KR102056557B1 - Copolymers and preparation methods thereof, and copolymer compositions - Google Patents

Abstract

Copolymer containing the structural unit (a) derived from the cellulose polymerizable compound which has a polymerizable unsaturated group, and the structural unit (b) derived from the polyvinyl acetal type polymeric compound which has a polymerizable unsaturated group, and its manufacturing method, and its Provided is a copolymer composition comprising a copolymer, inorganic particles, and an organic solvent.

Description

Copolymers and preparation methods thereof, and copolymer compositions

TECHNICAL FIELD This invention relates to a copolymer, its manufacturing method, and the copolymer composition containing this copolymer.

The demand for electronic components is increasing due to mobile devices such as mobile phones, smart phones, and automobiles. Among them, hundreds of multi-layer ceramic capacitors (called MLCCs), which are passive components, are used per smartphone, and demand is increasing rapidly.

An example of manufacture of MLCC is as follows. First, by applying a dielectric ceramic paste onto a release sheet, a green sheet having a dielectric layer is produced. Next, an electrode pattern (sometimes referred to as a "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 from the releasable sheet, and a plurality of the laminates are laminated and pressed before being cut into chips. Subsequently, the obtained chips are heated to several hundred degrees Celsius to 1000 degrees Celsius or more to bake, and a sintered compact chip in which a dielectric layer and an electrode layer are laminated in multiple layers is produced. Finally, an external electrode or the like is formed.

In recent years, the chip size has become smaller, and along with this, the thinning of each said layer which comprises a chip | tip, and the refinement | miniaturization of the electrode pattern printed are progressing. Under such a background, there is a strong demand for improved adhesion between the layers and excellent printability of the paste to be used.

Other electronic components such as chip inductors and chip resistors are also manufactured by a process such as MLCC. Moreover, the manufacturing process of solar cells, such as a silicon type | system | group, includes the printing and baking process using an electrode paste in formation of a collection electrode.

The ceramic paste and electrode paste used for manufacture of electronic components, such as MLCC, are the resin composition which contains the binder which is a polymeric material, and the organic solvent, and the inorganic particle was disperse | distributed uniformly to it. As 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. Conventionally, as a binder, polyvinyl butyral is mainly used in ceramic paste, and ethyl cellulose is mainly used in electrode paste (Japanese Patent Laid-Open No. 04-049766 (Patent Document 1)).

Japanese Patent Application Laid-Open No. 04-049766 Japanese Patent No. 4347440 Japanese Patent No. 5299904 International Publication No. 2015/107811

Paste, such as a ceramic paste and an electrode paste, especially the binder contained in it, has the following subjects, for example.

1) Improvement of pyrolysis (combustibility). If ash such as carbon remains after the pyrolysis treatment by firing, the electrical properties of the MLCC may be deteriorated or interlayer separation may occur.

2) Improved printability. These days, miniaturization and thinning of the electrode pattern formed by screen printing are progressing, and the pattern size is less than 100 micrometers. For this reason, the binder which does not produce what is called slip phenomenon is calculated | required in an electrode paste. Sliding phenomenon is a phenomenon in which the paste etc. which are used in the process of printing under the influence of a binder polymer come out like the elongate thread, and cause a defective article.

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 thinning of each layer which comprises a chip | tip.

In order to solve the said subject, various examination is conventionally performed about a binder. For example, Japanese Patent No. 4347440 (Patent Literature 2) and Japanese Patent No. 5299904 (Patent Literature 3) disclose an electrode paste in which polyvinyl butyral is blended with ethyl cellulose, such as film strength. Techniques for improving physical properties have been disclosed. International Publication No. 2015/107811 (Patent Document 4) discloses using a reaction product of ethyl cellulose, polyvinyl butyral, and a binder for bonding them as a binder.

The binder which blended the ethyl cellulose and polyvinyl butyral which are described in patent document 2 and 3 is bad in compatibility of these two types of polymers, and is an inorganic at the time of mixing inorganic particles, such as a metal, a ceramic, and glass, as a paste. The dispersibility of the particles is low. As a result, a defect arises in a coating film, or the uniformity of a coating film falls easily.

On the other hand, although Patent Document 4 improves compatibility by chemically bonding ethyl cellulose and polyvinyl butyral, since the binding efficiency between these two polymers is not high, there is room for improvement in uniformity of the coating film.

An object of the present invention is to provide a binder having good thermal degradability, adhesion, coating film quality, and printability, and a composition containing the same.

This invention provides the copolymer shown below, its manufacturing method, and a copolymer composition.

[1] A copolymer comprising a structural unit (a) derived from a cellulose polymerizable compound having a polymerizable unsaturated group and a structural unit (b) derived from a polyvinyl acetal polymerizable compound having a polymerizable unsaturated group.

[2] The copolymer according to [1], further comprising structural units (c) other than the structural unit (a) and the structural unit (b).

[3] The copolymer according to [1] or [2], wherein the number of the polymerizable unsaturated groups included in the cellulose polymerizable compound is 10 or less on average per molecule.

[4] The copolymer according to any one of [1] to [3], wherein the number of the polymerizable unsaturated groups of the polyvinyl acetal polymerizable compound is 10 or less per molecule.

[5] A method for producing a copolymer comprising the step of polymerizing a cellulose polymerizable compound having a polymerizable unsaturated group and a polyvinyl acetal polymerizable compound having a polymerizable unsaturated group in the presence of a polymerization initiator in an organic solvent. .

[6] A copolymer composition comprising the copolymer according to any one of [1] to [4], an inorganic particle, and an organic solvent.

A copolymer having good thermal degradability, adhesion, coating film quality, and printability, and a copolymer composition including the same can be provided. According to the copolymer, a film with high strength can be formed. The copolymer composition containing the copolymer as a binder is suitable as a paste (or slurry) such as a ceramic paste or an electrode paste. This paste (or slurry) can be used for production of electronic components, substrates and the like.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment is shown and this invention is demonstrated in detail.

In addition, in this specification, description of "A-B" (A and B are numerical values) shows "A or more and B or less" unless there is particular notice.

<Copolymer>

The copolymer according to the present invention is a polymer material suitably used as a binder of a copolymer composition (paste or slurry), and the structural unit (a) derived from a cellulose polymerizable compound having a polymerizable unsaturated group and a polymerizable unsaturated group The structural unit (b) derived from the polyvinyl acetal type polymeric compound which has is included. The cellulose polymerizable compound and the polyvinyl acetal polymerizable compound are polymerized by a polymerizable unsaturated group to form a structural unit (a) and a structural unit (b) in the copolymer, respectively. A copolymer can contain 1 type, or 2 or more types of structural unit (a), and can also contain 1 type or 2 or more types of structural units (b).

[1] structural unit (a)

The cellulose-based polymerizable compound having a polymerizable unsaturated group forming the structural unit (a) is a cellulose derivative having a polymerizable unsaturated group. A cellulose derivative means the modified cellulose which chemically modified the one part of the hydroxyl group which cellulose which is a natural polymer has. The chemical modification of the hydroxy group is not particularly limited, and examples thereof include alkyl etherification, hydroxyalkyl etherification and esterification of the hydroxy group. The cellulose derivative has at least one hydroxyl group in one molecule. Only 1 type may be used for a cellulose derivative and it may use 2 or more types together.

As a cellulose derivative, methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxybutyl methyl cellulose, cellulose acetate (acetyl cellulose, diacetyl cellulose, tri Acetyl cellulose and the like), cellulose acetate propionate, cellulose acetate butyrate, nitrocellulose and the like.

From the viewpoint of efficiently producing a cellulose polymerizable compound having a polymerizable unsaturated group, the cellulose derivative is preferably soluble in an organic solvent. In view of high solubility in an organic solvent, the cellulose derivative is more preferably ethyl cellulose.

The cellulose derivative affects the film strength and the viscosity at the time of solution by the molecular weight. Therefore, the number average molecular weight of the cellulose derivative is preferably in the range of 0.50,000 to 150,000, and more preferably in the range of 10,000 to 100,000 in terms of standard polystyrene in terms of gel permeation chromatography (GPC). If the number average molecular weight is less than 0.50,000, the solution viscosity becomes extremely low, making it difficult to adjust the viscosity of the copolymer composition (paste or slurry), and there is a possibility that the strength and adhesion of the film formed by applying and drying the copolymer composition may be reduced. . On the other hand, when the number average molecular weight exceeds 150,000, the solution viscosity becomes extremely large, making it difficult to adjust the viscosity of the copolymer composition, and there is a fear that the printability is lowered.

The cellulose derivative has at least one hydroxyl group in one molecule. This hydroxyl group can be used for introduction of a polymerizable unsaturated group. Specific examples of the polymerizable unsaturated group are polymerizable carbon-carbon double bonds, and suitable examples thereof are (meth) acrylate groups ((meth) acryloyloxy groups), vinyl groups, and allyl groups. In this specification, "(meth) acrylate" means an acrylate and / or methacrylate, and "(meth)" when it is referred to as (meth) acryl, (meth) acryloyl, etc. is also the same meaning. .

For example, a polymerizable unsaturated group can be introduced into a cellulose derivative by reacting a hydroxy group of the cellulose derivative with a compound having a group capable of reacting with the hydroxy group and a polymerizable unsaturated group, whereby a cellulose polymerizable compound having a polymerizable unsaturated group. Can be obtained. As a group which can react with a hydroxyl group, a carboxyl group, an acid anhydride group, an acid chloride group, an isocyanate group, a halogen group (halogen atom), etc. are mentioned.

As a compound which has a group which can react with a hydroxyl group, and a polymerizable unsaturated group, For example, Organic acid which has a polymerizable unsaturated group, such as (meth) acrylic acid, maleic acid, 4-vinyl benzoic acid, 4-ethenyl benzoic acid; Anhydride of this organic acid The acid chloride of the said organic acid; Isocyanate group containing (meth) acrylates, such as 2-isocyanate ethyl (meth) acrylate, the vinyl derivative which has a halogen group, and the allyl derivative which has a halogen group are mentioned. Only 1 type may be used for the compound which has a group which can react with a hydroxyl group, and a polymerizable unsaturated group, and may use 2 or more types together.

In the reaction (esterification reaction, urethaneization, etherification reaction, etc.) of the hydroxyl group of a cellulose derivative, the group which can react with the said hydroxyl group, and a polymerizable unsaturated group, a conventionally well-known method and reaction conditions can be employ | adopted. It is also effective to use a reaction catalyst (organic metal compound, metal, amine, condensing agent, etc.).

It is preferable that the number of the polymerizable unsaturated groups which a cellulose polymerizable compound has is an average of 10 or less per molecule. When the number of polymerizable unsaturated groups exceeds 10 averages per molecule, it becomes easy to produce gelation and insolubilization to the organic solvent accompanying this in manufacture of a copolymer. The gelled copolymer is not preferable as a binder of a paste or slurry. The number of the polymerizable unsaturated groups which the cellulose-based polymerizable compound has may be 8 or less, 5 or less, 3 or less, 2 or less, or 1 in average per molecule.

[2] structural unit (b)

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 monomer units of vinyl acetal / vinyl alcohol / vinyl acetate and can be obtained by acetalizing polyvinyl alcohol. Specific examples include a butyralized polyvinyl alcohol (polyvinyl butyral), and a formalized polyvinyl alcohol (polyvinyl formal).

A commercial item may be sufficient as polyvinyl acetal, and various polyvinyl acetals which differ from butyralization degree, formalization degree, an acetyl group amount, a hydroxyl group amount, molecular weight, etc. are sold from Sekisui Chemical Co., Kuraray Co., Eastman Chemical Co., Ltd., and the like. Polyvinyl acetal may use only 1 type, and may use 2 or more types together.

From the viewpoint of efficiently producing the polyvinyl acetal polymerizable compound having a polymerizable unsaturated group, the polyvinyl acetal is preferably soluble in an organic solvent. Since the solubility with respect to the organic solvent is high, it is more preferable that polyvinyl acetal is polyvinyl butyral.

Polyvinyl acetal affects the film strength and the viscosity at the time of solution by the molecular weight. Therefore, the number average molecular weight of the polyvinyl acetal is preferably in the range of 0.5 to 150,000, and more preferably in the range of 10,000 to 100,000 in terms of standard polystyrene in terms of GPC. If the number average molecular weight is less than 0.50,000, the solution viscosity becomes extremely low, making it difficult to adjust the viscosity of the copolymer composition (paste or slurry), and there is a possibility that the strength and adhesion of the film formed by applying and drying the copolymer composition may be reduced. . On the other hand, when the number average molecular weight exceeds 150,000, the solution viscosity becomes extremely large, making it difficult to adjust the viscosity of the copolymer composition, and there is a fear that printability may decrease.

Polyvinyl acetal has at least 1 hydroxyl group in 1 molecule. Generally, polyvinyl acetal has 20-40 mol% of hydroxyl groups as a vinyl alcohol unit which comprises a polymer. This hydroxyl group can be used for introduction of a polymerizable unsaturated group. Specific examples of the polymerizable unsaturated group are polymerizable carbon-carbon double bonds, and suitable examples thereof are (meth) acrylate groups ((meth) acryloyloxy groups), vinyl groups, and allyl groups.

For example, 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, whereby a polyvinyl acetal having a polymerizable unsaturated group. A system polymeric compound can be obtained. As a group which can react with a hydroxyl group, a carboxyl group, an acid anhydride group, an acid chloride group, an isocyanate group, a halogen group (halogen atom), etc. are mentioned. The specific example of the compound which has a group which can react with a hydroxyl group, and a polymerizable unsaturated group is the same as the compound quoted by the term of the said "[1] structural unit (a)." Only 1 type may be used for the compound which has a group which can react with a hydroxyl group, and a polymerizable unsaturated group, and may use 2 or more types together.

In the reaction (esterification, urethanization, etherification reaction, etc.) of the hydroxyl group of polyvinyl acetal, the group which can react with the said hydroxyl group, and a polymerizable unsaturated group, a conventionally well-known method and reaction conditions can be employ | adopted. It is also effective to use a reaction catalyst (organic metal compound, metal, amine, condensing agent, etc.).

It is preferable that the number of the polymerizable unsaturated groups which a polyvinyl acetal type polymeric compound has has an average of 10 or less per molecule. When the number of polymerizable unsaturated groups exceeds 10 per molecule on average, it becomes easy to produce gelation and insolubilization to the organic solvent accompanying this in manufacture of a copolymer. The gelled copolymer is not preferable as a binder of a paste or slurry. The number of the polymerizable unsaturated groups which a polyvinyl acetal type polymerizable compound has may be 8 or less, 5 or less, 3 or less, 2 or less, or 1 may be average per molecule.

[3] other structural units (c)

The copolymer may further include structural units (c) other than the structural unit (a) and the structural unit (b). The copolymer may include one or two or more structural units (c). By further including the structural unit (c), the copolymerization efficiency of the above two polymerizable compounds is increased, the solubility of the copolymer in an organic solvent, and dispersion of the inorganic particles in the copolymer composition (paste or slurry). Adjustment of a castle may become easy.

As a monomer which forms a structural unit (c), (meth) acrylate (compound which has a (meth) acryloyloxy group) is mentioned. Only 1 type may be used for (meth) acrylate and it may use 2 or more types together.

As (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl ( Alkyl (meth) acrylate having 1 to 20 carbon atoms of an alkyl group such as meth) acrylate, 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, Hydroxyalkyl (meth) acrylates such as 2-hydroxypropyl (meth) acrylate and glyceryl mono (meth) acrylate; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc. N, N-dialkylaminoalkyl (meth) acrylate; 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl Acid group-containing (meth) acrylates, such as an acid phosphate Methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, ethoxy polypropylene glycol (meth) acrylate, butoxydiethylene glycol (meth) acrylic Alkylene oxide modified (meth) acrylate whose repeating number of alkylene oxide site | parts, such as a rate, is 1-30; Tetrahydrofurfuryl (meth) acrylate, Isobonyl (meth) acrylate, Phenoxyethyl (meth) acrylate And other monofunctional (meth) acrylates such as benzyl (meth) acrylate and glycidyl (meth) acrylate.

As another example of (meth) acrylate, bifunctional functions, such as ethylene glycol di (meth) acrylate, the polyethyleneglycol di (meth) acrylate whose repeat number of an ethylene oxide site | part is 2-30, hexanediol di (meth) acrylate, etc. (Meth) acrylate; (meth) acrylate of trifunctional or more, such as pentaerythritol tri (meth) acrylate, is mentioned.

Monomers other than (meth) acrylate may be sufficient as the monomer which forms a structural unit (c). As monomers other than (meth) acrylate, Aromatic vinyl-type monomers, such as styrene, vinyltoluene, (alpha) -methylstyrene, p-methylstyrene, divinylbenzene; olefinic monomers, such as ethylene and propylene; (meth) acrylamide (Meth) acrylamides, such as (meth) acryloyl morpholine; (meth) acrylic acid, crotonic acid, cinnamic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, anhydrous Acids such as citraconic acid; N-vinylpyrrolidone, N-phenylmaleimide, N-cyclohexylmaleimide, (meth) acrylonitrile, vinyl chloride, vinyl acetate and the like.

When using a polyfunctional monomer, it is preferable to set it as the quantity which does not produce gelation in manufacture of a copolymer.

[4] structure of the copolymer

The content ratio of the structural unit (a) and the structural unit (b) contained in the copolymer is preferably in the range of 10:90 to 90:10, more preferably 20:80 to 80:20 on a mass basis. It is the range of, More preferably, it is the range of 25: 75-75: 25. When the content ratio of the structural unit (a) and the structural unit (b) is in the above range, the desired effect according to the copolymer including the structural unit (a) and the structural unit (b) (good thermal decomposition, adhesion, coating film quality, And printability) can be more effectively obtained. When the structural unit (a) is less than the above range, there is a possibility that the printability of the copolymer composition (paste or slurry) is lowered. When structural unit (b) is less than the said range, there exists a possibility that the intensity | strength, adhesiveness, and / or thermal decomposition property of the film | membrane formed from a copolymer composition may fall.

When a copolymer contains another structural unit (c), it is preferable that it is 0.1-200 mass parts with respect to 100 mass parts of total content of a structural unit (a) and a structural unit (b), and 100 mass parts It is more preferable that it is below, and it is still more preferable that it is 50 mass parts or less. If the structural unit (c) is in the above range, the desired effect (combination of good thermal decomposition, adhesion, coating film quality, and printability) by being a copolymer including the structural unit (a) and the structural unit (b) is likely to be secured. . When content of a structural unit (c) exceeds 200 mass parts, there exists a possibility that the printability of a copolymer composition (paste or slurry) may fall, or the intensity | strength of the film | membrane formed from a copolymer composition may fall.

As for the number average molecular weight of a copolymer, it is preferable that it is 10,000-200,000 in standard polystyrene conversion value by GPC, It is more preferable that it is 10,000-150,000, It is further more preferable that it is 20,000-120,000. If the number average molecular weight of a copolymer is less than 10,000, the viscosity as a copolymer composition (paste or slurry) may become low, and there exists a possibility that the intensity | strength and adhesiveness of a coating film may fall. On the other hand, when it exceeds 200,000, there exists a tendency for a viscosity to become high too much and also for printability to fall.

<Method for Producing Copolymer>

[1] Preparation of Cellulose Polymerizable Compound and Polyvinyl Acetal Polymerizable Compound

As described above, the cellulose polymerizable compound having a polymerizable unsaturated group forming the structural unit (a) of the copolymer and the polyvinyl acetal polymerizable compound having a polymerizable unsaturated group forming the structural unit (b) are each as described above. It can obtain by making the cellulose derivative and the hydroxyl group of polyvinyl acetal react with the compound which has the group which can react with this hydroxyl group, and a polymerizable unsaturated group.

The reaction is, for example, an esterification reaction, a urethanization reaction, or an etherification reaction. In the said reaction, a conventionally well-known method and reaction conditions can be employ | adopted. It is also effective to use a reaction catalyst (organic metal compound, metal, amine, condensing agent, etc.).

The esterification reaction can be performed using a condensation agent, for example. Examples of the condensing agent include carbodiimide, diphenyl phosphate amide, 1-hydroxybenzotriazole, and BOP reagent. Only 1 type may be used for a condensing agent, and may use 2 or more types together. Especially, carbodiimide is suitable because it is excellent in versatility and reactivity, and can advance reaction in low temperature conditions and without being influenced by water under reaction environment.

Examples of carbodiimides include dicyclohexylcarbodiimide, diisopropylcarbodiimide, N- [3- (dimethylamino) propyl] -N'-ethylcarbodiimide, and N- [3- (dimethylamino) propyl ] -N'-ethylcarbodiimide methoxide, etc. are mentioned. Especially, dicyclohexyl carbodiimide and diisopropyl carbodiimide are suitable from a viewpoint of availability. Moreover, when using carbodiimide, it is also preferable to use together dimethylaminopyridine and triethylamine which are bases as a reaction promoter in 0.01 mol%-10 mol% with respect to carbodiimide.

The urethanation reaction can be performed using a reaction catalyst, for example. As a reaction catalyst, Organometallic compounds, such as a dioctyl tin dilaurate, a dibutyl tin dilaurate, a stepner octoate, a zinc dinaphthenate; 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-methyl Amine compounds such as morpholine, N-ethyl morpholine, N, N-dimethylethanolamine and N, N-diethylethanolamine.

The etherification reaction can be efficiently carried out by using hydroxides of alkali metals such as KOH and NaOH; hydrogenated alkali metals such as NaH and KH as reaction catalysts.

It is preferable to perform reaction of the cellulose derivative and the hydroxyl group of polyvinyl acetal, the compound which has the group which can react with this hydroxyl group, and a polymerizable unsaturated group in an aprotic organic solvent.

As an aprotic organic solvent, 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 (butylcarbitol 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 ether, triethylene glycol dimethyl ether, triethylene glycol butylmethyl Ether, Propylene Glycol Monomethyl Ether Acetate Sites, and the like, propylene glycol dimethyl ether, propylene glycol diacetate, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, dihydro-emitter sulfinyl acetate. Only 1 type may be used for an organic solvent and it may use 2 or more types together.

The temperature of reaction of the cellulose derivative and the hydroxyl group of polyvinyl acetal, the compound which has the group which can react with the said hydroxyl group, and a polymerizable unsaturated group is about 0 degreeC-about 100 degreeC, for example. The introduction amount of a polymerizable unsaturated group can be measured by NMR analysis etc. When using carbodiimide as a condensing agent, you may add, after making the compound and carbodiimide which have a polymerizable unsaturated group react beforehand. In addition, when carbodiimide is used, urea is produced as a by-product and it may be insolubilized, but you may perform filtration purification and reprecipitation purification as needed.

The amount of the polymerizable unsaturated group introduced into the cellulose derivative or the polyvinyl acetal is determined by the number of hydroxy groups possessed by one molecule of the cellulose derivative or the polyvinyl acetal, the amount of the group capable of reacting with the hydroxy group and the compound having a polymerizable unsaturated group, and the condensing agent. Can be adjusted by The number of hydroxy groups which one molecule of a cellulose derivative or polyvinyl acetal has can be adjusted with the content rate of the hydroxy group contained in a cellulose derivative or polyvinyl acetal, the molecular weight of a cellulose derivative, polyvinyl acetal, etc.

Introduction of the polymerizable unsaturated group into the cellulose derivative and the polyvinyl acetal may be performed separately 1) or 2) the cellulose derivative and the polyvinyl acetal may be mixed in advance, and the hydroxy group may react with the mixture; You may carry out by making the compound which has a polymerizable unsaturated group react.

It is preferable that the mixing ratio of the cellulose derivative and polyvinyl acetal in the case of said 2) is the same as the above-mentioned "content ratio of the structural unit (a) and structural unit (b) contained in a copolymer". Moreover, also in the case of said 2), it is preferable to introduce a polymerizable unsaturated group so that the number of polymerizable unsaturated groups may be an average of 10 or less per molecule with respect to each of a cellulose derivative and polyvinyl acetal.

[2] Preparation of Copolymer

A copolymer can be obtained by copolymerizing the monomer composition containing the cellulose type polymerizable compound which has a polymerizable unsaturated group, the polyvinyl acetal type polymerizable compound which has a polymerizable unsaturated group, and the monomer which forms the structural unit (c) optionally used. have. This copolymerization reaction is performed by heating in presence of a radical polymerization initiator, for example in an organic solvent preferably in a non-oxygen atmosphere. As a specific example of the organic solvent which can be used for a copolymerization reaction, in addition to the aprotic organic solvent mentioned above [1], a protonic organic solvent can be used, and ethyl alcohol, isopropyl alcohol, butyl alcohol, benzyl 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, dihydroterpine Or the like. Only 1 type may be used for an organic solvent and it may use 2 or more types together.

As a radical polymerization initiator, a conventionally well-known thing (for example, a peroxide type or an azo type) can be used. The usage-amount of a radical polymerization initiator is 0.001 to 5% of range with respect to 100 mass% of total amounts of a monomer, for example.

The total concentration of all monomers in the copolymerization reaction solution is preferably 5 to 70% by mass. The temperature of a copolymerization reaction is about 40 degreeC-about 120 degreeC, for example.

After a copolymerization reaction, you may perform normal polymer purification processes, such as precipitation purification by a poor solvent, as needed. By a purification process, an unreacted monomer and a by-product can be removed and a solid copolymer can also be obtained.

<Copolymer Composition>

The copolymer composition according to the present invention comprises a binder which is the copolymer, inorganic particles and an organic solvent, and is suitable as a baking paste or slurry for producing various pastes or slurries, particularly electronic components or members of electronic devices. Do. In addition, although there is no clear distinction between paste and slurry, it is mainly distinguished from the point of viscosity, and the former is high viscosity.

For example, 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. Moreover, the copolymer composition containing a binder and an organic solvent which can also be a manufacturing intermediate of this copolymer composition also belongs to this invention.

As an inorganic material which comprises the inorganic particle contained in a copolymer composition, a conductive inorganic material, ceramic, glass, a pigment, fluorescent substance, etc. are mentioned. Examples of the conductive inorganic material include metals such as gold, silver, copper, platinum, palladium, nickel, aluminum, tungsten and iron; alloys containing any one of the above metals such as silver-palladium alloys; ITO and the like. The metal oxide which consists of; carbon powder etc. are mentioned. Examples of the ceramics include magnetic ceramics such as barium titanate, titanium oxide, alumina, zirconia, aluminum nitride, silicon nitride, boron nitride, silicon carbide, and ferrite. As glass, the thing containing silicon dioxide (usually, this being a main component) is mentioned, The melting point is not specifically limited. The particle diameter of an inorganic particle is the range of 20 nm-1 mm normally. Only 1 type may be used for an inorganic particle and may use 2 or more types together.

As the organic solvent contained in the copolymer composition, one or two or more kinds of the organic solvents exemplified in the above <Method for producing copolymer> [1] and [2] can be used. It is preferable that the organic solvent is a solvent which can melt | dissolve a binder, and is a high boiling point in a printing paste use.

The copolymer composition may further include an additive as necessary. Additives include surfactants, viscosity modifiers, defoamers, leveling agents, stabilizers, plasticizers, wetting agents, colorants, polymer particles and the like. Only 1 type may be used for an additive and it may use 2 or more types together. Moreover, a copolymer composition can contain polymers other than the copolymer mentioned above as a binder.

The content ratio of the inorganic particle (the total content when it contains 2 or more types of inorganic particles) and a binder in a copolymer composition is 100: 1-100: 50 normally on a mass basis, and the viscosity of a copolymer composition From a viewpoint of the dispersibility of an inorganic particle, etc., Preferably it is 100: 5-100: 30. Content of the organic solvent (total content in the case of containing 2 or more types of organic solvents) is 100 mass parts-10000 mass parts normally with respect to 100 mass parts of binders. When a copolymer composition contains an additive, the content (when it contains 2 or more types of additives, the total content) is 0.1-30 mass parts normally with respect to 100 mass parts of binders.

Inorganic particles, a binder (copolymer) dissolved in an organic solvent, and additives used as necessary are mixed by using a dispersing apparatus such as three roll mills, ball mills, media mills, homogenizers, and the inorganic particles are uniformly mixed. It is possible to prepare a copolymer composition by dispersing it in such a way as to be effective.

After coating the copolymer composition on a substrate or the like, the organic solvent is volatilized by subsequent firing, and the thermal decomposition of the binder can be used to form a layer or pattern made of inorganic particles. As coating methods of the copolymer composition, screen printing, die coating printing, doctor blade printing, roll coating printing, offset printing, gravure printing, flexographic printing, inkjet printing, dispense printing, cast method, dip coating, etc. may be mentioned. Among them, screen printing and dip coating are suitable. The layer or pattern obtained by firing usually consists of a sintered body of inorganic particles.

Example

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited by these examples. In the example,% and part which show content-usage-amount are a mass reference | standard unless there is particular notice.

Synthesis Example 1: Synthesis of Cellulose Polymerizable Compound (a1)

Ethyl cellulose ("ETHOCEL STD-100" by Dow Chemical Co., Ltd., number average molecular weight Mn (standard polystyrene conversion value by GPC): 63400, substitution degree (DS value, etherification degree): 2.52) was prepared, and it dried. In addition, substitution degree 2.52 means that on average among the three hydroxy groups which exist in one glucose ring, 2.52 are ethyl etherized and 0.48 hydroxyl groups remain. The average number of hydroxyl groups in one molecule calculated from the number average molecular weight Mn and the degree of substitution is about 131.

100 parts of the dried ethyl cellulose was dissolved in 400 parts of ethyl acetate. To the obtained solution, 0.27 parts of methacrylic acid, 0.4 part of diisopropylcarbodiimide as a condensation agent and 0.004 part of dimethylaminopyridine as a reaction accelerator were added to one molecule of ethyl cellulose, and at a temperature of 30 ° C. The reaction was carried out by stirring for 24 hours. Thereafter, ethyl acetate was distilled off to obtain a cellulose polymerizable compound (a1) in which a methacrylate group was introduced into ethyl cellulose as a solid.

Analysis of a part of the obtained solid by FT-IR and ¹ H-NMR confirmed the formation of ester bonds, and it was confirmed that the added methacrylic acid and the same molar amount of methacrylate groups were introduced into the ethyl cellulose.

Synthesis Example 2: Synthesis of Cellulose Polymerizable Compound (a2)

Ethyl cellulose ("ETHOCEL STD-10" by Dow Chemical Co., Ltd., number average molecular weight Mn (standard polystyrene conversion value by GPC): 22800, substitution degree: 2.52) was prepared, and it dried. The average number of hydroxyl groups in one molecule calculated from the number average molecular weight Mn and the degree of substitution is about 47.

100 parts of the dried ethyl cellulose was dissolved in 400 parts of ethyl acetate. To the obtained solution, 2.05 parts of 2-isocyanate ethyl methacrylate ("Karenz MOI" manufactured by Showa Denko) corresponding to an average amount of three introduced molecules per ethyl cellulose was added, and 0.01 part of dioctyl tin dilaurate as a catalyst was added. The mixture was stirred at a temperature of 60 ° C. for 5 hours. Thereafter, ethyl acetate was distilled off to obtain a cellulose polymerizable compound (a2) in which a methacrylate group was introduced into ethyl cellulose as a solid.

A part of the obtained solid was analyzed by FT-IR and ¹ H-NMR, and the formation of urethane bonds was confirmed, and the added 2-isocyanate ethyl methacrylate and the same molar amount of methacrylate group were introduced into the ethyl cellulose. It was confirmed.

Synthesis Example 3: Synthesis of Cellulose Polymerizable Compound (a3)

Ethyl cellulose ("ETHOCEL STD-200" manufactured by Dow Chemical Co., Ltd., number average molecular weight Mn (standard polystyrene conversion value by GPC): 80700, substitution degree: 2.52) was prepared and dried. The average number of hydroxyl groups in one molecule calculated from the number average molecular weight Mn and the degree of substitution is about 167.

100 parts of the dried ethyl cellulose was dissolved in 400 parts of ethyl acetate. 0.11 part of methacrylic acid, 0.16 part of diisopropylcarbodiimide as a condensation agent, and 0.0016 part of dimethylaminopyridine as a reaction accelerator are added to the obtained solution with respect to 1 molecule of ethyl cellulose, and the temperature is 30 degreeC. The reaction was carried out by stirring for 24 hours. Thereafter, 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.

Analysis of a part of the obtained solid by FT-IR and ¹ H-NMR confirmed the formation of ester bonds, and it was confirmed that the added methacrylic acid and the same molar amount of methacrylate groups were introduced into the ethyl cellulose.

Synthesis Example 4: Synthesis of Cellulose Polymerizable Compound (a4)

Ethyl cellulose ("ETHOCEL STD-100" by Dow Chemical Co., Ltd., number average molecular weight Mn (standard polystyrene conversion value by GPC): 63400, substitution degree: 2.52) was prepared, and it dried. The average number of hydroxyl groups in one molecule calculated from the number average molecular weight Mn and the degree of substitution is about 131.

100 parts of the dried ethyl cellulose was dissolved in 400 parts of ethyl acetate. To the obtained solution, 0.68 parts of methacrylic acid, 0.99 parts of diisopropylcarbodiimide as a condensation agent, and 0.001 part of dimethylaminopyridine as a reaction accelerator were added to one molecule of ethyl cellulose. The reaction was carried out by stirring for 24 hours. Thereafter, ethyl acetate was distilled off to obtain a cellulose polymerizable compound (a4) in which a methacrylate group was introduced into ethyl cellulose as a solid.

Analysis of a part of the obtained solid by FT-IR and ¹ H-NMR confirmed the formation of ester bonds, and it was confirmed that the added methacrylic acid and the same molar amount of methacrylate groups were introduced into the ethyl cellulose.

Synthesis Example 5: Synthesis of Cellulose Polymerizable Compound (a5)

Ethyl cellulose ("ETHOCEL STD-45" by Dow Chemical Company, number average molecular weight Mn (standard polystyrene conversion value by GPC): 56500, substitution degree: 2.52) was prepared, and it dried. The average number of hydroxyl groups in one molecule calculated from the number average molecular weight Mn and the degree of substitution is about 117.

100 parts of the dried ethyl cellulose was dissolved in 400 parts of ethyl acetate. To the obtained solution, 0.46 parts of methacrylic acid, 0.67 parts of diisopropylcarbodiimide as a condensation agent and 0.0067 parts of dimethylaminopyridine as a reaction accelerator were added to one molecule of ethyl cellulose, at a temperature of 30 ° C. The reaction was carried out by stirring for 24 hours. Thereafter, ethyl acetate was distilled off to obtain a cellulose polymerizable compound (a5) having a methacrylate group introduced into ethyl cellulose as a solid.

Analysis of a part of the obtained solid by FT-IR and ¹ H-NMR confirmed the formation of ester bonds, and it was confirmed that the added methacrylic acid and the same molar amount of methacrylate groups were introduced into the ethyl cellulose.

Synthesis Example 6: Synthesis of Cellulose Polymerizable Compound (a6)

Ethyl cellulose ("ETHOCEL STD-4" by Dow Chemical Company, number average molecular weight Mn (standard polystyrene conversion value by GPC): 13700, substitution degree: 2.52) was prepared, and it dried. The average number of hydroxyl groups in one molecule calculated from the number average molecular weight Mn and the degree of substitution is about 28.

100 parts of the dried ethyl cellulose was dissolved in 400 parts of ethyl acetate. To the obtained solution, 6.26 parts of methacrylic acid, 9.18 parts of diisopropylcarbodiimide as a condensation agent and 0.09 parts of dimethylaminopyridine as a reaction accelerator were added to one molecule of ethyl cellulose, at a temperature of 30 ° C. The reaction was carried out by stirring for 24 hours. Thereafter, ethyl acetate was distilled off to obtain a cellulose polymerizable compound (a6) in which a methacrylate group was introduced into ethyl cellulose as a solid.

Analysis of a part of the obtained solid by FT-IR and ¹ H-NMR confirmed the formation of ester bonds, and it was confirmed that the added methacrylic acid and the same molar amount of methacrylate groups were introduced into the ethyl cellulose.

Synthesis Example 7: Synthesis of Polyvinyl Acetal Polymerizable Compound (b1)

Polyvinyl butyral ("BM-S" by Sekisui Chemical Co., Ltd., number average molecular weight Mn (standard polystyrene conversion value by GPC): 53000, amount of hydroxyl groups: about 22 mol%) was prepared, and it dried. 100 parts of dried polyvinyl butyral was dissolved in 400 parts of ethyl acetate. To the obtained solution, 0.32 parts of methacrylic acid, 0.48 parts of diisopropylcarbodiimide as a condensation agent and 0.0048 parts of dimethylaminopyridine as a reaction accelerator were added to one molecule of polyvinyl butyral, and the temperature was 30. It stirred at 24 degreeC for 24 hours and reaction was performed. Thereafter, ethyl acetate was distilled off to obtain a polyvinyl acetal polymerizable compound (b1) having a methacrylate group introduced into the polyvinyl butyral as a solid.

Analysis of a part of the obtained solid by FT-IR and ¹ H-NMR confirmed the formation of ester bonds, and it was confirmed that added methacrylic acid and the same molar amount of methacrylate groups were introduced into the polyvinyl butyral. .

Synthesis Example 8: Synthesis of Polyvinyl Acetal Polymerizable Compound (b2)

Polyvinyl butyral ("BL-S" by Sekisui Chemical Co., Ltd., number average molecular weight Mn (standard polystyrene conversion value by GPC): 23000, amount of hydroxyl groups: about 22 mol%) was prepared, and it dried. 100 parts of dried polyvinyl butyral was dissolved in 400 parts of ethyl acetate. To the obtained solution, 2.02 parts of 2-isocyanate ethyl methacrylate ("Karenz MOI" manufactured by Showa Denko) corresponding to an average of three introduced amounts per one molecule of polyvinyl butyral, and 0.01 part of dioctyl tin dilaurate as a catalyst It added and stirred at the temperature of 60 degreeC for 5 hours, and reaction was performed. Thereafter, ethyl acetate was distilled off to obtain a polyvinyl acetal polymerizable compound (b2) having a methacrylate group introduced into the polyvinyl butyral as a solid.

Part of the obtained solid was analyzed by FT-IR and ¹ H-NMR, and the formation of urethane bonds was confirmed, and the added 2-isocyanate ethyl methacrylate and the same molar amount of methacrylate groups were introduced into the polyvinyl butyral. It was confirmed that it was done.

Synthesis Example 9: Synthesis of Polyvinyl Acetal Polymerizable Compound (b3)

Polyvinyl butyral ("BH-S" by Sekisui Chemical Co., Ltd.), number average molecular weight Mn (standard polystyrene conversion value by GPC): 6600, hydroxyl group amount: about 22 mol% were prepared, and it dried. 100 parts of dried polyvinyl butyral was dissolved in 400 parts of ethyl acetate. To the obtained solution, 0.13 parts of methacrylic acid, 0.19 parts of diisopropylcarbodiimide as a condensing agent and 0.002 parts of dimethylaminopyridine as a reaction accelerator were added to one molecule of polyvinyl butyral, and the temperature was 30. It stirred at 24 degreeC for 24 hours and reaction was performed. Thereafter, ethyl acetate was distilled off to obtain a polyvinyl acetal polymerizable compound (b3) having a methacrylate group introduced into the polyvinyl butyral as a solid.

Analysis of a part of the obtained solid by FT-IR and ¹ H-NMR confirmed the formation of ester bonds, and it was confirmed that added methacrylic acid and the same molar amount of methacrylate groups were introduced into the polyvinyl butyral. .

Synthesis Example 10 Synthesis of Polyvinyl Acetal Polymerizable Compound (b4)

Polyvinyl butyral ("BM-S" by Sekisui Chemical Co., Ltd.), number average molecular weight Mn (standard polystyrene conversion value by GPC): 53000, amount of hydroxy group: about 22 mol% were prepared, and it dried. 100 parts of dried polyvinyl butyral was dissolved in 400 parts of ethyl acetate. To the obtained solution, 0.81 parts of methacrylic acid, 1.19 parts of diisopropylcarbodiimide as a condensation agent and 0.012 parts of dimethylaminopyridine as a reaction accelerator were added to one molecule of polyvinyl butyral, and the temperature was 30. It stirred at 24 degreeC for 24 hours and reaction was performed. Thereafter, ethyl acetate was distilled off to obtain a polyvinyl acetal polymerizable compound (b4) having a methacrylate group introduced into the polyvinyl butyral as a solid.

Analysis of a part of the obtained solid by FT-IR and ¹ H-NMR confirmed the formation of ester bonds, and it was confirmed that added methacrylic acid and the same molar amount of methacrylate groups were introduced into the polyvinyl butyral. .

Synthesis Example 11: Synthesis of Polyvinyl Acetal Polymerizable Compound (b5)

Polyvinyl butyral ("BM-S" by Sekisui Chemical Co., Ltd.), number average molecular weight Mn (standard polystyrene conversion value by GPC): 53000, amount of hydroxy group: about 22 mol% were prepared, and it dried. 100 parts of dried polyvinyl butyral was dissolved in 400 parts of ethyl acetate. To the obtained solution, 0.48 parts of methacrylic acid, 0.72 parts of diisopropylcarbodiimide as a condensation agent and 0.0072 parts of dimethylaminopyridine as a reaction accelerator were added to one molecule of polyvinyl butyral, and the temperature was 30. It stirred at 24 degreeC for 24 hours and reaction was performed. Thereafter, ethyl acetate was distilled off to obtain a polyvinyl acetal polymerizable compound (b5) having a methacrylate group introduced into the polyvinyl butyral as a solid.

Analysis of a part of the obtained solid by FT-IR and ¹ H-NMR confirmed the formation of ester bonds, and it was confirmed that added methacrylic acid and the same molar amount of methacrylate groups were introduced into the polyvinyl butyral. .

Synthesis Example 12 Synthesis of Polyvinyl Acetal Polymerizable Compound (b6)

Polyvinyl butyral ("BL-S" by Sekisui Chemical Co., Ltd., number average molecular weight Mn (standard polystyrene conversion value by GPC): 23000, amount of hydroxyl groups: about 22 mol%) was prepared, and it dried. 100 parts of dried polyvinyl butyral was dissolved in 400 parts of ethyl acetate. To the obtained solution, 3.74 parts of methacrylic acid, 5.49 parts of diisopropylcarbodiimide as a condensation agent and 0.055 parts of dimethylaminopyridine as a reaction accelerator were added to one molecule of polyvinyl butyral, and the temperature was 30. It stirred at 24 degreeC for 24 hours and reaction was performed. Thereafter, ethyl acetate was distilled off to obtain a polyvinyl acetal polymerizable compound (b6) having a methacrylate group introduced into the polyvinyl butyral as a solid.

Analysis of a part of the obtained solid by FT-IR and ¹ H-NMR confirmed the formation of ester bonds, and it was confirmed that the added methacrylic acid and the same molar amount of methacrylate groups were introduced into the ethyl cellulose.

Synthesis Example 13: Synthesis of Mixture of Cellulose Polymerizable Compound (a7) and Polyvinyl Acetal Polymerizable Compound (b7)

Ethyl cellulose ("ETHOCEL STD-100" by Dow Chemical Co., Ltd., number average molecular weight Mn (standard polystyrene conversion value by GPC): 63400, substitution degree: 2.52) was prepared, and it dried. Moreover, polyvinyl butyral ("BM-S" by Sekisui Chemical Co., Ltd.), number average molecular weight Mn (standard polystyrene conversion value by GPC): 53000, amount of hydroxy group: about 22 mol% were prepared, and it dried.

50 parts of the dried ethyl cellulose and 50 parts of the dried polyvinyl butyral were dissolved in 400 parts of ethyl acetate. 0.30 parts of methacrylic acid, 0.44 parts of diisopropylcarbodiimide as a condensation agent, and dimethylaminopyridine as a reaction promoter, in the obtained solution, with respect to 1 molecule of ethyl cellulose and 1 molecule of polyvinyl butyral, respectively 0.0044 parts were added, and it stirred at the temperature of 30 degreeC for 24 hours, and reacted. Thereafter, the ethyl acetate is distilled off to obtain a cellulose polymerizable compound (a7) in which methacrylate group is introduced into ethyl cellulose and a polyvinyl acetal polymerizable compound in which methacrylate group is introduced into polyvinyl butyral ( A mixture of b7) was obtained.

Part of the obtained solid was analyzed by FT-IR and ¹ H-NMR to confirm the formation of ester bonds, and added methacrylic acid and the same molar amount of methacrylate groups were introduced into ethyl cellulose and polyvinyl butyral. It was confirmed.

Synthesis Example 14 Synthesis of Mixture of Cellulose Polymerizable Compound (a8) and Polyvinyl Acetal Polymerizable Compound (b8)

Ethyl cellulose ("ETHOCEL STD-10" by Dow Chemical Co., Ltd., number average molecular weight Mn (standard polystyrene conversion value by GPC): 22800, substitution degree: 2.52) was prepared, and it dried. Moreover, polyvinyl butyral ("BL-S" by Sekisui Chemical Co., Ltd.), number average molecular weight Mn (standard polystyrene conversion value by GPC): 23000, amount of hydroxyl groups: about 22 mol% were prepared, and it dried.

50 parts of the dried ethyl cellulose and 50 parts of the dried polyvinyl butyral were dissolved in 400 parts of ethyl acetate. To the obtained solution, 1.13 parts of methacrylic acid, 1.65 parts of diisopropylcarbodiimide as a condensation agent, and dimethylaminopyridine as a reaction accelerator, each corresponding to an average amount of three introduced amounts of 1 molecule of ethyl cellulose and 1 molecule of polyvinyl butyral. 0.016 parts were added, and it stirred at the temperature of 30 degreeC for 24 hours, and reacted. Thereafter, ethyl acetate is distilled off to remove the cellulose polymerizable compound (a8) in which methacrylate group is introduced into ethyl cellulose and the polyvinyl acetal polymerizable compound in which methacrylate group is introduced into polyvinyl butyral ( b8) was obtained.

Part of the obtained solid was analyzed by FT-IR and ¹ H-NMR to confirm the formation of ester bonds, and added methacrylic acid and the same molar amount of methacrylate groups were introduced into ethyl cellulose and polyvinyl butyral. It was confirmed.

Synthesis Example 15 Synthesis of Mixture of Cellulose Polymerizable Compound (a9) and Polyvinyl Acetal Polymerizable Compound (b9)

Ethyl cellulose ("ETHOCEL STD-4" by Dow Chemical Company, number average molecular weight Mn (standard polystyrene conversion value by GPC): 13700, substitution degree: 2.52) was prepared, and it dried. Moreover, polyvinyl butyral ("BL-S" by Sekisui Chemical Co., Ltd.), number average molecular weight Mn (standard polystyrene conversion value by GPC): 23000, amount of hydroxyl groups: about 22 mol% were prepared, and it dried.

50 parts of the dried ethyl cellulose and 50 parts of the dried polyvinyl butyral were dissolved in 400 parts of ethyl acetate. 0.30 parts of methacrylic acid, 0.44 parts of diisopropylcarbodiimide as a condensation agent, and dimethylaminopyridine as a reaction promoter, in the obtained solution, with respect to 1 molecule of ethyl cellulose and 1 molecule of polyvinyl butyral, respectively 0.0044 parts were added, and it stirred at the temperature of 30 degreeC for 24 hours, and reacted. Thereafter, ethyl acetate is distilled off to remove the cellulose polymerizable compound (a9) in which methacrylate group is introduced into ethyl cellulose and the polyvinyl acetal polymerizable compound in which methacrylate group is introduced into polyvinyl butyral ( b9) was obtained.

Part of the obtained solid was analyzed by FT-IR and ¹ H-NMR to confirm the formation of ester bonds, and added methacrylic acid and the same molar amount of methacrylate groups were introduced into ethyl cellulose and polyvinyl butyral. It was confirmed.

Synthesis Example 16: Synthesis of Mixture of Cellulose Polymerizable Compound (a10) and Polyvinyl Acetal Polymerizable Compound (b10)

Ethyl cellulose ("ETHOCEL STD-100" by Dow Chemical Co., Ltd., number average molecular weight Mn (standard polystyrene conversion value by GPC): 63400, substitution degree: 2.52) was prepared, and it dried. Moreover, polyvinyl butyral ("BH-S" by Sekisui Chemical Co., Ltd.), number average molecular weight Mn (standard polystyrene conversion value by GPC): 66000, amount of hydroxy group: about 22 mol% were prepared, and it dried.

50 parts of the dried ethyl cellulose and 50 parts of the dried polyvinyl butyral were dissolved in 400 parts of ethyl acetate. 0.27 parts of methacrylic acid, 0.4 part of diisopropylcarbodiimide as a condensation agent, and dimethylaminopyridine as a reaction accelerator in the obtained solution, with respect to 1 molecule of ethyl cellulose and 1 molecule of polyvinyl butyral, respectively 0.004 parts were added and stirred for 24 hours at a temperature of 30 deg. Thereafter, the ethyl acetate is distilled off to obtain a cellulose polymerizable compound (a10) in which methacrylate groups are introduced into ethyl cellulose and a polyvinyl acetal polymerizable compound in which methacrylate groups are introduced into polyvinyl butyral ( A mixture of b10) was obtained.

Part of the obtained solid was analyzed by FT-IR and ¹ H-NMR to confirm the formation of ester bonds, and added methacrylic acid and the same molar amount of methacrylate groups were introduced into ethyl cellulose and polyvinyl butyral. It was confirmed.

Synthesis Example 17 Synthesis of Mixture of Cellulose Polymerizable Compound (a11) and Polyvinyl Acetal Polymerizable Compound (b11)

Ethyl cellulose ("ETHOCEL STD-200" manufactured by Dow Chemical Co., Ltd., number average molecular weight Mn (standard polystyrene conversion value by GPC): 80700, substitution degree: 2.52) was prepared and dried. Moreover, polyvinyl butyral ("BH-S" by Sekisui Chemical Co., Ltd.), number average molecular weight Mn (standard polystyrene conversion value by GPC): 66000, amount of hydroxy group: about 22 mol% were prepared, and it dried.

50 parts of the dried ethyl cellulose and 50 parts of the dried polyvinyl butyral were dissolved in 400 parts of ethyl acetate. To the obtained solution, 0.24 parts of methacrylic acid, 0.35 parts of diisopropylcarbodiimide as a condensation agent and dimethylaminopyridine as a reaction accelerator, were added to each of 1 molecule of ethyl cellulose and 1 molecule of polyvinyl butyral. 0.004 parts were added and stirred for 24 hours at a temperature of 30 deg. Thereafter, ethyl acetate is distilled off to remove the cellulose polymerizable compound (a11) in which methacrylate group is introduced into ethyl cellulose and the polyvinyl acetal polymerizable compound in which methacrylate group is introduced into polyvinyl butyral ( b11) was obtained.

Part of the obtained solid was analyzed by FT-IR and ¹ H-NMR to confirm the formation of ester bonds, and added methacrylic acid and the same molar amount of methacrylate groups were introduced into ethyl cellulose and polyvinyl butyral. It was confirmed.

1. Synthesis of Binder (Copolymer)

Example 1: Synthesis of Copolymer (1)

In the polymerization reaction vessel, 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, and 80 parts of dihydroterpinyl acetate as an organic solvent. It 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, 0.01 part of azoisobutyronitrile (AIBN) as a polymerization initiator was mixed, and the reaction was carried out at 70 ° C for 5 hours to give a solution containing the copolymer (1) (binder solution). Got.

When the molecular weight of the obtained copolymer (1) was measured with the GPC apparatus, 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 and the number average molecular weight of polyvinyl butyral used as a raw material, it was confirmed that superposition | polymerization is advanced by the said reaction.

The number average molecular weight of the copolymer (1) was measured on condition of the following (the same also about the number average molecular weight of the copolymer obtained by the following example).

GPC apparatus: "HLC-8320GPC" made by TOSOH company,

Column ： TSKgel GMHXL,

Measurement temperature (setting temperature): 30 degrees Celsius,

Mobile phase: Tetrahydrofuran.

Example 2 Synthesis of Copolymer (2)

In the polymerization reaction vessel, 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 an organic solvent 80 parts of dihydroterpinyl acetate as a mixture 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, 0.01 part of azoisobutyronitrile (AIBN) as a polymerization initiator was mixed, and the reaction was carried out at 70 ° C. for 5 hours to give a solution containing the copolymer (2) (binder solution). Got.

When the molecular weight of the obtained copolymer (2) was measured with the GPC apparatus, the number average molecular weight (standard polystyrene conversion value) was 72000. Since this value is larger than the number average molecular weight of ethyl cellulose and the number average molecular weight of polyvinyl butyral used as a raw material, it was confirmed that superposition | polymerization is advanced by the said reaction.

Example 3: Synthesis of Copolymer (3)

A copolymer was obtained in the same manner as in Example 1 except that 5 parts of the cellulose polymerizable compound (a1) obtained in Synthesis Example 1 and 15 parts of the polyvinyl acetal polymerizable compound (b1) obtained in Synthesis Example 7 were used. ) Was obtained (binder solution).

When the molecular weight of the obtained copolymer (3) was measured with the GPC apparatus, the number average molecular weight (standard polystyrene conversion value) was 73000. Since this value is larger than the number average molecular weight of ethyl cellulose and the number average molecular weight of polyvinyl butyral used as a raw material, it was confirmed that superposition | polymerization is advanced by the said reaction.

Example 4 Synthesis of Copolymer (4)

A copolymer was obtained in the same manner as in Example 1 except that 15 parts of the cellulose polymerizable compound (a1) obtained in Synthesis Example 1 and 5 parts of the polyvinyl acetal polymerizable compound (b1) obtained in Synthesis Example 7 were used. ) Was obtained (binder solution).

When the molecular weight of the obtained copolymer (4) was measured with the GPC apparatus, 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 and the number average molecular weight of polyvinyl butyral used as a raw material, it was confirmed that superposition | polymerization is advanced by the said reaction.

Example 5 Synthesis of Copolymer (5)

In the polymerization reaction vessel, 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 80 parts of dihydroterpinyl acetate as an organic solvent. The mixture was added, mixed, and heated to 60 ° C, and stirred with a rotary blade to dissolve. After dissolution, nitrogen substitution was performed to remove oxygen in the system, 0.01 part of azoisobutyronitrile (AIBN) as a polymerization initiator was mixed, and the reaction was carried out at 70 ° C. for 5 hours to give a solution containing the copolymer (5) (binder solution). Got.

When the molecular weight of the obtained copolymer (5) was measured with the GPC apparatus, the number average molecular weight (standard polystyrene conversion value) was 42000. Since this value is larger than the number average molecular weight of ethyl cellulose and the number average molecular weight of polyvinyl butyral used as a raw material, it was confirmed that superposition | polymerization is advanced by the said reaction.

Example 6: Synthesis of Copolymer (6)

In the polymerization reaction vessel, 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 an organic solvent 80 parts of dihydroterpinyl acetate as a mixture was added and mixed, heated to 60 ° C, and stirred with a rotary blade to dissolve. After dissolution, nitrogen replacement was performed to remove oxygen in the system, 0.01 part of azoisobutyronitrile (AIBN) as a polymerization initiator was mixed, and the reaction was carried out at 70 ° C. for 5 hours to give a solution containing the copolymer (6) (binder solution). Got.

When the molecular weight of the obtained copolymer (6) was measured with the GPC apparatus, the number average molecular weight (standard polystyrene conversion value) was 45000. Since this value is larger than the number average molecular weight of ethyl cellulose and the number average molecular weight of polyvinyl butyral used as a raw material, it was confirmed that superposition | polymerization is advanced by the said reaction.

Example 7: Synthesis of Copolymer (7)

A liquid containing a copolymer (7) 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 ( Binder solution).

When the molecular weight of the obtained copolymer (7) was measured with the GPC apparatus, the number average molecular weight (standard polystyrene conversion value) was 68000. Since this value is larger than the number average molecular weight of ethyl cellulose and the number average molecular weight of polyvinyl butyral used as a raw material, it was confirmed that superposition | polymerization is advanced by the said reaction.

Example 8 Synthesis of Copolymer (8)

A copolymer (8) was prepared 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. The liquid (binder solution) to contain was obtained.

When the molecular weight of the obtained copolymer (8) was measured with the GPC apparatus, 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 and the number average molecular weight of polyvinyl butyral used as a raw material, it was confirmed that superposition | polymerization is advanced by the said reaction.

Example 9 Synthesis of Copolymer (9)

In the polymerization reaction vessel, a cellulose polymerizable compound (a7) in which methacrylate group is introduced into ethyl cellulose obtained in Synthesis Example 13 and a polyvinyl acetal polymerizable compound (b7) in which methacrylate group is introduced into polyvinyl butyral 20 parts of mixtures, 0.2 parts of isobutyl methacrylates, and 80 parts of dihydroterpinyl acetate as organic solvents were added and mixed, and it heated at 60 degreeC, stirred with a rotary blade, and dissolved. After dissolution, nitrogen substitution was performed to remove oxygen in the system, 0.01 part of azoisobutyronitrile (AIBN) as a polymerization initiator was mixed, and the reaction was carried out at 70 ° C. for 5 hours to give a solution containing a copolymer (9) (binder solution). Got.

When the molecular weight of the obtained copolymer (9) was measured with the GPC apparatus, the number average molecular weight (standard polystyrene conversion value) was 72000. Since this value is larger than the number average molecular weight of ethyl cellulose and the number average molecular weight of polyvinyl butyral used as a raw material, it was confirmed that superposition | polymerization is advanced by the said reaction.

Example 10 Synthesis of Copolymer (10)

A cellulose polymerizable compound (a8) having a methacrylate group introduced into the ethyl cellulose obtained in Synthesis Example 14 and a polyvinyl acetal polymerizable compound having a methacrylate group introduced into polyvinyl butyral instead of the mixture obtained in Synthesis Example 13 ( Except having used the mixture of b8), it carried out similarly to Example 9, and obtained the liquid (binder solution) containing the copolymer (10).

When the molecular weight of the obtained copolymer (10) was measured with the GPC apparatus, the number average molecular weight (standard polystyrene conversion value) was 48000. Since this value is larger than the number average molecular weight of ethyl cellulose and the number average molecular weight of polyvinyl butyral used as a raw material, it was confirmed that superposition | polymerization is advanced by the said reaction.

Example 11: Synthesis of Copolymer (11)

The polyvinyl acetal polymerizable polymer obtained in Synthesis Example 9 using the cellulose polymerizable compound (a3) obtained in Synthesis Example 3 instead of the cellulose polymerizable compound (a1) and replacing the polyvinyl acetal polymerizable compound (b1). Except having used the compound (b3), it carried out similarly to Example 1, and obtained the liquid (binder solution) containing the copolymer (11).

When the molecular weight of the obtained copolymer (11) was measured with the GPC apparatus, the number average molecular weight (standard polystyrene conversion value) was 78000. Since this value is larger than the number average molecular weight of ethyl cellulose and the number average molecular weight of polyvinyl butyral used as a raw material, it was confirmed that superposition | polymerization is advanced by the said reaction.

Example 12 Synthesis of Copolymer (12)

In the polymerization reaction vessel, 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 parts of isobutyl methacrylate, and an organic solvent 80 parts of dihydroterpinyl acetate as a mixture 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, 0.01 part of azoisobutyronitrile (AIBN) as a polymerization initiator was mixed, and the reaction was carried out at 70 ° C. for 5 hours to carry out a solution containing the copolymer (12) (binder solution). Got.

When the molecular weight of the obtained copolymer (12) was measured with the GPC apparatus, 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 and the number average molecular weight of polyvinyl butyral used as a raw material, it was confirmed that superposition | polymerization is advanced by the said reaction.

Example 13: Synthesis of Copolymer (13)

Except having changed the addition amount of isobutyl methacrylate to 0.2 part, it carried out similarly to Example 2, and obtained the liquid (binder solution) containing the copolymer (13).

When the molecular weight of the obtained copolymer (13) was measured with the GPC apparatus, the number average molecular weight (standard polystyrene conversion value) was 72000. Since this value is larger than the number average molecular weight of ethyl cellulose and the number average molecular weight of polyvinyl butyral used as a raw material, it was confirmed that superposition | polymerization is advanced by the said 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.

When the molecular weight of the obtained copolymer (14) was measured with the GPC apparatus, the number average molecular weight (standard polystyrene conversion value) was 73000. Since this value is larger than the number average molecular weight of ethyl cellulose and the number average molecular weight of polyvinyl butyral used as a raw material, it was confirmed that superposition | polymerization is advanced by the said reaction.

Example 15 Synthesis of Copolymer (15)

The polyvinyl acetal polymerizable polymer obtained in Synthesis Example 10 using the cellulose polymerizable compound (a4) obtained in Synthesis Example 4 instead of the cellulose polymerizable compound (a1) and replacing the polyvinyl acetal polymerizable compound (b1). Except having used the compound (b4), it carried out similarly to Example 1, and obtained the liquid (binder solution) containing the copolymer (15).

When the molecular weight of the obtained copolymer (15) was measured with the GPC apparatus, the number average molecular weight (standard polystyrene conversion value) was 78000. Since this value is larger than the number average molecular weight of ethyl cellulose and the number average molecular weight of polyvinyl butyral used as a raw material, it was confirmed that superposition | polymerization is advanced by the said reaction.

Example 16: Synthesis of Copolymer (16)

In the polymerization reaction vessel, 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 an organic solvent 80 parts of dihydroterpinyl acetate was added and mixed, and it heated at 60 degreeC, stirred with a rotary blade, and dissolved. After dissolution, nitrogen substitution was performed to remove oxygen in the system, 0.01 part of azoisobutyronitrile (AIBN) as a polymerization initiator was mixed, and the reaction was carried out at 70 ° C. for 5 hours to give a solution containing the copolymer (16) (binder solution). Got.

When the molecular weight of the obtained copolymer (16) was measured with the GPC apparatus, the number average molecular weight (standard polystyrene conversion value) was 81000. Since this value is larger than the number average molecular weight of ethyl cellulose and the number average molecular weight of polyvinyl butyral used as a raw material, it was confirmed that superposition | polymerization is advanced by the said reaction.

Example 17 Synthesis of Copolymer (17)

The polyvinyl acetal polymerizable polymer obtained in Synthesis Example 11 using the cellulose polymerizable compound (a5) obtained in Synthesis Example 5 instead of the cellulose polymerizable compound (a1) and replacing the polyvinyl acetal polymerizable compound (b1). Except having used the compound (b5), it carried out similarly to Example 1, and obtained the liquid (binder solution) containing the copolymer (17).

When the molecular weight of the obtained copolymer (17) was measured with the GPC apparatus, the number average molecular weight (standard polystyrene conversion value) was 68000. Since this value is larger than the number average molecular weight of ethyl cellulose and the number average molecular weight of polyvinyl butyral used as a raw material, it was confirmed that superposition | polymerization is advanced by the said reaction.

Example 18 Synthesis of Copolymer 18

In the polymerization reaction vessel, 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-hydrate 2.0 parts of oxyethyl methacrylate and 80 parts of dihydroterpinyl acetate as an organic solvent were added and mixed, and it heated at 60 degreeC, stirred with a rotary blade, and dissolved. After dissolution, nitrogen replacement was performed to remove oxygen in the system, 0.01 part of azoisobutyronitrile (AIBN) as a polymerization initiator was mixed, and the reaction was carried out at 70 ° C. for 5 hours to give a solution containing the copolymer (18) (binder solution). Got.

When the molecular weight of the obtained copolymer (18) was measured with the GPC apparatus, 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 and the number average molecular weight of polyvinyl butyral used as a raw material, it was confirmed that superposition | polymerization is advanced by the said reaction.

Example 19 Synthesis of Copolymer (19)

The polyvinyl acetal polymerizable polymer obtained in Synthesis Example 12 using the cellulose polymerizable compound (a6) obtained in Synthesis Example 6 instead of the cellulose polymerizable compound (a1) and replacing the polyvinyl acetal polymerizable compound (b1). Except having used the compound (b6), it carried out similarly to Example 1, and obtained the liquid (binder solution) containing the copolymer (19).

When the molecular weight of the obtained copolymer (19) was measured with the GPC apparatus, 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 and the number average molecular weight of polyvinyl butyral used as a raw material, it was confirmed that superposition | polymerization is advanced by the said reaction.

Example 20 Synthesis of Copolymer (20)

In the polymerization reaction vessel, a cellulose polymerizable compound (a9) in which methacrylate group is introduced into ethyl cellulose obtained in Synthesis Example 15 and a polyvinyl acetal polymerizable compound (b9) in which methacrylate group is 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 and mixed, it heated at 60 degreeC, it stirred with the rotary blade, and dissolved. After dissolution, nitrogen replacement was performed to remove oxygen in the system, 0.01 part of azoisobutyronitrile (AIBN) as a polymerization initiator was mixed, and the reaction was carried out at 70 ° C. for 5 hours to give a solution containing the copolymer (20) (binder solution). Got.

When the molecular weight of the obtained copolymer (20) was measured with the GPC apparatus, 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 and the number average molecular weight of polyvinyl butyral used as a raw material, it was confirmed that superposition | polymerization is advanced by the said reaction.

Example 21 Synthesis of Copolymer (21)

In the polymerization reaction vessel, a cellulose polymerizable compound (a10) in which methacrylate group is introduced into ethyl cellulose obtained in Synthesis Example 16 and a polyvinyl acetal polymerizable compound (b10) in which methacrylate group is introduced into polyvinyl butyral 20 parts of mixtures, 0.2 parts of isobutyl methacrylates, and 80 parts of dihydroterpinyl acetate as organic solvents were 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, 0.01 part of azoisobutyronitrile (AIBN) as a polymerization initiator was mixed, and the reaction was carried out at 70 ° C. for 5 hours to give a solution containing the copolymer (21) (binder solution). Got.

When the molecular weight of the obtained copolymer (21) was measured with the GPC apparatus, 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 and the number average molecular weight of polyvinyl butyral used as a raw material, it was confirmed that superposition | polymerization is advanced by the said reaction.

Example 22 Synthesis of Copolymer (22)

In the polymerization reaction vessel, a cellulose polymerizable compound (a11) in which methacrylate group is introduced into ethyl cellulose obtained in Synthesis Example 17 and a polyvinyl acetal polymerizable compound (b11) in which methacrylate group is introduced into polyvinyl butyral 20 parts of mixtures, 0.2 parts of isobutyl methacrylates, and 80 parts of dihydroterpinyl acetate as organic solvents were added and mixed, and it heated at 60 degreeC, stirred with a rotary blade, and dissolved. After dissolution, nitrogen substitution was performed to remove oxygen in the system, 0.01 part of azoisobutyronitrile (AIBN) as a polymerization initiator was mixed, and the reaction was carried out at 70 ° C for 5 hours to give a solution containing the copolymer (22) (binder solution). Got.

When the molecular weight of the obtained copolymer (22) was measured with the GPC apparatus, the number average molecular weight (standard polystyrene conversion value) was 63000. Since this value is larger than the number average molecular weight of ethyl cellulose and the number average molecular weight of polyvinyl butyral used as a raw material, it was confirmed that superposition | polymerization is advanced by the said reaction.

Comparative Example 1

10 parts of ethyl cellulose ("ETHOCEL STD-100" by Dow Chemical Co., Ltd.) and 10 parts of polyvinyl butyral ("BM-S" by Sekisui Chemical Co., Ltd.) are dissolved in 113.3 parts of dihydroterpinyl acetate, A binder solution was prepared.

Comparative Example 2

10 parts of ethyl cellulose ("ETHOCEL STD-10" by Dow Chemical Co., Ltd.) and 10 parts of polyvinyl butyral ("BL-S" by Sekisui Chemical Co., Ltd.) are dissolved in 113.3 parts of dihydroterpinyl acetate, A binder solution was prepared.

Comparative Example 3

20 parts of ethyl cellulose ("ETHOCEL STD-100" by the Dow Chemical company) were melt | dissolved in 113.3 parts of dihydroterpinyl acetate, and the binder solution was prepared.

<Comparative Example 4>

20 parts of polyvinyl butyral ("BM-S" by Sekisui Chemical Co., Ltd.) were melt | dissolved in 113.3 parts of dihydroterpinyl acetate, and the binder solution was prepared.

Comparative Example 5

20 parts of ethyl cellulose ("ETHOCEL STD-10" by a Dow Chemical company) were melt | dissolved in 113.3 parts of dihydroterpinyl acetate, and the binder solution was prepared.

Comparative Example 6

20 parts of polyvinyl butyral ("BL-S" by Sekisui Chemical Co., Ltd.) were melt | dissolved in 113.3 parts of dihydroterpinyl acetate, and the binder solution was prepared.

Comparative Example 7

10 parts of ethyl cellulose ("ETHOCEL STD-100" by Dow Chemical Co., Ltd.), and 10 parts of polyvinyl butyral ("BH-S" by Sekisui Chemical Co., Ltd.) are dissolved in 113.3 parts of dihydroterpinyl acetate, and a binder The solution was prepared.

<Comparative Example 8>

10 parts of ethyl cellulose ("ETHOCEL STD-200" 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, A binder solution was prepared.

Comparative Example 9

20 parts of ethyl cellulose ("ETHOCEL STD-200" by Dow Chemical Company) were melt | dissolved in 113.3 parts of dihydroterpinyl acetate, and the binder solution was prepared.

Comparative Example 10

20 parts of polyvinyl butyral ("BH-S" by Sekisui Chemical Co., Ltd.) were melt | dissolved in 113.3 parts of dihydroterpinyl acetate, and the binder solution was prepared.

Comparative Example 11

10 parts of cellulose polymerizable compounds (a1) in which methacrylate group was introduced into ethyl cellulose obtained in Synthesis Example 1, and polyvinyl acetal polymerizable compound in which methacrylate group was introduced into 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 influence was grasped without performing a polymerization reaction.

Comparative Example 12

Twenty parts of the mixture of the cellulose-based polymerizable compound (a7) and the polyvinyl acetal-based polymerizable compound (b7) obtained in Synthesis Example 13 were dissolved in 113.3 parts of dihydroterpinyl acetate as an organic solvent to prepare a binder solution. In this comparative example, the influence was grasped without performing a polymerization reaction.

The composition of the binder obtained by the Example and the comparative example was put together in Table 1. Details of the abbreviations shown in Table 1 are as follows.

iBMA: isobutyl methacrylate,

MMA: Methyl methacrylate,

HEMA: 2-hydroxyethyl methacrylate.

2. Evaluation of Binder

The following evaluation was performed about the binder obtained by the Example and the comparative example and the paste containing it. The results are shown in Table 2.

[1] Evaluation of pyrolytic property

Residue amount when 10 mg of dry solid samples of a binder were heated to 500 degreeC by the TG / DTA thermal analysis apparatus ("EXSTAR TG / DTA6200" of Seiko Instruments Co., Ltd.) at the temperature increase rate of 10 degree-C / min in nitrogen atmosphere. Was measured and the thermal decomposition property of the binder was evaluated based on the following evaluation criteria. Residual amount (mass%) shows the quantity of the residue after the measurement when the mass of the said dry solid sample is 100 mass%.

(Evaluation Criteria for Thermal Degradability)

A: Residual quantity is 1 mass% or less,

B: Residual quantity exceeds 1 mass%, and is 3 mass% or less,

C: The residual amount exceeds 3 mass%.

[2] Evaluation of adhesion to polyvinyl butyral

A case in which a binder is used for the electrode paste was assumed, and the adhesion to the green sheet was evaluated by the following model experiment.

On the adhesive layer of the polyethylene terephthalate (PET) film (100 micrometers in total thickness) in which an adhesive layer was formed, the binder solution obtained by the Example and the comparative example was apply | coated with the blade coater of 90 micrometers in thickness gap, and then heated and dried, and the binder about 10 micrometers thick The film which has a layer was produced. On the other hand, polyvinyl butyral ("BH-S" by Sekisui Chemical Co., Ltd.) as a model material of the binder for green sheets was dissolved in toluene, and the 15 mass% solution was prepared. The film which has a polyvinyl butyral layer of about 10 micrometers in thickness was produced by apply | coating this on the adhesive layer of the PET film with an adhesive layer in the same manner to the above, and then heating and drying. The rectangular sample of width 2cm and length 8cm was cut out from each obtained film.

On the binder layer of the film sample which has a binder layer, the polyvinyl butyral layer of the film sample which has a polyvinyl butyral layer was shifted and overlapped in the longitudinal direction. The area of the overlapped portion was made 2 cm in length x 2 cm in width. The heating plate of 1 cm x 2 cm (area 2 cm ² ) was pressed to the center of the overlapped portion, and thermally crimped for 5 minutes under conditions of a temperature of 130 ° C. and a pressure of 2 kg to partially bond the overlapped portion.

Using a tensile tester (AG-10N) manufactured by Shimadzu Corporation, the sample bonded to n = 3 was stretched in the longitudinal direction to measure the breaking strength, and adhered to polyvinyl butyral based on the following evaluation criteria. Evaluated.

(Evaluation standard of adhesion)

A: Breaking strength is 100N or more

B: Break strength is less than 100N, 50N or more,

C: Breaking strength is less than 50N.

[3] Preparation of Resin Composition (Paste) and Evaluation of Coating Film Quality

Dihydroterpinyl acetate was added to the binder solution obtained by the Example and the comparative example, and the binder concentration was adjusted to 15 mass%. Next, 100 mass parts of Ni particles ("NFP201S" by JFE Mineral Co., Ltd. and 0.2 micrometer of average particle diameters) as inorganic particles, and 25 mass parts of said binder solutions were mixed with three roll mills, and the paste was obtained.

The obtained paste was apply | coated on the glass substrate with the blade coater of thickness gap 30micrometer, the coating film after heat drying was observed with the scanning electron microscope (SEM), and the coating film quality was evaluated based on the following evaluation criteria. In the scanning electron microscope, the coating film was observed by 5000 times the magnification using "JSM-7800F" by the Japanese electronics company.

(Evaluation standard of coating film quality)

A: The defect (hole) of the size exceeding 1 micrometer is not seen,

B: The defect (hole) of the size exceeding 1 micrometer is seen.

[4] Evaluation of screen printability

The paste prepared in the above [3] was used as a screen plate with a mesh # 500 (manufactured by Naka Numa Art Screen) using a microtech printing apparatus (MT-320 series) to form a stripe-shaped pattern of L / S = 100 μm / 100 μm. Printed on PET film. The print pattern was observed under a microscope, and screen printability was evaluated based on the following evaluation criteria. In addition, a slippery defect produces a printing defect by the phenomenon in which the paste etc. come out as a thread which extends in the step of peeling a screen printing plate from a printed object at the time of printing. When this phenomenon occurs, a fibrous foreign matter is formed from the edge portion of the print pattern, and an electrical short occurs, resulting in a problem that the required characteristic cannot be obtained because the print pattern shape is uneven.

(Evaluation Criteria for Screen Printability)

A: There is no slipper defect in edge part,

B: There is a slipperiness in the edge part.

The binder of Examples 1-22 showed favorable evaluation in each item of thermal decomposition property, adhesiveness, coating film quality, and screen printability. On the other hand, in Comparative Examples 1-12, all of these evaluation items could not be satisfied.

The embodiments and examples disclosed herein are to be considered in all respects only as illustrative and not restrictive. It is intended that the scope of the invention be defined by the claims rather than the embodiments and examples described above, and include equivalents to the claims and all modifications within the scope.

Claims (6)

The copolymer containing the structural unit (a) derived from the cellulose polymerizable compound which has a polymerizable unsaturated group, and the structural unit (b) derived from the polyvinyl acetal type polymeric compound which has a polymerizable unsaturated group. The method according to claim 1,
The copolymer further containing structural units (c) other than the said structural unit (a) and the said structural unit (b). The method according to claim 1,
The number of the said polymerizable unsaturated groups which the said cellulose polymerizable compound has is an average of 10 or less per molecule. The method according to claim 1,
The number of the said polymerizable unsaturated groups which the said polyvinyl acetal type polymeric compound has is an average of 10 or less per molecule, The copolymer. A method for producing a copolymer, comprising the step of polymerizing a cellulose polymerizable compound having a polymerizable unsaturated group and a polyvinyl acetal polymerizable compound having a polymerizable unsaturated group in the presence of a polymerization initiator in an organic solvent. The copolymer composition containing the copolymer as described in any one of Claims 1-4, an inorganic particle, and the organic solvent.