JP2020029479A - Polymer compound and polymer composition containing the same, and inorganic particle-containing composition - Google Patents

Abstract

To provide a polymer compound which is suitable as a compatibilizer for improving compatibility of a polymer blend-type binder, and a composition containing the same.SOLUTION: Provided is a polymer compound comprising in the molecule: a first segment formed of a first cellulose-based compound; a second segment formed of a first polyvinyl acetal-based compound; and a linking group which links the first segment and the second segment, where the linking group contains a -S- group or a 1,2,3-triazole diyl group. Also provided are a polymer composition containing the polymer compound, and an inorganic particle-containing composition.SELECTED DRAWING: None

Description

  The present invention relates to a polymer compound, a polymer composition containing the same, and a composition containing inorganic particles.

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

  An example of the production of MLCC is as follows. First, a green sheet having a dielectric layer is produced by applying a dielectric ceramic paste on a release sheet. Next, an electrode pattern (electrode layer) is formed by printing an electrode paste (sometimes referred to as “conductive paste”) on the dielectric layer. Further, the laminate of the dielectric layer and the electrode layer is peeled from the release sheet, a plurality of the laminates are laminated and pressed, and then cut into chips. Next, the obtained chip is heated to several hundred degrees Celsius to 1000 ° C. or higher and fired to produce a sintered chip in which a dielectric layer and an electrode layer are stacked in multiple layers. Finally, external electrodes and the like are formed.

  In recent years, the size of the chip has been reduced, the thickness of each of the above-mentioned layers constituting the chip has been reduced, and the electrode pattern to be printed has been miniaturized. Against this background, there is a strong demand for improved adhesion between layers and excellent printability of the paste used.

  Other electronic components such as chip inductors and chip resistors are also manufactured by a process similar to MLCC. The manufacturing process of a silicon-based solar cell or the like also includes printing and baking steps using an electrode paste in forming a collector electrode.

  BACKGROUND ART A ceramic paste and an electrode paste used for manufacturing an electronic component such as MLCC are a resin composition containing a polymer binder and an organic solvent, in which inorganic particles are uniformly dispersed. 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 has been mainly used in a ceramic paste, and ethyl cellulose has been mainly used in an electrode paste [Japanese Patent Publication No. 04-49766 (Patent Document 1)].

Japanese Patent Publication No. 04-49766 Japanese Patent No. 4347440 Japanese Patent No. 5224722 Japanese Patent No. 5299904

Pastes such as ceramic pastes and electrode pastes, especially binders contained therein, have the following problems, for example.
1) Improvement of thermal decomposition (combustibility). If ash such as carbon remains even after the thermal decomposition treatment by firing, the electrical characteristics of the MLCC are deteriorated or delamination is caused.
2) Improvement of printability. Recently, electrode patterns formed by screen printing have become finer and thinner, and the pattern size has become smaller than 100 μm. For this reason, in the electrode paste, a binder that does not cause a so-called stringing phenomenon is required. The stringing phenomenon is a phenomenon in which a paste or the like used in a printing process under the influence of a binder polymer is stretched and a thin string is drawn, which causes a defective product.
3) Improvement of uniform dispersibility of inorganic particles, film strength (strength of layer formed from paste), and adhesion between layers. These are required characteristics accompanying thinning of each layer constituting the chip.

  In order to solve the above problems, various studies have been made on binders. For example, Japanese Patent No. 4347440 (Patent Document 2), Japanese Patent No. 5224722 (Patent Document 3) and Japanese Patent No. 5299904 (Patent Document 4) disclose blending polyvinyl butyral with ethyl cellulose in an electrode paste. Techniques for improving physical properties such as film strength have been disclosed.

  The binder obtained by blending ethylcellulose and polyvinyl butyral described in Patent Documents 2 to 4 has poor compatibility between these two polymers, and has an inorganic property when inorganic particles such as metal, ceramic, and glass are mixed to form a paste. Low dispersibility of particles. As a result, defects are likely to occur in the coating film, and the uniformity of the coating film is likely to decrease.

An object of the present invention is to provide a polymer compound suitable as a compatibilizer for improving the compatibility of a polymer blend type binder.
Another object of the present invention is to provide a polymer blend type polymer composition containing the above polymer compound.
Still another object of the present invention is to provide an inorganic particle-containing composition comprising the above polymer compound alone or a polymer blend type polymer composition containing the above polymer compound and inorganic particles.

The present invention provides a polymer compound, a compatibilizer, a polymer composition, and an inorganic particle-containing composition described below.
[1] a first segment formed from a first cellulosic compound,
A second segment formed from the first polyvinyl acetal-based compound,
A bonding group for bonding the first segment and the second segment;
In the molecule,
A polymer compound in which the bonding group contains a -S- group or a 1,2,3-triazoldiyl group.
[2] The first cellulose compound is a cellulose derivative having a reactive functional group (A),
The first polyvinyl acetal-based compound is a polyvinyl acetal having a reactive functional group (B),
The combination according to [1], wherein the combination of the reactive functional group (A) and the reactive functional group (B) is a combination of a thiol group and a vinyl group, or a combination of an alkynyl group and an azide group. High molecular compounds.
[3] A compatibilizer comprising the polymer compound according to [1] or [2].
[4] The polymer compound according to [1] or [2],
A second cellulosic compound,
A second polyvinyl acetal compound;
A polymer composition comprising:
[5] The second cellulosic compound is a cellulose derivative which may have a reactive functional group (C),
The second polyvinyl acetal compound is a polyvinyl acetal that may have a reactive functional group (D),
The combination according to [4], wherein the combination of the reactive functional group (C) and the reactive functional group (D) is a combination of a thiol group and a vinyl group, or a combination of an alkynyl group and an azide group. Polymer composition.
[6] The second cellulose derivative is a cellulose derivative having no reactive functional group (C),
The polymer composition according to [5], wherein the second polyvinyl acetal is a polyvinyl acetal having no reactive functional group (D).
[7] The polymer compound according to [1] or [2],
Inorganic particles,
An organic solvent,
An inorganic particle-containing composition comprising:
[8] The polymer compound according to [1] or [2],
A second cellulosic compound,
A second polyvinyl acetal compound;
Inorganic particles,
An organic solvent,
An inorganic particle-containing composition comprising:
[9] The second cellulose compound is a cellulose derivative which may have a reactive functional group (C),
The second polyvinyl acetal compound is a polyvinyl acetal that may have a reactive functional group (D),
The combination according to [8], wherein the combination of the reactive functional group (C) and the reactive functional group (D) is a combination of a thiol group and a vinyl group, or a combination of an alkynyl group and an azide group. An inorganic particle-containing composition.
[10] The second cellulose derivative is a cellulose derivative having no reactive functional group (C),
The inorganic particle-containing composition according to [9], wherein the second polyvinyl acetal is a polyvinyl acetal having no reactive functional group (D).

A polymer compound suitable as a compatibilizer for improving the compatibility of the polymer blend type binder can be provided.
A polymer blend-type polymer composition containing the above polymer compound can be provided.
An inorganic particle-containing composition comprising the polymer compound alone or a polymer blend polymer composition containing the polymer compound and inorganic particles can be provided.

Hereinafter, the present invention will be described in detail with reference to embodiments.
In this specification, the description “A to B” (A and B are numerical values) means “A or more and B or less” unless otherwise specified.

<Polymer compound>
The polymer compound according to the present invention (hereinafter, also simply referred to as “polymer compound”) includes a first segment formed from a first cellulose compound, a second segment formed from a first polyvinyl acetal compound, and , A polymer compound containing, in a molecule, a bonding group for bonding the first segment and the second segment.
This polymer compound is suitable as a compatibilizer for a polymer blend-type binder composed of two or more components, particularly a binder containing a cellulose compound and a polyvinyl acetal compound.

(1) First Cellulose Compound The first cellulose compound forming the first segment is a compound having a reactive functional group (A) that can react with the first polyvinyl acetal compound forming the second segment, Preferably, it is a cellulose derivative having a reactive functional group (A). The first cellulose compound may be used alone or in combination of two or more.
The cellulose derivative refers to a modified cellulose obtained by chemically modifying a part of the 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, hydroxyalkyl etherification, and esterification of the hydroxy group.

  Examples of the cellulose derivative include methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxybutyl methyl cellulose, cellulose acetate (acetyl cellulose, diacetyl cellulose, triacetyl cellulose, etc.), cellulose acetate propionate , Cellulose acetate butyrate, nitrocellulose and the like.

  From the viewpoint of efficiently producing a cellulose derivative having a reactive functional group (A), the cellulose derivative is preferably soluble in an organic solvent. The cellulose derivative is more preferably ethyl cellulose because of its high solubility in organic solvents.

Cellulose derivatives affect film strength and solution viscosity depending on their molecular weight. Therefore, the number average molecular weight of the cellulose derivative is preferably in the range of 50,000 to 150,000, and more preferably in the range of 10,000 to 100,000, in terms of standard polystyrene by gel permeation chromatography (GPC). Is more preferable.
When the number average molecular weight is less than 50,000, the solution viscosity becomes extremely low, and it becomes difficult to adjust the viscosity of the inorganic particle-containing composition (paste or slurry), and the inorganic particle-containing composition is applied and dried. The strength and adhesion of the film may be reduced.
On the other hand, when the number average molecular weight exceeds 150,000, the solution viscosity becomes extremely large, and it may be difficult to adjust the viscosity of the composition containing inorganic particles, and the printability may be reduced.

Cellulose derivatives have at least one hydroxy group in one molecule. This hydroxy group can be used for introducing the reactive functional group (A).
The reactive functional group (A) is preferably any functional group selected from the following group X or any functional group selected from the following group Y.
(Group X)
Thiol group (-SH), alkynyl group, amino group (Group Y)
Vinyl group, azide group, carboxyl group

For example, a reactive functional group (A) can be introduced into a cellulose derivative by reacting a compound having a group capable of reacting with the hydroxy group and a reactive functional group (A) with the hydroxy group of the cellulose derivative. Thereby, a cellulose derivative having a reactive functional group (A) can be obtained.
Examples of the group capable of reacting with the hydroxy group include a carboxyl group, an acid anhydride group, an acid chloride group, an isocyanate group, and a halogen group (halogen atom).

Examples of the compound having a group capable of reacting with a hydroxy group and the reactive functional group (A) include, for example, an organic carboxylic acid having a thiol group, a vinyl group, an azide group, an alkynyl group, an amino group or a carboxyl group; Acid anhydrides of the organic carboxylic acids; vinyl group-containing isocyanates such as (meth) acrylate group-containing isocyanates and allyl group-containing isocyanates; vinyl derivatives having a halogen group; allyl derivatives having a halogen group.
The vinyl group includes a (meth) acrylate group ((meth) acryloyloxy group), an allyl group, and the like.
In the present specification, “(meth) acrylate” means acrylate and / or methacrylate, and “(meth)” when referring to (meth) acryl, (meth) acryloyl and the like has the same meaning.

  In the reaction between a hydroxy group of a cellulose derivative and a compound having a group capable of reacting with the hydroxy group and a reactive functional group (A) (esterification reaction, urethane reaction, etherification reaction, etc.), a conventionally known method is used. And reaction conditions can be employed. It is also effective to use a reaction catalyst (organometallic compound, metal, amine, condensing agent, etc.).

  The number of reactive functional groups (A) contained in the first cellulose compound is preferably 10 or less on average per molecule. When the number of reactive functional groups (A) exceeds 10 on average per molecule, gelation and accompanying insolubilization in an organic solvent are likely to occur in the production of a polymer compound. The number of reactive functional groups (A) contained in the first cellulose compound may be, on average, 8 or less, 5 or less, 3 or less, or 2 per molecule. The number may be less than or equal to one.

(2) First polyvinyl acetal compound The first polyvinyl acetal compound forming the second segment is a reactive functional group capable of reacting with the reactive functional group (A) of the first cellulose compound forming the first segment. It is a polyvinyl acetal having (B).
Polyvinyl acetal is generally a polymer composed of monomer units of vinyl acetal / vinyl alcohol / vinyl acetate, and can be obtained by acetalizing polyvinyl alcohol. Specific examples include those obtained by converting polyvinyl alcohol into butyral (polyvinyl butyral) and those obtained by forming polyvinyl alcohol into formal (polyvinyl formal).

  Polyvinyl acetal may be a commercial product, and various polyvinyl acetals having different butyralization degree, formalization degree, acetyl group amount, hydroxy group amount and molecular weight are sold by Sekisui Chemical Co., Kuraray Co., Eastman Chemical Co., etc. Have been. As the polyvinyl acetal, one type may be used alone, or two or more types may be used in combination.

  From the viewpoint of efficiently producing a polyvinyl acetal having a reactive functional group (B), the polyvinyl acetal is preferably soluble in an organic solvent. The polyvinyl acetal is more preferably polyvinyl butyral because of its high solubility in organic solvents.

Polyvinyl acetal affects the film strength and solution viscosity depending on its molecular weight. Therefore, the number average molecular weight of polyvinyl acetal is preferably in the range of 50,000 to 150,000, more preferably in the range of 10,000 to 100,000 in terms of standard polystyrene by GPC.
When the number average molecular weight is less than 50,000, the solution viscosity becomes extremely low, and it becomes difficult to adjust the viscosity of the inorganic particle-containing composition (paste or slurry), and the inorganic particle-containing composition is applied and dried. The strength and adhesion of the film may be reduced.
On the other hand, when the number average molecular weight exceeds 150,000, the solution viscosity becomes extremely large, and it may be difficult to adjust the viscosity of the composition containing inorganic particles, and the printability may be reduced.

  Polyvinyl acetal has at least one hydroxy group in one molecule. Generally, polyvinyl acetal has 20 to 40 mol% of hydroxy groups as vinyl alcohol units constituting the polymer. This hydroxy group can be used for introducing a reactive functional group (B).

The reactive functional group (B) is a group capable of reacting with the reactive functional group (A), and is preferably selected from any of the functional groups selected from the group X or the group Y. Any functional group.
Here, when the reactive functional group (A) is selected from the group X, the reactive functional group (B) is selected from the group Y, and when the reactive functional group (A) is selected from the group Y, The functional group (B) is selected from group X.
More specifically, the combination of the reactive functional group (A) of the first cellulose compound and the reactive functional group (B) of the first polyvinyl acetal compound is a combination of a thiol group and a vinyl group. Preferably, it is a combination of an alkynyl group and an azide group, or a combination of an amino group and a carboxyl group.
When the combination referred to here is, for example, a combination of a thiol group and a vinyl group, the combination of (reactive functional group (A), reactive functional group (B)) is (thiol group, vinyl group). Or (vinyl group, thiol group).

For example, a reactive functional group (B) can be introduced into a polyvinyl acetal by reacting a compound having a reactive group and a group capable of reacting with the hydroxy group with a hydroxyl group of the polyvinyl acetal. Thereby, a polyvinyl acetal having a reactive functional group (B) can be obtained.
Examples of the group capable of reacting with the hydroxy 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 hydroxy group and the reactive functional group (B) are the same as the compounds described in the above section “(1) First Cellulose Compound”.

  In the reaction of a hydroxy group of polyvinyl acetal with a compound having a group capable of reacting with the hydroxy group and a reactive functional group (B) (esterification, urethanation, etherification, etc.), a conventionally known method or Reaction conditions can be employed. It is also effective to use a reaction catalyst (organometallic compound, metal, amine, condensing agent, etc.).

  The number of reactive functional groups (B) contained in the first polyvinyl acetal compound is preferably 10 or less per molecule on average. When the number of the reactive functional groups (B) exceeds 10 on average per molecule, gelation and accompanying insolubilization in an organic solvent are likely to occur in the production of the polymer compound. The number of reactive functional groups (B) in the first polyvinyl acetal compound may be an average of 8 or less, 5 or less, or 3 or less per molecule on average, The number may be two or less, or one or less.

(3) Bonding group The polymer compound according to the present invention is a reaction product of the first cellulose compound and the first polyvinyl acetal compound, and the reactive functional group (A) of the first cellulose compound and the first A bonding group is formed by a reaction with the reactive functional group (B) of the polyvinyl acetal compound.
The linking group includes a -S- group, a 1,2,3-triazoldiyl group or an amide group.

When the combination of (reactive functional group (A) and reactive functional group (B)) is (thiol group, vinyl group), the bonding group contains -S- group.
When the combination of the (reactive functional group (A) and the reactive functional group (B)) is (alkynyl group, azide group), the bonding group includes a 1,2,3-triazoldiyl group.
When the combination of (reactive functional group (A), reactive functional group (B)) is (amino group, carboxyl group), the bonding group contains an amide group.
The first segment refers to a structural part other than the structural part forming the binding group in the first cellulosic compound.
The second segment refers to a structural portion of the first polyvinyl acetal compound other than the structural portion forming the bonding group.

(4) Configuration of Polymer Compound The polymer compound preferably contains the first segment and the second segment in a mass ratio of 0.05: 0.95 to 0.95 to 0.05. Further, the weight ratio is preferably in the range of 0.1: 0.9 to 0.9: 0.1. If the ratio is out of this range, the desired properties of the compatibilizer or the polymer blend type polymer composition containing the compatibilizer may not be obtained.
The number average molecular weight of the high molecular compound is preferably 10,000 to 200,000, more preferably 10,000 to 150,000, more preferably 20,000 to 120,000, in terms of standard polystyrene by GPC. preferable. When the number average molecular weight of the polymer compound is less than 10,000, the function as a compatibilizer tends to be insufficient. On the other hand, if it exceeds 200,000, the viscosity tends to be too high.
In addition, the polymer material containing the cellulose derivative causes a change in the expansion of the polymer chains in the solution due to the binding reaction with the polyvinyl acetal, and the measured value of the molecular weight by GPC is different from the molecular weight of the raw material used. May not be correlated.

<Production method of polymer compound>
(1) Production of First Cellulose Compound and First Polyvinyl Acetal Compound The first cellulose compound having a reactive functional group (A) and the first polyvinyl acetal compound having a reactive functional group (B) are as described above. By reacting a hydroxy group of a cellulose derivative or polyvinyl acetal with a compound having a group capable of reacting with the hydroxy group and a reactive functional group (A) or a reactive functional group (B), respectively. Can be.

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

  The esterification reaction can be performed, for example, using a condensing agent. Examples of the condensing agent include carbodiimide, diphenylphosphoric acid azide, 1-hydroxybenzotriazole, BOP reagent and the like. Only one condensing agent may be used, or two or more condensing agents may be used in combination. Above all, carbodiimide is preferable because it has excellent versatility and reactivity, and can promote the reaction under low-temperature conditions and without being affected by moisture in the reaction environment.

  Examples of the carbodiimide include dicyclohexylcarbodiimide, diisopropylcarbodiimide, N- [3- (dimethylamino) propyl] -N′-ethylcarbodiimide, N- [3- (dimethylamino) propyl] -N′-ethylcarbodiimide methoxide, and the like. No. Among them, dicyclohexylcarbodiimide and diisopropylcarbodiimide are preferred from the viewpoint of availability. When carbodiimide is used, it is also preferable to use a base such as dimethylaminopyridine or triethylamine as a reaction accelerator in an amount of 0.01 mol% to 10 mol% based on carbodiimide.

  The urethanization reaction can be performed, for example, using a reaction catalyst. Examples of the reaction catalyst include organometallic compounds such as dioctyltin dilaurate, dibutyltin dilaurate, stannasoctoate, and zinc dibunaphthenate; 1,8-diazabicyclo [5,4,0] undecene-7 (DBU) or a salt thereof; , 4-diazabicyclo [2,2,2] octane, PMDETA (N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine), N, N-dimethylcyclohexylamine, N-methyldicyclohexylamine, N , N, N ', N'-tetramethylpropylenediamine, N, N, N', N'-tetramethylhexamethylenediamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, Examples include amine compounds such as N-diethylethanolamine.

  The etherification reaction can be carried out efficiently by using a hydroxide of an alkali metal such as KOH or NaOH; or an alkali metal hydride such as NaH or KH as a reaction catalyst.

  The reaction between a hydroxy group of a cellulose derivative and polyvinyl acetal and a compound having a group capable of reacting with the hydroxy group and a reactive functional group (A) or a reactive functional group (B) is performed in an aprotic organic solvent. It is preferred to do so.

  Examples of aprotic organic solvents include ethyl acetate, butyl acetate, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, toluene, xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethyl lactate, and ethylene glycol. Monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate (butyl carbitol acetate), diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, diethylene glycol diethyl ether , Diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, propylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, propylene glycol diacetate, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, dihydroterpi Nyl acetate and the like. The organic solvent may be used alone or in combination of two or more.

  The temperature of the reaction between the hydroxy group of the cellulose derivative and polyvinyl acetal and a compound having a group capable of reacting with the hydroxy group and the reactive functional group (A) or the reactive functional group (B) is, for example, 0 ° C to 100 ° C. It is about ° C. The amount of the reactive functional group (A) or the reactive functional group (B) introduced can be measured by NMR analysis or the like. When carbodiimide is used as a condensing agent, urea is generated as a by-product and may be insolubilized. However, if necessary, filtration purification or reprecipitation purification may be performed.

  The amount of the reactive functional group (A) or the reactive functional group (B) introduced into the cellulose derivative or the polyvinyl acetal depends on the number of hydroxy groups in one molecule of the cellulose derivative or the polyvinyl acetal, the group capable of reacting with the hydroxy group, The amount can be adjusted within the above-mentioned range by the amount of the compound having the reactive functional group (A) or the reactive functional group (B), the amount of the condensing agent, and the like. The number of hydroxy groups in one molecule of the cellulose derivative or polyvinyl acetal can be adjusted by the content of the hydroxy group contained in the cellulose derivative or polyvinyl acetal, the molecular weight of the cellulose derivative or polyvinyl acetal, or the like.

(2) Production of polymer compound The reactive functional group (A) of the first cellulose compound and the reactive functional group (B) of the first polyvinyl acetal compound are combined in an organic solvent or the like using a chemical reaction vessel. By reacting, a polymer compound is obtained.

The bonding reaction between the allyl group and the thiol group can be performed by heat treatment or heat treatment with the addition of a radical initiator.
In the click reaction between the azide group and the alkynyl group, a metal catalyst such as a copper catalyst or a ruthenium catalyst is used.
In the amidation reaction between the amine and the carboxylic acid, the above-described reaction using carbodiimide or the like as a catalyst can be performed.
In any of the above reactions, the amount of the catalyst and the reaction conditions used in the reaction can be carried out by the same general chemical reaction process as in the prior art.
In the binding reaction, it is not necessary to react all the functional groups introduced into each polymer, and even if a small amount of one of the excess functional groups remains, there is no significant effect on the characteristics.

<Compatibilizer>
The compatibilizer according to the present invention (hereinafter, also simply referred to as “compatibilizer”) includes the polymer compound according to the present invention. The compatibilizer may be composed of the polymer compound according to the present invention.
The compatibilizer may include one or more polymer compounds. The case where the type of the polymer compound is different includes, for example, the case where the type (chemical structure, molecular weight, etc.) of the first cellulose compound and / or the first polyvinyl acetal compound forming the polymer compound is different.

  The compatibilizer according to the present invention is suitable as a compatibilizer for compatibilizing a blend-type binder composed of two or more components, particularly a blend-type binder containing a cellulose compound and a polyvinyl acetal compound. By adding the compatibilizer according to the present invention, the cellulose compound and the polyvinyl acetal compound can be more uniformly mixed (the phase separation state can be miniaturized), and the cellulose compound and It is possible to improve the dispersibility of the inorganic particles when the polymer composition containing the polyvinyl acetal compound and the inorganic particles are mixed to form an inorganic particle-containing composition.

<Polymer composition>
The polymer composition according to the present invention (hereinafter, also simply referred to as “polymer composition”) includes the polymer compound according to the present invention, a second cellulose compound, and a second polyvinyl acetal compound. . Further, an organic solvent may be contained.
The polymer composition can include one or more polymer compounds (compatibilizers).
The polymer composition can include one or more second cellulosic compounds.
The polymer composition can include one or more second polyvinyl acetal-based compounds.
The second cellulose-based compound and the second polyvinyl acetal-based compound are polymer materials suitably used as a binder of the inorganic particle-containing composition (paste or slurry) or a part thereof.

Examples of the second cellulose compound include a cellulose derivative having a reactive functional group (C) and a cellulose derivative having no reactive functional group (C).
The cellulose derivative having the reactive functional group (C) may be the same as the cellulose derivative having the reactive functional group (A). As for the cellulose derivative having the reactive functional group (C), the above description of the cellulose derivative having the reactive functional group (A) is cited. The reactive functional group (A) of the first cellulose compound used in producing the polymer compound contained in the polymer composition and the reactive functional group of the second cellulosic compound contained in the polymer composition The group (C) may be the same or different.
Examples of the cellulose derivative having no reactive functional group (C) include the cellulose derivatives described for the first cellulosic compound, but those different from the components of the compatibilizer to be used may be used. Preferably, the cellulose derivative is ethyl cellulose.

The second cellulosic compound affects the film strength and the viscosity of the solution depending on its molecular weight. Therefore, the number average molecular weight of the second cellulosic compound is preferably in the range of 50,000 to 150,000 in terms of standard polystyrene by gel permeation chromatography (GPC), and is preferably in the range of 10,000 to 100,000. More preferably, it is within the range.
When the number average molecular weight is less than 50,000, the solution viscosity becomes extremely low, and it becomes difficult to adjust the viscosity of the inorganic particle-containing composition (paste or slurry), and the inorganic particle-containing composition is applied and dried. The strength and adhesion of the film may be reduced.
On the other hand, when the number average molecular weight exceeds 150,000, the solution viscosity becomes extremely large, and it may be difficult to adjust the viscosity of the composition containing inorganic particles, and the printability may be reduced.

Examples of the second polyvinyl acetal compound include a polyvinyl acetal having a reactive functional group (D), a polyvinyl acetal having no reactive functional group (D), and the like.
The polyvinyl acetal having the reactive functional group (D) may be the same as the polyvinyl acetal having the reactive functional group (B). As for the polyvinyl acetal having the reactive functional group (D), the above description about the polyvinyl acetal having the reactive functional group (B) is cited. The reactive functional group (B) of the first polyvinyl acetal compound used in producing the polymer compound contained in the polymer composition and the reaction of the second polyvinyl acetal compound contained in the polymer composition The functional group (D) may be the same or different.

The reactive functional group (C) is a group capable of reacting with the reactive functional group (D), and is preferably selected from any of the functional groups selected from the group X or the group Y. Any functional group.
The reactive functional group (D) is a group capable of reacting with the reactive functional group (C), and is preferably selected from any of the functional groups selected from the group X or the group Y. Any functional group.
Here, when the second cellulose-based compound has a reactive functional group (C) and the second polyvinyl acetal-based compound has a reactive functional group (D), the reactive functional group (C) is selected from group X. When selected, the reactive functional group (D) is preferably selected from Group Y, and when the reactive functional group (C) is selected from Group Y, the reactive functional group (D) is selected from Group X. Preferably, it is selected.
More specifically, the combination of the reactive functional group (C) of the second cellulose compound and the reactive functional group (D) of the second polyvinyl acetal compound is a combination of a thiol group and a vinyl group. Preferably, it is a combination of an alkynyl group and an azide group, or a combination of an amino group and a carboxyl group.
When the combination referred to here is, for example, a combination of a thiol group and a vinyl group, the combination of (reactive functional group (C), reactive functional group (D)) is (thiol group, vinyl group). Or (vinyl group, thiol group).

  Examples of the polyvinyl acetal having no reactive functional group (D) include the polyvinyl acetal described for the first polyvinyl acetal compound, but a different component from the compatibilizer used may be used. The polyvinyl acetal is preferably polyvinyl butyral.

The second polyvinyl acetal compound affects the film strength and the viscosity of the solution depending on its molecular weight. Therefore, the number average molecular weight of the second polyvinyl acetal-based compound is, in terms of standard polystyrene by GPC, preferably in a range of 50,000 to 150,000, and more preferably in a range of 10,000 to 100,000. .
When the number average molecular weight is less than 50,000, the solution viscosity becomes extremely low, and it becomes difficult to adjust the viscosity of the inorganic particle-containing composition (paste or slurry), and the inorganic particle-containing composition is applied and dried. The strength and adhesion of the film may be reduced.
On the other hand, when the number average molecular weight exceeds 150,000, the solution viscosity becomes extremely large, and it may be difficult to adjust the viscosity of the composition containing inorganic particles, and the printability may be reduced.

The polymer composition according to the present invention will be described in more detail with reference to embodiments.
The polymer composition according to the first embodiment includes a polymer blend-type binder and a compatibilizer, and the polymer blend-type binder and the compatibilizer are the production method described in the above <Method for producing polymer compound> Is the product obtained by In this embodiment, the product is not only a polymer blend type binder, but also the polymer compound according to the present invention contained therein functions as a compatibilizer.
The polymer composition according to the second embodiment includes a polymer blend-type binder and a compatibilizer, wherein the polymer blend-type binder includes a cellulose compound and a polyvinyl acetal-based compound, and the compatibilizer is the above-described polymer compound. Production Method>. A part other than the polymer compound according to the present invention contained in the product may form a part of a polymer blend type binder.

The product obtained by the production method described in the above <Production method of polymer compound> may be separately produced depending on whether it is used for the first embodiment or for the second embodiment. preferable. That is, in the method for producing a high molecular compound, the first compound and the second polyvinyl acetal compound can be separately formed by controlling the ratio of bonding the first cellulose compound and the first polyvinyl acetal compound, that is, the amount of reactive functional groups introduced into these compounds. .
When used for the first embodiment, it is preferable to relatively reduce the amount of reactive functional groups introduced. For example, the number of reactive functional groups to be introduced is preferably less than 2, more preferably 1 or less per molecule.
On the other hand, when used for the second embodiment, it is preferable to relatively increase the amount of reactive functional groups introduced. When used for the second embodiment, the number of reactive functional groups introduced into the first cellulose compound and the first polyvinyl acetal compound is preferably two or more per molecule on average.

In the second embodiment, the product obtained by the production method described in the above <Method for producing a polymer compound> is a cellulose compound and a polyvinyl acetal compound as a polymer blend type binder (a second cellulose compound and It is desirable that the content be in the range of 0.1% by mass to 50% by mass based on the total amount of the second polyvinyl acetal compound). Outside the range, there is a possibility that a compatibilizing effect is reduced or a problem such as a reduced viscosity is caused.
In the second embodiment, the content ratio of the cellulosic compound and the polyvinyl acetal compound (the second cellulosic compound and the second polyvinyl acetal compound) as the polymer blend type binder is preferably in a mass ratio of 1: 9 to The ratio is in the range of 9: 1, more preferably in the range of 2: 8 to 8: 2.

<Inorganic particle-containing composition>
The inorganic particle-containing composition according to the present invention (hereinafter, also simply referred to as “inorganic particle-containing composition”) contains the polymer compound according to the present invention, inorganic particles and an organic solvent, or the above-mentioned present invention. , A second cellulose-based compound, a second polyvinyl acetal-based compound, inorganic particles, and an organic solvent.
The inorganic particle-containing composition can include one or more polymer compounds (compatibilizers).
The composition containing inorganic particles can include one or more second cellulosic compounds.
The inorganic particle-containing composition can include one or more second polyvinyl acetal-based compounds.
The inorganic particle-containing composition can include one or more inorganic particles.
The composition containing inorganic particles can include one or more organic solvents.
The second cellulose-based compound and the second polyvinyl acetal-based compound are polymer materials suitably used as a binder for the composition (paste or slurry) containing the inorganic particles.

  The inorganic particle-containing composition is suitable as various pastes or slurries, in particular, sintering-type pastes or slurries for producing electronic components and members of electronic devices. In addition, although there is no clear distinction between the paste and the slurry, the distinction is mainly made in terms of viscosity, and the former has higher viscosity.

  For example, the composition containing inorganic particles according to the present invention can be suitably used as a paste or slurry for forming circuits, electrode patterns, dielectric layers, ceramic bodies, phosphor layers, and the like of various electronic components.

Examples of the inorganic material constituting the inorganic particles included in the inorganic particle-containing composition include a conductive inorganic material, ceramic, glass, a pigment, a phosphor, and the like.
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-palladium alloy; metals made of ITO and the like. Oxides; carbon powders and the like.
Examples of the ceramic include magnetic ceramics such as barium titanate, titanium oxide, alumina, zirconia, aluminum nitride, silicon nitride, boron nitride, silicon carbide, and ferrite.
Examples of the glass include those containing silicon dioxide (usually, those containing silicon dioxide as a main component), and the melting point is not particularly limited.
The particle diameter of the inorganic particles is usually in the range of 20 nm to 1 mm.

  As the organic solvent contained in the inorganic particle-containing composition, one selected from the organic solvents exemplified in the above <Production method of polymer compound> [1] and various organic solvents having active protons in addition thereto Alternatively, two or more kinds can be used. The organic solvent is a solvent capable of dissolving the second cellulose-based compound, the second polyvinyl acetal-based compound, and the polymer compound as binders, and preferably has a high boiling point in printing paste applications. For example, high-boiling organic solvents such as mono-, di-, tri-oligoethylene glycol, mono-, di-, tri-oligopropylene glycol, acetate, terpineol, and dihydroterpineol acetate are preferably used.

  The inorganic particle-containing composition can further include an additive as needed. Additives include surfactants, viscosity modifiers, defoamers, leveling agents, stabilizers, plasticizers, wetting agents, pigments, polymer particles, and the like. One type of additive may be used alone, or two or more types may be used in combination. Further, the composition containing inorganic particles may further include a polymer other than the second cellulose compound and the second polyvinyl acetal compound as a binder.

Inorganic particles-containing composition (when two or more inorganic particles are contained, the total content thereof) and the resin component (the total content of the polymer compound, the second cellulose-based compound, and the second polyvinyl acetal-based compound) in the inorganic particle-containing composition Is usually from 100: 1 to 100: 50 on a mass basis, and preferably from 100: 5 to 100: 30 from the viewpoint of the viscosity of the inorganic particle-containing composition and the dispersibility of the inorganic particles. is there.
The content of the organic solvent (when two or more organic solvents are contained, the total content thereof) is usually 100 parts by mass to 10,000 parts by mass based on 100 parts by mass of the resin component.
When the inorganic particle-containing composition contains an additive, its content (when two or more additives are contained, the total content) is usually 0.1 to 100 parts by mass of the resin component. 30 parts by mass.

  The inorganic particles, the resin component dissolved in an organic solvent, and additives used as necessary are mixed using a dispersing device such as a three-roll mill, a ball mill, a media mill, and a homogenizer to uniformly disperse the inorganic particles. By doing so, an inorganic particle-containing composition can be prepared.

After applying the inorganic particle-containing composition to a substrate or the like, the organic solvent is volatilized by subsequent baking, and the resin component is thermally decomposed to form a layer or a pattern of the inorganic particles. Examples of the method for applying the inorganic particle-containing composition include screen printing, die coat printing, doctor blade printing, roll coat printing, offset printing, gravure printing, flexographic printing, inkjet printing, dispense printing, casting, and dip coating. Among them, screen printing and dip coating are preferred.
The layer or pattern obtained by firing usually comprises a sintered body of inorganic particles.

  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 Examples,% and parts representing the content or the used amount are based on mass unless otherwise specified.

(Synthesis example 1)
(Synthesis of Cellulose Compound (1a) Having Allyl Group)
Ethyl cellulose (“Ethocel STD-200” manufactured by Dow Chemical Co., Ltd., number average molecular weight Mn (standard polystyrene conversion value by GPC): 80733, degree of substitution (DS value, degree of etherification): 2.52) was prepared and dried. . In addition, the substitution degree of 2.52 means that, on average, 2.52 of the three hydroxy groups present in one glucose ring are ethyl etherified, and 0.48 hydroxy groups remain. It means that.

  100 parts of the dried ethyl cellulose was dissolved in 900 parts of ethyl acetate. To the obtained solution, 0.81 part of 3-allyloxypropionic acid corresponding to an average introduction amount of 5 parts per one molecule of ethyl cellulose, 0.78 part of diisopropylcarbodiimide as a condensing agent, and dimethylamino as a reaction accelerator 0.015 parts of pyridine was added, and the mixture was stirred at a temperature of 40 ° C. for 5 hours to carry out a reaction. Thereafter, the ethyl acetate was distilled off to obtain a cellulose compound (1a) in which an allyl group was introduced into ethyl cellulose as a solid.

When a part of the obtained solid was analyzed by FT-IR and ¹ H-NMR, formation of an ester bond was confirmed, and an allyl group in the same molar amount as the charged 3-allyloxypropionic acid was introduced into ethyl cellulose. It was confirmed that it was.

(Synthesis of polyvinyl acetal compound (1b) having mercapto group)
Polyvinyl butyral ("BH-S" manufactured by Sekisui Chemical Co., Ltd., number average molecular weight Mn (standard polystyrene equivalent value by GPC): 66000, hydroxy group content: about 22 mol%) was prepared and dried. 100 parts of the dried polyvinyl butyral was dissolved in 900 parts of ethyl acetate. To the obtained solution, 0.80 part of 3-mercaptopropionic acid corresponding to an average of 5 introduced molecules per one molecule of polyvinyl butyral, 0.96 part of diisopropylcarbodiimide as a condensing agent, and dimethylamino as a reaction accelerator After adding 0.019 parts of pyridine, the mixture was stirred at a temperature of 40 ° C. for 5 hours to carry out a reaction. Thereafter, the ethyl acetate was distilled off to obtain a polyvinyl acetal compound (1b) having a mercapto group introduced into polyvinyl butyral as a solid.

When a part of the obtained solid was analyzed by FT-IR and ¹ H-NMR, formation of an ester bond was confirmed, and a mercapto group in the same molar amount as the charged 3-mercaptopropionic acid was introduced into polyvinyl butyral. It was confirmed that it was.
The average amount of functional groups introduced into ethyl cellulose and polyvinyl butyral as base polymers (in Table 1, the average amount of functional groups introduced into ethyl cellulose and polyvinyl butyral is the same in the same synthesis example) and used. Table 1 summarizes the types of base polymers.

(Synthesis Examples 2 and 3)
An amount of 3-allyloxypropionic acid corresponding to an average of 1 (Synthesis Example 2) and 0.1 (Synthesis Example 3) per one molecule of ethylcellulose was used, and diisopropylcarbodiimide and dimethyl were used in corresponding amounts. Cellulose compounds (2a) and (3a) in which an allyl group was introduced into ethyl cellulose were obtained in the same manner as in Synthesis Example 1 except that aminopyridine was used.
Further, 3-mercaptopropionic acid corresponding to the amount of one (Synthesis Example 2) and 0.1 (Synthesis Example 3) introduced on average per one molecule of polyvinyl butyral was used, and a corresponding amount of diisopropylcarbodiimide was used. In the same manner as in Synthesis Example 1 except that dimethylaminopyridine and dimethylaminopyridine were used, polyvinyl acetal compounds (2b) and (3b) in which a mercapto group was introduced into polyvinyl butyral were obtained.
Table 1 summarizes the average amount of functional groups introduced into ethyl cellulose and polyvinyl butyral, which are base polymers, and the types of base polymers used.
When each of the obtained compounds was analyzed by FT-IR and ¹ H-NMR, formation of an ester bond was confirmed, and a functional group in the same molar amount as the charged functional group-introducing reagent was added to the base polymer. It has been confirmed that it has been introduced.

(Synthesis examples 4 to 7)
The same as in Synthesis Example 1 except that the types of the base polymers ethyl cellulose and polyvinyl butyral were as shown in Table 1, and the average amount of functional groups introduced into the base polymer was as shown in Table 1. Thus, a cellulose compound and a polyvinyl acetal compound were obtained.
When each of the obtained compounds was analyzed by FT-IR and ¹ H-NMR, formation of an ester bond was confirmed, and a functional group in the same molar amount as the charged functional group-introducing reagent was added to the base polymer. It has been confirmed that it has been introduced.

Details of “STD 100”, “STD 45”, “BM-S”, and “BL-S” described in Table 1 are as follows.
STD 100: "Ethocel STD-100" manufactured by Dow Chemical Company, number average molecular weight Mn (standard polystyrene conversion value by GPC): 63400, degree of substitution (DS value, degree of etherification): 2.52
STD 45: "Ethocel STD-45" manufactured by Dow Chemical Company, number average molecular weight Mn (standard polystyrene conversion value by GPC): 56500, degree of substitution: 2.52
BM-S: “BM-S” manufactured by Sekisui Chemical Co., Ltd., number average molecular weight Mn (standard polystyrene conversion value by GPC): 53000, hydroxy group amount: about 22 mol%
BL-S: “BL-S” manufactured by Sekisui Chemical Co., Ltd., number average molecular weight Mn (standard polystyrene conversion value by GPC): 23000, hydroxy group amount: about 22 mol%

(Synthesis Examples 8 to 10)
Compounds in which the types of functional groups to be introduced into ethyl cellulose and polyvinyl butyral were exchanged with each other were synthesized. That is, a cellulose compound and a polyvinyl acetal compound were obtained in the same manner as in Synthesis Example 1 except that a mercapto group was introduced into ethyl cellulose and an allyl group was introduced into polyvinyl butyral.
Table 1 summarizes the average amount of functional groups introduced into ethyl cellulose and polyvinyl butyral, which are base polymers, and the types of base polymers used.
When each of the obtained compounds was analyzed by FT-IR and ¹ H-NMR, formation of an ester bond was confirmed, and a functional group in the same molar amount as the charged functional group-introducing reagent was added to the base polymer. It has been confirmed that it has been introduced.

(Synthesis example 11)
(Synthesis of Cellulose Compound (11a) Having Azide Group)
Ethyl cellulose ("Ethocel STD-200" manufactured by Dow Chemical) was prepared and dried. 100 parts of the dried ethyl cellulose was dissolved in 900 parts of ethyl acetate. To the obtained solution, 0.89 part of 5-azidopentanoic acid corresponding to an average of 5 introduced per one molecule of ethyl cellulose, 0.78 part of diisopropylcarbodiimide as a condensing agent, and dimethylaminopyridine as a reaction accelerator 0.015 parts was added and the mixture was stirred at a temperature of 40 ° C. for 5 hours to carry out a reaction. Thereafter, the ethyl acetate was distilled off to obtain a cellulose compound (11a) in which an azide group was introduced into ethyl cellulose as a solid.

  When a part of the obtained solid was analyzed by FT-IR and 1H-NMR, formation of an ester bond was confirmed, and an azido group in the same molar amount as the charged 5-azidopentanoic acid was introduced into ethyl cellulose. It was confirmed that.

(Synthesis of polyvinyl acetal compound (11b) having alkynyl group)
Polyvinyl butyral ("BH-S" manufactured by Sekisui Chemical Co., Ltd.) was prepared and dried. 100 parts of the dried polyvinyl butyral was dissolved in 900 parts of ethyl acetate. To the obtained solution, 0.85 part of 5-hexynic acid corresponding to an average of five introduced per one molecule of polyvinyl butyral, 0.96 part of diisopropylcarbodiimide as a condensing agent, and dimethylaminopyridine as a reaction accelerator 0.019 parts was added and the mixture was stirred at a temperature of 40 ° C. for 5 hours to carry out a reaction. Thereafter, the ethyl acetate was distilled off to obtain a polyvinyl acetal compound (11b) in which an alkynyl group was introduced into polyvinyl butyral as a solid.

When a part of the obtained solid was analyzed by FT-IR and ¹ H-NMR, formation of an ester bond was confirmed, and an alkynyl group in the same molar amount as the charged 5-hexynic acid was introduced into polyvinyl butyral. It was confirmed that.

(Synthesis examples 12 to 18)
Synthetic examples except that the types of the base polymers ethyl cellulose and polyvinyl butyral were as shown in Table 1, and the average amount of functional groups introduced into the base polymer and the combination of the functional groups were as shown in Table 1. In the same manner as in Example 11, a cellulose compound and a polyvinyl acetal compound were obtained.
When each of the obtained compounds was analyzed by FT-IR and ¹ H-NMR, formation of an ester bond was confirmed, and a functional group in the same molar amount as the charged functional group-introducing reagent was added to the base polymer. It has been confirmed that it has been introduced.

<Example 1: Synthesis of polymer compound (1ab)>
The cellulose compound (1a) into which the allyl group was introduced and the polyvinyl acetal compound (1b) into which the mercapto group was introduced, which was obtained in Synthesis Example 1, were reacted by the following method to obtain a polymer compound (1ab). .
5 parts by mass of the cellulose compound (1a) and 5 parts by mass of the polyvinyl acetal compound (1b) were dissolved in 60 parts by mass of dihydroterpineol acetate. This solution was transferred to a glass flask reaction vessel, and after purging with nitrogen, 0.1 parts by mass of azobisisobutyronitrile as a radical generator was added to the solution, and the mixture was reacted at 80 ° C. for 3 hours with stirring. Thus, a solution containing a polymer compound was obtained.
The resulting polymer compound was analyzed by FT-IR and ¹ H-NMR. As a result, an —S— bond was confirmed, and the desired structure was obtained.

The number average molecular weight (Mn: standard polystyrene conversion value by GPC) of the polymer compound (1ab) was measured using GPC.
GPC measurement conditions are as follows (the same applies to the number average molecular weight of the polymer compound obtained in the other examples).
GPC device: "HLC-8320GPC" manufactured by Tosoh Corporation
Column: TSKgel GMHXL
Measurement temperature (set temperature): 40 ° C
Mobile phase: tetrahydrofuran Table 2 summarizes the types of cellulose compound and polyvinyl acetal compound used, their mass ratios, and the number average molecular weight of the obtained polymer compound.

<Examples 2 to 12>
A high molecular compound was obtained in the same manner as in Example 1, except that the types of the cellulose compound and the polyvinyl acetal compound used and the used mass ratios thereof were as shown in Table 2.
Table 2 summarizes the types and mass ratios of the used cellulose compound and polyvinyl acetal compound, and the number average molecular weight of the obtained polymer compound.

<Example 13>
The cellulose compound (11a) into which the azide group was introduced and the polyvinyl acetal compound (11b) into which the alkynyl group was introduced were reacted by the following method to obtain a polymer compound (13ab). .
5 parts by mass of the cellulose compound (11a) and 5 parts by mass of the polyvinyl acetal compound (11b) were dissolved in 60 parts by mass of tetrahydrofuran (THF). This solution is transferred to a glass flask reaction vessel, 0.01 parts by mass of copper sulfate pentahydrate is added to the solution as a reaction catalyst, and the mixture is reacted at 60 ° C. for 24 hours with stirring to contain a polymer compound. A solution was obtained.
When the produced polymer compound was analyzed by FT-IR and ¹ H-NMR, a 1,2,3-triazoldiyl group was confirmed, and a target structure was obtained.
The number average molecular weight (Mn) of the polymer compound (13ab) was measured using GPC.
Table 2 summarizes the types and mass ratios of the used cellulose compound and polyvinyl acetal compound, and the number average molecular weight of the obtained polymer compound.

<Examples 14 to 22>
A high molecular compound was obtained in the same manner as in Example 1, except that the types of the cellulose compound and the polyvinyl acetal compound used and the used mass ratios thereof were as shown in Table 2.
Table 2 summarizes the types and mass ratios of the used cellulose compound and polyvinyl acetal compound, and the number average molecular weight of the obtained polymer compound.

<Examples 1A to 22A, Comparative Examples 1A to 3A>
(1) Preparation of Binder A blending component was mixed according to the blending composition shown in Table 3 to prepare a binder (solution). In Examples 1A to 22A, the binder was obtained by mixing the polymer compound alone or the polymer compound with the second cellulose compound and the second polyvinyl acetal compound obtained in the example of synthesizing the polymer compound. Prepared. In Table 3, "mixing mass ratio" is a solid content converted value.
As shown in Table 3, in Examples 1A to 22A, the binder consisted of only a polymer compound, or consisted of a polymer compound, a cellulose compound and a polyvinyl acetal compound. In Comparative Examples 1A to 3A, the binder consists of only a cellulose compound, only a polyvinyl acetal compound, or a cellulose compound and a polyvinyl acetal compound.

(2) Evaluation of binder The following evaluation was performed about the binder obtained by the Example and the comparative example, and the inorganic particle containing composition (paste) containing it. Table 3 shows the results.

(2-1) Evaluation of thermal decomposability 10 mg of a dry solid sample of the binder was measured at 10 ° C./min in a nitrogen atmosphere using a TG / DTA thermal analyzer (“EXSTAR TG / DTA6200” manufactured by Seiko Instruments Inc.). The amount of the residue when heated to 500 ° C. at a rate of temperature increase was measured, and the thermal decomposability of the binder was evaluated based on the following evaluation criteria. The residue amount (% by mass) indicates the amount of residue after measurement when the mass of the dry solid sample is 100% by mass.
(Evaluation criteria for thermal decomposition)
A: Residue amount is 1% by mass or less B: Residue amount exceeds 1% by mass and 3% by mass or less C: Residue amount exceeds 3% by mass

(2-2) Evaluation of Adhesion to Polyvinyl Butyral Assuming a case in which a binder is used for the electrode paste, the adhesion to the green sheet was evaluated by the following model experiment.

  The binder solution obtained in Examples and Comparative Examples is applied on an adhesive layer of a polyethylene terephthalate (PET) film (total thickness 100 μm) on which an adhesive layer is formed by a blade coater having a thickness gap of 90 μm, and then dried by heating. As a result, a film having a binder layer having a thickness of about 10 μm was prepared. 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% by mass solution. This was applied on the adhesive layer of the PET film on which the adhesive layer was formed in the same manner as described above, and then dried by heating to produce a film having a polyvinyl butyral layer having a thickness of about 10 μm. A strip 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 and 2 cm in width. A 1 cm × 2 cm (2 cm ² ) heating plate was pressed against the center of the overlapped portion, and thermocompression-bonded at 130 ° C. and a pressure of 2 kg for 5 minutes to partially bond the overlapped portion.

Using a tensile tester (AG-10N) manufactured by Shimadzu Corporation, a sample bonded at n = 3 was pulled in the longitudinal direction to measure the breaking strength, and the adhesion to polyvinyl butyral was determined based on the following evaluation criteria. Was evaluated.
(Evaluation criteria for adhesion)
A: Breaking strength is 100 N or more B: Breaking strength is less than 100 N, 50 N or more C: Breaking strength is less than 50 N

(2-3) Preparation of Inorganic Particle-Containing Composition (Paste) and Evaluation of Coating Film Quality When the solvent in the binder solution is not dihydroterpineol acetate, the content of dihydroterpineol acetate is adjusted after replacing the solvent with dihydroterpineol acetate. Thus, a binder solution having a binder concentration of 12% by mass was obtained.
Next, 100 parts by mass of Ni particles (“NFP201S” manufactured by JFE Mineral, average particle size 0.2 μm) as inorganic particles and 25 parts by mass of the binder solution were mixed by a three-roll mill to obtain a paste.

The obtained paste was applied on a glass substrate with a blade coater having a thickness gap of 30 μm, and the coated film after heating and drying was observed with a scanning electron microscope (SEM), and the quality of the coated film was evaluated based on the following evaluation criteria. . The coating film was observed at a magnification of 5000 times using "JSM-7800F" manufactured by JEOL Ltd. as a scanning electron microscope.
(Evaluation criteria for coating film quality)
A: No defect (hole) with a size exceeding 1 μm is observed B: Defect (hole) with a size exceeding 1 μm is observed

(2-4) Evaluation of Screen Printability The paste prepared in the above (2-3) was screen-printed using a Microtech printing machine (MT-320 series) and a mesh # 500 (manufactured by Nakanuma Art Screen) as a screen plate. A / S = 100 μm / 100 μm stripe pattern was printed on a PET film. The printed pattern was observed with a microscope, and the screen printability was evaluated based on the following evaluation criteria.
In addition, the stringing defect is a phenomenon in which a paste or the like is stretched at a stage where the screen printing plate is separated from the printing medium during printing, and a phenomenon in which a thin thread is drawn causes a printing defect. When this phenomenon occurs, problems such as the formation of fibrous foreign matter from the edge portion of the print pattern to cause an electrical short circuit and the non-uniform print pattern shape failing to obtain required characteristics are caused.
(Evaluation criteria for screen printability)
A: No stringing defect at the edge B: Stringing defect at the edge

Claims (10)

A first segment formed from a first cellulosic compound,
A second segment formed from the first polyvinyl acetal-based compound,
A bonding group for bonding the first segment and the second segment;
In the molecule,
A polymer compound in which the bonding group contains a -S- group or a 1,2,3-triazoldiyl group. The first cellulosic compound is a cellulose derivative having a reactive functional group (A),
The first polyvinyl acetal-based compound is a polyvinyl acetal having a reactive functional group (B),
The combination according to claim 1, wherein the combination of the reactive functional group (A) and the reactive functional group (B) is a combination of a thiol group and a vinyl group, or a combination of an alkynyl group and an azide group. High molecular compounds.   A compatibilizer comprising the polymer compound according to claim 1. A polymer compound according to claim 1 or 2,
A second cellulosic compound,
A second polyvinyl acetal compound;
A polymer composition comprising: The second cellulose compound is a cellulose derivative that may have a reactive functional group (C),
The second polyvinyl acetal compound is a polyvinyl acetal that may have a reactive functional group (D),
The combination according to claim 4, wherein the combination of the reactive functional group (C) and the reactive functional group (D) is a combination of a thiol group and a vinyl group or a combination of an alkynyl group and an azide group. Polymer composition. The second cellulose derivative is a cellulose derivative having no reactive functional group (C),
The polymer composition according to claim 5, wherein the second polyvinyl acetal is a polyvinyl acetal having no reactive functional group (D). A polymer compound according to claim 1 or 2,
Inorganic particles,
An organic solvent,
An inorganic particle-containing composition comprising: A polymer compound according to claim 1 or 2,
A second cellulosic compound,
A second polyvinyl acetal compound;
Inorganic particles,
An organic solvent,
An inorganic particle-containing composition comprising: The second cellulose compound is a cellulose derivative that may have a reactive functional group (C),
The second polyvinyl acetal compound is a polyvinyl acetal that may have a reactive functional group (D),
9. The combination according to claim 8, wherein the combination of the reactive functional group (C) and the reactive functional group (D) is a combination of a thiol group and a vinyl group, or a combination of an alkynyl group and an azide group. An inorganic particle-containing composition. The second cellulose derivative is a cellulose derivative having no reactive functional group (C),
The inorganic particle-containing composition according to claim 9, wherein the second polyvinyl acetal is a polyvinyl acetal having no reactive functional group (D).