WO2018135217A1 - 共重合体及びその製造方法、並びに共重合体組成物 - Google Patents
共重合体及びその製造方法、並びに共重合体組成物 Download PDFInfo
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- WO2018135217A1 WO2018135217A1 PCT/JP2017/045555 JP2017045555W WO2018135217A1 WO 2018135217 A1 WO2018135217 A1 WO 2018135217A1 JP 2017045555 W JP2017045555 W JP 2017045555W WO 2018135217 A1 WO2018135217 A1 WO 2018135217A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/36—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by a ketonic radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/10—Polymers provided for in subclass C08B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
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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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- 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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
Definitions
- the present invention relates to a copolymer, a method for producing the same, and a copolymer composition containing the copolymer.
- MLCC multilayer ceramic capacitor
- An example of the production of MLCC is as follows. First, a dielectric ceramic paste is applied on a releasable sheet to produce a green sheet having a dielectric layer. Next, an electrode paste (sometimes referred to as “conductive paste”) is printed on the dielectric layer to form an electrode pattern (electrode layer). Further, the laminate of the dielectric layer and the electrode layer is peeled off from the release sheet, and a plurality of the laminates are laminated and pressed, and then cut into chips. Next, the obtained chip is heated to several hundred ° C. to 1000 ° C. or higher and fired to produce a sintered body chip in which a dielectric layer and an electrode layer are laminated in multiple layers. Finally, external electrodes and the like are formed.
- the manufacturing process of a silicon-based solar cell includes a printing and firing process using an electrode paste in forming a collector electrode.
- Ceramic paste and electrode paste used for manufacturing electronic components such as MLCC are resin compositions containing a binder and an organic solvent, which are polymer materials, in which inorganic particles are uniformly dispersed.
- the inorganic particles dielectric particles such as barium titanate are used in the ceramic paste, and conductive metal particles such as nickel are used in the electrode paste.
- a binder polyvinyl butyral has been mainly used for ceramic pastes, and ethyl cellulose has been mainly used for electrode pastes [Japanese Patent Publication No. 04-049766 (Patent Document 1)].
- a paste such as a ceramic paste or an electrode paste, particularly a binder contained therein has the following problems, for example. 1) Improvement of thermal decomposability (combustibility). If ash such as carbon remains even after the thermal decomposition treatment by firing, the electrical characteristics of MLCC are deteriorated and delamination is caused. 2) Improved printability. In recent years, electrode patterns formed by screen printing have been miniaturized and thinned, and the pattern size has fallen below 100 ⁇ m. For this reason, in the electrode paste, a binder that does not cause a so-called stringing phenomenon is required.
- the yarn wrinkle phenomenon is a phenomenon in which a paste used in a printing process is stretched under the influence of a binder polymer and a thin yarn is wound, which causes a defective product. 3) Improvement of uniform dispersibility of inorganic particles, film strength (strength of layer formed from paste) and adhesion between layers. These are required characteristics accompanying the thinning of each layer constituting the chip.
- Patent Document 2 Japanese Patent No. 4347440 (Patent Document 2) and Japanese Patent No. 5299904 (Patent Document 3) disclose a technique for improving physical properties such as film strength by blending polyvinyl butyral with ethyl cellulose in an electrode paste.
- Patent Document 3 discloses a technique for improving physical properties such as film strength by blending polyvinyl butyral with ethyl cellulose in an electrode paste.
- Patent Document 4 describes that a reaction product of ethyl cellulose, polyvinyl butyral, and a binder that binds these is used as a binder.
- the binder blended with ethyl cellulose and polyvinyl butyral described in Patent Documents 2 and 3 has poor compatibility with these two polymers, and is an inorganic material when inorganic particles such as metals, ceramics, and glass are mixed to form a paste.
- the dispersibility of the particles is low. As a result, the coating film is likely to be defective or the uniformity of the coating film is likely to be reduced.
- Patent Document 4 compatibility is improved by chemically bonding ethyl cellulose and polyvinyl butyral. However, since the bonding efficiency between these two types of polymers is not high, the uniformity of the coating film is still improved. There is room for improvement.
- An object of the present invention is to provide a binder having good thermal decomposability, adhesion, coating film quality, and printability, and a composition containing the same.
- the present invention provides the following copolymer, a method for producing the same, and a copolymer composition.
- a copolymer comprising a structural unit (a) derived from a cellulose-based polymerizable compound having a polymerizable unsaturated group and a structural unit (b) derived from a polyvinyl acetal-based polymerizable compound having a polymerizable unsaturated group Coalescence.
- [5] including a step of polymerizing a cellulose polymerizable compound having a polymerizable unsaturated group and a polyvinyl acetal polymerizable compound having a polymerizable unsaturated group in an organic solvent in the presence of a polymerization initiator.
- a method for producing a copolymer including a step of polymerizing a cellulose polymerizable compound having a polymerizable unsaturated group and a polyvinyl acetal polymerizable compound having a polymerizable unsaturated group in an organic solvent in the presence of a polymerization initiator.
- copolymer composition comprising:
- a copolymer having good thermal decomposability, adhesion, coating film quality, and printability, and a copolymer composition containing the same can be provided. According to the copolymer, a highly strong film can be formed.
- a copolymer composition containing the copolymer as a binder is suitable as a paste (or slurry) such as a ceramic paste or an electrode paste. The paste (or slurry) can be used for the production of electronic components and substrates.
- the copolymer according to the present invention is a polymer material suitably used as a binder of a copolymer composition (paste or slurry), and is a structural unit derived from a cellulose-based polymerizable compound having a polymerizable unsaturated group (a). And a structural unit (b) derived from a polyvinyl acetal polymerizable compound having a polymerizable unsaturated group.
- the cellulose polymerizable compound and the polyvinyl acetal polymerizable compound are polymerized by a polymerizable unsaturated group to form the structural unit (a) and the structural unit (b) in the copolymer, respectively.
- a copolymer can contain 1 type, or 2 or more types of structural units (a), and can also include 1 type, or 2 or more types of structural units (b).
- the cellulose polymerizable compound having a polymerizable unsaturated group forming the structural unit (a) is a cellulose derivative having a polymerizable unsaturated group.
- the cellulose derivative refers to a modified cellulose obtained by chemically modifying a part of hydroxy groups of cellulose that is a natural polymer.
- the chemical modification of the hydroxy group is not particularly limited, and examples thereof include alkyl etherification, hydroxyalkyl etherification, esterification and the like of the hydroxy group.
- the cellulose derivative has at least one hydroxy group in one molecule.
- a cellulose derivative may use only 1 type and may use 2 or more types together.
- Cellulose derivatives include methylcellulose, ethylcellulose, propylcellulose, butylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxybutylmethylcellulose, cellulose acetate (acetylcellulose, diacetylcellulose, triacetylcellulose, etc.), cellulose acetate propionate , Cellulose acetate butyrate, nitrocellulose and the like.
- the cellulose derivative is preferably soluble in an organic solvent.
- the cellulose derivative is more preferably ethylcellulose.
- the number average molecular weight of the cellulose derivative is preferably in the range of 50,000 to 150,000, preferably in the range of 10,000 to 100,000 in terms of standard polystyrene conversion by gel permeation chromatography (GPC). It is more preferable.
- GPC gel permeation chromatography
- the number average molecular weight is less than 50,000, the solution viscosity becomes extremely low and it becomes difficult to adjust the viscosity of the copolymer composition (paste or slurry), and the copolymer composition is applied and dried. There exists a possibility that the intensity
- the number average molecular weight exceeds 150,000 the solution viscosity becomes extremely large, it may be difficult to adjust the viscosity of the copolymer composition, and printability may be deteriorated.
- the cellulose derivative has at least one hydroxy group in one molecule.
- This hydroxy group can be used for introducing a polymerizable unsaturated group.
- a specific example of the polymerizable unsaturated group is a polymerizable carbon-carbon double bond, and preferred examples thereof are a (meth) acrylate group ((meth) acryloyloxy group), a vinyl group, and an allyl group.
- (meth) acrylate” means acrylate and / or methacrylate
- “(meth)” in the case of (meth) acryl, (meth) acryloyl, etc. has the same meaning.
- a polymerizable unsaturated group can be introduced into a cellulose derivative by reacting a hydroxyl group of the cellulose derivative with a compound having a group capable of reacting with the hydroxy group and a polymerizable unsaturated group.
- a cellulose-based polymerizable compound having an unsaturated group can be obtained.
- the group capable of reacting with a hydroxy group include a carboxyl group, an acid anhydride group, an acid chloride group, an isocyanate group, and a halogen group (halogen atom).
- Examples of the compound having a group capable of reacting with a hydroxy group and a polymerizable unsaturated group include polymerizable unsaturated groups such as (meth) acrylic acid, maleic acid, 4-vinylbenzoic acid, 4-ethenylbenzoic acid and the like.
- the compound having a group capable of reacting with a hydroxy group and a polymerizable unsaturated group only one kind may be used, or two or more kinds may be used in combination.
- reaction esterification reaction, urethanization, etherification reaction, etc.
- a compound having a group capable of reacting with the hydroxy group and a polymerizable unsaturated group can be adopted. It is also effective to use a reaction catalyst (organic metal compound, metal, amine, condensing agent, etc.).
- the number of polymerizable unsaturated groups contained in the cellulose polymerizable compound is preferably 10 or less per molecule on average. If the number of polymerizable unsaturated groups exceeds 10 on average per molecule, gelation and insolubilization in an organic solvent accompanying the production of the copolymer are likely to occur.
- the gelled copolymer is not preferable as a binder for paste or slurry.
- the number of polymerizable unsaturated groups possessed by the cellulosic polymerizable compound may be an average of 8 or less per molecule, 5 or less, 3 or less, or 2 or less. May be sufficient.
- the polyvinyl acetal polymerizable compound having a polymerizable unsaturated group forming the structural unit (b) is a polyvinyl acetal having a polymerizable unsaturated group.
- Polyvinyl acetal is usually a polymer composed of vinyl acetal / vinyl alcohol / vinyl acetate monomer units, and can be obtained by acetalizing polyvinyl alcohol. Specific examples include polyvinyl alcohol butyral (polyvinyl butyral), polyvinyl alcohol formalized (polyvinyl formal), and the like.
- Polyvinyl acetal may be a commercial product, and various polyvinyl acetals with different butyralization degree, formalization degree, acetyl group amount, hydroxy group amount and molecular weight are sold by Sekisui Chemical Co., Kuraray, Eastman Chemical Co., Ltd. Has been. Polyvinyl acetal may use only 1 type and may use 2 or more types together.
- the polyvinyl acetal is preferably soluble in an organic solvent.
- the polyvinyl acetal is more preferably polyvinyl butyral because of its high solubility in organic solvents.
- the number average molecular weight of polyvinyl acetal is preferably in the range of 50,000 to 150,000, and more preferably in the range of 10,000 to 100,000, in terms of standard polystyrene conversion by GPC.
- the number average molecular weight is less than 50,000, the solution viscosity becomes extremely low and it becomes difficult to adjust the viscosity of the copolymer composition (paste or slurry), and the copolymer composition is applied and dried. There exists a possibility that the intensity
- the number average molecular weight exceeds 150,000 the solution viscosity becomes extremely large, it may be difficult to adjust the viscosity of the copolymer composition, and printability may be deteriorated.
- Polyvinyl acetal has at least one hydroxy group in one molecule. Generally, polyvinyl acetal has 20 to 40 mol% of hydroxy groups as vinyl alcohol units constituting the polymer. This hydroxy group can be used for introducing a polymerizable unsaturated group.
- a specific example of the polymerizable unsaturated group is a polymerizable carbon-carbon double bond, and preferred examples thereof are a (meth) acrylate group ((meth) acryloyloxy group), a vinyl group, and an allyl group.
- a polymerizable unsaturated group can be introduced into polyvinyl acetal by reacting a hydroxyl group of polyvinyl acetal with a compound having a group capable of reacting with the hydroxy group and a polymerizable unsaturated group.
- a polyvinyl acetal polymerizable compound having an unsaturated group can be obtained.
- the group capable of reacting with a hydroxy group include a carboxyl group, an acid anhydride group, an acid chloride group, an isocyanate group, and a halogen group (halogen atom).
- the compound having a group capable of reacting with a hydroxy group and a polymerizable unsaturated group are the same as those mentioned in the above-mentioned section “[1] Structural unit (a)”.
- the compound having a group capable of reacting with a hydroxy group and a polymerizable unsaturated group only one kind may be used, or two or more kinds may be used in combination.
- reaction esterification, urethanization, etherification reaction, etc.
- a compound having a group capable of reacting with the hydroxyl group and a polymerizable unsaturated group esterification, urethanization, etherification reaction, etc.
- reaction catalyst organic metal compound, metal, amine, condensing agent, etc.
- the number of polymerizable unsaturated groups contained in the polyvinyl acetal polymerizable compound is preferably 10 or less on average per molecule. If the number of polymerizable unsaturated groups exceeds 10 on average per molecule, gelation and insolubilization in an organic solvent accompanying the production of the copolymer are likely to occur.
- the gelled copolymer is not preferable as a binder for paste or slurry.
- the number of polymerizable unsaturated groups possessed by the polyvinyl acetal polymerizable compound may be an average of 8 or less per molecule, 5 or less, 3 or less, or 2 The following may be sufficient and one may be sufficient.
- the copolymer can further contain a structural unit (c) other than the structural unit (a) and the structural unit (b).
- the copolymer can contain 1 type, or 2 or more types of structural units (c).
- Examples of the monomer that forms the structural unit (c) include (meth) acrylate (a compound having a (meth) acryloyloxy group).
- (Meth) acrylate may use only 1 type and may use 2 or more types together.
- (Meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethyl Alkyl (meth) acrylates having an alkyl group of 1 to 20 carbon atoms such as hexyl (meth) acrylate and cyclohexyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glyceryl mono Hydroxyalkyl (meth) acrylates such as (meth) acrylate; N, N-dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate;
- (meth) acrylates include bifunctional (e.g., ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having 2 to 30 repeating ethylene oxide moieties, and hexanediol di (meth) acrylate).
- (Meth) acrylates Trifunctional or higher functional (meth) acrylates such as pentaerythritol tri (meth) acrylate may be mentioned.
- the monomer forming the structural unit (c) may be a monomer other than (meth) acrylate.
- monomers other than (meth) acrylate include aromatic vinyl monomers such as styrene, vinyl toluene, ⁇ -methyl styrene, p-methyl styrene, and divinylbenzene; olefin monomers such as ethylene and propylene; (meth) acrylamide, ( (Meth) acrylamides such as (meth) acryloylmorpholine; (meth) acrylic acid, crotonic acid, cinnamic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, etc. Acids: N-vinylpyrrolidone, N-phenylmaleimide, N-cyclohexylmaleimide, (meth) acrylonitrile, vinyl chloride, vinyl
- the content ratio of the constitutional unit (a) and constitutional unit (b) contained in the copolymer is preferably in the range of 10:90 to 90:10 on a mass basis. More preferably, it is in the range of 20:80 to 80:20, and still more preferably in the range of 25:75 to 75:25.
- the desired effect of being a copolymer containing the structural unit (a) and the structural unit (b) can be obtained more effectively.
- the structural unit (a) When the structural unit (a) is less than the above range, the printability of the copolymer composition (paste or slurry) may be lowered.
- the structural unit (b) When the structural unit (b) is less than the above range, the strength, adhesion and / or thermal decomposability of the film formed from the copolymer composition may be lowered.
- the content thereof is 0.1 to 200 parts by mass with respect to 100 parts by mass of the total content of the structural unit (a) and the structural unit (b). Preferably, it is 100 parts by mass or less, and more preferably 50 parts by mass or less. If the structural unit (c) is in the above range, the desired effect (good thermal decomposability, adhesion, coating film quality, and the like by being a copolymer containing the structural unit (a) and the structural unit (b). And printability) are easily secured. When the content of the structural unit (c) exceeds 200 parts by mass, the printability of the copolymer composition (paste or slurry) decreases, or the strength of the film formed from the copolymer composition decreases. there's a possibility that.
- the number average molecular weight of the copolymer is preferably 10,000 to 200,000, more preferably 10,000 to 150,000, and more preferably 20,000 to 120,000, in terms of standard polystyrene conversion by GPC. preferable.
- the number average molecular weight of the copolymer is less than 10,000, the viscosity of the copolymer composition (paste or slurry) is lowered, and the strength and adhesion of the coating film may be reduced.
- it exceeds 200,000 the viscosity tends to be too high, and the printability tends to decrease.
- the polyvinyl acetal polymerizable compound having a polymerizable unsaturated group comprises a cellulose derivative, a hydroxy group of polyvinyl acetal, a group capable of reacting with the hydroxy group, and a compound having a polymerizable unsaturated group, respectively. It can be obtained by reacting.
- the above reaction is, for example, an esterification reaction, a urethanization reaction, or an etherification reaction.
- conventionally known methods and reaction conditions can be employed. It is also effective to use a reaction catalyst (organic metal compound, metal, amine, condensing agent, etc.).
- the esterification reaction can be performed using, for example, a condensing agent.
- a condensing agent examples include carbodiimide, diphenyl phosphate azide, 1-hydroxybenzotriazole, BOP reagent and the like. Only 1 type may be used for a condensing agent and it may use 2 or more types together. Among these, carbodiimide is preferable because it is excellent in versatility and reactivity and can advance the reaction under low temperature conditions and without being affected by moisture in the reaction environment.
- carbodiimide examples include dicyclohexylcarbodiimide, diisopropylcarbodiimide, N- [3- (dimethylamino) propyl] -N′-ethylcarbodiimide, N- [3- (dimethylamino) propyl] -N′-ethylcarbodiimide methiodado and the like. Can be mentioned. Among these, dicyclohexylcarbodiimide and diisopropylcarbodiimide are preferable from the viewpoint of availability.
- dimethylaminopyridine or triethylamine which is a base
- a reaction accelerator in a range of 0.01 mol% to 10 mol% with respect to carbodiimide.
- the urethanization reaction can be performed using, for example, a reaction catalyst.
- the reaction catalyst include organometallic compounds such as dioctyltin dilaurate, dibutyltin dilaurate, stannous octoate, and zinc dibutafonate; 1,8-diazabicyclo [5,4,0] undecene-7 (DBU) or a salt thereof; 1 , 4-diazabicyclo [2,2,2] octane, PMDETA (N, N, N ′, N ′′, N ′′ -pentamethyldiethylenetriamine), N, N-dimethylcyclohexylamine, N-methyldicyclohexylamine, N , N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N-methylmorpholine, N-ethylmorpholine, N, N-di
- the etherification reaction can be efficiently carried out by using an alkali metal hydroxide such as KOH or NaOH; an alkali metal hydride such as NaH or KH as a reaction catalyst.
- an alkali metal hydroxide such as KOH or NaOH
- an alkali metal hydride such as NaH or KH as a reaction catalyst.
- reaction of the hydroxy group of the cellulose derivative or polyvinyl acetal with the compound having a group capable of reacting with the hydroxy group and a polymerizable unsaturated group is preferably carried out in an aprotic organic solvent.
- aprotic organic solvents examples include ethyl acetate, butyl acetate, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, toluene, xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethyl lactate, ethylene glycol Monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate (butyl carbitol acetate), diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, diethylene glycol diethyl ether Diethylene glycol butyl methyl ether, diethylene glycol dibutyl
- the temperature of the reaction between the hydroxy group of the cellulose derivative or polyvinyl acetal and the compound having a group capable of reacting with the hydroxy group and a polymerizable unsaturated group is, for example, about 0 ° C. to 100 ° C.
- the introduction amount of the polymerizable unsaturated group can be measured by NMR analysis or the like.
- carbodiimide When carbodiimide is used as the condensing agent, it may be added after reacting a compound having a polymerizable unsaturated group with carbodiimide in advance. When carbodiimide is used, urea may be generated as a by-product and insolubilized in some cases, but filtration purification or reprecipitation purification may be performed as necessary.
- the amount of polymerizable unsaturated groups introduced into the cellulose derivative or polyvinyl acetal is the number of hydroxy groups that one molecule of the cellulose derivative or polyvinyl acetal has, a compound that can react with a hydroxy group and a compound having a polymerizable unsaturated group, condensation It can be adjusted depending on the amount of the agent used.
- the number of hydroxy groups contained in one molecule of the cellulose derivative or polyvinyl acetal can be adjusted by the content of hydroxy groups contained in the cellulose derivative or polyvinyl acetal, the molecular weight of the cellulose derivative or polyvinyl acetal, and the like.
- the introduction of the polymerizable unsaturated group into the cellulose derivative and the polyvinyl acetal may be performed 1) individually, or 2) the cellulose derivative and the polyvinyl acetal are previously mixed, and the hydroxy group is added to the mixture. You may carry out by making the compound which has a group which can react and a polymerizable unsaturated group react.
- the mixing ratio of the cellulose derivative and the polyvinyl acetal in the case 2) is the same as the above-mentioned “content ratio of the structural unit (a) and the structural unit (b) contained in the copolymer”. preferable. Moreover, also in the case of said 2), it is preferable to introduce
- a copolymer can be obtained by copolymerizing a monomer composition containing. This copolymerization reaction is performed, for example, by heating in an organic solvent in the presence of a radical polymerization initiator, preferably in a non-oxygen atmosphere.
- examples include alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, dipropylene glycol monomethyl ether, terpineol, dihydroterpineol and the like. Only 1 type may be used for an organic solvent and it may use 2 or more types together.
- radical polymerization initiator conventionally known ones (for example, peroxides and azos) can be used.
- the amount of the radical polymerization initiator used is, for example, in the range of 0.001 to 5% with respect to 100% by mass of the total amount of monomers.
- the total concentration of all monomers in the copolymerization reaction solution is preferably 5 to 70% by mass.
- the temperature of the copolymerization reaction is, for example, about 40 ° C. to 120 ° C.
- a normal polymer purification treatment such as precipitation purification with a poor solvent may be performed as necessary.
- the purification treatment unreacted monomers and by-products can be removed, and a solid state copolymer can be obtained.
- the copolymer composition according to the present invention contains a binder, which is the copolymer, inorganic particles, and an organic solvent, and is used for producing various pastes or slurries, particularly electronic components and electronic device members. Suitable as a baking paste or slurry.
- a paste and a slurry it is distinguished mainly from the point of viscosity, and the former is higher viscosity.
- the copolymer composition according to the present invention can be suitably used as a paste or slurry for forming circuits, electrode patterns, dielectric layers, phosphor layers and the like of various electronic components.
- a copolymer composition containing a binder and an organic solvent which can be a production intermediate of the copolymer composition, also belongs to the present invention.
- Examples of inorganic materials constituting the inorganic particles contained in the copolymer composition include conductive inorganic materials, ceramics, glass, pigments, and phosphors.
- Examples of conductive inorganic materials include metals such as gold, silver, copper, platinum, palladium, nickel, aluminum, tungsten, and iron; alloys containing any of the above metals such as silver-palladium alloys; metals made of ITO or the like Oxides; carbon powder and the like.
- Examples of the ceramic include magnetic ceramics such as barium titanate, titanium oxide, alumina, zirconia, aluminum nitride, silicon nitride, boron nitride, silicon carbide, and ferrite.
- the glass examples include those containing silicon dioxide (usually those containing silicon dioxide as a main component), and the melting point thereof is not particularly limited.
- the particle size of the inorganic particles is usually in the range of 20 nm to 1 mm. Only one type of inorganic particles may be used, or two or more types may be used in combination.
- the organic solvent contained in the copolymer composition one or more of the organic solvents exemplified in the above ⁇ Method for producing copolymer> [1] and [2] can be used.
- the organic solvent is a solvent capable of dissolving the binder, and preferably has a high boiling point in printing paste applications.
- the copolymer composition may further contain an additive as necessary.
- Additives include surfactants, viscosity modifiers, antifoaming agents, leveling agents, stabilizers, plasticizers, wetting agents, dyes, polymer particles, and the like. Only 1 type may be used for an additive and it may use 2 or more types together.
- the copolymer composition may contain a polymer other than the above-mentioned copolymer as a binder.
- the content ratio of the inorganic particles in the copolymer composition (the total content when containing two or more inorganic particles) and the binder is usually 100: 1 to 100: 50 on a mass basis. From the viewpoint of the viscosity of the polymer composition and the dispersibility of the inorganic particles, the ratio is preferably 100: 5 to 100: 30.
- the content of the organic solvent (when two or more organic solvents are contained, the total content thereof) is usually 100 to 10,000 parts by mass with respect to 100 parts by mass of the binder.
- the content thereof is usually 0.1 to 30 masses per 100 mass parts of the binder. Part.
- Inorganic particles, a binder (copolymer) dissolved in an organic solvent, and additives used as necessary are mixed using a dispersing device such as a three-roll mill, a ball mill, a media mill, or a homogenizer, and the inorganic particles are mixed.
- a copolymer composition can be prepared by uniformly dispersing the copolymer composition.
- the organic solvent is volatilized by subsequent baking, and the binder is thermally decomposed to form a layer or pattern of inorganic particles.
- the coating method for the copolymer composition include screen printing, die coating printing, doctor blade printing, roll coating printing, offset printing, gravure printing, flexographic printing, inkjet printing, dispensing printing, casting method, dip coating, and the like. Of these, screen printing and dip coating are preferred.
- the layer or pattern obtained by firing usually comprises a sintered body of inorganic particles.
- ethylcellulose 100 parts of the dried ethylcellulose was dissolved in 400 parts of ethyl acetate.
- ethylcellulose 100 parts of the dried ethylcellulose was dissolved in 400 parts of ethyl acetate.
- ethyl acetate was distilled off to obtain a cellulose polymerizable compound (a3) in which a methacrylate group was introduced into ethyl cellulose as a solid.
- ethylcellulose 100 parts of the dried ethylcellulose was dissolved in 400 parts of ethyl acetate.
- the number average molecular weight (standard polystyrene conversion value) was 71000. Since this value is larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, it was confirmed that polymerization was proceeding by the above reaction.
- the number average molecular weight of the copolymer (1) was measured under the following conditions (the same applies to the number average molecular weight of the copolymer obtained in the following Examples).
- GPC device “HLC-8320GPC” manufactured by Tosoh Corporation Column: TSKgel GMHXL, Measurement temperature (set temperature): 30 ° C. Mobile phase: tetrahydrofuran.
- Example 2 Synthesis of copolymer (2)>
- 10 parts of the cellulose polymerizable compound (a1) obtained in Synthesis Example 1 10 parts of the polyvinyl acetal polymerizable compound (b1) obtained in Synthesis Example 7, 1.0 part of isobutyl methacrylate, And 80 parts of dihydroterpinyl acetate as an organic solvent was added, mixed, heated to 60 ° C. and stirred with a rotary blade to dissolve. After dissolution, nitrogen substitution was performed to remove oxygen in the system, and 0.01 part of azoisobutyronitrile (AIBN) as a polymerization initiator was mixed and reacted at 70 ° C. for 5 hours to obtain a copolymer ( A liquid (binder solution) containing 2) was obtained.
- AIBN azoisobutyronitrile
- the number average molecular weight (standard polystyrene conversion value) was 72,000. Since this value is larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, it was confirmed that polymerization was proceeding by the above reaction.
- Example 3 Synthesis of copolymer (3)> Example 1 was used except that 5 parts of the cellulose-based polymerizable compound (a1) obtained in Synthesis Example 1 and 15 parts of the polyvinyl acetal-based polymerizable compound (b1) obtained in Synthesis Example 7 were used. A liquid (binder solution) containing the copolymer (3) was obtained.
- the number average molecular weight (standard polystyrene conversion value) was 73,000. Since this value is larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, it was confirmed that polymerization was proceeding by the above reaction.
- Example 4 Synthesis of copolymer (4)> The same procedure as in Example 1 was conducted except that 15 parts of the cellulose-based polymerizable compound (a1) obtained in Synthesis Example 1 and 5 parts of the polyvinyl acetal-based polymerizable compound (b1) obtained in Synthesis Example 7 were used. A liquid (binder solution) containing the copolymer (4) was obtained.
- the number average molecular weight (standard polystyrene conversion value) was 70000. Since this value is larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, it was confirmed that polymerization was proceeding by the above reaction.
- Example 5 Synthesis of copolymer (5)>
- 10 parts of the cellulose polymerizable compound (a2) obtained in Synthesis Example 2 10 parts of the polyvinyl acetal polymerizable compound (b2) obtained in Synthesis Example 8, and dihydroter as an organic solvent 80 parts of pinyl acetate were added, mixed, heated to 60 ° C. and stirred with a rotary blade to dissolve. After dissolution, nitrogen substitution was performed to remove oxygen in the system, and 0.01 part of azoisobutyronitrile (AIBN) as a polymerization initiator was mixed and reacted at 70 ° C. for 5 hours to obtain a copolymer ( A liquid (binder solution) containing 5) was obtained.
- AIBN azoisobutyronitrile
- the number average molecular weight (standard polystyrene conversion value) was 42,000. Since this value is larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, it was confirmed that polymerization was proceeding by the above reaction.
- Example 6 Synthesis of copolymer (6)>
- 10 parts of the cellulose polymerizable compound (a2) obtained in Synthesis Example 2 10 parts of the polyvinyl acetal polymerizable compound (b2) obtained in Synthesis Example 8, 2 parts of isobutyl methacrylate, and organic 80 parts of dihydroterpinyl acetate as a solvent was added and mixed, heated to 60 ° C. and stirred with a rotary blade to dissolve. After dissolution, nitrogen substitution was performed to remove oxygen in the system, and 0.01 part of azoisobutyronitrile (AIBN) as a polymerization initiator was mixed and reacted at 70 ° C. for 5 hours to obtain a copolymer ( A liquid (binder solution) containing 6) was obtained.
- AIBN azoisobutyronitrile
- the number average molecular weight (standard polystyrene conversion value) was 45,000. Since this value is larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, it was confirmed that polymerization was proceeding by the above reaction.
- Example 7 Synthesis of copolymer (7)> A copolymer in the same manner as in Example 5 except that the cellulose polymerizable compound (a1) obtained in Synthesis Example 1 was used instead of the cellulose polymerizable compound (a2) obtained in Synthesis Example 2. A liquid (binder solution) containing (7) was obtained.
- the number average molecular weight (standard polystyrene conversion value) was 68,000. Since this value is larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, it was confirmed that polymerization was proceeding by the above reaction.
- Example 8 Synthesis of copolymer (8)> In the same manner as in Example 5, except that the polyvinyl acetal polymerizable compound (b1) obtained in Synthesis Example 7 was used instead of the polyvinyl acetal polymerizable compound (b2) obtained in Synthesis Example 8. A liquid (binder solution) containing the polymer (8) was obtained.
- the number average molecular weight (standard polystyrene conversion value) was 56000. Since this value is larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, it was confirmed that polymerization was proceeding by the above reaction.
- Example 9 Synthesis of copolymer (9)>
- a cellulose polymerizable compound (a7) in which a methacrylate group was introduced into ethyl cellulose obtained in Synthesis Example 13
- a polyvinyl acetal polymerizable compound (b7) in which a methacrylate group was introduced into polyvinyl butyral.
- 20 parts of the mixture, 0.2 parts of isobutyl methacrylate, and 80 parts of dihydroterpinyl acetate as an organic solvent were added, mixed, heated to 60 ° C., stirred with a rotary blade, and dissolved.
- the number average molecular weight (standard polystyrene conversion value) was 72,000. Since this value is larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, it was confirmed that polymerization was proceeding by the above reaction.
- Example 10 Synthesis of copolymer (10)> Cellulose polymerizable compound (a8) in which methacrylate groups are introduced into ethyl cellulose obtained in Synthesis Example 14 instead of the mixture obtained in Synthesis Example 13 and polyvinyl acetal polymerizable compounds in which methacrylate groups are introduced into polyvinyl butyral A liquid (binder solution) containing the copolymer (10) was obtained in the same manner as in Example 9 except that the mixture with (b8) was used.
- the number average molecular weight (standard polystyrene conversion value) was 48,000. Since this value is larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, it was confirmed that polymerization was proceeding by the above reaction.
- Example 11 Synthesis of copolymer (11)> Using the cellulose polymerizable compound (a3) obtained in Synthesis Example 3 in place of the cellulose polymerizable compound (a1), the polyvinyl obtained in Synthesis Example 9 instead of the polyvinyl acetal polymerizable compound (b1). A liquid (binder solution) containing the copolymer (11) was obtained in the same manner as in Example 1 except that the acetal polymerizable compound (b3) was used.
- the number average molecular weight (standard polystyrene conversion value) was 78,000. Since this value is larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, it was confirmed that polymerization was proceeding by the above reaction.
- Example 12 Synthesis of copolymer (12)>
- 10 parts of the cellulose polymerizable compound (a3) obtained in Synthesis Example 3 10 parts of the polyvinyl acetal polymerizable compound (b3) obtained in Synthesis Example 9, 0.2 part of isobutyl methacrylate, And 80 parts of dihydroterpinyl acetate as an organic solvent was added, mixed, heated to 60 ° C. and stirred with a rotary blade to dissolve. After dissolution, nitrogen substitution was performed to remove oxygen in the system, and 0.01 part of azoisobutyronitrile (AIBN) as a polymerization initiator was mixed and reacted at 70 ° C. for 5 hours to obtain a copolymer ( 12) was obtained (binder solution).
- AIBN azoisobutyronitrile
- the number average molecular weight (standard polystyrene conversion value) was 80000. Since this value is larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, it was confirmed that polymerization was proceeding by the above reaction.
- Example 13 Synthesis of copolymer (13)> A liquid (binder solution) containing the copolymer (13) was obtained in the same manner as in Example 2 except that the addition amount of isobutyl methacrylate was changed to 0.2 part.
- the number average molecular weight (standard polystyrene conversion value) was 72,000. Since this value is larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, it was confirmed that polymerization was proceeding by the above reaction.
- Example 14 Synthesis of copolymer (14)> A liquid (binder solution) containing the copolymer (14) was obtained in the same manner as in Example 13 except that methyl methacrylate was used instead of isobutyl methacrylate.
- the number average molecular weight (standard polystyrene conversion value) was 73,000. Since this value is larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, it was confirmed that polymerization was proceeding by the above reaction.
- Example 15 Synthesis of copolymer (15)> Using the cellulose polymerizable compound (a4) obtained in Synthesis Example 4 in place of the cellulose polymerizable compound (a1), the polyvinyl obtained in Synthesis Example 10 instead of the polyvinyl acetal polymerizable compound (b1). A liquid (binder solution) containing the copolymer (15) was obtained in the same manner as in Example 1 except that the acetal polymerizable compound (b4) was used.
- the number average molecular weight (standard polystyrene conversion value) was 78,000. Since this value is larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, it was confirmed that polymerization was proceeding by the above reaction.
- Example 16 Synthesis of copolymer (16)>
- 10 parts of the cellulose polymerizable compound (a4) obtained in Synthesis Example 4 10 parts of the polyvinyl acetal polymerizable compound (b4) obtained in Synthesis Example 10, 5.0 parts of methyl methacrylate, And 80 parts of dihydroterpinyl acetate as an organic solvent was added, mixed, heated to 60 ° C. and stirred with a rotary blade to dissolve. After dissolution, nitrogen substitution was performed to remove oxygen in the system, and 0.01 part of azoisobutyronitrile (AIBN) as a polymerization initiator was mixed and reacted at 70 ° C. for 5 hours to obtain a copolymer ( A liquid (binder solution) containing 16) was obtained.
- AIBN azoisobutyronitrile
- the number average molecular weight (standard polystyrene conversion value) was 81,000. Since this value is larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, it was confirmed that polymerization was proceeding by the above reaction.
- Example 17 Synthesis of copolymer (17)> Using the cellulose-based polymerizable compound (a5) obtained in Synthesis Example 5 instead of the cellulose-based polymerizable compound (a1), the polyvinyl obtained in Synthesis Example 11 instead of the polyvinyl acetal-based polymerizable compound (b1) A liquid (binder solution) containing the copolymer (17) was obtained in the same manner as in Example 1 except that the acetal polymerizable compound (b5) was used.
- the number average molecular weight (standard polystyrene conversion value) was 68,000. Since this value is larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, it was confirmed that polymerization was proceeding by the above reaction.
- Example 18 Synthesis of copolymer (18)>
- 10 parts of the cellulose polymerizable compound (a5) obtained in Synthesis Example 5 10 parts of the polyvinyl acetal polymerizable compound (b5) obtained in Synthesis Example 11, 3.0 parts of isobutyl methacrylate, 2.0 parts of 2-hydroxyethyl methacrylate and 80 parts of dihydroterpinyl acetate as an organic solvent were added, mixed, heated to 60 ° C., stirred with a rotary blade, and dissolved.
- the number average molecular weight (standard polystyrene conversion value) was 70000. Since this value is larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, it was confirmed that polymerization was proceeding by the above reaction.
- Example 19 Synthesis of copolymer (19)> Using the cellulose polymerizable compound (a6) obtained in Synthesis Example 6 in place of the cellulose polymerizable compound (a1), the polyvinyl obtained in Synthesis Example 12 instead of the polyvinyl acetal polymerizable compound (b1). A liquid (binder solution) containing the copolymer (19) was obtained in the same manner as in Example 1 except that the acetal polymerizable compound (b6) was used.
- the number average molecular weight (standard polystyrene conversion value) was 56000. Since this value is larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, it was confirmed that polymerization was proceeding by the above reaction.
- Example 20 Synthesis of copolymer (20)>
- a cellulose-based polymerizable compound (a9) in which a methacrylate group was introduced into ethylcellulose obtained in Synthesis Example 15 and a polyvinyl acetal-based polymerizable compound (b9) in which a methacrylate group was introduced into polyvinyl butyral 20 parts of the mixture, 0.1 part of isobutyl methacrylate and 80 parts of dihydroterpinyl acetate as an organic solvent were added, mixed, heated to 60 ° C. and stirred with a rotary blade to dissolve.
- the number average molecular weight (standard polystyrene conversion value) was 30500. Since this value is larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, it was confirmed that polymerization was proceeding by the above reaction.
- Example 21 Synthesis of copolymer (21)>
- the cellulose-based polymerizable compound (a10) in which the methacrylate group was introduced into the ethylcellulose obtained in Synthesis Example 16 and the polyvinyl acetal-based polymerizable compound (b10) in which the methacrylate group was introduced into polyvinyl butyral 20 parts of the mixture, 0.2 parts of isobutyl methacrylate, and 80 parts of dihydroterpinyl acetate as an organic solvent were added, mixed, heated to 60 ° C., stirred with a rotary blade, and dissolved.
- the number average molecular weight (standard polystyrene conversion value) was 59000. Since this value is larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, it was confirmed that polymerization was proceeding by the above reaction.
- Example 22 Synthesis of copolymer (22)>
- the cellulose-based polymerizable compound (a11) in which the methacrylate group was introduced into the ethylcellulose obtained in Synthesis Example 17 and the polyvinyl acetal-based polymerizable compound (b11) in which the methacrylate group was introduced into polyvinyl butyral 20 parts of the mixture, 0.2 parts of isobutyl methacrylate, and 80 parts of dihydroterpinyl acetate as an organic solvent were added, mixed, heated to 60 ° C., stirred with a rotary blade, and dissolved.
- the number average molecular weight (standard polystyrene conversion value) was 63,000. Since this value is larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, it was confirmed that polymerization was proceeding by the above reaction.
- ⁇ Comparative Example 1 10 parts of ethyl cellulose ("Etocel STD-100” manufactured by Dow Chemical Company) and 10 parts of polyvinyl butyral ("BM-S” manufactured by Sekisui Chemical Co., Ltd.) were dissolved in 113.3 parts of dihydroterpinyl acetate. A binder solution was prepared.
- ⁇ Comparative example 2 10 parts of ethyl cellulose ("Etocel STD-10" manufactured by Dow Chemical Company) and 10 parts of polyvinyl butyral ("BL-S” manufactured by Sekisui Chemical Co., Ltd.) were dissolved in 113.3 parts of dihydroterpinyl acetate. A binder solution was prepared.
- BM-S polyvinyl butyral
- ⁇ Comparative Example 7 10 parts of ethyl cellulose ("Etocel STD-100” manufactured by Dow Chemical Co., Ltd.) and 10 parts of polyvinyl butyral ("BH-S” manufactured by Sekisui Chemical Co., Ltd.) are dissolved in 113.3 parts of dihydroterpinyl acetate to form a binder. A solution was prepared.
- ⁇ Comparative Example 8 10 parts of ethyl cellulose ("Etocel STD-200" manufactured by Dow Chemical Company) and 10 parts of polyvinyl butyral ("BH-S” manufactured by Sekisui Chemical Co., Ltd.) were dissolved in 113.3 parts of dihydroterpinyl acetate. A binder solution was prepared.
- ⁇ Comparative Example 11 10 parts of a cellulose-based polymerizable compound (a1) in which a methacrylate group is introduced into ethylcellulose obtained in Synthesis Example 1 and a polyvinyl acetal-based polymerizable compound in which a methacrylate group is introduced into the polyvinyl butyral obtained in Synthesis Example 7 ( b1) 10 parts was dissolved in 113.3 parts of dihydroterpinyl acetate as an organic solvent to prepare a binder solution. In this comparative example, the effect was grasped without carrying out the polymerization reaction.
- ⁇ Comparative Example 12 20 parts of a mixture of the cellulose polymerizable compound (a7) and the polyvinyl acetal polymerizable compound (b7) obtained in Synthesis Example 13 were dissolved in 113.3 parts of dihydroterpinyl acetate as an organic solvent, A solution was prepared. In this comparative example, the effect was grasped without carrying out the polymerization reaction.
- Table 1 summarizes the binder compositions obtained in Examples and Comparative Examples. Details of the abbreviations shown in Table 1 are as follows.
- iBMA isobutyl methacrylate
- MMA methyl methacrylate
- HEMA 2-hydroxyethyl methacrylate
- the binder solutions obtained in Examples and Comparative Examples are applied with a blade coater having a thickness gap of 90 ⁇ m, and then dried by heating. Thus, a film having a binder layer with a thickness of about 10 ⁇ m was produced.
- polyvinyl butyral (“BH-S” manufactured by Sekisui Chemical Co., Ltd.) as a model material for the binder for green sheets was dissolved in toluene to prepare a 15% by mass solution.
- a film having a polyvinyl butyral layer having a thickness of about 10 ⁇ m was prepared by applying this to a PET film adhesive layer on which an adhesive layer was formed in the same manner as described above, followed by drying by heating.
- a strip sample having a width of 2 cm and a length of 8 cm was cut out from each of the obtained films.
- the polyvinyl butyral layer of the film sample having the polyvinyl butyral layer was superposed on the binder layer of the film sample having the binder layer while being shifted in the longitudinal direction.
- the area of the overlapped portion was 2 cm in the longitudinal direction and 2 cm in width.
- a 1 cm ⁇ 2 cm (area 2 cm 2 ) heating plate was pressed against the center of the overlapped portion and thermocompression bonded for 5 minutes under the conditions of a temperature of 130 ° C. and a pressure of 2 kg to partially adhere the overlapped portion.
- the obtained paste was applied onto a glass substrate with a blade coater having a thickness gap of 30 ⁇ m, the coating film after heat drying was observed with a scanning electron microscope (SEM), and the coating film quality was evaluated based on the following evaluation criteria. .
- SEM scanning electron microscope
- JSM-7800F manufactured by JEOL Ltd. was used, and the coating film was observed at a magnification of 5000 times.
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Abstract
Description
1)熱分解性(燃焼性)の向上。焼成による熱分解処理後においてもカーボン等の灰分が残存していると、MLCCの電気特性を悪化させたり層間の剥離を引き起こしてしまう。
2)印刷性の向上。昨今、スクリーン印刷によって形成される電極パターンの微細化や薄膜化が進んでおり、パターンサイズは100μmを下回るようになっている。このため、電極ペーストにおいては、いわゆる糸曳現象を生じないバインダーが求められる。糸曳現象とは、バインダーポリマーの影響で印刷する工程において用いるペースト等が伸長して細い糸を曳く現象であり、欠陥品を生じる原因となる。
3)無機粒子の均一分散性、膜強度(ペーストから形成される層の強度)及び各層間の密着性の向上。これらは、チップを構成する各層の薄膜化に伴う要求特性である。
[1] 重合性不飽和基を有するセルロース系重合性化合物由来の構成単位(a)と、重合性不飽和基を有するポリビニルアセタール系重合性化合物由来の構成単位(b)とを含む、共重合体。
を含む、共重合体組成物。
なお、本明細書において「A~B」(A及びBは数値である。)との記載は、特記ない限り「A以上B以下」を表す。
本発明に係る共重合体は、共重合体組成物(ペースト又はスラリー)のバインダーとして好適に用いられるポリマー材料であり、重合性不飽和基を有するセルロース系重合性化合物由来の構成単位(a)と、重合性不飽和基を有するポリビニルアセタール系重合性化合物由来の構成単位(b)とを含む。セルロース系重合性化合物及びポリビニルアセタール系重合性化合物は、重合性不飽和基によって重合し、共重合体においてそれぞれ構成単位(a)及び構成単位(b)を形成する。共重合体は、1種又は2種以上の構成単位(a)を含むことができ、また、1種又は2種以上の構成単位(b)を含むことができる。
構成単位(a)を形成する重合性不飽和基を有するセルロース系重合性化合物は、重合性不飽和基を有するセルロース誘導体である。セルロース誘導体とは、天然高分子であるセルロースが有するヒドロキシ基の一部に化学修飾を施した変性セルロースをいう。ヒドロキシ基の化学修飾としては、特に制限されないが、ヒドロキシ基のアルキルエーテル化、ヒドロキシアルキルエーテル化、エステル化等を挙げることができる。セルロース誘導体は、1分子中に少なくとも1つのヒドロキシ基を有する。セルロース誘導体は、1種のみを用いてもよいし、2種以上を併用してもよい。
構成単位(b)を形成する重合性不飽和基を有するポリビニルアセタール系重合性化合物は、重合性不飽和基を有するポリビニルアセタールである。ポリビニルアセタールは通常、ビニルアセタール/ビニルアルコール/酢酸ビニルのモノマー単位から構成されるポリマーであり、ポリビニルアルコールをアセタール化することによって得ることができる。具体的には、ポリビニルアルコールをブチラール化したもの(ポリビニルブチラール)、ポリビニルアルコールをホルマール化したもの(ポリビニルホルマール)等を挙げることができる。
共重合体は、構成単位(a)及び構成単位(b)以外の他の構成単位(c)をさらに含むことができる。共重合体は、1種又は2種以上の構成単位(c)を含むことができる。構成単位(c)をさらに含有させることにより、上記した2種の重合性化合物の共重合効率が高まったり、共重合体の有機溶剤への溶解性や、共重合体組成物(ペースト又はスラリー)における無機粒子の分散性の調整が容易になることがある。
共重合体に含有される構成単位(a)と構成単位(b)との含有量比は、質量基準で、好ましくは10:90~90:10の範囲であり、より好ましくは20:80~80:20の範囲であり、さらに好ましくは25:75~75:25の範囲である。構成単位(a)と構成単位(b)との含有量比が上記範囲であることにより、構成単位(a)と構成単位(b)とを含む共重合体であることによる所期の効果(良好な熱分解性、密着性、塗布膜質、及び印刷性の兼備)をより効果的に得ることができる。構成単位(a)が上記範囲より少ないと、共重合体組成物(ペースト又はスラリー)の印刷性が低下する可能性がある。構成単位(b)が上記範囲より少ないと、共重合体組成物から形成される膜の強度、密着性及び/又は熱分解性が低下する可能性がある。
〔1〕セルロース系重合性化合物及びポリビニルアセタール系重合性化合物の製造
共重合体の構成単位(a)を形成する重合性不飽和基を有するセルロース系重合性化合物及び構成単位(b)を形成する重合性不飽和基を有するポリビニルアセタール系重合性化合物は、上述のように、それぞれセルロース誘導体、ポリビニルアセタールのヒドロキシ基と、当該ヒドロキシ基と反応可能な基及び重合性不飽和基を有する化合物とを反応させることによって得ることができる。
重合性不飽和基を有するセルロース系重合性化合物、重合性不飽和基を有するポリビニルアセタール系重合性化合物、及び任意で使用される構成単位(c)を形成するモノマーを含むモノマー組成物を共重合させることにより共重合体を得ることができる。この共重合反応は、例えば、有機溶剤中、ラジカル重合開始剤の存在下に、好ましくは非酸素雰囲気下にて加熱することによって行われる。共重合反応に使用可能な有機溶剤の具体例は、上記〔1〕で例示した非プロトン性の有機溶剤に加えてプロトン性有機溶剤が使用可能であり、エチルアルコール、イソプロピルアルコール、ブチルアルコール、ベンジルアルコール、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールジメチルエーテル、ジプロピレングリコールモノメチルエーテル、ターピネオール、ジヒドロターピネオール等が挙げられる。有機溶剤は、1種のみを用いてもよいし、2種以上を併用してもよい。
本発明に係る共重合体組成物は、上記共重合体であるバインダーと、無機粒子と、有機溶剤とを含み、種々のペースト又はスラリー、特に電子部品や、電子機器の部材を製造するための焼成型のペースト又はスラリーとして好適である。なお、ペーストとスラリーとの間に明確な区別はないが、主に粘度の点から区別されており、前者の方が高粘度である。
エチルセルロース(ダウケミカル社製の「エトセルSTD-100」、数平均分子量Mn(GPCによる標準ポリスチレン換算値):63400、置換度(DS値、エーテル化度):2.52)を用意し、乾燥させた。なお、置換度2.52とは、1個のグルコース環に存在する3個のヒドロキシ基のうち平均して2.52個がエチルエーテル化されており、0.48個のヒドロキシ基が残存しているという意味である。数平均分子量Mn及び置換度から計算される一分子中の平均ヒドロキシ基数は、約131である。
エチルセルロース(ダウケミカル社製の「エトセルSTD-10」、数平均分子量Mn(GPCによる標準ポリスチレン換算値):22800、置換度:2.52)を用意し、乾燥させた。数平均分子量Mn及び置換度から計算される一分子中の平均ヒドロキシ基数は、約47である。
エチルセルロース(ダウケミカル社製の「エトセルSTD-200」、数平均分子量Mn(GPCによる標準ポリスチレン換算値):80700、置換度:2.52)を用意し、乾燥させた。数平均分子量Mn及び置換度から計算される一分子中の平均ヒドロキシ基数は、約167である。
エチルセルロース(ダウケミカル社製の「エトセルSTD-100」、数平均分子量Mn(GPCによる標準ポリスチレン換算値):63400、置換度:2.52)を用意し、乾燥させた。数平均分子量Mn及び置換度から計算される一分子中の平均ヒドロキシ基数は、約131である。
エチルセルロース(ダウケミカル社製の「エトセルSTD-45」、数平均分子量Mn(GPCによる標準ポリスチレン換算値):56500、置換度:2.52)を用意し、乾燥させた。数平均分子量Mn及び置換度から計算される一分子中の平均ヒドロキシ基数は、約117である。
エチルセルロース(ダウケミカル社製の「エトセルSTD-4」、数平均分子量Mn(GPCによる標準ポリスチレン換算値):13700、置換度:2.52)を用意し、乾燥させた。数平均分子量Mn及び置換度から計算される一分子中の平均ヒドロキシ基数は、約28である。
ポリビニルブチラール(積水化学社製の「BM-S」、数平均分子量Mn(GPCによる標準ポリスチレン換算値):53000、ヒドロキシ基量:約22モル%)を用意し、乾燥させた。乾燥させたポリビニルブチラール100部を酢酸エチル400部に溶解させた。得られた溶液に、ポリビニルブチラール一分子に対して平均2個の導入量に相当するメタクリル酸0.32部、縮合剤としてのジイソプロピルカルボジイミド0.48部、反応促進剤としてのジメチルアミノピリジン0.0048部を添加し、温度30℃で24時間撹拌して反応を行った。その後、酢酸エチルを留去することにより、固体として、ポリビニルブチラールにメタクリレート基が導入されたポリビニルアセタール系重合性化合物(b1)を得た。
ポリビニルブチラール(積水化学社製の「BL-S」、数平均分子量Mn(GPCによる標準ポリスチレン換算値):23000、ヒドロキシ基量:約22モル%)を用意し、乾燥させた。乾燥させたポリビニルブチラール100部を酢酸エチル400部に溶解させた。得られた溶液に、ポリビニルブチラール一分子に対して平均3個の導入量に相当する2-イソシアナトエチルメタクリレート(昭和電工社製の「カレンズMOI」)2.02部、触媒としてのジラウリン酸ジオクチルスズ0.01部を添加し、温度60℃で5時間撹拌して反応を行った。その後、酢酸エチルを留去することにより、固体として、ポリビニルブチラールにメタクリレート基が導入されたポリビニルアセタール系重合性化合物(b2)を得た。
ポリビニルブチラール(積水化学社製の「BH-S」、数平均分子量Mn(GPCによる標準ポリスチレン換算値):66000、ヒドロキシ基量:約22モル%)を用意し、乾燥させた。乾燥させたポリビニルブチラール100部を酢酸エチル400部に溶解させた。得られた溶液に、ポリビニルブチラール一分子に対して平均1個の導入量に相当するメタクリル酸0.13部、縮合剤としてのジイソプロピルカルボジイミド0.19部、反応促進剤としてのジメチルアミノピリジン0.002部を添加し、温度30℃で24時間撹拌して反応を行った。その後、酢酸エチルを留去することにより、固体として、ポリビニルブチラールにメタクリレート基が導入されたポリビニルアセタール系重合性化合物(b3)を得た。
ポリビニルブチラール(積水化学社製の「BM-S」、数平均分子量Mn(GPCによる標準ポリスチレン換算値):53000、ヒドロキシ基量:約22モル%)を用意し、乾燥させた。乾燥させたポリビニルブチラール100部を酢酸エチル400部に溶解させた。得られた溶液に、ポリビニルブチラール一分子に対して平均5個の導入量に相当するメタクリル酸0.81部、縮合剤としてのジイソプロピルカルボジイミド1.19部、反応促進剤としてのジメチルアミノピリジン0.012部を添加し、温度30℃で24時間撹拌して反応を行った。その後、酢酸エチルを留去することにより、固体として、ポリビニルブチラールにメタクリレート基が導入されたポリビニルアセタール系重合性化合物(b4)を得た。
ポリビニルブチラール(積水化学社製の「BM-S」、数平均分子量Mn(GPCによる標準ポリスチレン換算値):53000、ヒドロキシ基量:約22モル%)を用意し、乾燥させた。乾燥させたポリビニルブチラール100部を酢酸エチル400部に溶解させた。得られた溶液に、ポリビニルブチラール一分子に対して平均3個の導入量に相当するメタクリル酸0.48部、縮合剤としてのジイソプロピルカルボジイミド0.72部、反応促進剤としてのジメチルアミノピリジン0.0072部を添加し、温度30℃で24時間撹拌して反応を行った。その後、酢酸エチルを留去することにより、固体として、ポリビニルブチラールにメタクリレート基が導入されたポリビニルアセタール系重合性化合物(b5)を得た。
ポリビニルブチラール(積水化学社製の「BL-S」、数平均分子量Mn(GPCによる標準ポリスチレン換算値):23000、ヒドロキシ基量:約22モル%)を用意し、乾燥させた。乾燥させたポリビニルブチラール100部を酢酸エチル400部に溶解させた。得られた溶液に、ポリビニルブチラール一分子に対して平均10個の導入量に相当するメタクリル酸3.74部、縮合剤としてのジイソプロピルカルボジイミド5.49部、反応促進剤としてのジメチルアミノピリジン0.055部を添加し、温度30℃で24時間撹拌して反応を行った。その後、酢酸エチルを留去することにより、固体として、ポリビニルブチラールにメタクリレート基が導入されたポリビニルアセタール系重合性化合物(b6)を得た。
エチルセルロース(ダウケミカル社製の「エトセルSTD-100」、数平均分子量Mn(GPCによる標準ポリスチレン換算値):63400、置換度:2.52)を用意し、乾燥させた。また、ポリビニルブチラール(積水化学社製の「BM-S」、数平均分子量Mn(GPCによる標準ポリスチレン換算値):53000、ヒドロキシ基量:約22モル%)を用意し、乾燥させた。
エチルセルロース(ダウケミカル社製の「エトセルSTD-10」、数平均分子量Mn(GPCによる標準ポリスチレン換算値):22800、置換度:2.52)を用意し、乾燥させた。また、ポリビニルブチラール(積水化学社製の「BL-S」、数平均分子量Mn(GPCによる標準ポリスチレン換算値):23000、ヒドロキシ基量:約22モル%)を用意し、乾燥させた。
エチルセルロース(ダウケミカル社製の「エトセルSTD-4」、数平均分子量Mn(GPCによる標準ポリスチレン換算値):13700、置換度:2.52)を用意し、乾燥させた。また、ポリビニルブチラール(積水化学社製の「BL-S」、数平均分子量Mn(GPCによる標準ポリスチレン換算値):23000、ヒドロキシ基量:約22モル%)を用意し、乾燥させた。
エチルセルロース(ダウケミカル社製の「エトセルSTD-100」、数平均分子量Mn(GPCによる標準ポリスチレン換算値):63400、置換度:2.52)を用意し、乾燥させた。また、ポリビニルブチラール(積水化学社製の「BH-S」、数平均分子量Mn(GPCによる標準ポリスチレン換算値):66000、ヒドロキシ基量:約22モル%)を用意し、乾燥させた。
エチルセルロース(ダウケミカル社製の「エトセルSTD-200」、数平均分子量Mn(GPCによる標準ポリスチレン換算値):80700、置換度:2.52)を用意し、乾燥させた。また、ポリビニルブチラール(積水化学社製の「BH-S」、数平均分子量Mn(GPCによる標準ポリスチレン換算値):66000、ヒドロキシ基量:約22モル%)を用意し、乾燥させた。
<実施例1:共重合体(1)の合成>
重合反応容器内に、合成例1で得られたセルロース系重合性化合物(a1) 10部、合成例7で得られたポリビニルアセタール系重合性化合物(b1) 10部、及び有機溶剤としてのジヒドロターピニルアセテート80部を添加、混合し、60℃に加熱して回転翼で撹拌して溶解させた。溶解後に窒素置換を行って系内の酸素を除去し、重合開始剤としてのアゾイソブチロニトリル(AIBN)0.01部を混合して70℃で5時間反応を行って、共重合体(1)を含有する液(バインダー溶液)を得た。
カラム:TSKgel GMHXL、
測定温度(設定温度):30℃、
移動相:テトラヒドロフラン。
重合反応容器内に、合成例1で得られたセルロース系重合性化合物(a1) 10部、合成例7で得られたポリビニルアセタール系重合性化合物(b1) 10部、イソブチルメタクリレート1.0部、及び有機溶剤としてのジヒドロターピニルアセテート80部を添加、混合し、60℃に加熱して回転翼で撹拌して溶解させた。溶解後に窒素置換を行って系内の酸素を除去し、重合開始剤としてのアゾイソブチロニトリル(AIBN)0.01部を混合して70℃で5時間反応を行って、共重合体(2)を含有する液(バインダー溶液)を得た。
合成例1で得られたセルロース系重合性化合物(a1)を5部、合成例7で得られたポリビニルアセタール系重合性化合物(b1)を15部使用したこと以外は実施例1と同様にして、共重合体(3)を含有する液(バインダー溶液)を得た。
合成例1で得られたセルロース系重合性化合物(a1)を15部、合成例7で得られたポリビニルアセタール系重合性化合物(b1)を5部使用したこと以外は実施例1と同様にして、共重合体(4)を含有する液(バインダー溶液)を得た。
重合反応容器内に、合成例2で得られたセルロース系重合性化合物(a2) 10部、合成例8で得られたポリビニルアセタール系重合性化合物(b2) 10部、及び有機溶剤としてのジヒドロターピニルアセテート80部を添加、混合し、60℃に加熱して回転翼で撹拌して溶解させた。溶解後に窒素置換を行って系内の酸素を除去し、重合開始剤としてのアゾイソブチロニトリル(AIBN)0.01部を混合して70℃で5時間反応を行って、共重合体(5)を含有する液(バインダー溶液)を得た。
重合反応容器内に、合成例2で得られたセルロース系重合性化合物(a2) 10部、合成例8で得られたポリビニルアセタール系重合性化合物(b2) 10部、イソブチルメタクリレート2部、及び有機溶剤としてのジヒドロターピニルアセテート80部を添加、混合し、60℃に加熱して回転翼で撹拌して溶解させた。溶解後に窒素置換を行って系内の酸素を除去し、重合開始剤としてのアゾイソブチロニトリル(AIBN)0.01部を混合して70℃で5時間反応を行って、共重合体(6)を含有する液(バインダー溶液)を得た。
合成例2で得られたセルロース系重合性化合物(a2)の代わりに合成例1で得られたセルロース系重合性化合物(a1)を使用したこと以外は実施例5と同様にして、共重合体(7)を含有する液(バインダー溶液)を得た。
合成例8で得られたポリビニルアセタール系重合性化合物(b2)の代わりに合成例7で得られたポリビニルアセタール系重合性化合物(b1)を使用したこと以外は実施例5と同様にして、共重合体(8)を含有する液(バインダー溶液)を得た。
重合反応容器内に、合成例13で得られたエチルセルロースにメタクリレート基が導入されたセルロース系重合性化合物(a7)とポリビニルブチラールにメタクリレート基が導入されたポリビニルアセタール系重合性化合物(b7)との混合物20部、イソブチルメタクリレート0.2部、及び有機溶剤としてのジヒドロターピニルアセテート80部を添加、混合し、60℃に加熱して回転翼で撹拌して溶解させた。溶解後に窒素置換を行って系内の酸素を除去し、重合開始剤としてのアゾイソブチロニトリル(AIBN)0.01部を混合して70℃で5時間反応を行って、共重合体(9)を含有する液(バインダー溶液)を得た。
合成例13で得られた混合物の代わりに合成例14で得られたエチルセルロースにメタクリレート基が導入されたセルロース系重合性化合物(a8)とポリビニルブチラールにメタクリレート基が導入されたポリビニルアセタール系重合性化合物(b8)との混合物を使用したこと以外は実施例9と同様にして共重合体(10)を含有する液(バインダー溶液)を得た。
セルロース系重合性化合物(a1)の代わりに合成例3で得られたセルロース系重合性化合物(a3)を使用し、ポリビニルアセタール系重合性化合物(b1)の代わりに合成例9で得られたポリビニルアセタール系重合性化合物(b3)を使用したこと以外は実施例1と同様にして共重合体(11)を含有する液(バインダー溶液)を得た。
重合反応容器内に、合成例3で得られたセルロース系重合性化合物(a3) 10部、合成例9で得られたポリビニルアセタール系重合性化合物(b3) 10部、イソブチルメタクリレート0.2部、及び有機溶剤としてのジヒドロターピニルアセテート80部を添加、混合し、60℃に加熱して回転翼で撹拌して溶解させた。溶解後に窒素置換を行って系内の酸素を除去し、重合開始剤としてのアゾイソブチロニトリル(AIBN)0.01部を混合して70℃で5時間反応を行って、共重合体(12)を含有する液(バインダー溶液)を得た。
イソブチルメタクリレートの添加量を0.2部に変更したこと以外は実施例2と同様にして共重合体(13)を含有する液(バインダー溶液)を得た。
イソブチルメタクリレートの代わりにメチルメタクリレートを使用したこと以外は実施例13と同様にして共重合体(14)を含有する液(バインダー溶液)を得た。
セルロース系重合性化合物(a1)の代わりに合成例4で得られたセルロース系重合性化合物(a4)を使用し、ポリビニルアセタール系重合性化合物(b1)の代わりに合成例10で得られたポリビニルアセタール系重合性化合物(b4)を使用したこと以外は実施例1と同様にして共重合体(15)を含有する液(バインダー溶液)を得た。
重合反応容器内に、合成例4で得られたセルロース系重合性化合物(a4) 10部、合成例10で得られたポリビニルアセタール系重合性化合物(b4) 10部、メチルメタクリレート5.0部、及び有機溶剤としてのジヒドロターピニルアセテート80部を添加、混合し、60℃に加熱して回転翼で撹拌して溶解させた。溶解後に窒素置換を行って系内の酸素を除去し、重合開始剤としてのアゾイソブチロニトリル(AIBN)0.01部を混合して70℃で5時間反応を行って、共重合体(16)を含有する液(バインダー溶液)を得た。
セルロース系重合性化合物(a1)の代わりに合成例5で得られたセルロース系重合性化合物(a5)を使用し、ポリビニルアセタール系重合性化合物(b1)の代わりに合成例11で得られたポリビニルアセタール系重合性化合物(b5)を使用したこと以外は実施例1と同様にして共重合体(17)を含有する液(バインダー溶液)を得た。
重合反応容器内に、合成例5で得られたセルロース系重合性化合物(a5) 10部、合成例11で得られたポリビニルアセタール系重合性化合物(b5) 10部、イソブチルメタクリレート3.0部、2-ヒドロキシエチルメタクリレート2.0部、及び有機溶剤としてのジヒドロターピニルアセテート80部を添加、混合し、60℃に加熱して回転翼で撹拌して溶解させた。溶解後に窒素置換を行って系内の酸素を除去し、重合開始剤としてのアゾイソブチロニトリル(AIBN)0.01部を混合して70℃で5時間反応を行って、共重合体(18)を含有する液(バインダー溶液)を得た。
セルロース系重合性化合物(a1)の代わりに合成例6で得られたセルロース系重合性化合物(a6)を使用し、ポリビニルアセタール系重合性化合物(b1)の代わりに合成例12で得られたポリビニルアセタール系重合性化合物(b6)を使用したこと以外は実施例1と同様にして共重合体(19)を含有する液(バインダー溶液)を得た。
重合反応容器内に、合成例15で得られたエチルセルロースにメタクリレート基が導入されたセルロース系重合性化合物(a9)とポリビニルブチラールにメタクリレート基が導入されたポリビニルアセタール系重合性化合物(b9)との混合物20部、イソブチルメタクリレート0.1部、及び有機溶剤としてのジヒドロターピニルアセテート80部を添加、混合し、60℃に加熱して回転翼で撹拌して溶解させた。溶解後に窒素置換を行って系内の酸素を除去し、重合開始剤としてのアゾイソブチロニトリル(AIBN)0.01部を混合して70℃で5時間反応を行って、共重合体(20)を含有する液(バインダー溶液)を得た。
重合反応容器内に、合成例16で得られたエチルセルロースにメタクリレート基が導入されたセルロース系重合性化合物(a10)とポリビニルブチラールにメタクリレート基が導入されたポリビニルアセタール系重合性化合物(b10)との混合物20部、イソブチルメタクリレート0.2部、及び有機溶剤としてのジヒドロターピニルアセテート80部を添加、混合し、60℃に加熱して回転翼で撹拌して溶解させた。溶解後に窒素置換を行って系内の酸素を除去し、重合開始剤としてのアゾイソブチロニトリル(AIBN)0.01部を混合して70℃で5時間反応を行って、共重合体(21)を含有する液(バインダー溶液)を得た。
重合反応容器内に、合成例17で得られたエチルセルロースにメタクリレート基が導入されたセルロース系重合性化合物(a11)とポリビニルブチラールにメタクリレート基が導入されたポリビニルアセタール系重合性化合物(b11)との混合物20部、イソブチルメタクリレート0.2部、及び有機溶剤としてのジヒドロターピニルアセテート80部を添加、混合し、60℃に加熱して回転翼で撹拌して溶解させた。溶解後に窒素置換を行って系内の酸素を除去し、重合開始剤としてのアゾイソブチロニトリル(AIBN)0.01部を混合して70℃で5時間反応を行って、共重合体(22)を含有する液(バインダー溶液)を得た。
エチルセルロース(ダウケミカル社製の「エトセルSTD-100」)10部、及びポリビニルブチラール(積水化学社製の「BM-S」)10部を、ジヒドロターピニルアセテート113.3部に溶解して、バインダー溶液を調製した。
エチルセルロース(ダウケミカル社製の「エトセルSTD-10」)10部、及びポリビニルブチラール(積水化学社製の「BL-S」)10部を、ジヒドロターピニルアセテート113.3部に溶解して、バインダー溶液を調製した。
エチルセルロース(ダウケミカル社製の「エトセルSTD-100」)20部を、ジヒドロターピニルアセテート113.3部に溶解して、バインダー溶液を調製した。
ポリビニルブチラール(積水化学社製の「BM-S」)20部を、ジヒドロターピニルアセテート113.3部に溶解して、バインダー溶液を調製した。
エチルセルロース(ダウケミカル社製の「エトセルSTD-10」)20部を、ジヒドロターピニルアセテート113.3部に溶解して、バインダー溶液を調製した。
ポリビニルブチラール(積水化学社製の「BL-S」)20部を、ジヒドロターピニルアセテート113.3部に溶解して、バインダー溶液を調製した。
エチルセルロース(ダウケミカル社製の「エトセルSTD-100」)10部、及びポリビニルブチラール(積水化学社製の「BH-S」10部を、ジヒドロターピニルアセテート113.3部に溶解して、バインダー溶液を調製した。
エチルセルロース(ダウケミカル社製の「エトセルSTD-200」)10部、及びポリビニルブチラール(積水化学社製の「BH-S」)10部を、ジヒドロターピニルアセテート113.3部に溶解して、バインダー溶液を調製した。
エチルセルロース(ダウケミカル社製の「エトセルSTD-200」)20部を、ジヒドロターピニルアセテート113.3部に溶解して、バインダー溶液を調製した。
ポリビニルブチラール(積水化学社製の「BH-S」)20部を、ジヒドロターピニルアセテート113.3部に溶解して、バインダー溶液を調製した。
合成例1で得られたエチルセルロースにメタクリレート基が導入されたセルロース系重合性化合物(a1) 10部、及び合成例7で得られたポリビニルブチラールにメタクリレート基が導入されたポリビニルアセタール系重合性化合物(b1) 10部を有機溶剤としてのジヒドロターピニルアセテート113.3部に溶解して、バインダー溶液を調製した。本比較例では重合反応を実施せずにその影響を把握した。
合成例13で得られたセルロース系重合性化合物(a7)とポリビニルアセタール系重合性化合物(b7)との混合物20部を有機溶剤としてのジヒドロターピニルアセテート113.3部に溶解して、バインダー溶液を調製した。本比較例では重合反応を実施せずにその影響を把握した。
MMA : メチルメタクリレート、
HEMA: 2-ヒドロキシエチルメタクリレート。
実施例、比較例で得られたバインダー及びそれを含むペーストについて、次の評価を行った。結果を表2に示す。
バインダーの乾燥固体サンプル10mgを、TG/DTA熱分析装置(セイコーインスツルメンツ株式会社製の「EXSTAR TG/DTA6200」)にて、窒素雰囲気下、10℃/minの昇温速度で500℃まで加熱したときの残渣量を測定し、次の評価基準に基づいてバインダーの熱分解性を評価した。残渣量(質量%)とは、上記乾燥固体サンプルの質量を100質量%としたときの測定後の残渣の量を示す。
A:残渣量が1質量%以下である、
B:残渣量が1質量%を超え、3質量%以下である、
C:残渣量が3質量%を超える。
バインダーを電極ペーストに使用するケースを想定し、グリーンシートに対する密着性の評価を下記のモデル実験により実施した。
A:破断強度が100N以上である、
B:破断強度が100N未満、50N以上である、
C:破断強度が50N未満である。
実施例、比較例で得られたバインダー溶液にジヒドロターピニルアセテートを加えて、バインダー濃度を15質量%に調整した。次いで、無機粒子としてのNi粒子(JFEミネラル社製の「NFP201S」、平均粒径0.2μm)100質量部、及び上記バインダー溶液25質量部を3本ロールミルで混合して、ペーストを得た。
A:1μmを超えるサイズの欠陥(穴)が認められない、
B:1μmを超えるサイズの欠陥(穴)が認められる。
上記〔3〕で調製したペーストを、マイクロテック印刷装置(MT-320シリーズ)を用い、メッシュ#500(中沼アートスクリーン製)をスクリーン版として、L/S=100μm/100μmのストライプ状パターンをPETフィルム上に印刷した。印刷パターンを顕微鏡で観察し、次の評価基準に基づいてスクリーン印刷性を評価した。なお、糸曳欠陥とは、印刷時にスクリーン印刷版が被印刷体から引き離される段階でペースト等が伸長して細い糸を曳く現象によって印刷欠陥を生じるものである。この現象が起こると、印刷パターンのエッジ部から繊維状の異物が形成されてしまって電気的短絡が起こる、印刷パターン形状が不均一になることで要求特性が得られない等の問題を引き起こす。
A:エッジ部に糸曳欠陥がない、
B:エッジ部に糸曳欠陥がある。
Claims (6)
- 重合性不飽和基を有するセルロース系重合性化合物由来の構成単位(a)と、重合性不飽和基を有するポリビニルアセタール系重合性化合物由来の構成単位(b)とを含む、共重合体。
- 前記構成単位(a)及び前記構成単位(b)以外の他の構成単位(c)をさらに含む、請求項1に記載の共重合体。
- 前記セルロース系重合性化合物が有する前記重合性不飽和基の数は、1分子あたり平均10個以下である、請求項1又は2に記載の共重合体。
- 前記ポリビニルアセタール系重合性化合物が有する前記重合性不飽和基の数は、1分子あたり平均10個以下である、請求項1~3のいずれか1項に記載の共重合体。
- 重合性不飽和基を有するセルロース系重合性化合物と、重合性不飽和基を有するポリビニルアセタール系重合性化合物とを、有機溶剤中、重合開始剤の存在下に重合させる工程を含む、共重合体の製造方法。
- 請求項1~4のいずれか1項に記載の共重合体と、無機粒子と、有機溶剤と、
を含む、共重合体組成物。
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