpoint of allowing the metal to uniformly exist in the metal paste composition.
- the median particle diameter is preferably 0.01 to 200 ⁇ m, more preferably 0.05 to 100 ⁇ m.
- the median particle diameter of the metal is a value measured by a laser analysis scattering method, and is measured by, for example, LASER DIFFRATION PARTICIZE SIZE ANALYZER (manufactured by Shimadzu Corporation, trade name: SALD-200). Can do.
- the metal paste composition according to the present invention for the purpose of adjusting the volume resistivity, mullite (3Al 2 O 3 ⁇ 2SiO 2 ⁇ 2Al 2 O 3 ⁇ SiO 2), Alumina (Al 2 O 3 ), zirconia (ZrO 2 ), barium titanate (BaTiO 3 ), lead zirconate titanate (Pb (Zr, Ti) O 3 ), cordierite (2MgO ⁇ 2Al 2 O 3 ⁇ 5SiO 2 ), borosilicate barium, iron silicate, rutile (TiO 2 ), spinel (Al 2 O 3 ⁇ MgO), sillimanite (Al 2 O ⁇ SiO 4 ), magnesia (MgO), zircon (ZrO 2 ⁇ SiO 2 ) , steatite (MgO ⁇ SiO 2), forsterite (2MgO ⁇ SiO 2), ferrite (M
- the aliphatic polycarbonate used in the metal paste composition according to the present invention is not particularly limited, and examples thereof include those obtained by polymerizing epoxide and carbon dioxide.
- the epoxide is not particularly limited as long as it is an epoxide that undergoes a polymerization reaction with carbon dioxide to become an aliphatic polycarbonate having a structure containing an aliphatic in the main chain.
- the number average molecular weight of the aliphatic polycarbonate is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000.
- the resulting metal paste composition has a low viscosity, and bleeding may occur when a wiring board is produced.
- the number average molecular weight of an aliphatic polycarbonate exceeds 1,000,000, since the solubility to the said solvent of an aliphatic polycarbonate falls, there exists a possibility that a handleability may worsen.
- the number average molecular weight is a value measured by the method described later.
- the amount of the aliphatic polycarbonate used is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 10 parts by weight, and still more preferably 0.1 to 100 parts by weight of the metal. ⁇ 10 parts by mass.
- the amount of the aliphatic polycarbonate used is less than 0.001 part by mass, the resulting metal paste composition has a low viscosity, and bleeding may occur when a wiring board is produced.
- the amount of the aliphatic polycarbonate used exceeds 10 parts by mass, when the resulting metal paste composition is baked, a gas (carbon dioxide or the like) generated by the decomposition of the excess aliphatic polycarbonate increases, and the dense There is a possibility that a fired body is difficult to obtain.
- Examples of the method for producing the aliphatic polycarbonate include a method of polymerizing the epoxide and carbon dioxide in the presence of a metal catalyst.
- the metal catalyst examples include an aluminum catalyst and a zinc catalyst.
- a zinc catalyst is preferably used.
- zinc catalysts an organic zinc catalyst is preferably used.
- organic zinc catalyst examples include organic zinc catalysts such as zinc acetate, diethyl zinc, and dibutyl zinc; primary amines, divalent phenols, divalent aromatic carboxylic acids, aromatic hydroxy acids, aliphatic dicarboxylic acids, and fatty acids. And an organic zinc catalyst obtained by reacting a compound such as a group monocarboxylic acid with a zinc compound.
- organic zinc catalysts an organozinc catalyst obtained by reacting a zinc compound, an aliphatic dicarboxylic acid and an aliphatic monocarboxylic acid is preferable because it has higher polymerization activity.
- an organic zinc catalyst obtained by reacting a zinc compound, an aliphatic dicarboxylic acid, and an aliphatic monocarboxylic acid will be described in more detail as an example of an embodiment of an organic zinc catalyst.
- the zinc compound include inorganic zinc compounds such as zinc oxide, zinc hydroxide, zinc nitrate, and zinc carbonate; organic zinc compounds such as zinc acetate, diethyl zinc, and dibutyl zinc.
- inorganic zinc compounds such as zinc oxide, zinc hydroxide, zinc nitrate, and zinc carbonate
- organic zinc compounds such as zinc acetate, diethyl zinc, and dibutyl zinc.
- zinc oxide and zinc hydroxide are preferably used from the viewpoint of obtaining an organic zinc catalyst having high catalytic activity.
- These zinc compounds may be used alone or in combination of two or more.
- aliphatic dicarboxylic acid examples include malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid and the like.
- glutaric acid and adipic acid are preferably used from the viewpoint of obtaining an organozinc catalyst having high activity.
- these aliphatic dicarboxylic acids may be used alone or in combination of two or more.
- the proportion of the aliphatic dicarboxylic acid used is usually preferably from 0.1 to 1.5 mol, more preferably from 0.5 to 1.0 mol, based on 1 mol of the zinc compound.
- the use ratio of the aliphatic dicarboxylic acid is less than 0.1 mol, the reaction with the zinc compound may not easily proceed.
- the usage-amount of aliphatic dicarboxylic acid exceeds 1.5 mol, in the activity of the obtained organozinc catalyst, there is a possibility that it may not be economical because there is no effect corresponding to the amount used.
- aliphatic monocarboxylic acid examples include formic acid, acetic acid, propionic acid and the like.
- formic acid and acetic acid are preferably used from the viewpoint of obtaining an organozinc catalyst having high activity.
- These aliphatic monocarboxylic acids may be used alone or in combination of two or more.
- the proportion of the aliphatic monocarboxylic acid used is preferably 0.0001 to 0.1 mol, more preferably 0.001 to 0.05 mol, per 1 mol of the aliphatic dicarboxylic acid.
- the proportion of the aliphatic monocarboxylic acid used is less than 0.0001 mol, the resulting organozinc catalyst has a structure containing a carboxylic acid group at the end, which may result in a less active organozinc catalyst. There is.
- the usage-amount of aliphatic monocarboxylic acid exceeds 0.1 mol, in the activity of the obtained organozinc catalyst, there exists a possibility that it may not become economical without the effect corresponding to the usage-amount.
- the method of reacting the zinc compound, the aliphatic dicarboxylic acid and the aliphatic monocarboxylic acid is not particularly limited, and these may be reacted simultaneously, or the aliphatic dicarboxylic acid or the aliphatic monocarboxylic acid may be reacted. After reacting either one of the carboxylic acids with the zinc compound first, the reaction product and the other may be reacted successively.
- a solvent for preparing a metal catalyst may be used from the viewpoint of smoothly performing the reaction.
- the solvent for preparing the metal catalyst is not particularly limited as long as it does not inhibit the reaction.
- an aromatic hydrocarbon solvent such as benzene, toluene and xylene
- an ether solvent such as diethyl ether, tetrahydrofuran and dioxane
- carbonate solvents such as dimethyl carbonate, diethyl carbonate, and propylene carbonate
- aromatic hydrocarbon solvents such as benzene, toluene, xylene and the like are preferably used from the viewpoint of easy recycling of the metal catalyst preparation solvent.
- the amount of the metal catalyst preparation solvent used is preferably 500 to 10,000 parts by mass with respect to 100 parts by mass of the zinc compound from the viewpoint of smoothly performing the reaction.
- the reaction temperature at the time of reacting the zinc compound, aliphatic dicarboxylic acid and aliphatic monocarboxylic acid is not particularly limited, but is preferably 20 to 110 ° C., more preferably 50 to 100 ° C. preferable. Further, the reaction time varies depending on the reaction temperature and cannot be generally specified, but it is usually preferably 1 to 20 hours.
- the organozinc catalyst thus obtained is used for a polymerization reaction in which epoxide and carbon dioxide are reacted with each other after isolation by a conventional method such as filtration after completion of the reaction or without being isolated. Can do.
- the organozinc catalyst when it is used without being isolated and contained in the reaction solution, water that may adversely affect the reaction between epoxide and carbon dioxide is sufficiently removed. It is preferable to keep it.
- the amount of the metal catalyst used for the polymerization reaction is preferably 0.001 to 20 parts by mass, more preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the epoxide.
- the usage-amount of a metal catalyst is less than 0.001 mass part, there exists a possibility that a polymerization reaction may become difficult to advance.
- the usage-amount of a metal catalyst exceeds 20 mass parts, there exists a possibility that there may be no effect corresponding to a usage-amount and it may become economical.
- the reaction solvent used as necessary in the polymerization reaction is not particularly limited, and various organic solvents can be used.
- the organic solvent include aliphatic hydrocarbon solvents such as pentane, hexane, octane, decane, and cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; chloromethane, methylene dichloride, and the like.
- Chloroform carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, ethyl chloride, trichloroethane, 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane, chloro Halogenated hydrocarbon solvents such as benzene and bromobenzene; carbonate solvents such as dimethyl carbonate, diethyl carbonate, and propylene carbonate.
- chloro Halogenated hydrocarbon solvents such as benzene and bromobenzene
- carbonate solvents such as dimethyl carbonate, diethyl carbonate, and propylene carbonate.
- the amount of the reaction solvent used is preferably 500 to 10,000 parts by mass with respect to 100 parts by mass of the epoxide, from the viewpoint of facilitating the reaction.
- the method of reacting epoxide and carbon dioxide in the presence of a metal catalyst is not particularly limited.
- the epoxide, the metal catalyst, and, if necessary, a reaction solvent are charged in an autoclave. After mixing, there is a method in which carbon dioxide is injected and reacted.
- the working pressure of carbon dioxide used in the polymerization reaction is not particularly limited, but is usually preferably 0.1 to 20 MPa, more preferably 0.1 to 10 MPa, and more preferably 0.1 to 5 MPa. More preferably. When the use pressure of carbon dioxide exceeds 20 MPa, there is a possibility that the effect corresponding to the use pressure may not be obtained and it may not be economical.
- the polymerization reaction temperature in the polymerization reaction is not particularly limited, but is preferably 30 to 100 ° C, and more preferably 40 to 80 ° C. When the polymerization reaction temperature is less than 30 ° C., the polymerization reaction may take a long time. On the other hand, when the polymerization reaction temperature exceeds 100 ° C., side reactions occur and the yield may decrease.
- the polymerization reaction time varies depending on the polymerization reaction temperature and cannot be generally specified, but it is usually preferably 2 to 40 hours.
- an aliphatic polycarbonate can be obtained by filtering off by filtration or the like, washing with a solvent if necessary, and drying.
- the organic solvent used in the metal paste composition according to the present invention is not particularly limited, for example, alpha-terpineol, N- methyl-2-pyrrolidone, isopropyl alcohol, diethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether, toluene, cyclohexane , Methyl ethyl ketone, dimethyl carbonate, diethyl carbonate, propylene carbonate and the like.
- ⁇ -terpineol, N-methyl- and the like have a moderately high boiling point and little evaporation at room temperature, and can be uniformly removed when the resulting metal paste composition is fired.
- 2-pyrrolidone and propylene carbonate are preferably used.
- the amount of the organic solvent used is 0.001 to 50 parts by mass, preferably 0.01 to 50 parts by mass, more preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the metal. It is.
- the usage-amount of an organic solvent is less than 0.001 mass part, there exists a possibility that the fluidity
- the usage-amount of an organic solvent exceeds 50 mass parts, the viscosity of the obtained metal paste composition will become low, there exists a possibility that the dripping at the time of wiring, the bleeding at the time of printing, etc. may arise, and it may become difficult to handle.
- the method for producing the metal paste composition according to the present invention is not particularly limited, and examples thereof include a method of stirring each component of metal, aliphatic polycarbonate, and organic solvent using a conventionally known stirring method.
- Examples of the known stirring method include a method of kneading by rotating and vibrating using an apparatus such as a mill filled with ceramic balls; a method of kneading using a mortar, and the like.
- the metal paste composition according to the present invention can be obtained.
- the metal paste composition according to the present invention can further contain a dispersant, a plasticizer and the like as desired from the viewpoint of obtaining a metal paste composition that is easy to handle and excellent in metal dispersibility.
- the dispersant examples include polyhydric alcohol esters such as glycerin and sorbitan; polyether polyols such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol; amines such as polyethyleneimine; Examples include (meth) acrylic resins such as acrylic acid and polymethacryl; copolymers of isobutylene or styrene and maleic anhydride, and amine salts thereof.
- the amount of the dispersant to be used is preferably 15 parts by mass or less, more preferably 10 parts by mass or less with respect to 100 parts by mass of the metal.
- plasticizer examples include polyether polyol and phthalate ester.
- the amount of the plasticizer used is preferably 15 parts by mass or less, more preferably 10 parts by mass or less with respect to 100 parts by mass of the metal.
- the metal paste composition of this invention can use as a material for forming the conductive layer of a solar cell element.
- the method for forming the conductive layer of the solar cell element is not particularly limited.
- the present invention is performed after forming various layers on the front or back surface of a semiconductor substrate made of silicon or the like to obtain a laminate.
- the metal paste is applied onto the laminate, dried, and then fired.
- the metal paste composition according to the present invention becomes a fired body having a low volume resistivity when fired is not clear, but is presumed to be based on the following. That is, the aliphatic polycarbonate has good thermal decomposability and can be decomposed at a low temperature during firing. As a result, the aggregation of the metal is suppressed, and the metal is uniformly dispersed in the fired body. Therefore, it is considered that the fired body has a low volume resistivity.
- a slide glass (width: 26 mm, length: 76 mm, thickness: 1 mm) was prepared as an insulating substrate and washed with acetone. Thereafter, the surface of the slide glass was subjected to a surface treatment using a UV-ozone treatment device (trade name: tabletop optical surface treatment device PL16-110, manufactured by Sen Special Light Source Co., Ltd.) to obtain a test slide glass.
- a UV-ozone treatment device trade name: tabletop optical surface treatment device PL16-110, manufactured by Sen Special Light Source Co., Ltd.
- a rectangular (10 mm ⁇ 50 mm) pattern was formed on the test slide glass using a masking tape, and the metal paste composition was poured. After coating, the masking tape was removed and dried at 25 ° C. for 240 minutes. Five coatings were prepared in the same manner.
- the obtained coated material was heated to 150 ° C., 200 ° C., 250 ° C., 300 ° C., and 350 ° C. in 10 minutes. After heating and holding at the said temperature for 30 minutes, it air-cooled to 25 degreeC and obtained the sintered body. About the thickness of the obtained sintered body, it measured using the film thickness measuring apparatus (The Kosaka Laboratory Co., Ltd. make, brand name: fine shape measuring machine surfcorder ET3000i).
- volume resistivity of fired body using metal paste composition was used for the volume resistivity of the fired body obtained.
- a resistivity meter (trade name: Loresta EP MCP-T360, manufactured by Mitsubishi Chemical Corporation) was used. And measured. The volume resistivity was automatically calculated by inputting the thickness of the fired body into the resistivity meter.
- reaction solution containing an organozinc catalyst As a result of measuring IR for the organozinc catalyst obtained by separating a part of this reaction solution and filtering it (product name: AVATAR360, manufactured by Thermo Nicolet Japan Co., Ltd.), no peak based on the carboxylic acid group was observed. It was.
- polypropylene carbonate was identified from the following physical properties.
- the number average molecular weight of the obtained polypropylene carbonate was 52,000.
- Example 1 A 5 mL eggplant-shaped flask was charged with 0.12 g of polypropylene carbonate and 0.88 g of N-methyl-2-pyrrolidone obtained by the same method as in Production Example 2, and dissolved to obtain 1.00 g of a uniform solution. .
- 4.0 g of silver particles manufactured by Daiken Chemical Co., Ltd., trade name: S-211, medium particle size: 0.311 ⁇ m
- S-211 silver particles
- medium particle size 0.311 ⁇ m
- Example 2 In Example 1, 4.97 g of the metal paste composition was used in the same manner as in Example 1 except that 0.12 g of polyethylene carbonate obtained by the same method as in Production Example 3 was used instead of 0.12 g of polypropylene carbonate. Obtained. Table 1 shows the measurement results of the thickness of the obtained metal paste composition, and Table 2 shows the measurement results of the volume resistivity.
- Example 1 the metal paste composition was used in the same manner as in Example 1 except that 0.12 g of ethyl cellulose (manufactured by Nisshin Kasei Co., Ltd., trade name: Etcel 45) was used instead of 0.12 g of polypropylene carbonate. 98 g was obtained. Table 1 shows the measurement results of the thickness of the obtained metal paste composition, and Table 2 shows the measurement results of the volume resistivity.
- Example 2 In Example 1, in place of 0.12 g of polypropylene carbonate, Example 1 was used except that 0.12 g of acrylic resin (manufactured by Aldrich Co., Ltd., trade name: polymethyl methacrylate, weight average molecular weight: about 120,000) was used. In the same manner, 4.99 g of a metal paste composition was obtained. Table 1 shows the measurement results of the thickness of the obtained metal paste composition, and Table 2 shows the measurement results of the volume resistivity.
- acrylic resin manufactured by Aldrich Co., Ltd., trade name: polymethyl methacrylate, weight average molecular weight: about 120,000
- the metal paste composition obtained according to the example obtained a fired body having a low volume resistivity, particularly when fired at a low temperature of 200 ° C. or lower.
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Abstract
Description
前記金属ペースト組成物としては、種々検討されており、例えば、金属にエチルセルロースを配合した金属ペースト組成物(特許文献1参照)、金属にアクリル樹脂を配合した金属ペースト(特許文献2参照)が提案されている。
本発明の目的は、焼成後の配線基板において、低い体積抵抗率の焼成体が得られる金属ペースト組成物を提供することにある。
すなわち、
項1. 金属、脂肪族ポリカーボネート、および、有機溶媒を含む金属ペースト組成物、
項2. 脂肪族ポリカーボネートが、エポキシドと二酸化炭素とを重合させた脂肪族ポリカーボネートである項1に記載の金属ペースト組成物、
項3. 脂肪族ポリカーボネートが、ポリエチレンカーボネート、および、ポリプロピレンカーボネートからなる群より選ばれる少なくとも1種である項1または2に記載の金属ペースト組成物、
項4. 脂肪族ポリカーボネートの使用量が、金属100質量部に対して、0.001~10質量部である項1~3のいずれか1項に記載の金属ペースト組成物、
項5. 金属が、金、銀、白金、および、これらの合金からなる群より選ばれる少なくとも1種である項1~4のいずれか1項に記載の金属ペースト組成物、
項6. 有機溶媒が、α-ターピネオール、N-メチル-2-ピロリドン、および、プロピレンカーボネートからなる群より選ばれる少なくとも1種である項1~5のいずれか1項に記載の金属ペースト組成物、
項7. 有機溶媒の使用量が、金属100質量部に対して、0.001~50質量部である1~6のいずれか1項に記載の金属ペースト組成物、
に関する。
前記金属が粉末状である場合、その中位粒子径は、好ましくは0.01~200μmであり、より好ましくは0.05~100μmである。
なお、本発明において金属の中位粒子径は、レーザー解析散乱法により測定した値であり、例えば、LASER DIFFRACTION PARTICLE SIZE ANALYZER(株式会社島津製作所製、商品名:SALD-200)等により測定することができる。
前記重合反応における重合反応温度は、特に限定されないが、30~100℃であることが好ましく、40~80℃であることがより好ましい。重合反応温度が30℃未満の場合、重合反応に長時間を要するおそれがある。また、重合反応温度が100℃を超える場合、副反応が起こり、収率が低下するおそれがある。重合反応時間は、重合反応温度により異なるために一概にはいえないが、通常、2~40時間であることが好ましい。
前記公知の攪拌方法としては、例えば、セラミックスボールが充填されたミル等の装置を用い、回転、振動させることにより混練する方法;乳鉢を用いて混練する方法等が挙げられる。
かくして、本発明にかかる金属ペースト組成物を得ることができる。
前記分散剤の使用量としては、前記金属100質量部に対して、好ましくは15質量部以下であり、より好ましくは10質量部以下である。
前記可塑剤の使用量としては、前記金属100質量部に対して、好ましくは15質量部以下であり、より好ましくは10質量部以下である。
前記太陽電池素子の導電層を形成する方法は、特に限定されず、例えば、シリコン等からなる半導体基板の表面または裏面にそれぞれ必要な種々の層を形成して積層体を得た後、本発明の金属ペーストを上記積層体上に塗布し、乾燥させた後、焼成する方法等が挙げられる。
製造例により得られた脂肪族ポリカーボネートの数平均分子量、実施例および比較例により得られた金属ペースト組成物を用いた焼成体の厚みおよび体積抵抗率を以下の方法により測定し、評価した。
脂肪族ポリカーボネート濃度が0.5質量%のクロロホルム溶液を調製し、高速液体クロマトグラフを用いて測定した。測定後、同一条件で測定した数平均分子量が既知のポリスチレンと比較することにより、分子量を算出した。また、測定条件は、以下の通りである。
機種:HLC-8020
カラム:GPCカラム(東ソー株式会社の商品名、TSK GEL Multipore HXL-M)
カラム温度:40℃
溶出液:クロロホルム
流速:1mL/分
絶縁基板としてスライドガラス(幅:26mm、長さ:76mm、厚み:1mm)を用意し、アセトンを用いて洗浄した。その後、UV-オゾン処理装置(セン特殊光源株式会社製、商品名:卓上型光表面処理装置 PL16-110)を用いて、スライドガラスの表面処理を行い、試験用スライドガラスとした。
試験用スライドガラスに、マスキングテープを用いて、長方形(10mm×50mm)のパターンを形成し、金属ペースト組成物を流し込んだ。塗布後、マスキングテープを除去し、25℃で、240分間乾燥させた。同様の方法にて、塗布物を5つ作成した。
得られた塗布物を、卓上型電気マッフル炉(EYELA社製、商品名:KDF S90)を用いて、25℃から10分間でそれぞれ150℃、200℃、250℃、300℃、350℃まで昇温し、前記温度で30分間保持した後、25℃まで空冷して焼成体を得た。
得られた焼成体の厚みについては、膜厚測定装置(株式会社小坂研究所製、商品名:微細形状測定機 surfcorder ET3000i)を用いて測定した。
また、得られた焼成体の体積抵抗率については、抵抗率計(三菱化学株式会社製、商品名:ロレスタEP MCP-T360)を用いて測定した。なお、体積抵抗率は、前記抵抗率計に、前記焼成体の厚みを入力することにより、自動的に算出された。
攪拌機、窒素ガス導入管、温度計、還流冷却管を備えた300mL容の四つ口フラスコに、酸化亜鉛8.1g(100ミリモル)、グルタル酸12.7g(96ミリモル)、酢酸0.1g(2ミリモル)およびトルエン130g(150mL)を仕込んだ。次に、反応系内を窒素雰囲気に置換した後、55℃まで昇温し、同温度で4時間攪拌して反応させた。その後、110℃まで昇温し、さらに同温度で4時間攪拌して共沸脱水させ、水分のみを除去した後、室温まで冷却して、有機亜鉛触媒を含む反応液を得た。
この反応液の一部を分取し、ろ過して得た有機亜鉛触媒について、IRを測定(サーモニコレージャパン株式会社製、商品名:AVATAR360)した結果、カルボン酸基に基づくピークは認められなかった。
攪拌機、ガス導入管、温度計を備えた1L容のオートクレーブの系内をあらかじめ窒素雰囲気に置換した後、製造例1と同様の方法により得られた有機亜鉛触媒を含む反応液8.0mL(有機亜鉛触媒を1.0g含む)、ヘキサン131g(200mL)、プロピレンオキシド46.5g(0.80モル)を仕込んだ。次に、攪拌下、二酸化炭素を加え、反応系内を二酸化炭素雰囲気に置換し、反応系内が1.5MPaとなるまで二酸化炭素を充填した。その後、60℃に昇温し、反応により消費される二酸化炭素を補給しながら6時間重合反応を行なった。
反応終了後、オートクレーブを冷却して脱圧し、ろ過した後、減圧乾燥してポリプロピレンカーボネート80.8gを得た。
得られたポリプロピレンカーボネートは、下記の物性を有することから同定することができた。
(単位は全てcm-1)
製造例2において、プロピレンオキシド46.5g(0.80モル)に代えて、エチレンオキシド35.2g(0.80モル)を用いた以外は製造例2と同様にしてポリエチレンカーボネート68.4gを得た。
得られたポリエチレンカーボネートは、下記の物性を有することから同定することができた。
(単位は全てcm-1)
また、得られたポリエチレンカーボネートの数平均分子量は、47,500であった。
5mL容のナス型フラスコに、製造例2と同様の方法により得られたポリプロピレンカーボネート0.12g、N-メチル-2-ピロリドン0.88gを仕込み、溶解させ、均一な溶液1.00gを得た。
乳鉢に、銀粒子(大研化学工業株式会社製、商品名:S-211、中位粒子径:0.311μm)4.0gを計りとり、攪拌しながら、前記溶液の全量を徐々に加えて、金属ペースト組成物4.98gを得た。
得られた金属ペースト組成物の厚みの測定結果を表1に、体積抵抗率の測定結果を表2に示す。
実施例1において、ポリプロピレンカーボネート0.12gに代えて、製造例3と同様の方法により得られたポリエチレンカーボネート0.12gを用いた以外は実施例1と同様にして金属ペースト組成物4.97gを得た。
得られた金属ペースト組成物の厚みの測定結果を表1に、体積抵抗率の測定結果を表2に示す。
実施例1において、ポリプロピレンカーボネート0.12gに代えて、エチルセルロース(日新化成株式会社製、商品名:エトセル45)0.12gを用いた以外は実施例1と同様にして金属ペースト組成物4.98gを得た。
得られた金属ペースト組成物の厚みの測定結果を表1に、体積抵抗率の測定結果を表2に示す。
実施例1において、ポリプロピレンカーボネート0.12gに代えて、アクリル樹脂(アルドリッチ株式会社製、商品名:ポリメチルメタクリレート、重量平均分子量:約120,000)0.12gを用いた以外は実施例1と同様にして金属ペースト組成物4.99gを得た。
得られた金属ペースト組成物の厚みの測定結果を表1に、体積抵抗率の測定結果を表2に示す。
Claims (7)
- 金属、脂肪族ポリカーボネート、および、有機溶媒を含む金属ペースト組成物。
- 脂肪族ポリカーボネートが、エポキシドと二酸化炭素とを重合させた脂肪族ポリカーボネートである請求項1に記載の金属ペースト組成物。
- 脂肪族ポリカーボネートが、ポリエチレンカーボネート、および、ポリプロピレンカーボネートからなる群より選ばれる少なくとも1種である請求項1または2に記載の金属ペースト組成物。
- 脂肪族ポリカーボネートの使用量が、金属100質量部に対して、0.001~10質量部である請求項1~3のいずれか1項に記載の金属ペースト組成物。
- 金属が、金、銀、白金、および、これらの合金からなる群より選ばれる少なくとも1種である請求項1~4のいずれか1項に記載の金属ペースト組成物。
- 有機溶媒が、α-ターピネオール、N-メチル-2-ピロリドン、および、プロピレンカーボネートからなる群より選ばれる少なくとも1種である請求項1~5のいずれか1項に記載の金属ペースト組成物。
- 有機溶媒の使用量が、金属100質量部に対して、0.001~50質量部である請求項1~6のいずれか1項に記載の金属ペースト組成物。
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| CN201280014092.8A CN103430242B (zh) | 2011-03-18 | 2012-03-06 | 金属糊剂组合物 |
| JP2013505874A JPWO2012128028A1 (ja) | 2011-03-18 | 2012-03-06 | 金属ペースト組成物 |
| US14/005,618 US9414487B2 (en) | 2011-03-18 | 2012-03-06 | Metal paste composition |
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| JP2017066485A (ja) * | 2015-09-30 | 2017-04-06 | 日東電工株式会社 | シートおよび複合シート |
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| US10787540B2 (en) | 2016-07-08 | 2020-09-29 | National University Corporation Tokyo University Of Agriculture And Technology | Aliphatic polycarbonate and binder resin composition containing said polycarbonate |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN103430242B (zh) | 2018-09-07 |
| JP2017084823A (ja) | 2017-05-18 |
| US9414487B2 (en) | 2016-08-09 |
| US20140008588A1 (en) | 2014-01-09 |
| CN103430242A (zh) | 2013-12-04 |
| JPWO2012128028A1 (ja) | 2014-07-24 |
| KR20140038391A (ko) | 2014-03-28 |
| KR102011523B1 (ko) | 2019-08-16 |
| JP6336635B2 (ja) | 2018-06-06 |
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