JP2015108069A - Pyrolytic resin binder - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pyrolytic resin binder excellent in dispersion stability and heat decomposability of inorganic powder, further excellent in the property of efficiently dissolving a pyrolytic resin contained in a surplus material, such as cutting residues, generated in the production of a green tape when the surplus material is dissolved in solvent.SOLUTION: A pyrolytic resin binder contains a pyrolytic polymer obtained by polymerizing a monomer component containing a ring structure-containing monomer of 3 to 95 mass% and a polar functional group-containing monomer of 0.1 to 5 mass% and the balance of a monomer copolymerizable with the ring stricture-containing monomer and the polar functional group-containing monomer.

Description

  The present invention relates to a thermally decomposable resin binder. More specifically, the present invention relates to a thermally decomposable resin binder that can be suitably used as, for example, a thermally decomposable resin binder for sintered sheets.

  When manufacturing a ceramic sheet or a small ceramic molded body, a green sheet (pre-sintered green sheet) is used. The green sheet is obtained by, for example, applying a slurry obtained by mixing inorganic powder, which is a raw material of ceramics, and a resin binder to a substrate having releasability and drying, and then forming the formed green sheet. Manufactured by peeling from the substrate. A ceramic sheet or a small ceramic molded body is manufactured by removing the binder from the green sheet and then sintering the green sheet.

  By the way, in recent years, with the increase in functionality of ceramics, miniaturization of inorganic powder, which is a ceramic precursor (for example, adjusting the particle diameter to 1 μm or less) has been studied. With the miniaturization of the inorganic powder, the resin binder is required to improve the dispersion stability of the inorganic powder. In order to improve the dispersion stability of the inorganic powder in the resin binder, a (meth) acrylate polymer having a functional group capable of hydrogen bonding with a hydroxyl group, an organic compound having three or more hydroxyl groups, and a nonionic surfactant as a resin binder The use of a binder composition contained has been studied (see, for example, Patent Document 1).

  Generally, in order to effectively utilize surplus materials such as the cutting residue of the green tape produced as a by-product when the green tape is formed into a predetermined shape, the surplus material such as the cutting residue is dissolved in a solvent, and an inorganic solution is obtained from the obtained solution. The operation of separating the powder and collecting the inorganic powder is employed. However, surplus materials such as the cutting residue of the green tape are poor in solubility in a solvent and the resin binder used in the green tape is low in thermal decomposability, so that residual carbon is by-produced after firing.

JP 2006-249248 A

  The present invention has been made in view of the above prior art, is excellent in dispersion stability and thermal decomposability of inorganic powder, and further dissolves surplus materials such as cutting residue generated when producing a green tape in a solvent. It is an object of the present invention to provide a thermally decomposable resin binder that is also excellent in the property of efficiently dissolving the resin binder contained in the surplus (hereinafter referred to as re-solubility).

  The present invention contains 3 to 95% by mass of a ring structure-containing monomer and 0.1 to 5% by mass of a polar functional group-containing monomer, and the balance is the above-mentioned ring structure-containing monomer and polar functional group-containing monomer. The present invention relates to a thermally decomposable resin binder characterized by containing a thermally decomposable polymer obtained by polymerizing a monomer component that is a monomer copolymerizable with the body.

  The thermally decomposable resin binder of the present invention has an excellent effect of being excellent in dispersion stability and thermal decomposability of the inorganic powder and also excellent in re-dissolvability.

  As described above, the thermally decomposable resin binder of the present invention contains 3 to 95% by mass of a ring structure-containing monomer and 0.1 to 5% by mass of a polar functional group-containing monomer, with the balance being the ring structure. It contains a thermally decomposable polymer obtained by polymerizing a monomer component which is a monomer copolymerizable with the containing monomer and the polar functional group-containing monomer.

  Examples of the ring structure-containing monomer include cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, didiclopentanyl (meth) acrylate, didiclopentenyl (meth) acrylate, didiclopentenyloxyethyl (meth) ) Acrylate, didiclopentadienyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, dioxolane Although (meth) acrylate, N-vinylpyrrolidone, etc. are mentioned, this invention is not limited only to this illustration. These ring structure-containing monomers may be used alone or in combination of two or more. Among these ring structure-containing monomers, tetrahydrofurfuryl (meth) acrylate, etc., from the viewpoint of obtaining a thermally decomposable resin binder that is excellent in dispersion stability and thermal decomposability of inorganic powder and is also excellent in resolubility (Meth) acrylate, cyclohexyl (meth) acrylate and isobornyl (meth) acrylate having a ring structure containing oxygen atoms are preferred, (meth) acrylate having a ring structure containing oxygen atoms such as tetrahydrofurfuryl (meth) acrylate and Isobornyl (meth) acrylate is more preferred.

  In the present invention, “(meth) acrylate” means acrylate or methacrylate, but acrylate and methacrylate may be used alone or in combination.

  From the viewpoint of improving the dispersion stability of the inorganic powder, the content of the ring structure-containing monomer in the monomer component is 3% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably. Is 15% by mass or more, more preferably 20% by mass or more, and from the viewpoint of improving re-solubility, it is 95% by mass or less, preferably 93% by mass or less, more preferably 85% by mass or less, and still more preferably 80%. It is at most 75% by mass, even more preferably at most 75% by mass.

  Examples of the polar functional group-containing monomer include an acid group-containing monomer, a hydroxyl group-containing monomer, and an amino group-containing monomer. However, the present invention is not limited to such examples. Absent. These polar functional group-containing monomers may be used alone or in combination of two or more. In the present invention, from the viewpoint of obtaining a thermally decomposable resin binder that is excellent in dispersion stability and thermal decomposability of inorganic powder, and further excellent in re-solubility, as a polar functional group-containing monomer, an acid group-containing monomer It is preferable to use at least one selected from the group consisting of a polymer, a hydroxyl group-containing monomer and an amino group-containing monomer.

  Examples of the acid group-containing monomer include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; and monoisopropyl maleate and monoisopropyl fumarate. Although monoester of carboxylic acid etc. are mentioned, this invention is not limited only to this illustration. These acid group-containing monomers may be used alone or in combination of two or more. Of these acid group-containing monomers, (meth) acrylic acid is preferred from the viewpoint of obtaining a thermally decomposable resin binder that is excellent in dispersion stability and thermal decomposability of inorganic powder and also excellent in re-dissolvability. More preferred is methacrylic acid.

  In the present invention, (meth) acrylic acid means acrylic acid or methacrylic acid, but acrylic acid and methacrylic acid may be used alone or in combination.

  Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2 -Ring opening adduct of ε-caprolactone of hydroxyethyl (meth) acrylate, ethylene oxide adduct of (meth) acrylic acid ester, propylene oxide adduct of (meth) acrylic acid ester, ethylene oxide of (meth) acrylic acid ester And adducts of propylene oxide and the like, but the present invention is not limited to such examples. These hydroxyl group-containing monomers may be used alone or in combination of two or more. Among these hydroxyl group-containing monomers, 2-hydroxyethyl (meth) acrylate is used from the viewpoint of obtaining a thermally decomposable resin binder that is excellent in dispersion stability and thermal decomposability of inorganic powder and is also excellent in resolubility. , 1,4-butanediol mono (meth) acrylate, ethylene oxide adduct of (meth) acrylate ester, propylene oxide adduct of (meth) acrylate ester, and ethylene oxide and propylene oxide of (meth) acrylate ester Of 2-hydroxyethyl (meth) acrylate and 1,4-butanediol mono (meth) acrylate are more preferred, 2-hydroxyethyl (meth) acrylate is more preferred, and 2-hydroxyethyl methacrylate is even more preferred. preferable.

  Examples of the amino group-containing monomer include dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate, but the present invention is not limited to such examples. These amino group-containing monomers may be used alone or in combination of two or more. Among these amino group-containing monomers, dimethylaminoethyl (meth) acrylate is preferred from the viewpoint of obtaining a thermally decomposable resin binder that is excellent in dispersion stability and thermal decomposability of inorganic powder and is also excellent in resolubility. Is preferred, and dimethylaminoethyl methacrylate is more preferred.

  The content of the polar functional group-containing monomer in the monomer component is 0.1% by mass or more, preferably 0.3% by mass or more, more preferably 0.00% from the viewpoint of improving the dispersion stability of the inorganic powder. From the viewpoint of improving the dispersion stability of the inorganic powder, it is 5% by mass or less, preferably 3% by mass or less.

  Examples of the monomer copolymerizable with the ring structure-containing monomer and the polar functional group-containing monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and isopropyl (meth). Acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) Acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate Alkyl (meth) acrylates such as rate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, and the like can be mentioned. It is not limited to illustration only. These monomers may be used alone or in combination of two or more. Among these monomers, from the viewpoint of obtaining a thermally decomposable resin binder that is excellent in dispersion stability and thermal decomposability of the inorganic powder and also excellent in re-dissolvability, the alkyl group has 1 to 12 carbon atoms. A certain alkyl (meth) acrylate is preferable, and an alkyl (meth) acrylate having 1 to 8 carbon atoms in the alkyl group is more preferable.

  The amount of the monomer copolymerizable with the ring structure-containing monomer and the polar functional group-containing monomer is the balance of the ring structure-containing monomer and the polar functional group-containing monomer in the monomer component. . By appropriately adjusting the content of the monomer that is copolymerizable with the ring structure-containing monomer and the polar functional group-containing monomer in the monomer component, the glass transition temperature of the resulting thermally decomposable polymer is It can be adjusted to a desired value.

  Examples of the method for polymerizing the monomer component include a solution polymerization method, a dispersion polymerization method, a suspension polymerization method, an emulsion polymerization method, and the like, but the present invention is not limited to such examples.

  When the monomer component is polymerized by a solution polymerization method, examples of the solvent include aromatic solvents such as toluene and xylene; alcohol solvents such as isopropyl alcohol and n-butyl alcohol; propylene glycol methyl ether and dipropylene glycol methyl. Ether solvents such as ether, ethyl cellosolve, butyl cellosolve; ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol; amide solvents such as dimethylformamide However, the present invention is not limited to such examples. These solvents may be used alone or in combination of two or more. The amount of the solvent may be appropriately determined in consideration of the polymerization conditions, the composition of the monomer components, the concentration of the resulting thermally decomposable polymer, and the like.

  A polymerization initiator can be used when the monomer component is polymerized. Examples of the polymerization initiator include 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), tert-butylperoxy-2-ethylhexano And 2,2′-azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, and the like, but the present invention is not limited to such examples. These polymerization initiators may be used alone or in combination of two or more. The amount of the polymerization initiator per 100 parts by mass of the monomer component may be appropriately set according to the desired physical properties of the resulting thermally decomposable polymer, but is usually preferably 0.01 to 50 parts by mass, More preferably, it is 0.05-20 mass parts.

  The polymerization conditions for polymerizing the monomer components may be set as appropriate according to the polymerization method, and are not particularly limited. The polymerization temperature is preferably room temperature to 200 ° C, more preferably 40 to 140 ° C. What is necessary is just to set reaction time suitably so that the polymerization reaction of a monomer component may be completed.

  A thermodegradable polymer is obtained by polymerizing the monomer component as described above. The weight average molecular weight of the thermally decomposable polymer is preferably 5000 or more, more preferably 10,000 or more, from the viewpoint of increasing the mechanical strength of the green tape produced using the thermally decomposable resin composition of the present invention. From the viewpoint of improving re-solubility, it is preferably 500,000 or less, more preferably 300,000 or less.

  The weight average molecular weight of the thermally decomposable polymer was determined by using gel as a standard substance and tetrahydrofuran as an eluent. Gel permeation chromatography measuring apparatus [manufactured by Tosoh Corporation, product number: HLC-8220GPC, column: TSKgel SuperHZM -M] is a value measured by gel permeation chromatography (GPC).

  From the viewpoint of improving the heat resistance of the thermally decomposable polymer, the glass transition temperature of the thermally decomposable polymer (non-volatile content) is preferably −20 ° C. or higher, more preferably −10 ° C. or higher. From the viewpoint of improving, it is preferably 150 ° C or lower, more preferably 120 ° C or lower.

In the present invention, the glass transition temperature of the thermally decomposable polymer (nonvolatile content) is a single weight composed of monomers contained in the monomer component used as a raw material of the thermally decomposable polymer (nonvolatile content). From the glass transition temperature (Tg) (absolute temperature: K) of the coalescence and the mass fraction of the monomer, the formula (I):
1 / Tg = W ₁ / Tg ₁ + W ₂ / Tg ₂ + W ₃ / Tg ₃ +... + W _n / Tg _n (I)
[Wherein Tg is the glass transition temperature (K) of the thermally decomposable polymer to be obtained, W ₁ , W ₂ , W ₃ ... W _n is the mass fraction of each monomer, _{Tg 1, Tg 2, Tg 3} ···· Tg n are respectively the glass transition temperature (K) of a homopolymer composed of a monomer corresponding to the mass fraction of each monomer]
It can obtain | require based on the Formula of Fox (Fox) represented by these. The glass transition temperature of the thermally decomposable polymer (nonvolatile component) can also be measured by DSC (differential scanning calorimeter), DTA (differential thermal analyzer), and TMA (thermomechanical analyzer).

  Among these methods for measuring the glass transition temperature of the thermally decomposable polymer (nonvolatile component), from the viewpoint of convenience of resin design, the glass transition temperature of the thermally decomposable polymer (nonvolatile component) is mainly determined by the formula (I ) Is used.

  In the following examples and the like, the glass transition temperature of the thermally decomposable polymer (non-volatile content) corresponds to the mass fraction of each monomer in all the monomer components used for polymerization. It means the glass transition temperature determined from the glass transition temperature of the monomer homopolymer.

  For monomers with unknown glass transition temperature, such as special monomers and polyfunctional monomers, the total content of monomers with unknown glass transition temperature in the monomer component is 10%. If it is less than or equal to%, the glass transition temperature can be determined using only monomers whose glass transition temperature is known. In addition, when the total content of monomers with unknown glass transition temperature in the monomer component exceeds 10% by mass, the glass transition of the thermally decomposable polymer obtained by polymerizing the monomer component It is determined by measuring the temperature by differential scanning calorimetry (DSC), differential calorimetry (DTA), thermomechanical analysis (TMA) or the like.

  For example, Kyozo Kitaoka, “Introduction to Synthetic Resins for Paints”, First Edition, Kobunshi Publishing Co., Ltd., May 1974; edited by the Society of Polymer Science, “Polymer Data Handbook” (Basics) ”, first edition, Bafukan Co., Ltd., January 1986;“ Functional Chemicals Catalog ”, Kyoeisha Chemical Co., Ltd., October 2004, and the like. The glass transition temperature of the homopolymer is, for example, 130 ° C. for a homopolymer of methacrylic acid, 55 ° C. for a homopolymer of 2-hydroxyethyl methacrylate, 18 ° C. for a homopolymer of dimethylaminoethyl methacrylate, and n-butyl methacrylate. 20 ° C. for homopolymer of cyclohexyl methacrylate, 83 ° C. for homopolymer of cyclohexyl methacrylate, 180 ° C. for homopolymer of isobornyl methacrylate, 60 ° C. for homopolymer of tetrahydrofurfuryl methacrylate, homopolymer of 2-ethylhexyl acrylate Then, it is -70 degreeC.

  When the thermally decomposable polymer has an acid group, the acid value of the thermally decomposable polymer (nonvolatile content) is preferably 0.7 mgKOH / g or more, more preferably from the viewpoint of improving the dispersion stability of the inorganic powder. Is 1.0 mgKOH / g or more, and preferably 40 mgKOH / g or less, more preferably 25 mgKOH / g or less, from the viewpoint of improving re-solubility.

The acid value of the thermally decomposable polymer means the amount of COOH group (carboxyl group) contained in the unit mass of the thermally decomposable polymer, and the carboxyl group contained in 1 g of the thermally decomposable polymer. Is the amount of potassium hydroxide (KOH) required to neutralize (mg). The acid value of the thermally decomposable polymer is, for example, a thermally decomposable polymer prepared by polymerizing a monomer component containing 1% by mass of methacrylic acid as an acid group-containing monomer. The acid value of the thermally decomposable polymer is given by the formula:
[Acid value of thermally decomposable polymer]
= [0.01 / 86 (molecular weight of methacrylic acid)] x 56100
= 6.5 mg KOH / g
Can be determined based on

  When the thermally decomposable polymer has a hydroxyl group, the hydroxyl value of the thermally decomposable polymer (nonvolatile content) is preferably 0.4 mgKOH / g or more, more preferably from the viewpoint of improving the dispersion stability of the inorganic powder. From the viewpoint of improving re-solubility, it is preferably 24 mgKOH / g or less, and more preferably 15 mgKOH / g or less.

The hydroxyl value of the thermally decomposable polymer means the amount (mg) of potassium hydroxide corresponding to the hydroxyl group contained in 1 g of the thermally decomposable polymer, and is contained in 1 g of the thermally decomposable polymer. This is the amount (mg) of potassium hydroxide (KOH) required to acetylate the hydroxyl group. Examples of the hydroxyl value of the thermally decomposable polymer include a thermally decomposable polymer prepared by polymerizing a monomer component containing 1% by mass of 2-hydroxyethyl methacrylate as a hydroxyl group-containing monomer. And the hydroxyl value of the thermally decomposable polymer is represented by the formula:
[Hydroxyl value of thermally decomposable polymer]
= [0.01 / 130 (molecular weight of 2-hydroxyethyl methacrylate)] x 56100 = 4.3 mgKOH / g
Can be determined based on

  When the thermally decomposable polymer has an amino group, the amine value of the thermally decomposable polymer (nonvolatile component) is preferably 0.4 mgKOH / g or more, more preferably from the viewpoint of improving the dispersion stability of the inorganic powder. Is 1 mgKOH / g or more, and preferably 18 mgKOH / g or less, more preferably 10 mgKOH / g or less, from the viewpoint of improving re-solubility.

The amine value of the thermally decomposable polymer is the amount (mg) of potassium hydroxide corresponding to the amino group contained in 1 g of the thermally decomposable polymer. For example, taking as an example a thermally decomposable polymer prepared by polymerizing a monomer component containing 1% by mass of dimethylaminoethyl methacrylate as an amino group-containing monomer, the amine of the thermally decomposable polymer is used. The valence is the formula:
[Amine value of thermally decomposable polymer]
= [0.01 / 157 (Molecular weight of dimethylaminoethyl methacrylate)] x 56100 = 3.6 mg KOH / g
Can be determined based on

  The thermally decomposable resin binder of the present invention contains the above thermally decomposable polymer. The thermally decomposable resin binder of the present invention may be composed only of the thermally decomposable polymer, or may contain a solvent. When the thermally decomposable resin binder of the present invention contains a solvent, the solvent used when preparing the thermally decomposable polymer by solution polymerization can be used as the solvent. The content of the thermally decomposable polymer in the thermally decomposable resin binder can be easily adjusted by adjusting the amount of the solvent. Although the content rate of the heat decomposable polymer (nonvolatile content) in a heat decomposable resin binder is not specifically limited, Usually, it selects from the range of 5-80 mass%.

  The thermally decomposable resin binder of the present invention may contain other resin components, additives and the like within the range not impairing the object of the present invention.

  Examples of the additive include a leveling agent; a granular material; an antifoaming agent; an anti-sagging agent; a silane coupling agent; a dispersing agent; an antioxidant such as a phosphorus-based antioxidant and a phenol-based antioxidant; a viscosity modifier; UV stabilizers; metal deactivators; peroxide decomposers; flame retardants; reinforcing agents; plasticizers such as aliphatic plasticizers and aromatic plasticizers; lubricants; rust preventives; Organic and inorganic ultraviolet absorbers, inorganic heat ray absorbers; organic and inorganic flameproofing agents; organic and inorganic antistatic agents; and dehydrating agents such as methyl orthoformate, The present invention is not limited to such examples.

  The thermally decomposable resin binder of the present invention obtained as described above can be suitably used as a raw material for green sheets.

  For example, a green sheet is prepared by mixing an inorganic powder, which is a raw material of ceramics, and a thermally decomposable resin binder, and the slurry obtained above is applied to a sheet-like substrate having releasability. After drying, it can be produced by peeling the formed green sheet from the substrate. Moreover, a ceramic sheet or a small ceramic molded body can be manufactured by removing the binder contained in the green sheet from the green sheet and then sintering the green sheet.

Examples of the inorganic material used as the raw material of the inorganic powder that is a raw material of ceramics include, for example, lead borosilicate glass, lead glass, calcium oxide-alumina-silica inorganic glass, magnesia-alumina-silica inorganic glass, and lithium oxide-alumina. - low-melting glass such as silica-based inorganic glass; ZnS: Ag, Al, ZnS : Cu, Al, Y 2 O 2 S; Eu, (SrCaBaMg) 5 (PO 4) 3 Cl: Eu, LaPO 4: Ce, Tb Y ₂ O ₃ : Eu, Ca ₁₀ (PO ₄ ) ₆ FCl: Sb, Mn, BaMgAl ₁₀ O ₁₇ : Eu, Zn ₂ SiO ₄ : Mn, (Y, Gd) BO ₃ : Eu, CaWO ₄ , Gd _{2 O 2 S: Tb, (Y} , Sr) TaO 4: phosphor, such as Nb; aluminum, gold, platinum, silver, copper, nickel, metals such as palladium; silver oxide, aluminum , Titanium oxide, zirconium oxide, indium oxide, indium tin oxide (ITO), magnesium oxide, zinc oxide, nickel oxide, iron oxide, cerium oxide, chromium oxide and other metal oxides; silicon carbide and other metal carbides; aluminum nitride, Examples include metal nitrides such as boron nitride; alloys such as solder, but the present invention is not limited to such examples. These inorganic materials may be used alone or in combination of two or more.

  Among the inorganic powders, glass frit, alumina powder, silver powder, silver oxide powder, copper powder, indium tin oxide (ITO) powder, gold powder and solder powder are preferable, and glass frit, alumina powder and silver powder are more preferable. These inorganic powders may be used alone or in combination of two or more.

The average particle diameter of the inorganic powder is preferably 0.02 μm or more, more preferably 0.1 μm or more from the viewpoint of suppressing the generation of bubbles in the green sheet, and the viewpoint of improving the smoothness of the surface of the green sheet. Therefore, it is preferably 2 μm or less, more preferably 1 μm or less. Incidentally, the average particle size means median diameter determined from the particle size distribution, i.e. 50% by volume diameter (D _50).

  When mixing the inorganic powder and the resin binder, the inorganic powder and the resin binder are uniformly dispersed, and an appropriate amount of a solvent can be used to apply to the sheet-like substrate having releasability. .

  Examples of the solvent include ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, amyl acetate, acetone, dimethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, dibutyl ketone, acetylacetone, and ethylacetyl. Acetate, methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, toluene, xylene, mesitylene, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, butyl carbitol, butyl carbitol acetate, isophorone , Butyl lactate, dioctyl adipate, benzyl alcohol, phenylpropylene glycol , Cresol, menthene, menthane, menthone, myrcene, α-pinene, α-terpinene, γ-terpinene, limonene, perillyl acetate, perillyl alcohol, menthyl acetate, carbyl acetate, dihydrocarbyl acetate, dihydroterpineol acetate, turpi All acetate, dihydroterpineol, terpinyloxyethanol, dihydroterpinyloxyethanol, terpinyl methyl ether, dihydroterpinyl methyl ether, dihydroterpinyl propionate, isobornyl propionate, isobornyl Acetate, isobornyl propionate, isobornyl butyrate, isobornyl isobutyrate, nobyl acetate, octyl acetate, dimethyl octyl acetate, butyl carb Acetate, acetoxy-methoxyethoxy-cyclohexanol acetate, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, dihydrocarbol, 2-ethylhexyl glycol, benzyl glycol, phenylpropylene glycol, methyl decalin, amyl Examples include benzene, cumene, cymene, 1,1-diisopropylhexane, citronellol, and the like, but the present invention is not limited to such examples. These solvents may be used alone or in combination of two or more.

  The slurry may contain, for example, an additive such as a plasticizer and a dispersant as long as the object of the present invention is not impaired.

  The slurry obtained as described above can be obtained by applying to a substrate having releasability and drying, and then peeling the formed green sheet from the substrate. Examples of the method of applying the slurry to the substrate include gravure coating, roll coating, bar coating, reverse coating, and the like, but the present invention is not limited to such examples.

  Although the thickness of a green sheet is not specifically limited, Usually, it is preferable that it is about 10-800 micrometers.

  The green sheet may be punched using a punching device or the like so as to have a predetermined shape. Examples of the shape of the green sheet include a circle, an ellipse, a rectangle, a rectangle with rounded corners, and the like, but the present invention is not limited only to such examples.

  As described above, the heat-decomposable resin binder of the present invention is excellent in dispersion stability and heat-decomposability of inorganic powder, and is also excellent in re-dissolvability, so that it can be suitably used for green sheets. In addition, it is expected to be used for, for example, a low-temperature fired glass ceramic substrate, a photosensitive paste, a resin binder for a photolytic catalyst ceramic, an electrolyte sheet for a fuel cell, and the like.

  EXAMPLES Next, although this invention is demonstrated further in detail based on an Example, this invention is not limited only to this Example.

Example 1
100 g of toluene was charged into a 300 mL reactor equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer, and the temperature of the contents of the reactor was adjusted to 70 ° C. Next, 0.2 g of methacrylic acid, 2.8 g of 2-hydroxyethyl methacrylate, 30 g of n-butyl methacrylate, 57 g of cyclohexyl methacrylate, 2 g, while maintaining the temperature of the reactor contents at 70 ° C. in a nitrogen atmosphere in the reactor. -A mixture of 10 g of ethylhexyl acrylate and 0.3 g of tert-butylperoxy-2-ethylhexanoate as a polymerization initiator was dropped into the reactor over 1 hour.

  When 2 hours have elapsed from the end of the dropping, the temperature is raised to the reflux temperature and maintained at that temperature for 3 hours to terminate the polymerization reaction and obtain a reaction solution containing the produced thermally decomposable polymer. .

  The content of the thermally decomposable polymer (nonvolatile content) in the reaction solution obtained above was 50.0% by mass, the weight average molecular weight was 150,000, the acid value was 1.3 mgKOH / g, and the hydroxyl value. Was 12.1 mg KOH / g, the amine value was 0 mg KOH / g, and the glass transition temperature was 39 ° C.

  Using the reaction solution containing the thermally decomposable polymer obtained above as a thermally decomposable resin binder, the physical properties were evaluated based on the following methods. The results are shown in Table 1.

(1) Pyrolysis [Pyrolysis residue]
A sample was prepared by drying the thermally decomposable resin binder. A 5 mg sample is placed on an aluminum dish and mounted on a thermogravimetric analyzer (Seiko Instruments Co., Ltd., product number: TG / DTA6200). After cooling to room temperature, the formula:
[Residue rate (mass%)] = [(residue amount) ÷ 5] × 100
Based on the above, the residue rate was determined, and the pyrolysis residue of the pyrolyzable resin binder was evaluated based on the following evaluation criteria.
(Evaluation criteria)
A: Residue rate is less than 0.5% by mass (pass)
○: Residue rate is 0.5% by mass or more and less than 1.0% by mass (pass)
X: Residue rate is 1.0 mass% or more (failed)

[Occurrence of soot]
After performing the test of “(1) thermal decomposability”, whether or not wrinkles are present on an aluminum dish was visually observed, and wrinkle generation was evaluated based on the following evaluation criteria. .
(Evaluation criteria)
A: No generation of wrinkles (pass)
×: Wrinkle occurs (fails)

(2) Dispersion stability To 100 g of alumina powder as an inorganic powder, average particle size: 2 μm) 30 g of a thermally decomposable resin binder is added, and toluene is added to the resulting mixture, whereby the content of non-volatile content is 70. After adjusting to mass%, slurry was obtained by dispersing for 48 hours with a porcelain ball mill.

The appearance of the slurry immediately after completion of the slurry dispersion operation and the appearance of the slurry after standing for 7 days or 14 days were visually observed, and the dispersion stability was evaluated based on the following evaluation criteria.
(Evaluation criteria)
A: Separation of alumina powder is not recognized in the slurry (pass).
○: Some separation of alumina powder is recognized in the slurry (pass).
X: Alumina powder is separated in the slurry (failed).

(3) Re-dissolvability PET (polyethylene terephthalate) film obtained by releasing the slurry obtained in the above “(2) Dispersion stability” using a doctor blade so that the thickness after drying becomes 180 μm. After the solvent was removed by coating on and drying at a temperature of 100 ° C. for 10 minutes, the formed green film was peeled off from the PET film to obtain a green film. A sample was prepared by cutting the green film obtained above into a size of 1 cm in length and 1 cm in width. After the obtained sample is put in a sample bottle with a content of 50 mL, 40 mL of a mixed solvent consisting of 70% by volume of toluene and 30% by volume of ethyl acetate is put in the sample bottle, and the sample is immersed in the mixed solvent at room temperature. After leaving it to stand for 2 hours or 6 hours, the green film was visually observed, and re-solubility was evaluated based on the following evaluation criteria.
(Evaluation criteria)
A: The green film is completely dissolved (passed).
○: The green film is partially dissolved (passed).
X: The green film is not dissolved (failed).

(4) Comprehensive evaluation In the evaluation results of the thermal decomposability, dispersion stability and resolubility, the score of each evaluation item is totaled with 50 as the evaluation of ◎, 25 as the evaluation of ○, and 0 as the evaluation of x. (Maximum score: 350 points, Minimum score: 0 points), the heat decomposable resin binder was comprehensively evaluated.

Example 2
100 g of toluene was charged into a 300 mL reactor equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer, and the temperature of the contents of the reactor was adjusted to 70 ° C. Next, 0.2 g of methacrylic acid, 2.8 g of 2-hydroxyethyl methacrylate, 30 g of n-butyl methacrylate and 57 g of isobornyl methacrylate are maintained in the reactor while maintaining the temperature of the reactor contents at 70 ° C. in a nitrogen atmosphere. Then, a mixture of 10 g of 2-ethylhexyl acrylate and 0.3 g of tert-butylperoxy-2-ethylhexanoate as a polymerization initiator was dropped into the reactor over 1 hour.

  When 2 hours have elapsed from the end of the dropping, the temperature is raised to the reflux temperature and maintained at that temperature for 3 hours to terminate the polymerization reaction and obtain a reaction solution containing the produced thermally decomposable polymer. .

  The content of the thermally decomposable polymer (nonvolatile content) in the reaction solution obtained above was 50.1% by mass, the weight average molecular weight was 185000, the acid value was 1.3 mgKOH / g, and the hydroxyl value. Was 12.1 mg KOH / g, the amine value was 0 mg KOH / g, and the glass transition temperature was 76 ° C.

  Using the reaction solution containing the thermally decomposable polymer obtained above as a thermally decomposable resin binder, the physical properties were examined in the same manner as in Example 1. The results are shown in Table 1.

Example 3
100 g of toluene was charged into a 300 mL reactor equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer, and the temperature of the contents of the reactor was adjusted to 70 ° C. Next, 0.2 g of methacrylic acid, 2.8 g of 2-hydroxyethyl methacrylate, 30 g of n-butyl methacrylate and 57 g of tetrahydrofurfuryl methacrylate are maintained in the reactor under a nitrogen atmosphere while maintaining the temperature of the reactor contents at 70 ° C. Then, a mixture of 10 g of 2-ethylhexyl acrylate and 0.3 g of tert-butylperoxy-2-ethylhexanoate as a polymerization initiator was dropped into the reactor over 1 hour.

  When 2 hours have elapsed from the end of the dropping, the temperature is raised to the reflux temperature and maintained at that temperature for 3 hours to terminate the polymerization reaction and obtain a reaction solution containing the produced thermally decomposable polymer. .

  The content of the thermally decomposable polymer (nonvolatile content) in the reaction solution obtained above was 49.9% by mass, the weight average molecular weight was 165000, the acid value was 1.3 mgKOH / g, and the hydroxyl value. Was 12.1 mg KOH / g, the amine value was 0 mg KOH / g, and the glass transition temperature was −5 ° C.

  Using the reaction solution containing the thermally decomposable polymer obtained above as a thermally decomposable resin binder, the physical properties were examined in the same manner as in Example 1. The results are shown in Table 1.

Example 4
100 g of toluene was charged into a 300 mL reactor equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer, and the temperature of the contents of the reactor was adjusted to 70 ° C. Next, 0.2 g of methacrylic acid, 2-hydroxyethyl methacrylate 4.8, 30 g of n-butyl methacrylate and 60 g of tetrahydrofurfuryl methacrylate are maintained in the reactor while maintaining the temperature of the reactor contents at 70 ° C. in a nitrogen atmosphere. A mixture of 5 g of 2-ethylhexyl acrylate and 0.3 g of tert-butylperoxy-2-ethylhexanoate as a polymerization initiator was dropped into the reactor over 1 hour.

  When 2 hours have elapsed from the end of the dropping, the temperature is raised to the reflux temperature and maintained at that temperature for 3 hours to terminate the polymerization reaction and obtain a reaction solution containing the produced thermally decomposable polymer. .

  The content of the thermally decomposable polymer (non-volatile content) in the reaction solution obtained above was 50.0% by mass, the weight average molecular weight was 162000, the acid value was 1.3 mgKOH / g, and the hydroxyl value. Was 20.7 mgKOH / g, the amine value was 0 mgKOH / g, and the glass transition temperature was 8 ° C.

  Using the reaction solution containing the thermally decomposable polymer obtained above as a thermally decomposable resin binder, the physical properties were examined in the same manner as in Example 1. The results are shown in Table 1.

Example 5
100 g of toluene was charged into a 300 mL reactor equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer, and the temperature of the contents of the reactor was adjusted to 70 ° C. Next, 0.1 g of methacrylic acid, 30 g of n-butyl methacrylate, 64.9 g of tetrahydrofurfuryl methacrylate, 5 g of 2-ethylhexyl acrylate, while maintaining the temperature of the reactor contents at 70 ° C. under a nitrogen atmosphere in the reactor. As a polymerization initiator, a mixture of 0.3 g of tert-butylperoxy-2-ethylhexanoate was dropped into the reactor over 1 hour.

  When 2 hours have elapsed from the end of the dropping, the temperature is raised to the reflux temperature and maintained at that temperature for 3 hours to terminate the polymerization reaction and obtain a reaction solution containing the produced thermally decomposable polymer. .

  The content of the thermally decomposable polymer (nonvolatile content) in the reaction solution obtained above was 50.1% by mass, the weight average molecular weight was 163,000, the acid value was 0.7 mgKOH / g, and the hydroxyl value. Was 12.1 mg KOH / g, the amine value was 0 mg KOH / g, and the glass transition temperature was 3 ° C.

  Using the reaction solution containing the thermally decomposable polymer obtained above as a thermally decomposable resin binder, the physical properties were examined in the same manner as in Example 1. The results are shown in Table 1.

Example 6
100 g of toluene was charged into a 300 mL reactor equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer, and the temperature of the contents of the reactor was adjusted to 70 ° C. Next, 0.2 g of methacrylic acid, 2 g of 2-hydroxyethyl methacrylate, 0.8 g of dimethylaminoethyl methacrylate, and 30 g of n-butyl methacrylate while maintaining the temperature of the contents of the reactor at 70 ° C. in a nitrogen atmosphere in the reactor. A mixture of 62 g of tetrahydrofurfuryl methacrylate, 5 g of 2-ethylhexyl acrylate and 0.3 g of tert-butylperoxy-2-ethylhexanoate as a polymerization initiator was dropped into the reactor over 1 hour.

  When 2 hours have elapsed from the end of the dropping, the temperature is raised to the reflux temperature and maintained at that temperature for 3 hours to terminate the polymerization reaction and obtain a reaction solution containing the produced thermally decomposable polymer. .

  The content of the thermally decomposable polymer (nonvolatile content) in the reaction solution obtained above was 50.0% by mass, the weight average molecular weight was 172,000, the acid value was 1.3 mgKOH / g, and the hydroxyl value. Was 12.1 mg KOH / g, the amine value was 2.9 mg KOH / g, and the glass transition temperature was 5 ° C.

  Using the reaction solution containing the thermally decomposable polymer obtained above as a thermally decomposable resin binder, the physical properties were examined in the same manner as in Example 1. The results are shown in Table 1.

Example 7
100 g of toluene was charged into a 300 mL reactor equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer, and the temperature of the contents of the reactor was adjusted to 70 ° C. Next, 0.2 g of methacrylic acid, 2.8 g of 2-hydroxyethyl methacrylate, 94 g of n-butyl methacrylate and 3 g of tetrahydrofurfuryl methacrylate are maintained in the reactor while maintaining the temperature of the reactor contents at 70 ° C. in a nitrogen atmosphere. As a polymerization initiator, a mixture of 0.3 g of tert-butylperoxy-2-ethylhexanoate was dropped into the reactor over 1 hour.

  When 2 hours have elapsed from the end of the dropping, the temperature is raised to the reflux temperature and maintained at that temperature for 3 hours to terminate the polymerization reaction and obtain a reaction solution containing the produced thermally decomposable polymer. .

  The content of the thermally decomposable polymer (nonvolatile content) in the reaction solution obtained above was 50.1% by mass, the weight average molecular weight was 125,000, the acid value was 1.3 mgKOH / g, and the hydroxyl value. Was 12.1 mg KOH / g, the amine value was 0 mg KOH / g, and the glass transition temperature was 21 ° C.

  Using the reaction solution containing the thermally decomposable polymer obtained above as a thermally decomposable resin binder, the physical properties were examined in the same manner as in Example 1. The results are shown in Table 1.

Example 8
100 g of toluene was charged into a 300 mL reactor equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer, and the temperature of the contents of the reactor was adjusted to 70 ° C. Next, 1 g of methacrylic acid, 2 g of 2-hydroxyethyl methacrylate, 2 g of n-butyl methacrylate, 95 g of tetrahydrofurfuryl methacrylate and a polymerization initiator are maintained in the reactor while maintaining the temperature of the contents of the reactor at 70 ° C. in a nitrogen atmosphere. As a mixture, 0.3 g of tert-butylperoxy-2-ethylhexanoate was dropped into the reactor over 1 hour.

  When 2 hours have elapsed from the end of the dropping, the temperature is raised to the reflux temperature and maintained at that temperature for 3 hours to terminate the polymerization reaction and obtain a reaction solution containing the produced thermally decomposable polymer. .

  The content of the thermally decomposable polymer (nonvolatile content) in the reaction solution obtained above was 50.0% by mass, the weight average molecular weight was 182000, the acid value was 6.5 mgKOH / g, and the hydroxyl value. Was 8.6 mgKOH / g, the amine value was 0 mgKOH / g, and the glass transition temperature was 52 ° C.

  Using the reaction solution containing the thermally decomposable polymer obtained above as a thermally decomposable resin binder, the physical properties were examined in the same manner as in Example 1. The results are shown in Table 1.

Example 9
100 g of toluene was charged into a 300 mL reactor equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer, and the temperature of the contents of the reactor was adjusted to 70 ° C. Next, 1 g of methacrylic acid, 2 g of 2-hydroxyethyl methacrylate, 4 g of n-butyl methacrylate, 93 g of tetrahydrofurfuryl methacrylate and a polymerization initiator are maintained in the reactor while maintaining the temperature of the contents of the reactor at 70 ° C. in a nitrogen atmosphere. As a mixture, 0.3 g of tert-butylperoxy-2-ethylhexanoate was dropped into the reactor over 1 hour.

  When 2 hours have elapsed from the end of the dropping, the temperature is raised to the reflux temperature and maintained at that temperature for 3 hours to terminate the polymerization reaction and obtain a reaction solution containing the produced thermally decomposable polymer. .

  The content of the thermally decomposable polymer (nonvolatile content) in the reaction solution obtained above was 50.0% by mass, the weight average molecular weight was 182000, the acid value was 6.5 mgKOH / g, and the hydroxyl value. Was 8.6 mg KOH / g, the amine value was 0 mg KOH / g, and the glass transition temperature was 42 ° C.

  Using the reaction solution containing the thermally decomposable polymer obtained above as a thermally decomposable resin binder, the physical properties were examined in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1
100 g of toluene was charged into a 300 mL reactor equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer, and the temperature of the contents of the reactor was adjusted to 70 ° C. Next, 0.2 g of methacrylic acid, 2.8 g of 2-hydroxyethyl methacrylate, 87 g of n-butyl methacrylate, and 10 g of 2-ethylhexyl acrylate while maintaining the temperature of the contents of the reactor at 70 ° C. in a nitrogen atmosphere in the reactor. As a polymerization initiator, a mixture of 0.3 g of tert-butylperoxy-2-ethylhexanoate was dropped into the reactor over 1 hour.

  When 2 hours have elapsed from the end of the dropping, the temperature is raised to the reflux temperature and maintained at that temperature for 3 hours to terminate the polymerization reaction and obtain a reaction solution containing the produced thermally decomposable polymer. .

  The content of the thermally decomposable polymer (nonvolatile content) in the reaction solution obtained above was 49.9% by mass, the weight average molecular weight was 143,000, the acid value was 1.3 mgKOH / g, and the hydroxyl value. Was 12.1 mg KOH / g, the amine value was 0 mg KOH / g, and the glass transition temperature was 9 ° C.

  Using the reaction solution containing the thermally decomposable polymer obtained above as a thermally decomposable resin binder, the physical properties were examined in the same manner as in Example 1. The results are shown in Table 1.

  From the results shown in Table 1, the heat-decomposable resin binder obtained in each example was compared with the heat-decomposable resin binder obtained in Comparative Example 1, and all of them were heat-decomposable, dispersion stability and It turns out that it is excellent in re-solubility. Moreover, it turns out that the heat-decomposable resin binder obtained in Examples 2, 3, 6 and 9 is excellent in heat decomposability, dispersion stability and re-dissolvability among the examples.

  Since the thermally decomposable resin binder of the present invention is generally excellent in thermal decomposability, dispersion stability and re-dissolvability, it can be suitably used for a green sheet, for example, a low-temperature fired glass ceramic substrate, It is expected to be used for photosensitive pastes, resin binders for photolytic catalyst ceramics, electrolyte sheets for fuel cells, and the like.

Claims (1)

  It contains 3-95% by mass of a ring structure-containing monomer and 0.1-5% by mass of a polar functional group-containing monomer, and the remainder is copolymerized with the ring structure-containing monomer and the polar functional group-containing monomer. A thermally decomposable resin binder comprising a thermally decomposable polymer obtained by polymerizing a monomer component which is a possible monomer.