JP2023127556A - Dispersant, filler dispersion, filler dispersion slurry composition, and filler dispersion molding - Google Patents

Abstract

To provide a dispersant that enables effective dispersion of a filler and is suitable for making a molding with excellent moldability, adhesion and mechanical characteristics, and to provide a filler dispersion, a filler dispersion slurry composition, and a filler dispersion molding, each including the dispersant.SOLUTION: A dispersant contains a compound having a constitutional unit (A), which is at least one selected from the group consisting of the following constitutional units (A-1), (A-1'), (A-2), (A-2') and the like.SELECTED DRAWING: None

Description

The present invention relates to a dispersant that can be used for dispersing fillers. The present invention also relates to a filler dispersion, a filler-dispersed slurry composition, and a filler-dispersed molded product using the dispersant.

Conventionally, dispersants have been used to disperse fillers such as inorganic particles. For example, in the manufacture of electronic components such as ceramic capacitors, compositions in which inorganic particles such as ceramic powder are dispersed in binder resin are used, and such compositions also contain a dispersant.
Ceramic capacitors are generally manufactured by the following method. First, additives such as plasticizers and dispersants are added to a solution of binder resin dissolved in an organic solvent, and then ceramic raw material powder is added and mixed uniformly using a ball mill etc. to form an inorganic particle dispersed slurry composition. obtain.
The obtained inorganic particle-dispersed slurry composition is cast onto the surface of a support such as a release-treated polyethylene terephthalate film or SUS plate using a doctor blade, reverse roll coater, etc. to remove volatile components such as organic solvents. After distillation, it is peeled off from the support to obtain a ceramic green sheet.
Next, a conductive paste that will become internal electrodes is coated on the obtained ceramic green sheets by screen printing or the like, and a plurality of sheets are stacked, heated and pressed to obtain a laminate. The obtained laminate is heated to perform a so-called degreasing process, which is a process of thermally decomposing and removing components such as a binder resin, and then fired to obtain a fired ceramic body having internal electrodes. Further, an external electrode is applied to the end face of the obtained ceramic fired body and fired, thereby completing a ceramic capacitor.

Regarding an inorganic particle dispersed slurry composition used for manufacturing a ceramic capacitor, for example, Patent Document 1 describes a composition in which ceramic powder such as calcium titanate, a solvent such as glycols, and a resin such as polyvinyl butyral (PVB) resin are used. A ceramic slurry containing the above-mentioned ceramic slurry is disclosed, and it is also stated that a dispersant such as a maleic acid-based dispersant may be added.
Further, as a conventional dispersant, for example, Patent Document 2 discloses a filler dispersant using a hydroxyl group-containing petroleum resin, and it is described that it has excellent compatibility with polyolefin resins.

JP2011-84433A Japanese Patent Application Publication No. 2003-268243

In recent years, with the miniaturization and higher performance of ceramic capacitors, the fillers used have also become smaller. The fine filler tends to aggregate in the paste, and when agglomeration occurs, voids tend to remain during the degreasing and firing processes, and the dispersibility of the filler decreases, resulting in poor electrical performance in the product when made into a ceramic capacitor. This may cause deterioration of characteristics. For this reason, there has been a need for a dispersant that can effectively suppress the aggregation of fillers in slurry.

In contrast, conventional dispersants had to be selected depending on the type of resin and filler used. For example, when a conventional dispersant is added to a polyvinyl butyral (PVB) resin or an acrylic resin, the dispersant lowers the adhesion and sometimes causes problems when molding a ceramic capacitor. In addition, conventional dispersants do not sufficiently improve dispersibility and may increase viscosity, resulting in insufficient moldability and mechanical properties.

An object of the present invention is to provide a dispersant that effectively disperses a filler and is suitable for producing a molded article having excellent moldability, adhesiveness, and mechanical properties. Another object of the present invention is to provide a filler dispersion, a filler-dispersed slurry composition, and a filler-dispersed molded product using the dispersant.

The present disclosure 1 provides structural units (A-1), structural units (A-1'), structural units (A-2), structural units (A-2'), and structural units (A- 3) Contains a compound having a structural unit (A) that is at least one type selected from the group consisting of a structural unit (A-3'), a structural unit (A-4), and a structural unit (A-4'). , is a dispersant.

In the formula, R ¹ , R ² , R ³ and R ⁵ are each a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a polar functional group, an aliphatic hydrocarbon group having a polar functional group, or a polar functional group. represents an aromatic hydrocarbon group having a group. R ⁴ each represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aliphatic hydrocarbon group having a polar functional group, or an aromatic hydrocarbon group having a polar functional group. R ⁶ and R ⁷ each represent a hydrogen atom or an aliphatic hydrocarbon group. n represents an integer of 2 or more and 4 or less, and n' represents an integer of 2 or more and 5 or less. m represents an integer of 1 or more and 4 or less, and m' represents an integer of 1 or more and 5 or less. l represents an integer of 2 or more and 4 or less, and l' represents an integer of 2 or more and 5 or less. k represents an integer of 1 or more and 4 or less, and k' represents an integer of 1 or more and 5 or less.
The present disclosure 2 further provides the dispersant of the present disclosure 1, which further has a structural unit (B) derived from at least one monomer (b) selected from the group consisting of terpene monomers, vinyl monomers, and conjugated diene monomers. It is.
Present disclosure 3 is the dispersant according to present disclosure 1 or 2, wherein the compound has a content of the structural unit (A) of 1 mol% or more and 60 mol% or less.
Present disclosure 4 is the dispersant according to any one of present disclosures 1 to 3, wherein the compound has a content of the structural unit (A) of 0.9% by weight or more and 60% by weight or less.
The present disclosure 5 is the dispersant according to any one of the present disclosures 1 to 4, wherein the compound has a weight average molecular weight of 400 or more and 10,000 or less.
The present disclosure 6 is the dispersant according to any one of the present disclosures 1 to 5, wherein n and n' are 2 in the structural unit (A-1) or the structural unit (A-1').
Present disclosure 7 is the dispersant according to any one of present disclosures 1 to 5, wherein n and n' are 3 in the structural unit (A-1) or the structural unit (A-1').
The present disclosure 8 is the dispersant of any of the present disclosures 1 to 7, wherein the compound is an at least partially hydrogenated hydrogenated product.
The present disclosure 9 is a filler dispersion containing the dispersant according to any one of the present disclosures 1 to 8 and a filler.
The present disclosure 10 is the filler dispersion of the present disclosure 9, which further contains a solvent.
Present disclosure 11 is the filler dispersion according to present disclosure 9 or 10, which further contains a resin component.
The present disclosure 12 is the filler dispersion of the present disclosure 11, wherein the resin component includes a (meth)acrylic resin.
Present disclosure 13 is the filler dispersion of present disclosure 12, wherein the (meth)acrylic resin has a structural unit derived from a monomer having a hydroxyl group.
Present disclosure 14 is a filler-dispersed slurry composition consisting of the filler dispersion according to any of present disclosures 9-13.
The present disclosure 15 is a filler-dispersed molded product that is a cured product of the filler-dispersed slurry composition of the present disclosure 14.
The present invention will be explained in detail below.

As a result of studies conducted in order to solve the above problems, the present inventors found that a compound having the structural unit (A) causes chelate coordination between a polyvalent functional group such as phenol and a metal atom. It has been found that it has excellent dispersibility in fillers such as ceramics, and can improve adhesive strength as a binder by exhibiting the effect as a tackifying resin. Therefore, it has been discovered that by blending a compound having the structural unit (A), it is possible to effectively disperse fine fillers and produce a molded article with excellent moldability, adhesiveness, and mechanical properties. , we have completed the present invention.

The dispersant of the present invention comprises a structural unit (A-1), a structural unit (A-1'), a structural unit (A-2), a structural unit (A-2'), a structural unit ( A-3), a compound having a structural unit (A) that is at least one type selected from the group consisting of a structural unit (A-3'), a structural unit (A-4), and a structural unit (A-4'). contains. In particular, the above structural unit (A) is at least one selected from the group consisting of the above structural units (A-1) to (A-3) and the above structural units (A-1') to (A-3'). It is preferably a species, and more preferably at least one selected from the group consisting of the above structural unit (A-1) and the above structural unit (A-1').

In the formula, R ¹ , R ² , R ³ and R ⁵ are each a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a polar functional group, an aliphatic hydrocarbon group having a polar functional group, or a polar functional group. represents an aromatic hydrocarbon group having a group. R ⁴ each represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aliphatic hydrocarbon group having a polar functional group, or an aromatic hydrocarbon group having a polar functional group. R ⁶ and R ⁷ each represent a hydrogen atom or an aliphatic hydrocarbon group. n represents an integer of 2 or more and 4 or less, and n' represents an integer of 2 or more and 5 or less. m represents an integer of 1 or more and 4 or less, and m' represents an integer of 1 or more and 5 or less. l represents an integer of 2 or more and 4 or less, and l' represents an integer of 2 or more and 5 or less. k represents an integer of 1 or more and 4 or less, and k' represents an integer of 1 or more and 5 or less. Note that * represents a connecting part.

The above compound may have the above structural unit (A) in the side chain, in the main chain skeleton, or at the end of the main chain skeleton. Among these, the compound preferably has the structural unit (A) in the main chain skeleton or at the end of the main chain skeleton, since it can have physical properties suitable as a dispersant.

In the structural unit (A-1) and the structural unit (A-1'), R ¹ is a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a polar functional group, or an aliphatic group having a polar functional group, respectively. Represents a hydrocarbon group or an aromatic hydrocarbon group having a polar functional group.
The aliphatic hydrocarbon group is not particularly limited, and examples thereof include linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms. The aromatic hydrocarbon group is not particularly limited, and examples thereof include substituted or unsubstituted aryl groups having 1 to 20 carbon atoms.
The polar functional group is not particularly limited, and examples thereof include an amino group, a carboxyl group, a carbonyl group, an alkoxy group, a hydroxyl group, a nitrile group, and a nitro group.
The aliphatic hydrocarbon group having a polar functional group is not particularly limited, and for example, a group in which one or more hydrogens in the aliphatic hydrocarbon group as described above is substituted with a polar functional group as described above may be used. can. The aromatic hydrocarbon group having the polar functional group is not particularly limited, and for example, a group in which one or more hydrogens in the aromatic hydrocarbon group as described above is substituted with a polar functional group as described above may be used. can.
In the above compound, the plurality of R ¹ 's contained in one structural unit (A-1) may be the same or different. Furthermore, the plurality of R ^1s contained in different structural units (A-1) may be the same or different. Similarly, a plurality of R ¹ 's contained in one structural unit (A-1') may be the same or different. Further, a plurality of R ¹ 's contained in different structural units (A-1') may be the same or different.

In the structural unit (A-1) and the structural unit (A-1'), n is an integer of 2 or more and 4 or less, and n' is not particularly limited as long as it is an integer of 2 or more and 5 or less, From the viewpoint of easy availability of raw materials, it is preferable that n and n' are 2 or 3.

More specifically, the structural unit (A-1) and the structural unit (A-1') include, for example, a structural unit derived from dihydroxybenzene or a derivative thereof (when n and n' are 2), trihydroxy Examples include structural units derived from benzene or derivatives thereof (when n and n' are 3). These structural units may be used alone, or two or more types may be used in combination.
The above-mentioned dihydroxybenzene or its derivatives are not particularly limited, and examples thereof include resorcinol, pyrocatechol, hydroquinone, dihydroxytoluene, dihydroxyxylene, dihydroxyphenylethylamine hydrochloride, dihydroxybenzoic acid, dihydroxyphenylacetic acid, dihydroxyhydrocinnamic acid, and dihydroxyphenylpropionic acid. , dihydroxyphenylalanine, dihydroxybenzaldehyde, dihydroxyacetophenone, diacetyldihydroxybenzene, dihydroxyphenyl-2-butanone, methyl dihydroxyphenylacetate, benzyl dihydroxyphenyl ketone, dihydroxybenzamide, dihydroxymethoxybenzene, dihydroxybenzyl alcohol, dihydroxyphenylethanol, dihydroxyphenyl glycol, Examples include dihydroxyphenylacetonitrile, dihydroxynitrobenzene, and the like. These dihydroxybenzenes or derivatives thereof may be used alone or in combination of two or more. Among these, pyrocatechol is preferred because it has little steric hindrance and easily interacts with fillers.
The above trihydroxybenzene or its derivatives are not particularly limited, and examples include pyrogallol, 1,2,4-trihydroxybenzene, phloroglucinol, trihydroxytoluene, trihydroxydiphenylmethane, 6-hydroxy-L-dopa, gallic acid, Methyl gallate, butyl gallate, isobutyl gallate, isoamyl gallate, hexadecyl gallate, stearyl gallate, trihydroxyacetophenone, trihydroxyphenylethanone, trihydroxyphenylbutanone, trihydroxybenzaldehyde, trihydroxybenzamide, trihydroxynitrobenzene etc. These trihydroxybenzenes or derivatives thereof may be used alone or in combination of two or more. Among these, pyrogallol is preferred because it has little steric hindrance and easily interacts with fillers.

In the structural unit (A-2) and the structural unit (A-2'), R ² is a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a polar functional group, or an aliphatic group having a polar functional group, respectively. Represents a hydrocarbon group or an aromatic hydrocarbon group having a polar functional group.
The aliphatic hydrocarbon group is not particularly limited, and examples thereof include linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms. The aromatic hydrocarbon group is not particularly limited, and examples thereof include substituted or unsubstituted aryl groups having 1 to 20 carbon atoms.
The above polar functional group is not particularly limited, and examples thereof include an amino group, a carbonyl group, an alkoxy group, a hydroxyl group, a nitrile group, a nitro group, and the like.
The aliphatic hydrocarbon group having a polar functional group is not particularly limited, and for example, a group in which one or more hydrogens in the aliphatic hydrocarbon group as described above is substituted with a polar functional group as described above may be used. can. The aromatic hydrocarbon group having the polar functional group is not particularly limited, and for example, a group in which one or more hydrogens in the aromatic hydrocarbon group as described above is substituted with a polar functional group as described above may be used. can.
In the above compound, the plurality of R ² 's contained in one structural unit (A-2) may be the same or different. Further, the plurality of R ² contained in different structural units (A-2) may be the same or different. Similarly, a plurality of R ² 's contained in one structural unit (A-2') may be the same or different. Furthermore, the plurality of R ² contained in different structural units (A-2') may be the same or different.

In the structural unit (A-2) and the structural unit (A-2'), m is an integer of 1 or more and 4 or less, and m' is not particularly limited as long as it is an integer of 1 or more and 5 or less, From the viewpoint of easy availability of raw materials, m and m' are preferably 1 or 2.

More specifically, the structural unit (A-2) and the structural unit (A-2') include benzoic acid, salicylic acid, dihydroxybenzoic acid, gallic acid, 2-methylbenzoic acid, and 3-methylbenzoic acid. , 4-methylbenzoic acid, 2-ethylbenzoic acid, 3-ethylbenzoic acid, 4-ethylbenzoic acid, 4-tert-butylbenzoic acid, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid , 4,4'-stilbenedicarboxylic acid, and derivatives thereof. These structural units may be used alone, or two or more types may be used in combination. Among these, 4-vinylbenzoic acid is preferred because it has little steric hindrance and easily interacts with fillers.

In the structural unit (A-3) and the structural unit (A-3'), R ³ is a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a polar functional group, or an aliphatic group having a polar functional group, respectively. Represents a hydrocarbon group or an aromatic hydrocarbon group having a polar functional group.
The aliphatic hydrocarbon group is not particularly limited, and examples thereof include linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms. The aromatic hydrocarbon group is not particularly limited, and examples thereof include substituted or unsubstituted aryl groups having 1 to 20 carbon atoms.
The above polar functional group is not particularly limited, and examples thereof include an amino group, a carboxyl group, a carbonyl group, a hydroxyl group, a nitrile group, a nitro group, and the like.
The aliphatic hydrocarbon group having a polar functional group is not particularly limited, and for example, a group in which one or more hydrogens in the aliphatic hydrocarbon group as described above is substituted with a polar functional group as described above may be used. can. The aromatic hydrocarbon group having the polar functional group is not particularly limited, and for example, a group in which one or more hydrogens in the aromatic hydrocarbon group as described above is substituted with a polar functional group as described above may be used. can.
In the above compound, the plurality of R ³ 's contained in one structural unit (A-3) may be the same or different. Furthermore, the plurality of R ³ 's contained in different structural units (A-3) may be the same or different. Similarly, a plurality of R ³ 's contained in one structural unit (A-3') may be the same or different. Furthermore, the plurality of R ³ 's contained in different structural units (A-3') may be the same or different.

In the above structural unit (A-3) and the above structural unit (A-3'), R ⁴ is an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aliphatic hydrocarbon group having a polar functional group, or a polar Represents an aromatic hydrocarbon group having a functional group.
The aliphatic hydrocarbon group is not particularly limited, and examples thereof include linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms. The aromatic hydrocarbon group is not particularly limited, and examples thereof include substituted or unsubstituted aryl groups having 1 to 20 carbon atoms. In the above compound, the plurality of R ^4s contained in one structural unit (A-3) may be the same or different. Furthermore, the plurality of R ^4s contained in different structural units (A-3) may be the same or different. Similarly, a plurality of R ⁴ 's contained in one structural unit (A-3') may be the same or different. Furthermore, the plurality of R ^4s contained in different structural units (A-3') may be the same or different.

In the structural unit (A-3) and the structural unit (A-3'), l is an integer of 2 or more and 4 or less, and l' is not particularly limited as long as it is an integer of 2 or more and 5 or less, From the viewpoint of easy availability of raw materials, l and l' are preferably 2 or 3.

More specifically, the structural unit (A-3) and the structural unit (A-3') include, for example, a structural unit derived from dialkoxybenzene or a derivative thereof (when l and l' are 2), Examples include structural units derived from alkoxybenzene or derivatives thereof (when 1 and 1' are 3). The dialkoxybenzene or its derivative is not particularly limited, and examples thereof include 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, 1,4-dimethoxybenzene, and the like. The trialkoxybenzene or its derivative is not particularly limited, and examples thereof include 1,2,3-trimethoxybenzene, 1,2,4-trimethoxybenzene, 1,3,5-trimethoxybenzene, and the like. These trialkoxybenzenes or derivatives thereof may be used alone or in combination of two or more. Among these, 1,2,3-trimethoxybenzene is preferred because it has little steric hindrance and easily interacts with fillers.

In the structural unit (A-4) and the structural unit (A-4'), R ⁵ is a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a polar functional group, or an aliphatic group having a polar functional group, respectively. Represents a hydrocarbon group or an aromatic hydrocarbon group having a polar functional group.
The aliphatic hydrocarbon group is not particularly limited, and examples thereof include linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms. The aromatic hydrocarbon group is not particularly limited, and examples thereof include substituted or unsubstituted aryl groups having 1 to 20 carbon atoms.
The above polar functional group is not particularly limited, and examples thereof include carboxyl group, carbonyl group, alkoxy group, hydroxyl group, nitrile group, and nitro group.
The aliphatic hydrocarbon group having a polar functional group is not particularly limited, and for example, a group in which one or more hydrogens in the aliphatic hydrocarbon group as described above is substituted with a polar functional group as described above may be used. can. The aromatic hydrocarbon group having the polar functional group is not particularly limited, and for example, a group in which one or more hydrogens in the aromatic hydrocarbon group as described above is substituted with a polar functional group as described above may be used. can.
In the above compound, the plurality of R ⁵ 's contained in one structural unit (A-4) may be the same or different. Furthermore, the plurality of R ^5s contained in different structural units (A-4) may be the same or different. Similarly, a plurality of R ⁵ 's contained in one structural unit (A-4') may be the same or different. Furthermore, the plurality of R ⁵ 's contained in different structural units (A-4') may be the same or different.

In the structural unit (A-4) and the structural unit (A-4'), R ⁶ and R ⁷ each represent a hydrogen atom or an aliphatic hydrocarbon group.
The aliphatic hydrocarbon group is not particularly limited, and examples thereof include linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms. In the above compound, the plurality of R ⁶ and R ⁷ contained in one structural unit (A-4) may be the same or different. Furthermore, the plurality of R ⁶ and R ⁷ contained in different structural units (A-4) may be the same or different. Similarly, a plurality of R ⁶ and R ⁷ contained in one structural unit (A-4') may be the same or different. Furthermore, the plurality of R ⁶ and R ⁷ contained in different structural units (A-4') may be the same or different.

In the structural unit (A-4) and the structural unit (A-4'), k is an integer of 1 or more and 4 or less, and k' is not particularly limited as long as it is an integer of 1 or more and 5 or less, From the viewpoint of easy availability of raw materials, it is preferable that k and k' are 1, 2 or 3.

More specifically, the structural unit (A-4) and the structural unit (A-4') include, for example, a structural unit derived from aminobenzene or a derivative thereof (when k is 1). The above aminobenzene or its derivative is not particularly limited, and examples thereof include aniline, methylaniline, ethylaniline, dimethylaniline, diethylaniline, and the like. These aminobenzenes or derivatives thereof may be used alone or in combination of two or more.

The structural unit (A) may be composed only of a petroleum-derived material, but preferably contains a biologically-derived material. The depletion of petroleum resources and the emission of carbon dioxide from the combustion of petroleum-derived products are viewed as problems. Therefore, attempts are being made to save petroleum resources by using biological materials instead of petroleum-derived materials. It is preferable that the structural unit (A) contains a biological material from the viewpoint of saving petroleum resources. In addition, if the above structural unit (A) contains a biological material, the biological material is originally produced by taking in carbon dioxide from the atmosphere, so even if it is burned, the total amount of carbon dioxide in the atmosphere will be This is preferable from the perspective of reducing carbon dioxide emissions.
Examples of monomers constituting the structural unit (A) containing biological materials include resorcinol, dihydroxyphenylethylamine hydrochloride, dihydroxyhydrocinnamic acid, dihydroxyphenylalanine, dihydroxybenzaldehyde, dihydroxybenzyl alcohol, pyrogallol, 1,2,4 - Trihydroxybenzene, phloroglucinol, 6-hydroxy-L-dopa, gallic acid, methyl gallate, butyl gallate, isobutyl gallate, isoamyl gallate, hexadecyl gallate, stearyl gallate, trihydroxyacetophenone, trihydroxy Examples include benzaldehyde, trihydroxybenzamide, trihydroxynitrobenzene, and the like.

The content (on a molar basis) of the structural unit (A) in the compound is not particularly limited, but the preferable lower limit is 1 mol%, and the preferable upper limit is 60 mol%. When the content of the structural unit (A) is 1 mol % or more, the dispersibility with respect to the filler can be further improved by blending the compound with the dispersant. When the content of the structural unit (A) is 60 mol% or less, the compound can have suitable physical properties required when used as a dispersant. A more preferable lower limit of the content of the structural unit (A) is 5 mol%, a more preferable upper limit is 50 mol%, an even more preferable lower limit is 10 mol%, and an even more preferable upper limit is 30 mol%.

The content (by weight) of the structural unit (A) in the compound is not particularly limited, but the preferred lower limit is 0.9% by weight, and the preferred upper limit is 60% by weight. When the content of the structural unit (A) is 0.9% by weight or more, the dispersibility with respect to the filler can be further improved by blending the compound with the dispersant. When the content of the structural unit (A) is 60% by weight or less, the compound can have suitable physical properties required when used as a dispersant. A more preferable lower limit of the content of the structural unit (A) is 5% by weight, a more preferable upper limit is 50% by weight, an even more preferable lower limit is 10% by weight, and an even more preferable upper limit is 30% by weight.

It is preferable that the above compound further has a structural unit (B) derived from at least one monomer (b) selected from the group consisting of terpene monomers, vinyl monomers, and conjugated diene monomers. That is, in addition to the structural unit (A), the compound further contains a structural unit derived from at least one monomer (b) selected from the group consisting of terpene monomers, vinyl monomers, and conjugated diene monomers. It is preferable to have B). By having the above structural unit (B), the compound can improve compatibility with the resin component while ensuring suitable physical properties required when used as a dispersant.
Among these, structural units derived from terpene monomers or structural units derived from vinyl monomers are preferable because they can further enhance the adhesiveness when the compound is blended into the resin component. It is also preferable to use the unit and a structural unit derived from a vinyl monomer in combination. Moreover, from the viewpoint of improving the compatibility between the compound and the resin component, a structural unit derived from a terpene monomer or a structural unit derived from a conjugated diene monomer is preferable. These structural units have aliphatic hydrocarbon groups with unsaturated double bonds, so when a compound has these structural units, the compatibility between the compound and the resin component improves, and It is possible to suppress deterioration of moldability and adhesiveness when producing a molded product.

The above-mentioned terpene monomer is not particularly limited, and examples thereof include α-pinene, β-pinene, limonene, dipentene, δ-3-carene, dimethyloctatriene, alloocimene, myrcene, ocimene, linalool, and cosmene. Among these, α-pinene, β-pinene, or limonene are preferred because they can further enhance the adhesiveness when the compound is blended with the resin component.
The above-mentioned vinyl monomer is not particularly limited, but from the viewpoint of improving the compatibility between the compound and the resin component, especially the compatibility between the compound and the (meth)acrylic resin, the vinyl monomer has a structure containing two or more aromatic rings in one molecule (e.g. , naphthalene structure, anthracene structure, biphenyl structure, anthraquinone structure, benzophenone structure, etc.) is preferable. Examples of vinyl monomers that do not have a structure containing two or more aromatic rings in one molecule include ethylene, propylene, butylene, hexene, vinyl acetate, vinyl chloride, styrene, α-methylstyrene, coumaron, indene, and vinyltoluene. , divinylbenzene, divinyltoluene, 2-phenyl-2-butene and the like. Among these, styrene is preferred because it can further improve the adhesiveness when the compound is blended into the resin component.
The conjugated diene monomer is not particularly limited, and examples thereof include butadiene, isoprene, piperylene, cyclopentadiene, and the like. Among these, isoprene is preferred because it can further enhance the adhesiveness when the compound is blended into the resin component.
These monomers (b) may be used alone or in combination of two or more.

The structural unit (B) may be composed only of a petroleum-derived material, but preferably contains a biologically-derived material. The depletion of petroleum resources and the emission of carbon dioxide from the combustion of petroleum-derived products are viewed as problems. Therefore, attempts are being made to save petroleum resources by using biological materials instead of petroleum-derived materials. It is preferable that the structural unit (B) contains a biological material from the viewpoint of saving petroleum resources. In addition, if the above structural unit (B) contains a biological material, the biological material is originally produced by taking in carbon dioxide from the atmosphere, so even if it is burned, the total amount of carbon dioxide in the atmosphere will be This is preferable from the perspective of reducing carbon dioxide emissions.
Examples of the monomer (b) constituting the structural unit (B) containing a biological material include terpene monomers, ethylene, propylene, hexene, butadiene, and isoprene.

The content of the structural unit (B) in the compound is not particularly limited, but the preferable lower limit is 40 mol%, and the preferable upper limit is 99 mol%. When the content of the structural unit (B) is 40 mol% or more, the compound improves compatibility with the resin component while ensuring suitable physical properties required when used as a dispersant. I can do it. If the content of the structural unit (B) is 99 mol% or less, a sufficient content of the structural unit (A) can be ensured, so the compound is not required when used as a dispersant. It can have suitable physical properties. A more preferable lower limit of the content of the structural unit (B) is 50 mol%, and a more preferable upper limit is 90 mol%.

The above compound is preferably a copolymer having a structure represented by the following formula. A copolymer having such a structure is a copolymer obtained by a method using cationic polymerization as described below, and while ensuring suitable physical properties required when used as a dispersant, it can be used as a resin. Compatibility with components can be improved.

In the formula, A represents a structural unit (A), B represents a structural unit (B), and s and t each represent an integer of 1 or more. Note that * represents a connecting part.

The above compound is preferably a compound having the above structural unit (A) and the above structural unit (B), and more preferably a copolymer having the above structural unit (A) and the above structural unit (B). , may further include other structural units. In the case of a copolymer, the structural unit (A) and the structural unit (B) may be randomly copolymerized, or, for example, each may form a block segment and then the block segments are bonded to each other. The copolymerization may be carried out with regularity or periodicity as in the case of the present invention.

The above compound preferably has an aliphatic hydrocarbon group having an unsaturated double bond.
The above compound may have an aliphatic hydrocarbon group having the unsaturated double bond in the above structural unit (A) or the above structural unit (B), or may have it in another structural unit. It's okay. In particular, from the viewpoint of ease of synthesis and from the viewpoint of improving the compatibility between the compound and the resin component, the aliphatic hydrocarbon group having the unsaturated double bond is replaced with the structural unit (B) or other components. It is preferable to have it in the structural unit. The structural unit (B) having an aliphatic hydrocarbon group having an unsaturated double bond or other structural units is not particularly limited, but at least one selected from the group consisting of terpene monomers and conjugated diene monomers. A structural unit (B) derived from one type of monomer (b) is preferred. That is, in the above compound, the aliphatic hydrocarbon group having the unsaturated double bond is combined with a structural unit (B) derived from at least one monomer (b) selected from the group consisting of terpene monomers and conjugated diene monomers. ) is preferable. Among these, it is preferable to have the compound in a structural unit derived from a terpene monomer because it can further enhance the adhesiveness when the compound is blended into a resin component.

Examples of the other structural units include, for example, structural units derived from other phenolic monomers not included in the structural unit (A), structural units derived from maleic anhydride, and the like.
The other phenolic monomers mentioned above are not particularly limited, and include, for example, phenol, cresol, xylenol, propylphenol, norylphenol, methoxyphenol, bromophenol, bisphenol A, bisphenol F, bisphenol S, dihydroxynaphthalene, and the like. These other phenolic monomers may be used alone or in combination of two or more.

The molecular weight of the above compound is not particularly limited, but the preferable lower limit of the weight average molecular weight (Mw) is 400, and the preferable upper limit is 10,000. When the weight average molecular weight (Mw) is within the above range, the compound can have suitable physical properties required when used as a dispersant. A more preferable lower limit of the weight average molecular weight (Mw) is 500, a more preferable upper limit is 5,000, an even more preferable lower limit is 700, and an even more preferable upper limit is 3,000.
In order to adjust the weight average molecular weight (Mw) to the above range, for example, the composition of the compound, the polymerization method, the polymerization conditions, etc. may be adjusted.

Note that the weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) as described below can be measured by the following method.
The compound solution is filtered through a filter (material: polytetrafluoroethylene, pore diameter: 0.2 μm). The obtained filtrate is supplied to a gel permeation chromatograph (for example, 2690 Separations Model manufactured by Waters), and GPC measurement is performed at a sample flow rate of 1 ml/min and a column temperature of 40°C to determine the polystyrene equivalent molecular weight of the compound. The weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) are determined by measurement. For example, GPC KF-802.5L (manufactured by Showa Denko) is used as the column, and a differential refractometer is used as the detector.

Although the content of biologically derived carbon (carbon atoms) in the carbon (carbon atoms) in the above compound is not particularly limited, it is preferable that the content of biologically derived carbon in the carbon is 10% or more. A ``bio-based product'' is defined as having a biologically derived carbon content of 10% or more.
It is preferable that the content of biologically derived carbon is 10% or more from the viewpoint of saving petroleum resources and reducing carbon dioxide emissions. The lower limit of the biologically derived carbon content is more preferably 30%, still more preferably 60%, even more preferably 70%, and still more preferably 90%. The upper limit of the content of the biologically derived carbon is not particularly limited, and may be 100%.
Note that carbon derived from living organisms contains a certain proportion of radioactive isotope (C-14), whereas carbon derived from petroleum contains almost no C-14. Therefore, the content of biologically derived carbon can be calculated by measuring the concentration of C-14 contained in the compound. Specifically, it can be measured according to ASTM D6866-20, a standard used in many bioplastic industries.

The above-mentioned compounds also include hydrogenated products (hydrogenated products) of the above-mentioned compounds. That is, the above-mentioned compound may be an at least partially hydrogenated hydrogenated product. Note that the hydrogenated product is a compound in which the carbon-carbon double bond present in the above-mentioned compound is at least partially saturated by hydrogenation. That is, the above-mentioned compound may be a hydrogenated product in which a part of the carbon-carbon double bonds in the above-mentioned compound is hydrogenated; The hydrogenated product may be entirely hydrogenated. Even with such a hydrogenated body, fine fillers can be effectively dispersed. Among these, it is preferable that the carbon-carbon double bond in the structural unit derived from the terpene monomer as the structural unit (B) is at least partially hydrogenated.

The method for producing the above compound is not particularly limited, but when the structural unit (A) is present in the main chain skeleton or at the end of the main chain skeleton, the following method is preferred, for example. That is, at least one monomer selected from the group consisting of the monomer (a) constituting the structural unit (A) and the terpene monomer, vinyl monomer, and conjugated diene monomer constituting the structural unit (B) ( b) (hereinafter also referred to as production method [I]).

The monomer (a) is at least one selected from the group consisting of monomer (a-1), monomer (a-2), monomer (a-3), and monomer (a-4) represented by the following formula: can be mentioned.

In the formula, R ¹ , R ² , R ³ and R ⁵ are each a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a polar functional group, an aliphatic hydrocarbon group having a polar functional group, or a polar functional group. represents an aromatic hydrocarbon group having a group. R ⁴ each represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aliphatic hydrocarbon group having a polar functional group, or an aromatic hydrocarbon group having a polar functional group. R ⁶ and R ⁷ each represent a hydrogen atom or an aliphatic hydrocarbon group. n'' represents an integer of 2 or more and 5 or less. m'' represents an integer of 1 or more and 5 or less. l'' represents an integer of 2 or more and 5 or less. k'' represents an integer greater than or equal to 1 and less than or equal to 5.

In the method for producing the compound [I], the monomer (a) and the monomer (b) are preferably copolymerized by cationic polymerization.
By using cationic polymerization, the above monomer (a) and the above monomer (b) can be combined without previously protecting functional groups such as phenolic hydroxyl groups, carboxy groups, alkoxy groups, and amino groups of the above monomer (a) through chemical modification. can be copolymerized, and subsequent deprotection is not necessary. Therefore, the above monomer (a) and the above monomer (b) can be copolymerized through a simpler one-step reaction process, which also leads to a reduction in impurities and an improvement in the yield.

As a method for copolymerizing the above monomer (a) and the above monomer (b) by cationic polymerization, a method in which the above monomer (a) and the above monomer (b) are reacted in the presence of a Lewis acid is preferred. According to such a method, cations of the monomer (b) are generated, cationic polymerization of the monomers (b) proceeds, and Fridel-Crafts alkyl of the monomer (a) and the monomer (b) is formed. It is thought that the chemical reaction proceeds. By repeating such a reaction, a copolymer having a structural unit (A) derived from the monomer (a) and a structural unit (B) derived from the monomer (b) can be obtained.
The above Lewis acid is not particularly limited, and conventionally known Lewis acids can be used, such as aluminum chloride (AlCl ₃ ), diethylaluminum chloride (Et ₂ AlCl ₂ ), tin (IV) chloride (SnCl ₄ ), chloride Examples include titanium (IV) (TiCl ₄ ), boron trichloride (BCl ₃ ), boron trifluoride ether complex (BF ₃ ·EtO), and the like. Among them, aluminum chloride (AlCl ₃ ) is preferred because it provides a higher yield.

More specifically, for example, when pyrogallol is used as the monomer (a) and α-pinene is used as the monomer (b), and these are reacted in the presence of aluminum chloride (AlCl ₃ ), which is a Lewis acid, the following reaction occurs. It is thought that the reaction shown in the scheme proceeds.
That is, cations of α-pinene, which is the monomer (b), are generated, and cationic polymerization between α-pinenes proceeds (upper part of the scheme below), and pyrogallol, which is the monomer (a), and the monomer (b) A Fridel-Crafts alkylation reaction with α-pinene proceeds (middle stage of the scheme below). By repeating such a reaction, a copolymer having a structural unit derived from pyrogallol and a structural unit derived from α-pinene can be obtained (lower part of the scheme below). Note that such a copolymer has a structural unit derived from pyrogallol in the main chain skeleton or at the end of the main chain skeleton.

In the formula, s and t each represent an integer of 1 or more. Note that * represents a connecting part.

As a method for producing the above-mentioned compound, when the above-mentioned structural unit (A) is present in the side chain, the following method is preferable, for example. That is, a monomer (a') in which an unsaturated double bond is further introduced into the monomer (a) constituting the above structural unit (A), a terpene monomer, a vinyl monomer, and a conjugated monomer constituting the above structural unit (B). This is a method (hereinafter also referred to as production method [II]) of copolymerizing at least one monomer (b) selected from the group consisting of diene monomers.

Examples of the monomer (a') include 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 4,4'-stilbenedicarboxylic acid, and 4-vinylcatechol. These monomers (a') may be used alone or in combination of two or more. Among these, 4-vinylbenzoic acid is preferred because it has little steric hindrance and easily interacts with fillers.

In the method for producing the compound [II] as well, it is preferable to copolymerize the monomer (a') and the monomer (b) by cationic polymerization similarly to the method for producing the compound [I].
As a method for copolymerizing the monomer (a') and the monomer (b) by cationic polymerization, the monomer (a') and the monomer (b) are reacted in the presence of a Lewis acid as described above. The method is preferred. According to such a method, cationic polymerization between the unsaturated double bond in the monomer (a') and the unsaturated double bond in the monomer (b) proceeds, and the monomer (a') undergoes cationic polymerization. A copolymer having a structural unit (A) derived from the monomer (A) and a structural unit (B) derived from the monomer (b) can be obtained.

The dispersant is not particularly limited as long as it contains the above compound, but may contain conventionally known additives.

The above-mentioned dispersants can be used for dispersing various types of fillers. A filler dispersion containing the above-mentioned dispersant and filler is also one of the aspects of the present invention.

The filler is not particularly limited and includes pigments, fillers, fibers, wood flour, asbestos, paper, and the like. Pigments include organic pigments and inorganic pigments, and various known pigments conventionally used for coloring can be used. Such pigments include organic pigments such as azo, anthraquinone, phthalocyanine, quinacridone, isoindolinone, dioxane, berylene, quinophthalone, and berinone; cadmium sulfide, cadmium selenide, ultramarine, and dioxide. Examples include inorganic pigments such as titanium, iron oxide, chromate oxide, Bengara, and carbon black. Examples of the filler include silica, mica, talc, stone powder, clay, graphite, calcium carbonate, alumina, aluminum hydroxide, aluminum powder, ferrite, molybdenum disulfide, and the like. Examples of the fiber include carbon, alumina, aramid, calcium titanate whisker, glass, and metal. One or more of these fillers can be appropriately selected and used depending on the purpose.

The content of the dispersant in the filler dispersion is not particularly limited, but a preferable lower limit is 1 part by weight and a preferable upper limit is 100 parts by weight based on 100 parts by weight of the filler. When the content of the dispersant is 1 part by weight or more, the filler can be effectively dispersed. When the content of the dispersant is 100 parts by weight or less, it is possible to prevent the mechanical properties of the obtained molded article from deteriorating. A more preferable lower limit of the content of the dispersant is 5 parts by weight, a more preferable upper limit is 50 parts by weight, an even more preferable lower limit is 10 parts by weight, and an even more preferable upper limit is 30 parts by weight.

The filler dispersion of the present invention is not limited as long as it contains a dispersant and a filler, and may also contain a solvent and a resin component, for example, a dispersant, a filler, a solvent. Of the four components of the and resin components, it may contain only the dispersant, filler, and resin component, or it may contain only the dispersant, filler, and solvent, or it may contain only the dispersant, filler, and solvent. , a filler, a solvent, and a resin component. By containing a solvent, the handling properties such as the coating properties of the filler dispersion can be improved. Moreover, by containing a resin component, the filler dispersion can be applied to various uses.

The above solvent is not particularly limited, and water and organic solvents can be used. Examples of the organic solvent include alcohols such as aliphatic alcohols, cyclic alcohols, and alicyclic alcohols.
Examples of the aliphatic alcohol include ethanol, propanol, isopropanol, heptanol, octanol, decanol, tridecanol, lauryl alcohol, tetradecyl alcohol, cetyl alcohol, 2-ethyl-1-hexanol, octadecyl alcohol, hexadecenol, oleyl alcohol, and texanol. , 2-butyl-2-ethyl-1,3-propanediol, neopentyl glycol, and the like.
Examples of the cyclic alcohol include cresol, eugenol, and the like.
Examples of the alicyclic alcohol include cycloalkanols such as cyclohexanol, and terpene alcohols such as terpineol and dihydroterpineol.
Among these, ethanol, isopropanol, 2-butyl-2-ethyl-1,3-propanediol, neopentyl glycol, and texanol are preferred.
Examples of other organic solvents include ketones such as acetone, methyl ethyl ketone, dipropyl ketone, and diisobutyl ketone, aromatic hydrocarbons such as toluene and xylene, methyl propionate, ethyl propionate, butyl propionate, and butane. Methyl acid, ethyl butanoate, butyl butanoate, methyl pentanoate, ethyl pentanoate, butyl pentanoate, methyl hexanoate, ethyl hexanoate, butyl hexanoate, ethyl acetate, butyl acetate, hexyl acetate, 2-ethylhexyl acetate, butyric acid Examples include esters such as 2-ethylhexyl.

The content of the solvent in the filler dispersion is preferably 20% by weight or more, more preferably 30% by weight or more, preferably 70% by weight or less, and 60% by weight or less. It is more preferable.

The boiling point of the above solvent is preferably 70 to 160°C. When the boiling point is 70° C. or higher, evaporation does not occur too quickly and the product is easy to handle. By setting the boiling point to 160°C or less, it is possible to improve the strength of the molded product obtained.

The resin constituting the resin component is not particularly limited, and examples include (meth)acrylic resin, polyolefin, polymethylpentene, polystyrene, alkyd resin, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, acrylonitrile-butadiene-styrene ( ABS) resin, vinyl resin, acrylonitrile-EPDM-styrene (AES) resin, polyamide, polyimide, polycarbonate, polyacetal, polyurethane, phenol resin, amino resin, polyether resin, polyphenylene oxide, polyarylate, polysulfone, epoxy resin, etc. It will be done. Among these, (meth)acrylic resins are preferred because of their excellent thermal decomposition properties, and (meth)acrylic resins having structural units derived from monomers having hydroxyl groups are preferred because they have excellent filler dispersibility and agglomeration inhibiting effects. More preferred.

The (meth)acrylic resin preferably contains a high molecular weight (meth)acrylic resin.
In this specification, the high molecular weight (meth)acrylic resin has a weight average molecular weight of 120,000 to 300,000.
By setting it as the said range, when it forms a filler dispersion slurry composition, the dispersibility of a filler can be improved enough. Furthermore, aggregation of the filler can be suppressed.
The weight average molecular weight is preferably 150,000 or more, more preferably 180,000 or more, preferably 250,000 or less, and more preferably 220,000 or less.
By setting it as the said range, when it forms a filler dispersion slurry composition, it will have sufficient viscosity and printability can be improved.
Further, the ratio (Mw/Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the high molecular weight (meth)acrylic resin is preferably 2 or more, and preferably 8 or less.
By setting the content within the above range, since a component with a low degree of polymerization is appropriately contained, the viscosity of the filler-dispersed slurry composition falls within a suitable range, and productivity can be improved. Moreover, the sheet strength of the obtained filler-dispersed sheet can be made appropriate. Furthermore, the surface smoothness of the obtained molded body (ceramic green sheet) can be sufficiently improved.
The above Mw/Mn is more preferably 3 or more, and more preferably 6 or less.
Note that the weight average molecular weight (Mw) and number average molecular weight (Mn) are average molecular weights in terms of polystyrene, and can be obtained by performing GPC measurement using, for example, column LF-804 (manufactured by Showa Denko) as a column. can.

It is preferable that the weight concentration of OH groups contained in the high molecular weight (meth)acrylic resin is 0.4% by weight or more and 2.0% by weight or less.
By setting it as the said range, the binder resin can express extremely excellent decomposability even at low temperatures, and can further improve the dispersibility of the filler and the agglomeration suppressing effect.
The weight concentration of the OH group is preferably 0.5% by weight or more, more preferably 0.6% by weight or more, and preferably 1.6% by weight or less, and 1.4% by weight. It is more preferable that it is below.
The above weight concentration of OH groups means the ratio of the weight of OH groups to the weight of the entire high molecular weight (meth)acrylic resin, and can be calculated based on the following formula.
Weight concentration of OH groups contained in high molecular weight (meth)acrylic resin = [weight of OH groups contained in all monomers/(weight of all monomers + weight of polymerization initiator)] x 100

The high molecular weight (meth)acrylic resin preferably has a structural unit represented by the following formula (1), and preferably has a structural unit represented by the following formula (2).

In formula (1), R ¹ represents a linear or branched alkyl group having 1 to 8 carbon atoms, and in formula (2), R ² represents a carbon number in which at least one hydrogen atom is substituted with an OH group. Represents 2 to 4 linear or branched alkyl groups.
The above R ¹ is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, or isobutyl group. etc.
The above R ² is preferably a linear or branched alkyl group having 2 to 4 carbon atoms in which at least one hydrogen atom is substituted with an OH group, such as a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 2-hydroxypropyl group, or a 2-hydroxypropyl group. -Hydroxybutyl group and the like.

The content of the structural unit represented by the formula (1) in the high molecular weight (meth)acrylic resin is preferably 79% by weight or more, and preferably 96% by weight or less.
By setting it as the said range, low-temperature decomposability can fully be improved.
The content of the structural unit represented by the above formula (1) is more preferably 85% by weight or more, and more preferably 95% by weight or less.

The content of the structural unit represented by the formula (2) in the high molecular weight (meth)acrylic resin is preferably 3.1% by weight or more, and preferably 17% by weight or less.
Ethanol is often used as a solvent for binder resin, but acrylic resin generally has lower solubility in ethanol than polyvinyl acetal resin, and there is a problem that the filler will aggregate if acrylic resin is added after primary crushing. However, by setting it within the above range, it is possible to improve the dispersibility and aggregation suppressing effect of the filler.
Moreover, the solubility in ethanol can be further improved.
The content of the structural unit represented by the above formula (2) is more preferably 4% by weight or more, and more preferably 15% by weight or less.

The high molecular weight (meth)acrylic resin preferably has a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group having 3 to 4 carbon atoms.
By having the above-mentioned segments, it is possible to obtain more excellent low-temperature decomposition properties.
Examples of the (meth)acrylic ester having a linear or branched alkyl group having 3 to 4 carbon atoms include n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-(meth)acrylate. -butyl, isobutyl (meth)acrylate, etc. Among these, isobutyl (meth)acrylate is preferred.

The content of segments derived from a (meth)acrylic acid ester having a linear or branched alkyl group having 3 to 4 carbon atoms in the high molecular weight (meth)acrylic resin is preferably 30% by weight or more, It is more preferably 40% by weight or more, preferably 95% by weight or less, and even more preferably 88% by weight or less.

The high molecular weight (meth)acrylic resin may have a segment derived from a (meth)acrylic acid ester having an alkyl group having 1 to 2 carbon atoms.
Examples of the (meth)acrylic ester having an alkyl group having 1 to 2 carbon atoms include methyl (meth)acrylate and ethyl (meth)acrylate.

The content of segments derived from (meth)acrylic acid ester having an alkyl group having 1 to 2 carbon atoms in the high molecular weight (meth)acrylic resin is preferably 0% by weight or more, and preferably 10% by weight or more. More preferably, it is 66.8% by weight or less, and more preferably 46% by weight or less.

The high molecular weight (meth)acrylic resin may have a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group having 5 to 8 carbon atoms.
The above (meth)acrylic esters having a linear or branched alkyl group having 5 to 8 carbon atoms include n-pentyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, Examples include n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. Among these, (meth)acrylic acid esters having a linear or branched alkyl group having 6 to 8 carbon atoms are preferred, and 2-ethylhexyl (meth)acrylate is more preferred.

The content of segments derived from (meth)acrylic acid ester having a linear or branched alkyl group having 5 to 8 carbon atoms in the high molecular weight (meth)acrylic resin is preferably 0% by weight or more. , more preferably 9% by weight or more, preferably 25% by weight or less, and more preferably 20% by weight or less.

The high molecular weight (meth)acrylic resin may have a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group having 9 or more carbon atoms.
Examples of the (meth)acrylic ester having a linear or branched alkyl group having 9 or more carbon atoms include n-nonyl (meth)acrylate, isononyl (meth)acrylate, and n-(meth)acrylate. -decyl, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, isolauryl (meth)acrylate, n-stearyl (meth)acrylate, isostearyl (meth)acrylate, and the like.

The high molecular weight (meth)acrylic resin preferably has a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group in which at least one of the hydrogen atoms is substituted with an OH group.
By having the above segment, the binder resin exhibits extremely excellent decomposability even at low temperatures, and can further improve the dispersibility and aggregation suppressing effect of the filler.

The (meth)acrylic acid ester having a linear or branched alkyl group in which at least one of the hydrogen atoms is substituted with an OH group is preferably one in which the weight ratio of the OH group is 10.5% by weight or more. , more preferably 11.5% by weight or more, and preferably 13.1% by weight or less.

The high molecular weight (meth)acrylic resin has a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group having 2 to 4 carbon atoms in which at least one hydrogen atom is substituted with an OH group. It is preferable.
Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 2 to 4 carbon atoms in which at least one of the hydrogen atoms is substituted with an OH group include 2-hydroxyethyl (meth)acrylate; 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. can be mentioned. Among these, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate are preferred.

Content of segments derived from (meth)acrylic acid ester having a linear or branched alkyl group having 2 to 4 carbon atoms in which at least one hydrogen atom in the high molecular weight (meth)acrylic resin is substituted with an OH group. is preferably 3.1% by weight or more, more preferably 5.0% by weight or more, preferably 17.0% by weight or less, and more preferably 12.2% by weight or less. preferable.

The high molecular weight (meth)acrylic resin has a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group having 5 or more carbon atoms in which at least one hydrogen atom is substituted with an OH group. is preferred.
Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 5 or more carbon atoms in which at least one of the hydrogen atoms is substituted with an OH group include hydroxypentyl (meth)acrylate, (meth)acrylate Examples include hydroxyhexyl acrylate, hydroxyheptyl (meth)acrylate, hydroxyoctyl (meth)acrylate, and the like.

The above-mentioned high molecular weight (meth)acrylic resin includes segments derived from the above-mentioned (meth)acrylic esters, segments derived from (meth)acrylic acid, and other (meth)acrylic esters such as (meth)acrylic esters having a glycidyl group. ) May have a segment derived from an acrylic ester.

The glass transition temperature (Tg) of the high molecular weight (meth)acrylic resin is preferably 40°C or more and 60°C or less.
By setting it as the said range, the addition amount of a plasticizer can be reduced and low-temperature decomposability can be improved.
The above Tg is more preferably 42°C or higher, even more preferably 45°C or higher, more preferably 47°C or lower, and even more preferably 58°C or lower.
Note that the glass transition temperature (Tg) can be measured using, for example, a differential scanning calorimeter (DSC).

The high molecular weight (meth)acrylic resin preferably has a solubility in ethanol of 10 parts by weight/100 parts by weight of ethanol or more.
By setting it as the said range, the dispersibility of a filler and the aggregation suppression effect can be improved. Moreover, the solubility in organic solvents can be sufficiently increased.
The solubility in ethanol is more preferably 50 parts by weight or more, and even more preferably 100 parts by weight or more.
The solubility in ethanol means the amount of resin required to form a precipitate when dissolved in 100 parts by weight of ethanol in an environment of 25°C.

The content of the high molecular weight (meth)acrylic resin in the (meth)acrylic resin composition of the present invention is preferably 10% by weight or more, more preferably 30% by weight or more, and 70% by weight or less. The amount is preferably 60% by weight or less, and more preferably 60% by weight or less.

The method for producing the high molecular weight (meth)acrylic resin is not particularly limited. For example, an organic solvent or the like is added to a raw material monomer mixture containing (meth)acrylic acid ester, etc. to prepare a monomer mixture, and then a polymerization initiator is added to the obtained monomer mixture to co-incorporate the raw material monomers. Examples include a method of polymerization.
The polymerization method is not particularly limited, and examples include emulsion polymerization, suspension polymerization, bulk polymerization, interfacial polymerization, and solution polymerization. Among these, solution polymerization is preferred.

Examples of the polymerization initiator include t-butylperoxypivalate, P-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroxyperoxide, Examples include t-butyl hydroxy peroxide, cyclohexanone peroxide, and disuccinic acid peroxide.

The above (meth)acrylic resin may contain a low molecular weight (meth)acrylic resin.
In the present specification, the low molecular weight (meth)acrylic resin preferably has a weight average molecular weight of 0.5 million or more and 100,000 or less.
By containing the above-mentioned low molecular weight (meth)acrylic resin, the dispersibility of the filler can be further improved.
The weight average molecular weight is more preferably 60,000 or more, still more preferably 08,000 or more, more preferably 90,000 or less, and even more preferably 30,000 or less.
Further, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the low molecular weight (meth)acrylic resin is preferably 2 or more, and preferably 8 or less.
By setting the content within the above range, since a component with a low degree of polymerization is appropriately contained, the viscosity of the filler-dispersed slurry composition falls within a suitable range, and productivity can be improved. Moreover, the sheet strength of the obtained filler-dispersed sheet can be made appropriate. Furthermore, the surface smoothness of the resulting molded product (ceramic green sheet) can be sufficiently improved.
The above Mw/Mn is more preferably 3 or more, and more preferably 6 or less.
Note that the weight average molecular weight (Mw) and number average molecular weight (Mn) are average molecular weights in terms of polystyrene, and can be obtained by performing GPC measurement using, for example, column LF-804 (manufactured by Showa Denko) as a column. can.

The weight concentration of OH groups contained in the low molecular weight (meth)acrylic resin is preferably 1.3% by weight or more, and preferably 3.5% by weight or less.
By setting it within the above range, the binder resin exhibits extremely excellent decomposability even at low temperatures, and further improves the dispersibility and aggregation suppressing effect of the filler.
The weight concentration of the OH group is preferably 1.4% by weight or more, preferably 3.3% by weight or less, and more preferably 3.2% by weight or less.
The weight concentration of the OH group means the ratio of the weight of the OH group to the weight of the entire low molecular weight (meth)acrylic resin, and can be calculated based on the following formula.
Weight concentration of OH groups contained in low molecular weight (meth)acrylic resin = [(Weight of OH groups contained in all monomers + Weight of OH groups contained in chain transfer agent) / (Weight of all monomers + Start of polymerization weight of agent + weight of chain transfer agent)] x 100

The low molecular weight (meth)acrylic resin preferably has a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group having 3 to 4 carbon atoms.
By having the above-mentioned segments, it is possible to obtain more excellent low-temperature decomposition properties.
Examples of the (meth)acrylic ester having a linear or branched alkyl group having 3 to 4 carbon atoms include n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-(meth)acrylate. -butyl, isobutyl (meth)acrylate, etc. Among these, isobutyl (meth)acrylate is preferred.

The content of segments derived from a (meth)acrylic acid ester having a linear or branched alkyl group having 3 to 4 carbon atoms in the low molecular weight (meth)acrylic resin is preferably 38% by weight or more, It is more preferably 50% by weight or more, preferably 80% by weight or less, and even more preferably 75% by weight or less.

The low molecular weight (meth)acrylic resin may have a segment derived from a (meth)acrylic acid ester having an alkyl group having 1 to 2 carbon atoms.
Examples of the (meth)acrylic ester having an alkyl group having 1 to 2 carbon atoms include methyl (meth)acrylate and ethyl (meth)acrylate.

The content of segments derived from (meth)acrylic acid ester having an alkyl group having 1 to 2 carbon atoms in the low molecular weight (meth)acrylic resin is preferably 0% by weight or more, and preferably 7% by weight or more. More preferably, it is 33% by weight or less, and more preferably 20.5% by weight or less.

The low molecular weight (meth)acrylic resin may have a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group having 5 to 8 carbon atoms.
The above (meth)acrylic esters having a linear or branched alkyl group having 5 to 8 carbon atoms include n-pentyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, Examples include n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. Among these, (meth)acrylic acid esters having a linear or branched alkyl group having 6 to 8 carbon atoms are preferred, and 2-ethylhexyl (meth)acrylate is more preferred.

The content of segments derived from a (meth)acrylic acid ester having a linear or branched alkyl group having 5 to 8 carbon atoms in the low molecular weight (meth)acrylic resin is preferably 0% by weight or more. , more preferably 10% by weight or more, preferably 30% by weight or less, and more preferably 40% by weight or less.

The low molecular weight (meth)acrylic resin may have a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group having 9 or more carbon atoms.
Examples of the (meth)acrylic ester having a linear or branched alkyl group having 9 or more carbon atoms include n-nonyl (meth)acrylate, isononyl (meth)acrylate, and n-(meth)acrylate. -decyl, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, isolauryl (meth)acrylate, n-stearyl (meth)acrylate, isostearyl (meth)acrylate, and the like.

The low molecular weight (meth)acrylic resin preferably has a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group in which at least one of the hydrogen atoms is substituted with an OH group.
By having the above segment, the binder resin exhibits extremely excellent decomposability even at low temperatures, and can further improve the dispersibility and aggregation suppressing effect of the filler.

The (meth)acrylic acid ester having a linear or branched alkyl group in which at least one of the hydrogen atoms is substituted with an OH group is preferably one in which the weight ratio of the OH group is 10.5% by weight or more. , more preferably 11.5% by weight or more, and preferably 13.1% by weight or less.

The low molecular weight (meth)acrylic resin has a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group having 2 to 4 carbon atoms in which at least one hydrogen atom is substituted with an OH group. It is preferable.
Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 2 to 4 carbon atoms in which at least one of the hydrogen atoms is substituted with an OH group include 2-hydroxyethyl (meth)acrylate; 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. can be mentioned. Among these, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate are preferred.

Content of segments derived from (meth)acrylic acid ester having a linear or branched alkyl group having 2 to 4 carbon atoms in which at least one hydrogen atom in the low molecular weight (meth)acrylic resin is substituted with an OH group. is preferably 7% by weight or more, more preferably 10% by weight or more, preferably 20% by weight or less, and more preferably 16% by weight or less.

The low molecular weight (meth)acrylic resin has a segment derived from a (meth)acrylic acid ester having a linear or branched alkyl group having 5 or more carbon atoms in which at least one hydrogen atom is substituted with an OH group. is preferred.
Examples of the (meth)acrylic acid ester having a linear or branched alkyl group having 5 or more carbon atoms in which at least one of the hydrogen atoms is substituted with an OH group include hydroxypentyl (meth)acrylate, (meth)acrylate Examples include hydroxyhexyl acrylate, hydroxyheptyl (meth)acrylate, hydroxyoctyl (meth)acrylate, and the like.

The above-mentioned low molecular weight (meth)acrylic resin includes segments derived from the above-mentioned (meth)acrylic acid esters, segments derived from (meth)acrylic acid, and other (meth)acrylic esters such as (meth)acrylic esters having a glycidyl group. ) May have a segment derived from an acrylic ester.

The glass transition temperature (Tg) of the low molecular weight (meth)acrylic resin is 40°C or more and 60°C or less.
By setting it as the said range, the addition amount of a plasticizer can be reduced and low-temperature decomposability can be improved.
The above Tg is preferably 42°C or higher, more preferably 45°C or higher, preferably 47°C or lower, and more preferably 58°C or lower.
Note that the glass transition temperature (Tg) can be measured using, for example, a differential scanning calorimeter (DSC).

The content of the low molecular weight (meth)acrylic resin in the (meth)acrylic resin composition of the present invention is preferably 0.1 parts by weight or more based on 100 parts by weight of the high molecular weight (meth)acrylic resin. , preferably 10 parts by weight or less.
By setting it as the said range, the dispersibility of a filler can be improved more.
The content of the low molecular weight (meth)acrylic resin is more preferably 0.3 parts by weight or more, and more preferably 7.5 parts by weight or less.

The method for producing the above-mentioned low molecular weight (meth)acrylic resin is not particularly limited. For example, an organic solvent or the like is added to a raw material monomer mixture containing (meth)acrylic acid ester, etc. to prepare a monomer mixture, and then a polymerization initiator and a chain transfer agent are added to the obtained monomer mixture, and the above-mentioned Examples include a method of copolymerizing raw material monomers.
The polymerization method is not particularly limited, and examples include emulsion polymerization, suspension polymerization, bulk polymerization, interfacial polymerization, and solution polymerization. Among these, solution polymerization is preferred.

Examples of the polymerization initiator include t-butylperoxypivalate, P-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroxyperoxide, Examples include t-butyl hydroxy peroxide, cyclohexanone peroxide, and disuccinic acid peroxide.

Examples of the chain transfer agent include 3-mercapto-1,2-propanediol, 3-mercapto-1-propanol, 3-mercapto-2-butanol, 8-mercapto-1-octanol, mercaptosuccinic acid, and mercaptoacetic acid. etc.

The above-mentioned filler dispersion may contain stabilizers such as antioxidants and ultraviolet absorbers, surfactants, tackifiers, plasticizers, lubricants, foaming agents, antistatic agents, antistatic agents, etc., to the extent that the effects of the present invention are not impaired. It may contain various additives such as impact strengtheners, flame retardants, antifog agents, waxes, and metal soaps.

Since the filler dispersion described above has excellent filler dispersibility and agglomeration suppressing effect, it can be suitably used as a filler-dispersed slurry composition by combining a filler and a plasticizer. A filler-dispersed slurry composition comprising the filler dispersion described above is also one of the aspects of the present invention.

The filler-dispersed slurry composition of the present invention preferably contains inorganic particles as the filler.
The inorganic particles are not particularly limited, and include, for example, glass powder, ceramic powder, phosphor fine particles, silicon oxide, metal fine particles, and the like.

The above-mentioned glass powder is not particularly limited, and includes, for example, glass powder such as bismuth oxide glass, silicate glass, lead glass, zinc glass, boron glass, CaO-Al ₂ O ₃ -SiO ₂ system, MgO-Al ₂ O Examples include glass powders of various silicon oxides such as _3- SiO ₂ series, LiO ₂ -Al ₂ O ₃ -SiO ₂ series, and the like.
In addition, as the above-mentioned glass powder, SnO-B ₂ O ₃ -P ₂ O ₅ -Al ₂ O ₃ mixture, PbO-B ₂ O ₃ -SiO ₂ mixture, BaO-ZnO-B ₂ O ₃ -SiO ₂ mixture, ZnO -Bi ₂ O ₃ -B ₂ O ₃ -SiO ₂ mixture, Bi ₂ O ₃ -B ₂ O ₃ -BaO-CuO mixture, Bi ₂ O ₃ -ZnO-B ₂ O ₃ -Al ₂ O ₃ -SrO mixture, ZnO-Bi ₂ O ₃ -B ₂ O ₃ mixture, Bi ₂ O ₃ -SiO ₂ mixture, P ₂ O ₅ -Na ₂ O-CaO-BaO-Al ₂ O ₃ -B ₂ O ₃ mixture, P ₂ O ₅ -SnO mixture, P ₂ O ₅ -SnO-B ₂ O ₃ mixture, P ₂ O ₅ -SnO-SiO ₂ mixture, CuO-P ₂ O ₅ -RO mixture, SiO ₂ -B ₂ O ₃ -ZnO-Na ₂ O-Li ₂ O-NaF-V ₂ O ₅ mixture, P ₂ O ₅ -ZnO-SnO-R ₂ O-RO mixture, B ₂ O ₃ -SiO ₂ -ZnO mixture, B ₂ O ₃ -SiO ₂ -Al ₂ O ₃ -ZrO ₂ mixture, SiO ₂ -B ₂ O ₃ -ZnO-R ₂ O-RO mixture, SiO ₂ -B ₂ O ₃ -Al ₂ O ₃ -RO-R ₂ O mixture, SrO-ZnO-P Glass powders such as ₂ O ₅ mixture, SrO-ZnO-P ₂ O ₅ mixture, BaO-ZnO-B ₂ O ₃ -SiO ₂ mixture can also be used. Note that R is an element selected from the group consisting of Zn, Ba, Ca, Mg, Sr, Sn, Ni, Fe, and Mn.
In particular, glass powder of PbO-B ₂ O ₃ -SiO ₂ mixture, lead-free BaO-ZnO-B ₂ O ₃ -SiO ₂ mixture or ZnO-Bi ₂ O ₃ -B ₂ O ₃ -SiO ₂ mixture, etc. Lead-free glass powder is preferred.

The above ceramic powder is not particularly limited, and examples thereof include alumina, ferrite, zirconia, zircon, barium zirconate, calcium zirconate, titanium oxide, barium titanate, strontium titanate, calcium titanate, magnesium titanate, zinc titanate, Lanthanum titanate, neodymium titanate, lead zirconium titanate, alumina nitride, silicon nitride, boron nitride, boron carbide, barium stannate, calcium stannate, magnesium silicate, mullite, steatite, cordierite, forsterite, etc. It will be done.
ITO, FTO, niobium oxide, vanadium oxide, tungsten oxide, lanthanum strontium manganite, lanthanum strontium cobalt ferrite, yttrium-stabilized zirconia, gadolinium-doped ceria, nickel oxide, lanthanum chromite, and the like can also be used.
The phosphor fine particles are not particularly limited, and for example, blue phosphor substances, red phosphor substances, green phosphor substances, etc., which are conventionally known as phosphor substances for displays, can be used as the phosphor substance. Examples of blue phosphor substances include MgAl ₁₀ O ₁₇ :Eu, Y ₂ SiO ₅ :Ce system, CaWO ₄ :Pb system, BaMgAl ₁₄ O ₂₃ :Eu system, BaMgAl ₁₆ O ₂₇ :Eu system, BaMg ₂ Al ₁₄ O ₂₃ :Eu-based, BaMg ₂ Al ₁₄ O ₂₇ :Eu-based, and ZnS:(Ag,Cd)-based are used. Examples of red phosphor substances include Y ₂ O ₃ :Eu-based, Y ₂ SiO ₅ :Eu-based, Y ₃ Al ₅ O ₁₂ :Eu-based, Zn ₃ (PO ₄ ) ₂ :Mn-based, YBO ₃ :Eu. (Y,Gd)BO ₃ :Eu system, GdBO ₃ :Eu system, ScBO ₃ :Eu system, and LuBO ₃ :Eu system. Examples of green phosphor substances include Zn ₂ SiO ₄ :Mn system, BaAl ₁₂ O ₁₉ :Mn system, SrAl ₁₃ O ₁₉ :Mn system, CaAl ₁₂ O ₁₉ :Mn system, YBO ₃ :Tb system, BaMgAl ₁₄ O ₂₃ : Mn type, LuBO ₃ : Tb type, GdBO ₃ : Tb type, ScBO ₃ : Tb type, and Sr6Si ₃ O ₃ Cl ₄ : Eu type are used. Others include ZnO:Zn series _{, ZnS} :(Cu,Al) series, ZnS:Ag series, Y2O2S:Eu series, ZnS:Zn series, ( _Y ,Cd) _BO3 :Eu series, _BaMgAl12O23 :Eu-based materials can also be used.

The metal fine particles are not particularly limited, and include, for example, powders made of iron, copper, nickel, palladium, platinum, gold, silver, aluminum, tungsten, and alloys thereof.
Further, metals such as copper and iron, which have good adsorption properties with carboxyl groups, amino groups, amide groups, etc. and are easily oxidized, can also be suitably used. These metal powders may be used alone or in combination of two or more.
In addition to metal complexes, various carbon blacks, carbon nanotubes, etc. may be used as the metal fine particles.

The inorganic particles preferably contain lithium or titanium. Specifically, for example, low melting point glass such as LiO ₂ / Al ₂ O ₃ / SiO ₂ type inorganic glass, lithium sulfur type glass such as Li ₂ S-M _x S _y (M=B, Si, Ge, P), etc. , lithium cobalt composite oxide such as _LiCeO2 , lithium manganese composite oxide such as _LiMnO4 , lithium nickel composite oxide, lithium vanadium composite oxide, lithium zirconium composite oxide, lithium hafnium composite oxide, lithium silicate (Li _3.5 Si _0.5 P _0.5 O ₄ ), lithium titanium phosphate (LiTi ₂ (PO ₄ ) ₃ ), lithium titanate (Li ₄ Ti ₅ O ₁₂ ), Li _4/3 Ti _5/3 O ₄ , LiCoO ₂ , lithium germanium phosphate (LiGe ₂ (PO ₄ ) ₃ ), Li ₂ -SiS glass, Li ₄ GeS ₄ -Li ₃ PS ₄ glass, LiSiO ₃ , LiMn ₂ O ₄ , Li ₂ S- P ₂ S ₅ -based glass/ceramic, Li ₂ O-SiO ₂ , Li ₂ O-V ₂ O ₅ -SiO ₂ , LiS-SiS ₂ -Li ₄ SiO ₄ -based glass, ion conductive oxides such as LiPON, Li Lithium oxide compounds such as ₂ O-P ₂ O ₅ -B ₂ O ₃ and Li ₂ O-GeO ₂ Ba, Li _x Al _y T _z (PO ₄ ) ₃ -based glass, La _x Li _y TiO _z -based glass, Li _x Ge _y P _z O ₄ -based glass, Li ₇ La ₃ Zr ₂ O ₁₂ -based glass, Li _v Si _w P _x S _y Cl _z -based glass, lithium niobium oxide such as LiNbO ₃ , Li-β-alumina, etc. Examples include lithium alumina compounds, lithium zinc oxides such as Li ₁₄ Zn(GeO ₄ ) ₄ , and the like.

The content of the filler in the filler-dispersed slurry composition of the present invention is not particularly limited, but a preferable lower limit is 10% by weight, and a preferable upper limit is 90% by weight. By setting the content to 10% by weight or more, it can have sufficient viscosity and excellent coating properties, and by setting it to 90% by weight or less, it can provide excellent dispersibility of the filler.

The filler-dispersed slurry composition may further contain a plasticizer.
Examples of the plasticizers include di(butoxyethyl) adipate, dibutoxyethoxyethyl adipate, triethylene glycol dibutyl, triethylene glycol bis(2-ethylhexanoate), triethylene glycol dihexanoate, acetyl Triethyl citrate, acetyl tributyl citrate, acetyl diethyl citrate, acetyl dibutyl citrate, dibutyl sebacate, triacetin, diethyl acetyloxymalonate, diethyl ethoxymalonate, and the like.
By using these plasticizers, it is possible to reduce the amount of plasticizer added compared to when using normal plasticizers (approximately 30% by weight of the binder, but 25% by weight) Below, it can be further reduced to 20% by weight or less).
Among them, it is preferable to use a non-aromatic plasticizer that does not contain an aromatic ring such as a benzene ring in its structure, and it is more preferable to use a non-aromatic plasticizer that does not contain an aromatic ring such as a benzene ring in its structure. preferable. Note that plasticizers having aromatic rings are not preferred because they tend to burn and turn into soot.

Moreover, as the above-mentioned plasticizer, one having an alkyl group having two or more carbon atoms such as an ethyl group or a butyl group is preferable, and one having an alkyl group having four or more carbon atoms is more preferable.
The above plasticizer contains an alkyl group having 2 or more carbon atoms to suppress moisture absorption into the plasticizer and prevent defects such as voids and blisters from occurring in the resulting molded product. I can do it. In particular, the alkyl group of the plasticizer is preferably located at the end of the molecule.
Further, the plasticizer preferably has a functional group having 2 carbon atoms such as an ethyl group, a functional group having 4 carbon atoms such as a butyl group, and a functional group such as a butoxyethyl group. It is preferable that the functional group is present in the terminal molecular chain.
Plasticizers that have a functional group with 2 carbon atoms such as ethyl group in the terminal molecular chain are compatible with segments derived from ethyl methacrylate, and plasticizers with a functional group with 4 carbon atoms such as butyl group in the terminal molecule have good compatibility with segments derived from ethyl methacrylate The agent is compatible with segments derived from butyl methacrylate. A plasticizer having a functional group having 2 or 4 carbon atoms has good compatibility with the above-mentioned high molecular weight (meth)acrylic resin, and can preferably improve the brittleness of the resin. Furthermore, the butoxyethyl group is compatible with both the composition of the segment derived from ethyl methacrylate and the segment derived from butyl methacrylate, and can be preferably used.

The plasticizer preferably has a carbon:oxygen ratio of 5:1 to 3:1.
By setting the carbon:oxygen ratio within the above range, the combustibility of the plasticizer can be improved and generation of residual carbon can be prevented. Furthermore, by improving the compatibility with the (meth)acrylic resin, the plasticizing effect can be exerted even with a small amount of plasticizer.
Further, a high boiling point organic solvent having a propylene glycol skeleton or a trimethylene glycol skeleton can also be preferably used if it contains an alkyl group having 4 or more carbon atoms and has a carbon:oxygen ratio of 5:1 to 3:1.

The boiling point of the plasticizer is preferably 240°C or more and less than 390°C. When the boiling point is 240° C. or higher, it easily evaporates in the drying process and can prevent it from remaining in the molded product. Furthermore, by setting the temperature to be less than 390°C, generation of residual carbon can be prevented. Note that the above boiling point refers to the boiling point at normal pressure.

The content of the plasticizer in the filler-dispersed slurry composition is not particularly limited, but the preferred lower limit is 0.1% by weight, and the preferred upper limit is 3.0% by weight. By keeping it within the above range, it is possible to reduce the firing residue of the plasticizer.

The content of the (meth)acrylic resin in the filler-dispersed slurry composition is not particularly limited, but the preferred lower limit is 0.5% by weight, and the preferred upper limit is 10% by weight.
By setting it as the said range, it can be made into the filler dispersion slurry composition which can be degreased even if it bakes at low temperature, and is excellent in the dispersibility of a filler and the agglomeration suppression effect.
A more preferable lower limit of the content of the (meth)acrylic resin is 1% by weight, and a more preferable upper limit is 7% by weight.

The filler-dispersed slurry composition may further contain additives such as surfactants.
The above-mentioned surfactant is not particularly limited, and examples thereof include cationic surfactants, anionic surfactants, and nonionic surfactants.
The nonionic surfactant is not particularly limited, but preferably has an HLB value of 10 or more and 20 or less. Here, the HLB value is used as an index representing the hydrophilicity and lipophilicity of a surfactant, and several calculation methods have been proposed.For example, for ester surfactants, the saponification value There are definitions such as S, the acid value of the fatty acid constituting the surfactant, A, and the HLB value of 20 (1-S/A). Specifically, a nonionic surfactant having polyethylene oxide with an alkylene ether added to a fatty chain is suitable, and specifically, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, etc. are preferably used. It will be done. The above-mentioned nonionic surfactant has good thermal decomposition properties, but if added in large quantities, the thermal decomposition properties of the filler-dispersed slurry composition may decrease, so the preferable upper limit of the content is 5% by weight. .

The viscosity of the filler-dispersed slurry composition of the present invention is not particularly limited, but the preferable lower limit of the viscosity is 0.1 Pa·s when measured at 20°C using a B-type viscometer and setting the probe rotation speed to 5 rpm. A preferable upper limit is 100 Pa·s.
By setting the above-mentioned viscosity to 0.1 Pa·s or more, the resulting filler-dispersed sheet can maintain a predetermined shape after coating by die coating printing or the like. Furthermore, by setting the viscosity to 100 Pa·s or less, problems such as inability to erase die coating marks can be prevented, and printability can be excellent.

The method for producing the filler-dispersed slurry composition is not particularly limited, and examples thereof include conventionally known stirring methods, and specifically, for example, the (meth)acrylic resin, the filler, the solvent and, if necessary, Examples include a method of stirring other components such as a plasticizer to be added using a three-roll roll or the like. The order of addition of the constituent components of the filler-dispersed slurry composition can be set as appropriate.

A filler-dispersed molded product can be produced by coating the filler-dispersed slurry composition on a support film that has been subjected to a release treatment on one side, drying the solvent, and molding the composition. A filler-dispersed molded product, which is a cured product of such a filler-dispersed slurry composition, is also one of the aspects of the present invention.
Although the shape of the filler-dispersed molded product of the present invention is not particularly limited, it can be, for example, in the shape of a sheet or the like.

As a method for manufacturing the filler-dispersed molded product of the present invention, for example, the filler-dispersed slurry composition of the present invention is uniformly coated on a support film using a coating method such as a roll coater, die coater, squeeze coater, curtain coater, etc. Examples include a method of forming a film.
In addition, when producing a filler-dispersed molded product, it is preferable to use the polymerization liquid as it is as a filler-dispersed slurry composition and process it into a filler-dispersed molded product without drying the high molecular weight (meth)acrylic resin.
When high molecular weight (meth)acrylic resin is dried, undried particles called particles are generated when it is reconstituted into a solution.These particles are difficult to remove even by filtration using a cartridge filter, etc. This is because it adversely affects the strength of the dispersion molded product.

For example, when the filler dispersion molded product of the present invention is in the form of a sheet, the support film used when manufacturing the filler dispersion molded product of the present invention is made of a resin having heat resistance, solvent resistance, and flexibility. Preferably, it is a film. Due to the flexibility of the support film, the filler-dispersed slurry composition can be applied to the surface of the support film using a roll coater, blade coater, etc., and the resulting filler-dispersed sheet-forming film is wound into a roll. It can be stored and supplied in this state.

Examples of the resin forming the support film include fluorine-containing resins such as polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, and polyfluoroethylene, nylon, and cellulose.
The thickness of the support film is preferably, for example, 20 to 100 μm.
Moreover, it is preferable that the surface of the support film is subjected to a release treatment, so that the peeling operation of the support film can be easily performed in the transfer process.

A filler-dispersed molded product can be produced by applying and drying the filler-dispersed slurry composition of the present invention.
Moreover, a multilayer ceramic capacitor can be manufactured by using the filler-dispersed slurry composition and the filler-dispersed molded product of the present invention for dielectric green sheets and electrode pastes. Moreover, a magnetic material can be manufactured by using the filler-dispersed slurry composition and the filler-dispersed molded product of the present invention.

The method for producing the multilayer ceramic capacitor includes the steps of printing a conductive paste on the filler-dispersed molded product of the present invention and drying it to produce a dielectric sheet, and laminating the dielectric sheets. There are several methods.

The conductive paste contains conductive powder.
The material of the conductive powder is not particularly limited as long as it is conductive, and examples thereof include nickel, palladium, platinum, gold, silver, copper, molybdenum, tin, and alloys thereof. These conductive powders may be used alone or in combination of two or more.

The method for printing the conductive paste is not particularly limited, and examples thereof include screen printing, die coat printing, offset printing, gravure printing, inkjet printing, and the like.

In the method for manufacturing a multilayer ceramic capacitor, a multilayer ceramic capacitor is obtained by laminating dielectric sheets printed with the conductive paste.

According to the present invention, it is possible to provide a dispersant that effectively disperses a filler and is suitable for producing a molded article having excellent moldability, adhesiveness, and mechanical properties. Further, according to the present invention, it is possible to provide a filler dispersion, a filler-dispersed slurry composition, and a filler-dispersed molded product using the dispersant.

The embodiments of the present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples.

<Preparation of acrylic polymer>
(Synthesis example 1)
100 parts by weight of ethyl acetate was put into a reactor equipped with a thermometer, a stirrer, and a cooling tube, and the atmosphere was purged with nitrogen, and then the reactor was heated to start reflux. Thirty minutes after the ethyl acetate boiled, 0.08 parts by weight of azobisisobutyronitrile was added as a polymerization initiator. The monomer mixture shown in Table 1 was added dropwise evenly and gradually over 1 hour and 30 minutes to react. 30 minutes after the completion of the dropwise addition, 0.1 part by weight of azobisisobutyronitrile was added, and the polymerization reaction was further carried out for 5 hours. Ethyl acetate was added to the reactor and cooled while diluting to obtain a solid content of 25% by weight. An acrylic polymer solution was obtained.
The obtained acrylic polymer solution was filtered with a filter (material: polytetrafluoroethylene, pore diameter: 0.2 μm). The obtained filtrate was supplied to a gel permeation chromatograph (2690 Separations Model, manufactured by Waters), and GPC measurement was performed at a sample flow rate of 1 ml/min and a column temperature of 40°C to determine the polystyrene equivalent molecular weight of the acrylic polymer. The weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) were determined by measurement. GPC KF-806L (manufactured by Showa Denko) was used as a column, and a differential refractometer was used as a detector.

(Synthesis example 2)
An acrylic polymer was obtained in the same manner as in Synthesis Example 1 except that the monomer mixture was changed as shown in Table 1.

<Preparation of resinous compound>
(Synthesis example A)
50 parts by weight of toluene was put into a reactor equipped with a thermometer, a stirrer, and a cooling tube, and after the atmosphere was replaced with nitrogen, the reactor was heated to start reflux. After 30 minutes, 2 parts by weight of aluminum chloride (AlCl ₃ ) were added while maintaining the toluene at 75°C. Here, a total of 50 parts by weight of the monomer (a) for forming the structural unit (A) shown in Table 2 and the monomer (b) for forming the structural unit (B) (the molar ratio is as shown in Table 2) was added to toluene. A solution prepared by dissolving 50 parts by weight was gradually added dropwise over 1 hour and 30 minutes to cause a reaction. After a 4-hour polymerization reaction, 0.1 part by weight of pyridine was added into the reactor while cooling to neutralize hydrochloric acid generated from aluminum chloride (AlCl ₃ ). The precipitate produced by the neutralization was filtered, and the resulting filtrate was subjected to a liquid separation operation, and then toluene was evaporated to obtain a solid resinous compound.
The obtained resinous compound was subjected to ¹ H-NMR measurement, and the resinous compound was found to have a constituent unit (A) derived from catechol, which is the monomer (a), and a structure derived from α-pinene, which is the monomer (b). It was confirmed that it was a copolymer having the unit (B).
A solution of the obtained resinous compound dissolved in tetrahydrofuran was filtered through a filter (material: polytetrafluoroethylene, pore diameter: 0.2 μm). The obtained filtrate was supplied to a gel permeation chromatograph (manufactured by Waters, 2690 Separations Model), and GPC measurement was performed at a sample flow rate of 1 ml/min and a column temperature of 40°C to determine the polystyrene equivalent molecular weight of the resinous compound. The weight average molecular weight (Mw) was determined by measurement. GPC KF-802.5L (manufactured by Showa Denko) was used as a column, and a differential refractometer was used as a detector.
Furthermore, the content of biologically derived carbon in the obtained resinous compound was measured according to ASTM D6866-20.

(Synthesis examples B to I and K to M)
A resinous compound was prepared in the same manner as in Synthesis Example A except that the monomer (a) for forming the structural unit (A) and the monomer (b) for forming the structural unit (B) were changed as shown in Table 2. I got it. The same monomers were used in Synthesis Example D and I, but in Synthesis Example I, a total of 70 parts by weight of pyrogallol (n=3) and α-pinene (the molar ratio is shown in Table 2) was mixed with 30 parts by weight of toluene. Compounds having different weight-average molecular weights (Mw) were obtained by dropping the solution dissolved in each part.

(Synthesis example J)
50 parts by weight of toluene was put into a reactor equipped with a thermometer, a stirrer, and a cooling tube, and after the atmosphere was replaced with nitrogen, the reactor was heated to start reflux. After 30 minutes, 2 parts by weight of aluminum chloride (AlCl ₃ ) were added while maintaining the toluene at 75°C. A solution of a total of 70 parts by weight of 4-vinylbenzoic acid (m = 1) and α-pinene (the molar ratio is as shown in Table 2) dissolved in 50 parts by weight of toluene was gradually added over 1 hour and 30 minutes. It was added dropwise to react. After a 4-hour polymerization reaction, 0.1 part by weight of pyridine was added into the reactor while cooling to neutralize hydrochloric acid generated from aluminum chloride (AlCl ₃ ). The precipitate produced by the neutralization was filtered, and the resulting filtrate was subjected to a liquid separation operation, and then toluene was evaporated to obtain a solid resinous compound.
The obtained resinous compound was subjected to ¹ H-NMR measurement, and the compound was found to be a copolymer having a structural unit (A) derived from 4-vinylbenzoic acid and a structural unit (B) derived from α-pinene. (a copolymer having structural unit (A) in its side chain).
Furthermore, the content of biologically derived carbon in the obtained resinous compound was measured according to ASTM D6866-20.

<Manufacture of filler dispersion>
(Example 1)
10 parts by weight of solid content of acrylic polymer (Synthesis Example 1) as a resin component, 10 parts by weight of a resinous compound (Synthesis Example A) as a dispersant, ceramic powder (copper powder: glass frit = 9: 1) 100 parts by weight, 1 part by weight of adipic acid (dibutoxyethyl) as a plasticizer, and 90 parts by weight of toluene as an organic solvent were mixed and stirred to obtain a solution of a filler dispersion.

(Examples 2 to 13, 15, 16 and Comparative Examples 1 to 3)
A filler dispersion was obtained in the same manner as in Example 1, except that the types and amounts of the resin component and dispersant were changed as shown in Table 3. Among the resin components and dispersants used, those not listed in Table 1 or 2 are shown below.

<Resin component>
Polyvinyl butyral resin (manufactured by Sekisui Chemical Co., Ltd., product name "BH6")
<Dispersant>
Rosin ester resin (manufactured by Arakawa Chemical Industry Co., Ltd., product name "Pine Crystal KE359")
Terpene phenol resin (manufactured by Yasuhara Chemical Co., Ltd., product name "YS Polyster G150")

(Example 14)
10 parts by weight of a resinous compound (Synthesis Example D) as a dispersant, 100 parts by weight of ceramic powder (copper powder: glass frit = 9:1) as a filler, and 90 parts by weight of toluene as an organic solvent were mixed and stirred. A solution of the filler dispersion was obtained. Regarding Example 14, only the dispersibility was evaluated.

<Evaluation>
The filler dispersions obtained in Examples and Comparative Examples were evaluated by the following method. The results are shown in Table 3.

(1) After adding the dispersible resin component, dispersant, filler, organic solvent, etc. to prepare a filler dispersion, the rotation speed is 800 rpm using a planetary stirring device (manufactured by Shinky Co., Ltd., "Awatori Rentaro"). The mixture was stirred for 3 minutes. After stirring, the mixture was allowed to stand for 24 hours. After standing still, it was visually confirmed whether sedimentation of the filler was observed in the filler dispersion.
○: No sedimentation ×: Sedimentation

(2) Sheet formability After coating a filler dispersion on a release-treated polyethylene terephthalate (PET) film so that the film thickness after drying is 50 μm, air is blown at 100°C for 30 minutes. A sheet was prepared by solvent drying in an oven.
The surface roughness of the obtained sheet was measured at 10 points using a surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd., "Surfcom").
○: Surface roughness is less than 5 μm ×: Surface roughness is 5 μm or more -: Not evaluated

(3) Adhesion The sheets prepared in the above sheet formability evaluation were cut into 10 cm squares, and then three sheets were stacked together under thermocompression bonding conditions of a temperature of 80° C., a pressure of 180 kg/cm ² , and a time of 5 minutes. The adhesion between the layers was visually observed and evaluated based on the following criteria.
○: No interlayer peeling was observed, and strong adhesion was observed.
×: Quite a lot of interlayer peeling was observed.
-:Unrated

(4) Sheet strength Regarding the sheets prepared in the sheet formability evaluation above, the state of the sheets after peeling from the polyester film was visually observed, and the sheet strength was evaluated according to the following criteria.
Good: The sheet could be peeled cleanly from the polyester film, and no cuts or tears were observed in the peeled sheet.
Δ: The sheet could be peeled cleanly from the polyester film, and small cuts were observed in a small portion of the peeled sheet.
×: The sheet could not be peeled off from the polyester film, or cuts and tears were observed in most of the peeled sheet.
-:Unrated

According to the present invention, it is possible to provide a dispersant that effectively disperses a filler and is suitable for producing a molded article having excellent moldability, adhesiveness, and mechanical properties. Further, according to the present invention, it is possible to provide a filler dispersion, a filler-dispersed slurry composition, and a filler-dispersed molded product using the dispersant.

Claims (15)

Constituent unit (A-1), constituent unit (A-1'), constituent unit (A-2), constituent unit (A-2'), constituent unit (A-3), constituent unit expressed by the following formula (A-3′), a structural unit (A-4), and a structural unit (A-4′).

In the formula, R ¹ , R ² , R ³ and R ⁵ are each a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a polar functional group, an aliphatic hydrocarbon group having a polar functional group, or a polar functional group. represents an aromatic hydrocarbon group having a group. R ⁴ each represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aliphatic hydrocarbon group having a polar functional group, or an aromatic hydrocarbon group having a polar functional group. R ⁶ and R ⁷ each represent a hydrogen atom or an aliphatic hydrocarbon group. n represents an integer of 2 or more and 4 or less, and n' represents an integer of 2 or more and 5 or less. m represents an integer of 1 or more and 4 or less, and m' represents an integer of 1 or more and 5 or less. l represents an integer of 2 or more and 4 or less, and l' represents an integer of 2 or more and 5 or less. k represents an integer of 1 or more and 4 or less, and k' represents an integer of 1 or more and 5 or less. The dispersant according to claim 1, wherein the compound further has a structural unit (B) derived from at least one monomer (b) selected from the group consisting of terpene monomers, vinyl monomers, and conjugated diene monomers. . The dispersant according to claim 1, wherein the content of the structural unit (A) in the compound is 1 mol% or more and 60 mol% or less. The dispersant according to claim 1, wherein the content of the structural unit (A) in the compound is 0.9% by weight or more and 60% by weight or less. The dispersant according to claim 1, wherein the compound has a weight average molecular weight of 400 or more and 10,000 or less. The dispersant according to claim 1, wherein n and n' are 2 in the structural unit (A-1) or the structural unit (A-1'). The dispersant according to claim 1, wherein n and n' are 3 in the structural unit (A-1) or the structural unit (A-1'). 2. The dispersant of claim 1, wherein the compound is an at least partially hydrogenated hydrogenate. A filler dispersion containing the dispersant according to any one of claims 1 to 8 and a filler. The filler dispersion according to claim 9, further comprising a solvent. The filler dispersion according to claim 9, further comprising a resin component. The filler dispersion according to claim 11, wherein the resin component includes a (meth)acrylic resin. The filler dispersion according to claim 12, wherein the (meth)acrylic resin has a structural unit derived from a monomer having a hydroxyl group. A filler-dispersed slurry composition comprising the filler dispersion according to claim 9. A filler-dispersed molded product, which is a cured product of the filler-dispersed slurry composition according to claim 14.