KR20180135925A - Copolymer, process for its preparation, and copolymer composition - Google Patents

Abstract

A copolymer comprising a constituent unit (a) derived from a cellulose-based polymerizable compound having a polymerizable unsaturated group and a constituent unit (b) derived from a polyvinyl acetal-based polymerizable compound having a polymerizable unsaturated group, There is provided a copolymer composition comprising a copolymer, inorganic particles and an organic solvent.

Description

Copolymer, process for its preparation, and copolymer composition

The present invention relates to a copolymer, a process for producing the same, and a copolymer composition comprising the copolymer.

Demand for electronic components is increasing due to the electrification of mobile devices such as mobile phones and smart phones and automobiles. Among them, several hundreds of multilayer ceramic capacitors (called "MLCCs"), which are passive components, are used per smartphone, and demand is rapidly increasing.

An example of the preparation of MLCC is as follows. First, a green sheet having a dielectric layer is produced by applying a dielectric ceramic paste onto a releasable sheet. Then, an electrode paste (also referred to as " conductive paste ") is printed on the dielectric layer to form an electrode pattern (electrode layer). Further, the laminate of the dielectric layer and the electrode layer is peeled off from the releasable sheet, and a plurality of the laminate are laminated and compressed, and then cut into chips. Then, the resulting chip is heated to several hundreds of degrees Celsius to 1000 degrees Celsius or more and fired to produce a sintered chip chip in which a dielectric layer and an electrode layer are laminated in multiple layers. Finally, an external electrode or the like is formed.

In recent years, there has been progressed in miniaturization of chips, and thinning of each of the layers constituting the chips and miniaturization of printed electrode patterns. Under such a background, there is a strong demand for improvement in adhesion between layers and excellent printing property of a paste to be used.

Other electronic components such as chip inductors and chip resistors are also manufactured by a process such as MLCC. In addition, a manufacturing process of a solar cell such as a silicon system includes a printing and a firing process using an electrode paste in forming a collector electrode.

BACKGROUND OF THE INVENTION [0002] Ceramic pastes and electrode pastes used in the manufacture of electronic components such as MLCC are resin compositions containing a binder, which is a polymer material, and an organic solvent, and inorganic particles uniformly dispersed in the binder. 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 the ceramic paste, and ethyl cellulose is mainly used in the electrode paste (Japanese Patent Application 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

BACKGROUND ART A paste such as a ceramic paste or an electrode paste, particularly a binder contained therein, has the following problems, for example.

1) Improvement of pyrolysis (combustibility). If ash such as carbon remains after the pyrolysis treatment by firing, the electric characteristics of the MLCC are deteriorated or peeling between the layers is caused.

2) Improvement of printability. Nowadays, miniaturization and thinning of the electrode pattern formed by screen printing are progressing, and the pattern size is less than 100 占 퐉. For this reason, in the electrode paste, a binder which does not cause so-called dragging phenomenon is required. The drawstring phenomenon is a phenomenon in which the paste or the like used in the printing process due to the influence of the binder polymer comes out like a stretched yarn, which causes defective products.

3) Improvement of uniform dispersibility of inorganic particles, film strength (strength of layer formed from paste) and adhesion between layers. These are required characteristics accompanying the thinning of each layer constituting the chip.

In order to solve the above problems, various examinations of binders have conventionally been made. For example, Japanese Patent No. 4347440 (Patent Literature 2) and Japanese Patent No. 5299904 (Patent Literature 3) disclose a method of blending polyvinylbutyral with ethylcellulose in an electrode paste, A technique for improving physical properties is disclosed. International Publication No. 2015/107811 (Patent Document 4) discloses that a reaction product of ethyl cellulose and polyvinyl butyral and a binder for bonding them is used as a binder.

The binders obtained by blending ethyl cellulose and polyvinyl butyral described in Patent Documents 2 and 3 have poor compatibility with these two kinds of polymers and are not compatible with inorganic materials such as metals, The dispersibility of the particles is low. As a result, defects may be formed in the coating film or the uniformity of the coating film may be deteriorated.

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

An object of the present invention is to provide a binder having good thermal decomposition property, adhesion property, coating film property, and printability, and a composition comprising the same.

The present invention provides the following copolymer, a process for producing the same, and a copolymer composition.

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

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

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

[5] A process for producing a copolymer, which comprises a step of polymerizing a cellulose-based polymerizable compound having a polymerizable unsaturated group and a polyvinyl acetal-based polymerizable compound having a polymerizable unsaturated group in an organic solvent in the presence of a polymerization initiator .

[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 decomposition property, adhesion, coating film quality, and printability, and a copolymer composition containing the same can be provided. According to the copolymer, a film having high strength can be formed. And a copolymer composition containing the copolymer as a binder is suitable as a paste (or slurry) such as a ceramic paste or an electrode paste. This paste (or slurry) can be used for the production of electronic parts, substrates, and the like.

Hereinafter, the present invention will be described in detail with reference to embodiments.

In the present specification, the description "A to B" (A and B are numerical values) indicates "A or more and B or less" unless otherwise specified.

<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 is composed of a structural unit (a) derived from a cellulose polymerizable compound having a polymerizable unsaturated group and a polymerizable unsaturated group (B) derived from a polyvinyl acetal-based polymerizable compound. The cellulose-based polymerizable compound and the polyvinyl acetal-based polymerizable compound are polymerized by a polymerizable unsaturated group to form the constituent unit (a) and the constituent unit (b), respectively, in the copolymer. The copolymer may contain one or more kinds of the structural units (a) and may include one or more structural units (b).

(1) The structural unit (a)

The cellulosic polymerizable compound having a polymerizable unsaturated group forming the constituent unit (a) is a cellulose derivative having a polymerizable unsaturated group. The cellulose derivative refers to a modified cellulose obtained by chemically modifying a part of a hydroxy group of cellulose, which is a natural polymer. The chemical modification of the hydroxy group is not particularly limited, and examples thereof include alkyl etherification of a hydroxy group, hydroxyalkyl etherification, esterification and the like. The cellulose derivative has at least one hydroxy group in one molecule. The cellulose derivative may be used alone or in combination of two or more.

Examples of the cellulose derivative include cellulose derivatives such as methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose, hydroxybutyl methyl cellulose, acetyl cellulose (acetyl cellulose, diacetyl cellulose, Acetyl cellulose, etc.), cellulose acetate propionate, cellulose acetate butyrate, nitrocellulose and the like.

From the viewpoint of efficiently producing a cellulose-based polymerizable compound having a polymerizable unsaturated group, the cellulose derivative is preferably soluble in an organic solvent. From the viewpoint of high solubility in an organic solvent, it is more preferable that the cellulose derivative is ethyl cellulose.

The cellulose derivative influences the film strength and the viscosity at the time of solution depending on the molecular weight thereof. Therefore, the number average molecular weight of the cellulose derivative is preferably in the range of 0.5 to 150,000, more preferably in the range of 10,000 to 100,000, in terms of standard polystyrene by gel permeation chromatography (GPC). If the number average molecular weight is less than 0.5 million, the viscosity of the solution becomes extremely low to make it difficult to adjust the viscosity of the copolymer composition (paste or slurry), and the strength and adhesiveness of the film formed by coating and drying the copolymer composition may decrease . On the other hand, if the number average molecular weight exceeds 1,500,000, the solution viscosity becomes extremely large, and viscosity adjustment of the copolymer composition may become difficult, and the printability may be lowered.

The cellulose derivative has at least one hydroxy group in one molecule. This hydroxy group can be used for introducing a polymerizable unsaturated group. Specific examples of the polymerizable unsaturated group include a polymerizable carbon-carbon double bond. Suitable examples thereof include a (meth) acrylate group ((meth) acryloyloxy group), a vinyl group and an allyl group. In the present specification, "(meth) acrylate" means acrylate and / or methacrylate, and "(meth)" when referring to (meth) acryl or .

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. Examples of the group capable of reacting with a hydroxyl group include a carboxyl group, an acid anhydride group, an acid chloride group, an isocyanate group, and a halogen group (halogen atom).

Examples of the compound having a group capable of reacting with a hydroxyl group and a polymerizable unsaturated group include an organic acid having a polymerizable unsaturated group such as (meth) acrylic acid, maleic acid, 4-vinylbenzoic acid and 4-ethenylbenzoic acid, (Meth) acrylate containing an isocyanate group such as 2-isocyanatoethyl (meth) acrylate, a vinyl derivative having a halogen group, and an allyl derivative having a halogen group. The compound having a group capable of reacting with a hydroxyl group and a polymerizable unsaturated group may be used alone or in combination of two or more.

Conventionally known methods and reaction conditions may be employed in the reaction (esterification reaction, urethane formation, etherification reaction, etc.) of a hydroxy group of a cellulose derivative with a compound having a group capable of reacting with the hydroxy group and a polymerizable unsaturated group. It is also effective to use a reaction catalyst (organometallic compound, metal, amine, condensing agent, etc.).

The number of polymerizable unsaturated groups contained in the cellulose-based polymerizable compound is preferably 10 or less per molecule on average. When the number of the polymerizable unsaturated groups per molecule exceeds 10 on average, gelation in the production of the copolymer and accompanying insolubilization with organic solvents tend to occur. The gelled copolymer is not preferable as a binder for a paste or a slurry. The number of polymerizable unsaturated groups contained in the cellulose-based polymerizable compound may be 8 or less on average, 5 or less, 3 or less, or 2 or less.

(2) The structural unit (b)

The polyvinyl acetal-based 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 thereof include butyralized polyvinyl alcohol (polyvinyl butyral) and polyvinyl alcohol (polyvinyl formal).

Polyvinyl acetal may be a commercially available product, and various polyvinyl acetals having different degrees of butyralization degree, formalization degree, acetyl group amount, hydroxyl group amount and molecular weight are sold by Sekisui Chemical Co., Ltd., Kuraray Co., Eastman Chemical Co., The polyvinyl acetal may be used alone or in combination of two or more.

From the viewpoint of efficiently producing a polyvinyl acetal-based polymerizable compound having a polymerizable unsaturated group, the polyvinyl acetal is preferably soluble in an organic solvent. From the viewpoint of high solubility in an organic solvent, polyvinyl acetal is more preferably polyvinyl butyral.

Polyvinyl acetal affects the film strength and the viscosity at the time of solution depending on its molecular weight. Therefore, the number average molecular weight of the polyvinyl acetal is preferably in the range of 0.5 to 150,000, more preferably in the range of 10,000 to 100,000, in terms of standard polystyrene by GPC. If the number average molecular weight is less than 0.5 million, the viscosity of the solution becomes extremely low to make it difficult to adjust the viscosity of the copolymer composition (paste or slurry), and the strength and adhesiveness of the film formed by coating and drying the copolymer composition may decrease . On the other hand, if the number average molecular weight exceeds 150,000, the viscosity of the solution becomes extremely large, which may make it difficult to adjust the viscosity of the copolymer composition, and the printing property may be deteriorated.

The polyvinyl acetal has at least one hydroxyl group in one molecule. Generally, the polyvinyl acetal has a hydroxyl group of 20 to 40 mol% as a vinyl alcohol unit constituting the polymer. This hydroxy group can be used for introducing a polymerizable unsaturated group. Specific examples of the polymerizable unsaturated group include a polymerizable carbon-carbon double bond. Suitable examples thereof include a (meth) acrylate group ((meth) acryloyloxy group), a vinyl group and an allyl group.

For example, a polymerizable unsaturated group can be introduced into a polyvinyl acetal by reacting a hydroxy group of the 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 polymerizable compound can be obtained. Examples of the group capable of reacting with a hydroxyl group include a carboxyl group, an acid anhydride group, an acid chloride group, an isocyanate group, and a halogen group (halogen atom). Specific examples of the compound having a group capable of reacting with a hydroxyl group and a polymerizable unsaturated group are the same as the compound exemplified in the section of the aforementioned [1] structural unit (a). The compound having a group capable of reacting with a hydroxyl group and a polymerizable unsaturated group may be used alone or in combination of two or more.

Conventional known methods and reaction conditions can be employed in the reaction (esterification, urethanation, etherification, etc.) of the hydroxy group of the polyvinyl acetal with a compound having a group capable of reacting with the hydroxy group and a polymerizable unsaturated group. It is also effective to use a reaction catalyst (organometallic compound, metal, amine, condensing agent, etc.).

The number of polymerizable unsaturated groups contained in the polyvinyl acetal-based polymerizable compound is preferably 10 or less per molecule on average. When the number of the polymerizable unsaturated groups is more than 10 per molecule on average, gelation in the production of the copolymer and insolubilization with the organic solvent accompanied by the gelation are likely to occur. The gelled copolymer is not preferable as a binder for a paste or a slurry. The number of the polymerizable unsaturated groups contained in the polyvinyl acetal-based polymerizable compound may be 8 or less on average, 5 or less, 3 or less, or 2 or less.

[3] The other constituent unit (c)

The copolymer may further contain other constituent unit (c) other than the constituent unit (a) and the constituent unit (b). The copolymer may contain one or more kinds of the constituent units (c). By further containing the structural unit (c), the copolymerization efficiency of the two polymerizable compounds can be increased, or the solubility of the copolymer in the organic solvent and the dispersion of the inorganic particles in the copolymer composition (paste or slurry) It may be easy to adjust the property.

Examples of the monomer forming the constituent unit (c) include (meth) acrylate (a compound having a (meth) acryloyloxy group). (Meth) acrylate may be used alone or in combination of two or more.

Examples of the (meth) acrylate include (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n- butyl (meth) acrylate, Alkyl (meth) acrylates having 1 to 20 carbon atoms in the alkyl group such as methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) (Meth) acrylate such as 2-hydroxypropyl (meth) acrylate, glyceryl mono (meth) acrylate, and the like; dimethylaminoethyl (meth) acrylate and diethylaminoethyl (Meth) acryloyloxyalkyl (meth) acrylates such as 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- Acid group-containing (meth) acrylates such as acid phosphates Methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, butoxyethylene glycol (Meth) acrylate, isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobutyl (meth) acrylate, , And other monofunctional (meth) acrylates such as benzyl (meth) acrylate and glycidyl (meth) acrylate.

Other examples of the (meth) acrylate include bifunctional (meth) acrylates such as ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having repeating number of ethylene oxide moiety of 2 to 30, and hexanediol di (Meth) acrylate and trifunctional or higher (meth) acrylate such as pentaerythritol tri (meth) acrylate.

The monomer forming the constituent unit (c) may be a monomer other than (meth) acrylate. Examples of the monomer other than the (meth) acrylate include aromatic vinyl monomers such as styrene, vinyl toluene,? -Methyl styrene, p-methyl styrene and divinyl benzene; olefin monomers such as ethylene and propylene; (Meta) acrylamides such as (meth) acryloylmorpholine, (meth) acrylamides such as (meth) acrylic acid, crotonic acid, cinnamic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, N-vinylpyrrolidone, N-phenylmaleimide, N-cyclohexylmaleimide, (meth) acrylonitrile, vinyl chloride, and vinyl acetate can be given.

In the case of using a multifunctional monomer, it is preferable that the amount is such that gelation is not generated in the production of the copolymer.

[4] Composition of Copolymer

The content ratio of the constituent unit (a) to the constituent unit (b) contained in the copolymer is preferably in the range of 10:90 to 90:10, more preferably 20:80 to 80:20, , And more preferably in the range of 25:75 to 75:25. When the content ratio of the constituent unit (a) to the constituent unit (b) is in the above range, it is possible to obtain the desired effect (good thermal decomposition property, adhesion property, And printability) can be obtained more effectively. When the content of the constituent unit (a) is smaller than the above range, there is a possibility that the printability of the copolymer composition (paste or slurry) is lowered. When the content of the constituent unit (b) is smaller than the above range, the strength, adhesiveness and / or thermal decomposition property of the film formed of the copolymer composition may be lowered.

When the copolymer contains the other constituent unit (c), the content thereof is preferably 0.1 to 200 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the total content of the constituent unit (a) and the constituent unit (b) More preferably 50 parts by mass or less, and still more preferably 50 parts by mass or less. When the content of the constituent unit (c) is within the above range, the desired effect (favorable thermal decomposition property, adhesion property, coating film property, and printability) due to the copolymer containing the constituent unit (a) and the constituent unit . When the content of the constituent unit (c) exceeds 200 parts by mass, there is a possibility that the printing property of the copolymer composition (paste or slurry) is lowered or the strength of the film formed of the copolymer composition is lowered.

The number average molecular weight of the copolymer is preferably from 10,000 to 200,000, more preferably from 10,000 to 150,000, and even more preferably from 20,000 to 120,000, in terms of standard polystyrene by GPC. If the number average molecular weight of the copolymer is less than 10,000, the viscosity of the copolymer composition (paste or slurry) is lowered, and the strength and adhesion of the coating film may be lowered. On the other hand, if it exceeds 20,000, the viscosity tends to become too high, and the printability tends to decrease.

&Lt; Process for producing copolymer &

[1] Production of Cellulose-Based Polymerizable Compound and Polyvinyl acetal-based Polymerizable Compound

As described above, the cellulose-based polymerizable compound having a polymerizable unsaturated group forming the structural unit (a) of the copolymer and the polyvinyl acetal-based polymerizable compound having a polymerizable unsaturated group forming the structural unit (b) A cellulose derivative, a polyvinyl acetal, and a compound having a group capable of reacting with the hydroxy group and a polymerizable unsaturated group.

The reaction is, for example, an esterification reaction, a urethanization reaction, or an etherification reaction. In the reaction, conventionally known methods and reaction conditions can be employed. It is also effective to use a reaction catalyst (organometallic compound, metal, amine, condensing agent, etc.).

The esterification reaction can be carried out, for example, using a condensing agent. Examples of the condensing agent include carbodiimide, diphenylphosphoric acid amide, 1-hydroxybenzotriazole, and BOP reagent. The condensing agent may be used alone or in combination of two or more. Among them, carbodiimides are suitable because they are excellent in versatility and reactivity and can proceed the reaction under low temperature conditions and under the influence of moisture under a reaction environment.

Examples of the carbodiimide include dicyclohexylcarbodiimide, diisopropylcarbodiimide, N- [3- (dimethylamino) propyl] -N'-ethylcarbodiimide, N- [3- (dimethylamino) ] -N'-ethylcarbodiimide methide and the like. Among them, from the viewpoint of availability, dicyclohexylcarbodiimide and diisopropylcarbodiimide are suitable. When a carbodiimide is used, it is also preferable to use a combination of dimethylaminopyridine or triethylamine as a reaction accelerator in a range of 0.01 mol% to 10 mol% with respect to the carbodiimide.

The urethanization reaction can be carried out, for example, using a reaction catalyst. Examples of the reaction catalyst include organometallic compounds such as dioctyltin dilaurate, dibutyltin dilaurate, stannus octoate and zinc dinaphthenate; 1,8-diazabicyclo [5,4,0] undecene- N, N ', N' '- pentamethyldiethylenetriamine), N (N, N' N, N ', N'-tetramethylpropylenediamine, N, N, N', N'-tetramethylhexamethylenediamine, N-methyldicyclohexylamine, And amine compounds such as morpholine, N-ethylmorpholine, 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; and alkali metal hydrides such as NaH and KH as reaction catalysts.

The reaction of the hydroxy group of the cellulose derivative or polyvinyl acetal with the compound capable of reacting with the hydroxy group and the compound having a polymerizable unsaturated group is preferably carried out in an aprotic organic solvent.

Examples of the aprotic organic solvent include ethyl acetate, butyl acetate, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, toluene, xylene, dimethylformamide, dimethylacetamide, N (Ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate (butyl carbitol acetate)), diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, 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. The organic solvent may be used alone or in combination of two or more.

The reaction temperature of the hydroxy group of the cellulose derivative or polyvinyl acetal with the compound having a group capable of reacting with the hydroxy group and the polymerizable unsaturated group is, for example, about 0 ° C to 100 ° C. The introduction amount of the polymerizable unsaturated group can be measured by NMR analysis or the like. When a carbodiimide is used as a condensing agent, a compound having a polymerizable unsaturated group may be reacted with a carbodiimide in advance and then added. When carbodiimide is used, urea is produced as a by-product, which may be insolubilized. However, filtration purification or reprecipitation purification may be carried out if necessary.

The amount of the polymerizable unsaturated group introduced into the cellulose derivative or the polyvinyl acetal is preferably set such that the number of hydroxyl groups contained in one molecule of the cellulose derivative or polyvinyl acetal, the amount of a compound having a group capable of reacting with a hydroxy group and a polymerizable unsaturated group, . The number of hydroxy groups contained in one molecule of the cellulose derivative or polyvinyl acetal can be adjusted by the content of the hydroxyl group contained in the cellulose derivative or polyvinyl acetal, the molecular weight of the cellulose derivative, the polyvinyl acetal, and the like.

The introduction of the polymerizable unsaturated group into the cellulose derivative and the polyvinyl acetal may be carried out either individually or in combination of 2) a method in which a cellulose derivative and polyvinyl acetal are mixed in advance, and a group capable of reacting with the hydroxy group, May be carried out by reacting a compound having a polymerizable unsaturated group.

The mixing ratio of the cellulose derivative and the polyvinyl acetal in the case of the above 2) is preferably the same as the above-mentioned "content ratio of the constituent unit (a) and the constituent unit (b) contained in the copolymer". Also in the case of the above 2), it is preferable to introduce a polymerizable unsaturated group so that the number of the polymerizable unsaturated groups per each of the cellulose derivative and the polyvinyl acetal is 10 or less per molecule on average.

[2] Production of Copolymer

A copolymer is obtained by copolymerizing a monomer composition comprising a cellulose-based polymerizable compound having a polymerizable unsaturated group, a polyvinyl acetal-based polymerizable compound having a polymerizable unsaturated group, and optionally a monomer constituting the constituent unit (c) have. This copolymerization reaction is carried out, for example, by heating in an organic solvent in the presence of a radical polymerization initiator, preferably under a non-oxygen atmosphere. Specific examples of the organic solvent that can be used in the copolymerization reaction include a protonic organic solvent in addition to the aprotic organic solvent exemplified in [1] above, 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, dihydrotopine And the like. The organic solvent may be used alone or in combination of two or more.

As the radical polymerization initiator, conventionally known ones (for example, a peroxide system or an azo system) can be used. The amount of the radical polymerization initiator used is, for example, in the range of 0.001 to 5% based on 100% by mass of the total amount of the monomers.

The total concentration of the total monomers in the copolymerization reaction solution is preferably 5 to 70 mass%. The temperature of the copolymerization reaction is, for example, about 40 ° C to 120 ° C.

After the copolymerization reaction, if necessary, ordinary polymer purification treatment such as precipitation purification with a poor solvent may be carried out. Unreacted monomers and by-products can be removed by a purification treatment, and a solid state copolymer can be obtained.

&Lt; Copolymer composition >

The copolymer composition according to the present invention is suitable as a paste or slurry containing a binder which is the above copolymerization and inorganic particles and an organic solvent and is used for producing various pastes or slurries, particularly electronic components or members of electronic devices Do. Further, although there is no clear distinction between the paste and the slurry, it is mainly distinguished in terms of the viscosity, and the former is the high viscosity.

For example, the copolymer composition according to the present invention can be suitably used as a paste or a slurry for forming a circuit of various electronic parts, an electrode pattern, a dielectric layer, a phosphor layer, and the like. Also included in the present invention is a copolymer composition comprising a binder and an organic solvent, which may also be an intermediate for preparing the copolymer composition.

Examples of the inorganic material constituting the inorganic particles contained in the copolymer composition include conductive inorganic materials, ceramics, glass, pigments, and phosphors. Examples of the conductive inorganic material include metals such as gold, silver, copper, platinum, palladium, nickel, aluminum, tungsten and iron; alloys containing any of the above metals such as silver and palladium alloys; And a carbon powder, and the like. 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 the glass, there may be mentioned silicon dioxide (which is usually composed mainly of silicon dioxide), and its melting point is not particularly limited. The particle size of the inorganic particles is usually in the range of 20 nm to 1 mm. The inorganic particles may be used alone or in combination of two or more.

As the organic solvent to be contained in the copolymer composition, one or more of the organic solvents exemplified in [1] and [2] above may be used. The organic solvent is a solvent capable of dissolving the binder, and is preferably a high boiling point in the use of a printing paste.

The copolymer composition may further contain additives as required. Additives include surfactants, viscosity regulators, defoamers, leveling agents, stabilizers, plasticizers, wetting agents, pigments, polymer particles and the like. The additives may be used alone or in combination of two or more. In addition, the copolymer composition may contain a polymer other than the above-mentioned copolymer as a binder.

The content ratio of the inorganic particles (the total content when two or more kinds of inorganic particles are contained) and the binder in the copolymer composition is usually 100: 1 to 100: 50 on a mass basis, and the viscosity of the copolymer composition From the viewpoint of dispersibility of the inorganic particles and the like, it is preferably 100: 5 to 100: 30. The content of the organic solvent (the total content in the case of containing two or more kinds of organic solvents) is usually 100 parts by mass to 10000 parts by mass with respect to 100 parts by mass of the binder. When the copolymer composition contains an additive, the content thereof (the total content thereof when containing two or more additives) is usually 0.1 to 30 parts by mass with respect to 100 parts by mass of the binder.

Inorganic particles, a binder (copolymer) dissolved in an organic solvent, and additives to be used as needed are mixed using a dispersing device such as a three roll mill, a ball mill, a media mill, a homogenizer, To prepare a copolymer composition.

After the copolymer composition is coated on a substrate or the like, the organic solvent is volatilized by subsequent firing, and the layer or pattern of inorganic particles can be formed by thermally decomposing the binder. Examples of coating methods of the copolymer composition include screen printing, die coating printing, doctor blade printing, roll coating printing, offset printing, gravure printing, flexographic printing, inkjet printing, dispensing printing, casting, Among them, screen printing and dip painting are suitable. The layer or pattern obtained by firing usually comprises a sintered body of inorganic particles.

Example

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In the examples, "%" and "part" indicating the content or amount are based on mass unless otherwise specified.

(Synthesis Example 1: Synthesis of cellulose-based polymerizable compound (a1)) [

Ethyl cellulose ("ETHOCEL STD-100" manufactured by Dow Chemical Company, number average molecular weight Mn (standard polystyrene equivalent value by GPC): 63400, degree of substitution (DS value, degree of etherification): 2.52) was prepared and dried. The substitution degree 2.52 means that 2.52 of the three hydroxyl groups present in one glucose ring are ethyl etherified, and 0.48 hydroxyl groups remain. The number average molecular weight Mn and the average number of hydroxyl groups in one molecule calculated from the degree of substitution are about 131. [

100 parts of the dried ethylcellulose was dissolved in 400 parts of ethyl acetate. 0.27 parts of methacrylic acid corresponding to two introduced amounts per molecule of ethyl cellulose per molecule, 0.4 parts of diisopropyl carbodiimide as a condensing agent and 0.004 parts of dimethylaminopyridine as a reaction promoter were added to the obtained solution, The reaction was carried out with stirring for 24 hours. Thereafter, ethyl acetate was distilled off to obtain a cellulose polymerizable compound (a1) having a methacrylate group introduced into ethylcellulose as a solid.

A part of the obtained solid was analyzed by FT-IR and ¹ H-NMR. As a result, it was confirmed that the formation of an ester bond was confirmed and that a methacrylate group having the same molar amount as the added methacrylic acid was introduced into ethylcellulose.

Synthesis Example 2: Synthesis of cellulose-based polymerizable compound (a2)

Ethylcellulose ("ETHOCEL STD-10" manufactured by Dow Chemical Company, number average molecular weight Mn (standard polystyrene equivalent value by GPC): 22800, degree of substitution: 2.52) was prepared and dried. The number average molecular weight Mn and the average number of hydroxyl groups in one molecule calculated from the degree of substitution are about 47. [

100 parts of the dried ethylcellulose was dissolved in 400 parts of ethyl acetate. 2.05 parts of 2-isocyanate ethyl methacrylate ("Karenz MOI" manufactured by Showa Denko K.K.) corresponding to an average of three introduced amounts per molecule of ethylcellulose and 0.01 parts of dioctyltin dilaurate as a catalyst were added to the obtained solution , And the mixture was stirred at a temperature of 60 ° C for 5 hours to carry out the reaction. Thereafter, ethyl acetate was distilled off to obtain a cellulose-based polymerizable compound (a2) having a methacrylate group introduced into ethylcellulose as a solid.

A part of the obtained solid was analyzed by FT-IR and ¹ H-NMR to confirm the formation of a urethane bond, and a methacrylate group of the same molar amount as that of the added 2-isocyanate ethyl methacrylate was introduced into ethylcellulose .

Synthesis Example 3: Synthesis of cellulose-based polymerizable compound (a3)

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

100 parts of the dried ethylcellulose was dissolved in 400 parts of ethyl acetate. 0.11 part of methacrylic acid corresponding to one introduced amount per molecule of ethyl cellulose per molecule, 0.16 part of diisopropyl carbodiimide as a condensing agent and 0.0016 part of dimethylaminopyridine as a reaction promoter were added to the obtained solution, The reaction was carried out with stirring for 24 hours. Thereafter, ethyl acetate was distilled off to obtain a cellulose polymerizable compound (a3) having a methacrylate group introduced into ethylcellulose as a solid.

A part of the obtained solid was analyzed by FT-IR and ¹ H-NMR. As a result, it was confirmed that the formation of an ester bond was confirmed and that a methacrylate group having the same molar amount as the added methacrylic acid was introduced into ethylcellulose.

(Synthesis Example 4: Synthesis of cellulose-based polymerizable compound (a4)) [

Ethylcellulose ("ETHOCEL STD-100" manufactured by Dow Chemical Company, number average molecular weight Mn (standard polystyrene equivalent value by GPC): 63400, degree of substitution: 2.52) was prepared and dried. The number average molecular weight Mn and the average number of hydroxyl groups in one molecule calculated from the degree of substitution are about 131. [

100 parts of the dried ethylcellulose was dissolved in 400 parts of ethyl acetate. 0.68 parts of methacrylic acid corresponding to an average of five introduced amounts per molecule of ethylcellulose, 0.99 part of diisopropyl carbodiimide as a condensing agent and 0.001 part of dimethylaminopyridine as a reaction promoter were added to the obtained solution, The reaction was carried out with stirring for 24 hours. Thereafter, ethyl acetate was distilled off to obtain a cellulose-based polymerizable compound (a4) having a methacrylate group introduced into ethylcellulose as a solid.

A part of the obtained solid was analyzed by FT-IR and ¹ H-NMR. As a result, it was confirmed that the formation of an ester bond was confirmed and that a methacrylate group having the same molar amount as the added methacrylic acid was introduced into ethylcellulose.

(Synthesis Example 5: Synthesis of cellulose-based polymerizable compound (a5)) [

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

100 parts of the dried ethylcellulose was dissolved in 400 parts of ethyl acetate. 0.46 parts of methacrylic acid corresponding to an average of three introduced amounts per molecule of ethylcellulose, 0.67 part of diisopropyl carbodiimide as a condensing agent and 0.0067 parts of dimethylaminopyridine as a reaction promoter were added to the obtained solution, The reaction was carried out with stirring for 24 hours. Thereafter, ethyl acetate was distilled off to obtain a cellulose polymerizable compound (a5) having a methacrylate group introduced into ethylcellulose as a solid.

A part of the obtained solid was analyzed by FT-IR and ¹ H-NMR. As a result, it was confirmed that the formation of an ester bond was confirmed and that a methacrylate group having the same molar amount as the added methacrylic acid was introduced into ethylcellulose.

(Synthesis Example 6: Synthesis of cellulose-based polymerizable compound (a6)

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

100 parts of the dried ethylcellulose was dissolved in 400 parts of ethyl acetate. To the resulting solution, 6.26 parts of methacrylic acid corresponding to an average of 10 introduced amounts per molecule of ethyl cellulose, 9.18 parts of diisopropyl carbodiimide as a condensing agent and 0.09 part of dimethylaminopyridine as a reaction promoter were added, The reaction was carried out with stirring for 24 hours. Thereafter, ethyl acetate was distilled off to obtain a cellulose-based polymerizable compound (a6) having a methacrylate group introduced into ethylcellulose as a solid.

A part of the obtained solid was analyzed by FT-IR and ¹ H-NMR. As a result, it was confirmed that the formation of an ester bond was confirmed and that a methacrylate group having the same molar amount as the added methacrylic acid was introduced into ethylcellulose.

(Synthesis Example 7: Synthesis of polyvinyl acetal-based polymerizable compound (b1)

(Number average molecular weight Mn (standard polystyrene equivalent value by GPC): 53000, hydroxyl group content: about 22 mol%) was prepared and dried. 100 parts of dried polyvinyl butyral was dissolved in 400 parts of ethyl acetate. 0.32 parts of methacrylic acid corresponding to two introduced amounts per molecule of polyvinyl butyral, 0.48 part of diisopropyl carbodiimide as a condensing agent and 0.0048 parts of dimethylaminopyridine as a reaction promoter were added to the obtained solution, Lt; 0 &gt; C for 24 hours. Thereafter, ethyl acetate was distilled off to obtain a polyvinyl acetal-based polymerizable compound (b1) having a methacrylate group introduced into polyvinyl butyral as a solid.

A part of the obtained solid was analyzed by FT-IR and ¹ H-NMR, and it was confirmed that the formation of ester bond was confirmed and that a methacrylate group having the same molar amount as the added methacrylic acid was introduced into polyvinyl butyral .

(Synthesis Example 8: Synthesis of polyvinyl acetal-based polymerizable compound (b2)

(Number-average molecular weight Mn (standard polystyrene equivalent value by GPC): 23000, hydroxyl group content: about 22 mol%) was prepared and dried in the same manner as in Example 1, except that polyvinyl butyral (BL-S manufactured by Sekisui Chemical Co., Ltd.) 100 parts of dried polyvinyl butyral was dissolved in 400 parts of ethyl acetate. 2.02 parts of 2-isocyanate ethyl methacrylate ("Karenz MOI" manufactured by Showa Denko K.K.) equivalent to an average of three introduced amounts per molecule of polyvinyl butyral and 0.01 part of di-octyltin dilaurate as a catalyst were added to the obtained solution And the mixture was stirred at a temperature of 60 ° C for 5 hours to carry out the reaction. Thereafter, ethyl acetate was distilled off to obtain a polyvinyl acetal-based polymerizable compound (b2) having a methacrylate group introduced into polyvinyl butyral as a solid.

A part of the obtained solid was analyzed by FT-IR and ¹ H-NMR to confirm formation of a urethane bond, and a methacrylate group of the same molar amount as the added 2-isocyanate ethyl methacrylate was introduced into polyvinyl butyral .

(Synthesis Example 9: Synthesis of polyvinyl acetal-based polymerizable compound (b3)

Polyvinyl butyral ("BH-S" manufactured by Sekisui Chemical Co., Ltd., number average molecular weight Mn (standard polystyrene conversion value by GPC): 66000, hydroxyl group content: about 22 mol%) was prepared and dried. 100 parts of dried polyvinyl butyral was dissolved in 400 parts of ethyl acetate. 0.13 part of methacrylic acid corresponding to one introduced amount per molecule of polyvinyl butyral, 0.19 part of diisopropyl carbodiimide as a condensing agent and 0.002 part of dimethylaminopyridine as a reaction promoter were added to the obtained solution, Lt; 0 &gt; C for 24 hours. Thereafter, ethyl acetate was distilled off to obtain a polyvinyl acetal-based polymerizable compound (b3) having a methacrylate group introduced into polyvinyl butyral as a solid.

A part of the obtained solid was analyzed by FT-IR and ¹ H-NMR, and it was confirmed that the formation of ester bond was confirmed and that a methacrylate group having the same molar amount as the added methacrylic acid was introduced into polyvinyl butyral .

(Synthesis Example 10: Synthesis of polyvinyl acetal-based polymerizable compound (b4)

("BM-S" manufactured by Sekisui Chemical Co., Ltd., number average molecular weight Mn (standard polystyrene equivalent value by GPC): 53,000, hydroxyl group content: about 22 mol%) was prepared and dried. 100 parts of dried polyvinyl butyral was dissolved in 400 parts of ethyl acetate. To the resulting solution, 0.81 part of methacrylic acid corresponding to an average of five introduced amounts per molecule of polyvinyl butyral, 1.19 parts of diisopropyl carbodiimide as a condensing agent and 0.012 part of dimethylaminopyridine as a reaction promoter were added, Lt; 0 &gt; C for 24 hours. Thereafter, ethyl acetate was distilled off to obtain a polyvinyl acetal-based polymerizable compound (b4) having a methacrylate group introduced into polyvinyl butyral as a solid.

A part of the obtained solid was analyzed by FT-IR and ¹ H-NMR, and it was confirmed that the formation of ester bond was confirmed and that a methacrylate group having the same molar amount as the added methacrylic acid was introduced into polyvinyl butyral .

(Synthesis Example 11: Synthesis of polyvinyl acetal-based polymerizable compound (b5)

("BM-S" manufactured by Sekisui Chemical Co., Ltd., number average molecular weight Mn (standard polystyrene equivalent value by GPC): 53,000, hydroxyl group content: about 22 mol%) was prepared and dried. 100 parts of dried polyvinyl butyral was dissolved in 400 parts of ethyl acetate. 0.48 parts of methacrylic acid corresponding to an average of three introduced amounts per molecule of polyvinyl butyral, 0.72 part of diisopropyl carbodiimide as a condensing agent and 0.0072 parts of dimethylaminopyridine as a reaction promoter were added to the obtained solution, Lt; 0 &gt; C for 24 hours. Thereafter, ethyl acetate was distilled off to obtain a polyvinyl acetal-based polymerizable compound (b5) having a methacrylate group introduced into polyvinyl butyral as a solid.

A part of the obtained solid was analyzed by FT-IR and ¹ H-NMR, and it was confirmed that the formation of ester bond was confirmed and that a methacrylate group having the same molar amount as the added methacrylic acid was introduced into polyvinyl butyral .

(Synthesis Example 12: Synthesis of polyvinyl acetal-based polymerizable compound (b6)

(Number-average molecular weight Mn (standard polystyrene equivalent value by GPC): 23000, hydroxyl group content: about 22 mol%) was prepared and dried in the same manner as in Example 1, except that polyvinyl butyral (BL-S manufactured by Sekisui Chemical Co., Ltd.) 100 parts of dried polyvinyl butyral was dissolved in 400 parts of ethyl acetate. To the resulting solution, 3.74 parts of methacrylic acid corresponding to an average of 10 introduced amounts per molecule of polyvinyl butyral, 5.49 parts of diisopropyl carbodiimide as a condensing agent and 0.055 part of dimethylaminopyridine as a reaction promoter were added, Lt; 0 &gt; C for 24 hours. Thereafter, ethyl acetate was distilled off to obtain a polyvinyl acetal-based polymerizable compound (b6) having a methacrylate group introduced into polyvinyl butyral as a solid.

A part of the obtained solid was analyzed by FT-IR and ¹ H-NMR. As a result, it was confirmed that the formation of an ester bond was confirmed and that a methacrylate group having the same molar amount as the added methacrylic acid was introduced into ethylcellulose.

(Synthesis Example 13: Synthesis of a mixture of a cellulose-based polymerizable compound (a7) and a polyvinyl acetal-based polymerizable compound (b7)

Ethylcellulose ("ETHOCEL STD-100" manufactured by Dow Chemical Company, number average molecular weight Mn (standard polystyrene equivalent value by GPC): 63400, degree of substitution: 2.52) was prepared and dried. Further, polyvinyl butyral ("BM-S" manufactured by Sekisui Chemical Co., Ltd., number average molecular weight Mn (standard polystyrene equivalent value by GPC: 53000) and hydroxyl group content: about 22 mol%) were prepared and dried.

50 parts of the dried ethylcellulose and 50 parts of the dried polyvinyl butyral were dissolved in 400 parts of ethyl acetate. To the obtained solution, 0.30 part of methacrylic acid corresponding to an average of two introduced amounts per one molecule of ethylcellulose and one molecule of polyvinyl butyral, 0.44 part of diisopropyl carbodiimide as a condensing agent, And the mixture was stirred at a temperature of 30 ° C for 24 hours to carry out the reaction. Thereafter, ethyl acetate was distilled off to obtain a cellulose polymeric compound (a7) having a methacrylate group introduced into ethylcellulose as a solid and a polyvinyl acetal polymerizable compound (a7) having a methacrylate group introduced into polyvinyl butyral b7) was obtained.

Analysis of a part of the obtained solid by FT-IR and ¹ H-NMR showed that ester bond formation was confirmed and that methacrylate groups having the same molar amount as the added methacrylic acid were introduced into ethyl cellulose and polyvinyl butyral .

Synthesis Example 14: Synthesis of a mixture of cellulose-based polymerizable compound (a8) and polyvinyl acetal-based polymerizable compound (b8)

Ethylcellulose ("ETHOCEL STD-10" manufactured by Dow Chemical Company, number average molecular weight Mn (standard polystyrene equivalent value by GPC): 22800, degree of substitution: 2.52) was prepared and dried. Further, polyvinyl butyral ("BL-S" manufactured by Sekisui Chemical Co., Ltd., number average molecular weight Mn (standard polystyrene equivalent value by GPC: 23000) and hydroxyl group content: about 22 mol%) were prepared and dried.

50 parts of the dried ethylcellulose and 50 parts of the dried polyvinyl butyral were dissolved in 400 parts of ethyl acetate. To the resulting solution, 1.13 parts of methacrylic acid corresponding to an average of three introduced amounts per one molecule of ethylcellulose and one molecule of polyvinyl butyral, 1.65 parts of diisopropyl carbodiimide as a condensing agent, dimethylaminopyridine And the mixture was stirred at a temperature of 30 占 폚 for 24 hours to carry out the reaction. Thereafter, ethyl acetate was distilled off to obtain a cellulose polymeric compound (a8) having a methacrylate group introduced into ethylcellulose as a solid and a polyvinyl acetal polymerizable compound (a8) having a methacrylate group introduced into polyvinyl butyral b8) was obtained.

Analysis of a part of the obtained solid by FT-IR and ¹ H-NMR showed that ester bond formation was confirmed and that methacrylate groups having the same molar amount as the added methacrylic acid were introduced into ethyl cellulose and polyvinyl butyral .

(Synthesis Example 15: synthesis of mixture of cellulose-based polymerizable compound (a9) and polyvinyl acetal-based polymerizable compound (b9)

Ethylcellulose ("ETHOCEL STD-4" manufactured by Dow Chemical Company, number average molecular weight Mn (standard polystyrene equivalent value by GPC): 13700, degree of substitution: 2.52) was prepared and dried. Further, polyvinyl butyral ("BL-S" manufactured by Sekisui Chemical Co., Ltd., number average molecular weight Mn (standard polystyrene equivalent value by GPC: 23000) and hydroxyl group content: about 22 mol%) were prepared and dried.

50 parts of the dried ethylcellulose and 50 parts of the dried polyvinyl butyral were dissolved in 400 parts of ethyl acetate. To the obtained solution, 0.30 part of methacrylic acid corresponding to an average of two introduced amounts per one molecule of ethylcellulose and one molecule of polyvinyl butyral, 0.44 part of diisopropyl carbodiimide as a condensing agent, And the mixture was stirred at a temperature of 30 ° C for 24 hours to carry out the reaction. Thereafter, ethyl acetate was distilled off to obtain a cellulose polymeric compound (a9) having a methacrylate group introduced into ethylcellulose as a solid and a polyvinyl acetal polymerizable compound (a9) having a methacrylate group introduced into polyvinyl butyral b9) was obtained.

Analysis of a part of the obtained solid by FT-IR and ¹ H-NMR showed that ester bond formation was confirmed and that methacrylate groups having the same molar amount as the added methacrylic acid were introduced into ethyl cellulose and polyvinyl butyral .

(Synthesis Example 16: synthesis of mixture of cellulose-based polymerizable compound (a10) and polyvinyl acetal-based polymerizable compound (b10)

Ethylcellulose ("ETHOCEL STD-100" manufactured by Dow Chemical Company, number average molecular weight Mn (standard polystyrene equivalent value by GPC): 63400, degree of substitution: 2.52) was prepared and dried. Further, polyvinyl butyral ("BH-S" manufactured by Sekisui Chemical Co., Ltd., number average molecular weight Mn (standard polystyrene equivalent value by GPC): 66000, hydroxyl group content: about 22 mol%) was prepared and dried.

50 parts of the dried ethylcellulose and 50 parts of the dried polyvinyl butyral were dissolved in 400 parts of ethyl acetate. To the obtained solution, 0.27 parts of methacrylic acid corresponding to an average of two introduced amounts of one molecule of ethylcellulose and one molecule of polyvinyl butyral, 0.4 part of diisopropyl carbodiimide as a condensing agent, dimethylaminopyridine And the mixture was stirred at a temperature of 30 占 폚 for 24 hours to carry out the reaction. Thereafter, ethyl acetate was distilled off to obtain a cellulose polymeric compound (a10) having a methacrylate group introduced into ethylcellulose as a solid and a polyvinyl acetal polymerizable compound (a10) having a methacrylate group introduced into polyvinyl butyral b10) was obtained.

Analysis of a part of the obtained solid by FT-IR and ¹ H-NMR showed that ester bond formation was confirmed and that methacrylate groups having the same molar amount as the added methacrylic acid were introduced into ethyl cellulose and polyvinyl butyral .

(Synthesis Example 17: synthesis of mixture of cellulose-based polymerizable compound (a11) and polyvinyl acetal-based polymerizable compound (b11)

Ethylcellulose ("ETHOCEL STD-200" manufactured by Dow Chemical Company, number average molecular weight Mn (standard polystyrene equivalent value by GPC): 80700, degree of substitution: 2.52) was prepared and dried. Further, polyvinyl butyral ("BH-S" manufactured by Sekisui Chemical Co., Ltd., number average molecular weight Mn (standard polystyrene equivalent value by GPC): 66000, hydroxyl group content: about 22 mol%) was prepared and dried.

50 parts of the dried ethylcellulose 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 corresponding to an average of two introduced amounts of one molecule of ethylcellulose and one molecule of polyvinyl butyral, 0.35 part of diisopropyl carbodiimide as a condensing agent, and 0.35 parts of dimethylaminopyridine And the mixture was stirred at a temperature of 30 占 폚 for 24 hours to carry out the reaction. Thereafter, ethyl acetate was distilled off to obtain a cellulose-based polymerizable compound (a11) having a methacrylate group introduced into ethylcellulose as a solid and a polyvinyl acetal-based polymerizable compound (a11) having a methacrylate group introduced into polyvinylbutyral b11) was obtained.

Analysis of a part of the obtained solid by FT-IR and ¹ H-NMR showed that ester bond formation was confirmed and that methacrylate groups having the same molar amount as the added methacrylic acid were introduced into ethyl cellulose and polyvinyl butyral .

1. Synthesis of Binder (Copolymer)

&Lt; Example 1: Synthesis of Copolymer (1) >

10 parts of the cellulose-based polymerizable compound (a1) obtained in Synthesis Example 1, 10 parts of the polyvinyl acetal-based polymerizable compound (b1) obtained in Synthesis Example 7, and 80 parts of dihydroterpinylacetate as an organic solvent And the mixture was heated to 60 DEG C and dissolved by stirring with a rotating blade. After the dissolution, the inside of the system was removed by nitrogen substitution, and 0.01 part of azoisobutyronitrile (AIBN) as a polymerization initiator was mixed and reacted at 70 ° C for 5 hours to obtain a solution (binder solution) containing the copolymer (1) &Lt; / RTI &gt;

The molecular weight of the obtained copolymer (1) was measured by a GPC apparatus, and the number average molecular weight (in terms of standard polystyrene) was 71,000. This value was larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, and it was confirmed that the polymerization proceeded by the above reaction.

The number average molecular weight of the copolymer (1) was measured under the following conditions (the same applies to the number average molecular weight of the copolymer obtained in the following examples).

GPC apparatus: "HLC-8320 GPC" manufactured by TOSOH Corporation,

Column: TSKgel GMHXL,

Measurement temperature (set temperature): 30 ° C,

Mobile phase: tetrahydrofuran.

&Lt; Example 2: Synthesis of copolymer (2) >

10 parts of the cellulose-based polymerizable compound (a1) obtained in Synthesis Example 1, 10 parts of the polyvinyl acetal-based polymerizable compound (b1) obtained in Synthesis Example 7, 1.0 part of isobutyl methacrylate, , 80 parts of dihydrotriphenyl acetate as a solvent were added and mixed, and the mixture was heated to 60 占 폚 and stirred with a rotating blade to dissolve. After the dissolution, nitrogen was substituted to remove oxygen in the system, and 0.01 part of azoisobutyronitrile (AIBN) as a polymerization initiator was mixed and reacted at 70 캜 for 5 hours to obtain a solution (binder solution) containing the copolymer (2) &Lt; / RTI &gt;

The molecular weight of the obtained copolymer (2) was measured by a GPC apparatus, and the number average molecular weight (standard polystyrene conversion value) was 72000. This value was larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, and it was confirmed that the polymerization proceeded by the above reaction.

&Lt; Example 3: Synthesis of copolymer (3) >

5 parts of the cellulose-based polymerizable compound (a1) obtained in Synthesis Example 1 and 15 parts of the polyvinyl acetal-based polymerizable compound (b1) obtained in Synthesis Example 7 were used to obtain the copolymer (3 ) (Binder solution) was obtained.

The molecular weight of the obtained copolymer (3) was measured by a GPC apparatus, and the number average molecular weight (in terms of standard polystyrene) was 73,000. This value was larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, and it was confirmed that the polymerization proceeded by the above reaction.

Example 4: Synthesis of copolymer (4)

15 parts of the cellulose-based polymerizable compound (a1) obtained in Synthesis Example 1 and 5 parts of the polyvinyl acetal-based polymerizable compound (b1) obtained in Synthesis Example 7 were used, ) (Binder solution) was obtained.

The molecular weight of the obtained copolymer (4) was measured by a GPC apparatus, and the number average molecular weight (in terms of standard polystyrene) was 70000. This value was larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, and it was confirmed that the polymerization proceeded by the above reaction.

Example 5: Synthesis of copolymer (5)

10 parts of the cellulose-based polymerizable compound (a2) obtained in Synthesis Example 2, 10 parts of the polyvinyl acetal-based polymerizable compound (b2) obtained in Synthesis Example 8, and 80 parts of dihydroterpinylacetate as an organic solvent And the mixture was heated to 60 DEG C and dissolved by stirring with a rotating blade. After the dissolution, the atmosphere in the system was removed by nitrogen substitution, and 0.01 part of azoisobutyronitrile (AIBN) as a polymerization initiator was mixed and reacted at 70 DEG C for 5 hours to obtain a solution (binder solution) containing the copolymer (5) &Lt; / RTI &gt;

The molecular weight of the obtained copolymer (5) was measured by a GPC apparatus, and the number average molecular weight (in terms of standard polystyrene) was 42000. This value was larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, and it was confirmed that the polymerization proceeded by the above reaction.

Example 6: Synthesis of copolymer (6)

10 parts of the cellulose-based polymerizable compound (a2) obtained in Synthesis Example 2, 10 parts of the polyvinyl acetal-based polymerizable compound (b2) obtained in Synthesis Example 8, 2 parts of isobutyl methacrylate, , 80 parts of dihydroterpinylacetate as a binder were added and mixed, and the mixture was heated to 60 DEG C and dissolved by stirring with a rotating blade. After the dissolution, nitrogen was substituted to remove oxygen in the system, and 0.01 part of azoisobutyronitrile (AIBN) as a polymerization initiator was mixed and reacted at 70 캜 for 5 hours to obtain a solution (binder solution) containing the copolymer (6) &Lt; / RTI &gt;

The molecular weight of the obtained copolymer (6) was measured by a GPC apparatus, and the number average molecular weight (in terms of standard polystyrene) was 45,000. This value was larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, and it was confirmed that the polymerization proceeded by the above reaction.

Example 7: Synthesis of copolymer (7)

(7) was obtained in the same manner as in Example 5, except that the cellulose-based polymerizable compound (a1) obtained in Synthesis Example 1 was used instead of the cellulose-based polymerizable compound (a2) obtained in Synthesis Example 2 Binder solution).

The molecular weight of the obtained copolymer (7) was measured by a GPC apparatus, and the number average molecular weight (in terms of standard polystyrene) was 68,000. This value was larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, and it was confirmed that the polymerization proceeded by the above reaction.

Example 8: Synthesis of copolymer (8)

(8) was obtained in the same manner as in Example 5, except that the polyvinyl acetal-based polymerizable compound (b1) obtained in Synthesis Example 7 was used in place of the polyvinyl acetal-based polymerizable compound (b2) obtained in Synthesis Example 8 (Binder solution) was obtained.

The molecular weight of the obtained copolymer (8) was measured by a GPC apparatus, and the number average molecular weight (in terms of standard polystyrene) was 56,000. This value was larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, and it was confirmed that the polymerization proceeded by the above reaction.

&Lt; Example 9: Synthesis of copolymer (9) >

(A7) in which a methacrylate group was introduced into ethylcellulose obtained in Synthesis Example 13 and a polyvinyl acetal polymerizable compound (b7) having a methacrylate group introduced into polyvinyl butyral 20 parts of a mixture, 0.2 parts of isobutyl methacrylate, and 80 parts of dihydroterpinylacetate as an organic solvent were added and mixed, and the mixture was heated to 60 占 폚 and stirred with a rotating blade to dissolve. After the dissolution, the inside of the system was subjected to nitrogen substitution to remove oxygen, and 0.01 part of azoisobutyronitrile (AIBN) as a polymerization initiator was mixed and reacted at 70 ° C for 5 hours to obtain a solution (binder solution) containing the copolymer (9) &Lt; / RTI &gt;

The molecular weight of the obtained copolymer (9) was measured by a GPC apparatus, and the number average molecular weight (in terms of standard polystyrene) was 72,000. This value was larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, and it was confirmed that the polymerization proceeded by the above reaction.

Example 10: Synthesis of copolymer (10)

(A8) having a methacrylate group introduced into ethylcellulose obtained in Synthesis Example 14 and a polyvinyl acetal-based polymerizable compound (a8) having a methacrylate group introduced into polyvinyl butyral (binder solution) containing the copolymer (10) was obtained in the same manner as in Example 9 except that a mixture of the copolymer (10) was used.

The molecular weight of the obtained copolymer (10) was measured by a GPC apparatus, and the number average molecular weight (in terms of standard polystyrene) was 48,000. This value was larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, and it was confirmed that the polymerization proceeded by the above reaction.

&Lt; Example 11: Synthesis of copolymer (11) >

(A3) obtained in Synthesis Example 3 was used instead of the cellulose-based polymerizable compound (a1), and the polyvinyl acetal-based polymerizable compound (a1) obtained in Synthesis Example 9 was used instead of the polyvinyl acetal- A solution (binder solution) containing the copolymer (11) was obtained in the same manner as in Example 1 except that the compound (b3) was used.

The molecular weight of the obtained copolymer (11) was measured by a GPC apparatus, and the number average molecular weight (in terms of standard polystyrene) was 78,000. This value was larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, and it was confirmed that the polymerization proceeded by the above reaction.

Example 12: Synthesis of copolymer (12)

10 parts of the cellulose-based polymerizable compound (a3) obtained in Synthesis Example 3, 10 parts of the polyvinyl acetal-based polymerizable compound (b3) obtained in Synthesis Example 9, 0.2 part of isobutyl methacrylate, , 80 parts of dihydrotriphenyl acetate as a solvent were added and mixed, and the mixture was heated to 60 占 폚 and stirred with a rotating blade to dissolve. After the dissolution, nitrogen was substituted to remove oxygen in the system, and 0.01 part of azoisobutyronitrile (AIBN) as a polymerization initiator was mixed and reacted at 70 캜 for 5 hours to obtain a solution (binder solution) containing the copolymer (12) &Lt; / RTI &gt;

The molecular weight of the obtained copolymer (12) was measured by a GPC apparatus, and the number average molecular weight (in terms of standard polystyrene) was 80,000. This value was larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, and it was confirmed that the polymerization proceeded by the above reaction.

&Lt; Example 13: Synthesis of copolymer (13) >

A solution (binder solution) containing the copolymer (13) was obtained in the same manner as in Example 2 except that the amount of isobutyl methacrylate was changed to 0.2 part.

The molecular weight of the obtained copolymer (13) was measured by a GPC apparatus, and the number average molecular weight (in terms of standard polystyrene) was 72,000. This value was larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, and it was confirmed that the polymerization proceeded by the above reaction.

Example 14: Synthesis of copolymer (14)

A solution (binder solution) containing the copolymer (14) was obtained in the same manner as in Example 13 except that methyl methacrylate was used instead of isobutyl methacrylate.

The molecular weight of the obtained copolymer (14) was measured by a GPC apparatus, and the number average molecular weight (standard polystyrene conversion value) was 73,000. This value was larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, and it was confirmed that the polymerization proceeded by the above reaction.

Example 15: Synthesis of copolymer (15)

Except that the cellulose-based polymerizable compound (a4) obtained in Synthesis Example 4 was used in place of the cellulose-based polymerizable compound (a1) and the polyvinyl acetal-based polymerizable compound (a1) obtained in Synthesis Example 10 was used instead of the polyvinyl acetal- A solution (binder solution) containing the copolymer (15) was obtained in the same manner as in Example 1 except that the compound (b4) was used.

The molecular weight of the obtained copolymer (15) was measured by a GPC apparatus, and the number average molecular weight (standard polystyrene conversion value) was 78,000. This value was larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, and it was confirmed that the polymerization proceeded by the above reaction.

Example 16: Synthesis of copolymer (16)

10 parts of the cellulose-based polymerizable compound (a4) obtained in Synthesis Example 4, 10 parts of the polyvinyl acetal-based polymerizable compound (b4) obtained in Synthesis Example 10, 5.0 parts of methyl methacrylate, And 80 parts of dihydrotophenyl acetate were added and mixed, and the mixture was heated to 60 DEG C and dissolved by stirring with a rotating blade. After the dissolution, the atmosphere in the system was removed by nitrogen substitution, and 0.01 part of azoisobutyronitrile (AIBN) as a polymerization initiator was mixed and reacted at 70 DEG C for 5 hours to obtain a solution (binder solution) containing the copolymer (16) &Lt; / RTI &gt;

The molecular weight of the obtained copolymer (16) was measured by a GPC apparatus, and the number average molecular weight (in terms of standard polystyrene) was 81000. This value was larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, and it was confirmed that the polymerization proceeded by the above reaction.

Example 17: Synthesis of copolymer (17)

Except that the cellulose-based polymerizable compound (a5) obtained in Synthesis Example 5 was used in place of the cellulose-based polymerizable compound (a1), and the polyvinyl acetal-based polymerizable compound (a5) obtained in Synthesis Example 11 was used instead of the polyvinyl acetal- A solution (binder solution) containing the copolymer (17) was obtained in the same manner as in Example 1 except that the compound (b5) was used.

The molecular weight of the obtained copolymer (17) was measured by a GPC apparatus, and the number average molecular weight (in terms of standard polystyrene) was 68,000. This value was larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, and it was confirmed that the polymerization proceeded by the above reaction.

Example 18: Synthesis of copolymer (18)

10 parts of the cellulose-based polymerizable compound (a5) obtained in Synthesis Example 5, 10 parts of the polyvinyl acetal-based polymerizable compound (b5) obtained in Synthesis Example 11, 3.0 parts of isobutyl methacrylate, 2.0 parts of hydroxyethyl methacrylate, and 80 parts of dihydroterpinylacetate as an organic solvent were added and mixed, and the mixture was heated to 60 DEG C and dissolved by stirring with a rotating blade. After the dissolution, nitrogen was substituted to remove oxygen in the system, and 0.01 part of azoisobutyronitrile (AIBN) as a polymerization initiator was mixed and reacted at 70 캜 for 5 hours to obtain a solution (binder solution) containing the copolymer (18) &Lt; / RTI &gt;

The molecular weight of the obtained copolymer (18) was measured by a GPC apparatus, and the number average molecular weight (in terms of standard polystyrene) was 70000. This value was larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, and it was confirmed that the polymerization proceeded by the above reaction.

Example 19: Synthesis of copolymer (19)

Except that the cellulose-based polymerizable compound (a6) obtained in Synthesis Example 6 was used instead of the cellulose-based polymerizable compound (a1), and the polyvinyl acetal-based polymerizable compound (a6) obtained in Synthesis Example 12 was used instead of the polyvinyl acetal- A solution (binder solution) containing the copolymer (19) was obtained in the same manner as in Example 1 except that the compound (b6) was used.

The molecular weight of the obtained copolymer (19) was measured by a GPC apparatus, and the number average molecular weight (in terms of standard polystyrene) was 56,000. This value was larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, and it was confirmed that the polymerization proceeded by the above reaction.

Example 20: Synthesis of copolymer (20)

(A9) having a methacrylate group introduced into ethylcellulose obtained in Synthesis Example 15 and a polyvinyl acetal-based polymerizable compound (b9) having a methacrylate group introduced into polyvinyl butyral 20 parts of the mixture, 0.1 part of isobutyl methacrylate, and 80 parts of dihydroterpinylacetate as an organic solvent were added and mixed, and the mixture was heated to 60 占 폚 and dissolved by stirring with a rotating blade. After the dissolution, the inside of the system was subjected to nitrogen substitution to remove oxygen, and 0.01 part of azoisobutyronitrile (AIBN) as a polymerization initiator was mixed and reacted at 70 캜 for 5 hours to obtain a solution (binder solution) containing the copolymer (20) &Lt; / RTI &gt;

The molecular weight of the obtained copolymer (20) was measured by a GPC apparatus, and the number average molecular weight (in terms of standard polystyrene) was 30500. This value was larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, and it was confirmed that the polymerization proceeded by the above reaction.

&Lt; Example 21: Synthesis of copolymer (21) >

(A10) in which a methacrylate group was introduced into ethylcellulose obtained in Synthesis Example 16 and a polyvinyl acetal-based polymerizable compound (b10) in which a methacrylate group was introduced into polyvinyl butyral 20 parts of the mixture, 0.2 parts of isobutyl methacrylate, and 80 parts of dihydroterpinylacetate as an organic solvent were added and mixed, and the mixture was heated to 60 占 폚 and dissolved by stirring with a rotating blade. After the dissolution, nitrogen was substituted to remove oxygen in the system, and 0.01 part of azoisobutyronitrile (AIBN) as a polymerization initiator was mixed and reacted at 70 캜 for 5 hours to obtain a solution (binder solution) containing the copolymer (21) &Lt; / RTI &gt;

The molecular weight of the obtained copolymer (21) was measured by a GPC apparatus, and the number average molecular weight (in terms of standard polystyrene) was 59,000. This value was larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, and it was confirmed that the polymerization proceeded by the above reaction.

Example 22: Synthesis of copolymer (22)

(A11) in which a methacrylate group was introduced into ethylcellulose obtained in Synthesis Example 17 and a polyvinyl acetal polymerizable compound (b11) in which a methacrylate group was introduced into polyvinyl butyral 20 parts of a mixture, 0.2 parts of isobutyl methacrylate, and 80 parts of dihydroterpinylacetate as an organic solvent were added and mixed, and the mixture was heated to 60 占 폚 and stirred with a rotating blade to dissolve. After the dissolution, the inside of the system was removed by nitrogen substitution, and 0.01 part of azoisobutyronitrile (AIBN) as a polymerization initiator was mixed and reacted at 70 캜 for 5 hours to obtain a solution (binder solution) containing the copolymer (22) &Lt; / RTI &gt;

The molecular weight of the obtained copolymer (22) was measured by a GPC apparatus, and the number average molecular weight (standard polystyrene conversion value) was 63000. This value was larger than the number average molecular weight of ethyl cellulose used as a raw material and the number average molecular weight of polyvinyl butyral, and it was confirmed that the polymerization proceeded by the above reaction.

&Lt; Comparative Example 1 &

10 parts of ethyl cellulose ("ETHOCEL STD-100" manufactured by Dow Chemical Company) and 10 parts of polyvinyl butyral ("BM-S" manufactured by Sekisui Chemical Co., Ltd.) were dissolved in 113.3 parts of dihydroterpinylacetate, To prepare a binder solution.

&Lt; Comparative Example 2 &

10 parts of ethyl cellulose ("ETHOCEL STD-10" manufactured by Dow Chemical Company) and 10 parts of polyvinyl butyral ("BL-S" manufactured by Sekisui Chemical Co., Ltd.) were dissolved in 113.3 parts of dihydroterpinylacetate, To prepare a binder solution.

&Lt; Comparative Example 3 &

20 parts of ethyl cellulose ("ETHOCEL STD-100" manufactured by Dow Chemical Company) was dissolved in 113.3 parts of dihydroterpinylacetate to prepare a binder solution.

&Lt; Comparative Example 4 &

20 parts of polyvinyl butyral ("BM-S" manufactured by Sekisui Chemical Co., Ltd.) was dissolved in 113.3 parts of dihydroterpinylacetate to prepare a binder solution.

&Lt; Comparative Example 5 &

20 parts of ethyl cellulose ("ETHOCEL STD-10" manufactured by Dow Chemical Company) was dissolved in 113.3 parts of dihydroterpinylacetate to prepare a binder solution.

&Lt; Comparative Example 6 >

20 parts of polyvinyl butyral ("BL-S" manufactured by Sekisui Chemical Co., Ltd.) was dissolved in 113.3 parts of dihydroterpinylacetate to prepare a binder solution.

&Lt; Comparative Example 7 &

10 parts of ethylcellulose ("ETHOCEL STD-100" manufactured by Dow Chemical Company) and 10 parts of polyvinyl butyral ("BH-S" manufactured by Sekisui Chemical Co., Ltd.) were dissolved in 113.3 parts of dihydrotophenylacetate, Solution.

&Lt; Comparative Example 8 >

10 parts of ethyl cellulose ("ETHOCEL STD-200" manufactured by Dow Chemical Company) and 10 parts of polyvinyl butyral ("BH-S" manufactured by Sekisui Chemical Co., Ltd.) were dissolved in 113.3 parts of dihydroterpinylacetate, To prepare a binder solution.

&Lt; Comparative Example 9 &

20 parts of ethyl cellulose ("ETHOCEL STD-200" manufactured by Dow Chemical Company) was dissolved in 113.3 parts of dihydroterpinylacetate to prepare a binder solution.

&Lt; Comparative Example 10 &

20 parts of polyvinyl butyral ("BH-S" manufactured by Sekisui Chemical Co., Ltd.) was dissolved in 113.3 parts of dihydroterpinylacetate to prepare a binder solution.

&Lt; Comparative Example 11 &

10 parts of the cellulose-based polymerizable compound (a1) having a methacrylate group introduced into ethylcellulose obtained in Synthesis Example 1 and 10 parts of a polyvinyl acetal-based polymerizable compound having a methacrylate group introduced into the polyvinyl butyral obtained in Synthesis Example 7 b1) was dissolved in 113.3 parts of dihydroterpinylacetate as an organic solvent to prepare a binder solution. In this Comparative Example, the effect of the polymerization reaction was determined without performing the polymerization reaction.

&Lt; Comparative Example 12 >

20 parts of a mixture of the cellulose-based polymerizable compound (a7) obtained in Synthesis Example 13 and the polyvinyl acetal-based polymerizable compound (b7) was dissolved in 113.3 parts of dihydrotopinylacetate as an organic solvent to prepare a binder solution. In this Comparative Example, the effect of the polymerization reaction was determined without performing the polymerization reaction.

Table 1 shows the compositions of the binders obtained in Examples and Comparative Examples. Details of the abbreviations shown in Table 1 are as follows.

iBMA: isobutyl methacrylate,

MMA: methyl methacrylate,

HEMA: 2-hydroxyethyl methacrylate.

2. Evaluation of binder

The following evaluations were performed on the binders obtained in Examples and Comparative Examples and the pastes containing them. The results are shown in Table 2.

[1] Evaluation of thermal degradability

10 mg of a dried solid sample of the binder was measured with a TG / DTA thermal analyzer (&quot; EXSTAR TG / DTA6200 &quot;, manufactured by Seiko Instruments Inc.) under a nitrogen atmosphere at a temperature raising rate of 10 캜 / And the thermal decomposability of the binder was evaluated based on the following evaluation criteria. The amount of the residue (% by mass) indicates the amount of the residue after measurement when the mass of the dry solid sample is 100% by mass.

(Evaluation Criteria of Pyrolysis)

A: a residual amount of 1% by mass or less,

B: a residual amount exceeding 1% by mass and not more than 3% by mass,

C: The residual amount exceeds 3% by mass.

[2] Evaluation of adhesion to polyvinyl butyral

Assuming a case where the binder is used for the electrode paste, the adhesion to the green sheet was evaluated by the following model test.

The binder solution obtained in Examples and Comparative Examples was coated on a bonding layer of a polyethylene terephthalate (PET) film (total thickness 100 占 퐉) having an adhesive layer formed thereon with a blade coater having a thickness gap of 90 占 퐉 and then heated and dried to obtain a binder Layer. On the other hand, polyvinyl butyral ("BH-S" manufactured by Sekisui Chemical Co., Ltd.) as a model material of a binder for a green sheet was dissolved in toluene to prepare a 15 mass% solution. This was coated on the adhesive layer of the PET film having the adhesive layer formed thereon in the same manner as described above and then heated and dried to produce a film having a polyvinyl butyral layer having a thickness of about 10 탆. A rectangular sample having a width of 2 cm and a length of 8 cm was cut out from each of the obtained films.

On the binder layer of the film sample having the binder layer, the polyvinyl butyral layer of the film sample having the polyvinyl butyral layer was overlapped while being shifted in the longitudinal direction. The area of the overlapped portion was 2 cm in the longitudinal direction x 2 cm in width. A heating plate of 1 cm x 2 cm (area: 2 cm ² ) was pressed against the center of the overlapping portion by thermocompression for 5 minutes at a temperature of 130 DEG C and a pressure of 2 kg to partially adhere the overlapped portions.

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

(Evaluation Criteria of Adhesion)

A: a tensile strength of 100 N or more,

B: breaking strength less than 100 N, not less than 50 N,

C: The breaking strength is less than 50N.

[3] Preparation of resin composition (paste) and evaluation of coating film quality

Dihydrotopyran acetate was added to the binder solution obtained in Examples and Comparative Examples to adjust the binder concentration to 15 mass%. Subsequently, 100 parts by mass of Ni particles ("NFP201S" manufactured by JFE Mineral Co., Ltd., average particle diameter 0.2 μm) as inorganic particles and 25 parts by mass of the above binder solution were mixed by three roll mills to obtain a paste.

The obtained paste was applied on a glass substrate with a blade coater having a thickness gap of 30 mu m and the coated film after heating and drying was observed with a scanning electron microscope (SEM), and the coating film quality was evaluated based on the following evaluation criteria. For the scanning electron microscope, the coating film was observed at a magnification of 5000 times using "JSM-7800F" manufactured by Japan Electronics Co.,

(Evaluation Criteria of Coating Film Quality)

A: Defects (holes) of a size exceeding 1 占 퐉 were not observed,

B: Defects (holes) having a size exceeding 1 μm are observed.

[4] Evaluation of screen printing property

The paste prepared in [3] was applied to a stripe pattern of L / S = 100 μm / 100 μm using a mesh # 500 (manufactured by Nakanuma Art Screen) as a screen plate using a microtec printer (MT-320 series) And printed on a PET film. The print pattern was observed with a microscope and the screen printability was evaluated based on the following evaluation criteria. In addition, a threading defect is a phenomenon in which a paste or the like comes out like a thread that is stretched at a stage where the screen printing plate is removed from the substrate at the time of printing, thereby causing a printing defect. If this phenomenon occurs, foreign matter of a fibrous shape is formed from the edge portion of the print pattern, electrical short-circuiting occurs, and the print pattern shape becomes nonuniform, which causes a problem that the required characteristics are not obtained.

(Evaluation Criteria of Screen Printability)

A: There is no thread drag defect at the edge portion,

B: There is a thread drag defect at the edge portion.

The binders of Examples 1 to 22 exhibited satisfactory evaluation in the respective items of thermal decomposition property, adhesion property, coating film property and screen printing property. On the other hand, in Comparative Examples 1 to 12, all of these evaluation items could not be satisfied.

It is to be understood that the embodiments and examples disclosed herein are illustrative in all respects and are not intended to be limiting. The scope of the present invention is not limited to the above-described embodiments and examples, but is defined by the scope of the claims, and is intended to include all modifications within the meaning and range equivalent to the claims.

Claims (6)

A copolymer comprising a structural unit (a) derived from a cellulose-based polymerizable compound having a polymerizable unsaturated group and a structural unit (b) derived from a polyvinyl acetal-based polymerizable compound having a polymerizable unsaturated group. The method according to claim 1,
(C) other than the structural unit (a) and the structural unit (b). The method according to claim 1 or 2,
Wherein the number of the polymerizable unsaturated groups in the cellulose-based polymerizable compound is not more than 10 on an average per molecule. The method according to any one of claims 1 to 3,
Wherein the number of the polymerizable unsaturated groups in the polyvinyl acetal-based polymerizable compound is 10 or less on an average per molecule. A process for producing a copolymer, which comprises a step of polymerizing a cellulose-based polymerizable compound having a polymerizable unsaturated group and a polyvinyl acetal-based polymerizable compound having a polymerizable unsaturated group in an organic solvent in the presence of a polymerization initiator. A copolymer composition comprising the copolymer according to any one of claims 1 to 4, inorganic particles, and an organic solvent.