Composition, sheet-like object, laminate, method for producing composition, and chip-type laminated electronic component

Abstract

The present invention provides a composition comprising a glass transition temperature regulator capable of increasing the Tg of a binder resin. The composition contains an inorganic powder, a binder resin, and a glass transition temperature regulator, and the glass transition temperature regulator contains a compound having a structure represented by general formula (1). In general formula (1), R1 represents a hydrogen atom or a hydrocarbon group having 1-12 carbon atoms. In general formula (1), R2 represents a hydrocarbon group having 1-12 carbon atoms. In general formula (1), R3 represents a hydrogen atom or a hydrocarbon group having 1-12 carbon atoms. In general formula (1), R4 represents a hydrogen atom or a hydrocarbon group having 1-12 carbon atoms.

Description

Technical Field

[0001] This invention relates to compositions, sheets, laminates, methods for manufacturing compositions, and chip-type laminated electronic components. Background Technology

[0002] Generally, ceramic green sheets for laminated ceramic electronic components are manufactured by molding a slurry made of mixed ceramic particles and binder resin into sheets. For example, vinyl acetate resin can be used as the binder resin.

[0003] Plasticizers are added to the slurry to improve its formability when molded into sheets and to enhance the adhesion when the molded sheets are stacked. By adding plasticizers, the glass transition temperature (Tg) of the binder resin is lowered, thereby improving the plasticity of the slurry.

[0004] Phthalate esters have been used as such plasticizers.

[0005] Patent Document 1 discloses a ceramic green sheet, characterized in that it contains ceramic powder, binder resin, plasticizer added in a proportion exceeding the saturation amount of the binder resin, and solvent, and discloses the use of phthalate as plasticizer.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2002-179925 Summary of the Invention

[0009] When the plasticizer described in Patent Document 1 is used, the Tg of the binder resin decreases, but from the viewpoint of moldability, it is necessary to increase the Tg of the binder resin (adhesive resin).

[0010] In addition, the phthalates used as plasticizers in Patent Document 1 have worrying effects on human health, and the use of such compounds poses a problem of high environmental impact.

[0011] This invention was made to solve the above-mentioned problems, and the object of this invention is to provide a composition containing a glass transition temperature regulator that can increase the Tg of an adhesive resin.

[0012] The composition of the present invention comprises an inorganic powder, a binder resin and a glass transition temperature regulator, wherein the glass transition temperature regulator comprises a compound having a structure represented by the following general formula (1).

[0013]

[0014] (In general formula (1), R)1 It consists of a hydrocarbon group with 1 to 12 hydrogen and carbon atoms.

[0015] In general formula (1), R 2 It consists of hydrocarbon groups with 1 to 12 carbon atoms.

[0016] In general formula (1), R 3 It consists of a hydrocarbon group with 1 to 12 hydrogen and carbon atoms.

[0017] In general formula (1), R 4 (A hydrocarbon group consisting of 1 to 12 hydrogen and carbon atoms.)

[0018] The sheet-like material of the present invention contains the composition of the present invention described above.

[0019] The laminate of the present invention is formed by stacking the sheet-like material described above.

[0020] The method for manufacturing the composition of the present invention includes: a pulverizing step of pulverizing inorganic materials into inorganic powder, and a mixing step of mixing the inorganic powder, adhesive resin and glass transition temperature regulator, wherein the glass transition temperature regulator comprises a compound having a structure represented by the following general formula (1).

[0021]

[0022] (In general formula (1), R) 1 It consists of a hydrocarbon group with 1 to 12 hydrogen and carbon atoms.

[0023] In general formula (1), R 2 It consists of hydrocarbon groups with 1 to 12 carbon atoms.

[0024] In general formula (1), R 3 It consists of a hydrocarbon group with 1 to 12 hydrogen and carbon atoms.

[0025] In general formula (1), R 4 (A hydrocarbon group consisting of 1 to 12 hydrogen and carbon atoms.)

[0026] The chip-type stacked electronic component of the present invention comprises a blank formed by stacking multiple ceramic calcined sheets. When viewed from the side, the blank has a stripe pattern perpendicular to the stacking direction.

[0027] According to the present invention, a composition comprising a glass transition temperature regulator capable of increasing the Tg of an adhesive resin can be provided. Attached Figure Description

[0028] Figure 1A This is a cross-sectional view schematically illustrating an example of the sheet-like material of the present invention.

[0029] Figure 1B yes Figure 1A Enlarged view of the dotted line portion.

[0030] Figure 2A This is a schematic diagram illustrating an example of a process for fabricating a laminate using the sheet material of the present invention.

[0031] Figure 2B This is a schematic diagram illustrating an example of a process for fabricating a laminate using the sheet material of the present invention.

[0032] Figure 3 This is a side view schematically showing an example of a blank composed of multiple stacked calcined sheets.

[0033] Figure 4 This is a graph of the loss factor (Tanδ) measured by dynamic viscoelasticity in an embodiment of the present invention.

[0034] Symbol Explanation

[0035] 10 calcined sheets 10

[0036] 10a flakes

[0037] 11 Stomata

[0038] 11a Adhesive Resin

[0039] 20 billet

[0040] 20a mother block Detailed Implementation

[0041] The following describes the compositions, sheets, laminates, methods for manufacturing the compositions, and chip-type laminated electronic components of the present invention.

[0042] However, the present invention is not limited to the following embodiments, and can be appropriately modified and applied without changing the spirit of the invention. Any combination of two or more preferred configurations of the present invention described in the following embodiments is also considered part of the present invention.

[0043] The attached diagrams are schematic diagrams, and their dimensions, aspect ratios, and scales may sometimes differ from the actual product.

[0044] Furthermore, the embodiments shown below are examples, and of course, the components shown in the embodiments can be arbitrarily replaced or combined.

[0045] The composition of the present invention comprises an inorganic powder, a binder resin and a glass transition temperature regulator, wherein the glass transition temperature regulator comprises a compound having a structure represented by the following general formula (1).

[0046]

[0047] (In general formula (1), R) 1 It consists of a hydrocarbon group with 1 to 12 hydrogen and carbon atoms.

[0048] In general formula (1), R 2 It consists of hydrocarbon groups with 1 to 12 carbon atoms.

[0049] In general formula (1), R 3 It consists of a hydrocarbon group with 1 to 12 hydrogen and carbon atoms.

[0050] In general formula (1), R 4 (A hydrocarbon group consisting of 1 to 12 hydrogen and carbon atoms.)

[0051] The compound represented by the above general formula (1) can increase the Tg of the adhesive resin. Therefore, the composition containing inorganic powder, adhesive resin and glass transition temperature regulator becomes easier to adjust plasticity and improves moldability. Therefore, when using the composition of the present invention, it can be properly molded into sheets. In addition, the molded sheets are not easily deformed.

[0052] Furthermore, when this sheet-like material is stacked to form a laminate, deformation of the laminate can be prevented. Therefore, when this laminate is calcined to form a blank for a chip-type multilayer electronic component, deviations in the blank's appearance quality and electrical properties are reduced. As a result, the yield rate is improved.

[0053] The principle behind increasing the Tg of adhesive resin is as follows.

[0054] Adhesive resins are generally composed of molecules with polar groups.

[0055] Because compounds having the structure represented by the above general formula (1) are relatively large, they are difficult to orient in the polar groups of the molecules constituting the adhesive resin. Therefore, compounds having the structure represented by the above general formula (1) are difficult to enter the intermolecular spaces of the adhesive resin. Consequently, the molecules constituting the adhesive resin tend to aggregate. This results in an increase in the Tg of the adhesive resin.

[0056] Additionally, R 1 R 2 R 3 and R 4 When the structure is as described above, the compound having the structure represented by general formula (1) is a liquid at room temperature (25°C) and is easy to handle.

[0057] The composition of the present invention will now be described in detail.

[0058] (Inorganic powder)

[0059] In the composition of this invention, the inorganic powder may also be a ceramic powder.

[0060] In this case, ceramic green sheets can be produced by molding the composition of the present invention into sheets.

[0061] In the composition of the present invention, the inorganic powder preferably comprises at least one selected from zirconium oxide, titanium dioxide, aluminum oxide, barium titanate, ferrite, lead zirconate titanate, zinc oxide, glass, and glass ceramics.

[0062] These materials are suitable for using the compositions of the present invention to manufacture chip-type stacked electronic components.

[0063] In the composition of the present invention, the size of the inorganic powder is not particularly limited, but the average particle size is preferably 0.01 μm to 50 μm.

[0064] In the composition of the present invention, the inorganic powder content is preferably 65% ​​to 96% by weight, more preferably 74% to 95% by weight.

[0065] As will be described in detail below, the composition of the present invention is used to manufacture sheet-like materials. These sheet-like materials are stacked and calcined to form a blank for a chip-type stacked electronic component.

[0066] When the inorganic powder content is within the above range, the prepared blank has appropriate density and strength to function as part of a chip-type multilayer electronic component.

[0067] (Adhesive resin)

[0068] In the compositions of the present invention, the adhesive resin preferably comprises at least one selected from polyvinyl acetate, polyvinyl butyral, polyvinyl alcohol, acrylic acid, and polyurethane, and more preferably comprises polyvinyl acetate.

[0069] These adhesive resins can bond inorganic powders together, and are therefore suitable for molding the compositions of the present invention into a specified shape.

[0070] In particular, when the adhesive resin is polyvinyl acetate, the compound having the structure represented by the above general formula (1) has a large volume and is therefore not easily oriented toward the acetoxy group of the molecule constituting polyvinyl acetate.

[0071] Therefore, compounds with the structure represented by the above general formula (1) readily enter the intermolecular space of polyvinyl acetate, thus causing polyvinyl acetate to easily aggregate. Consequently, the Tg of polyvinyl acetate increases.

[0072] Therefore, glass transition temperature regulators can be used to adjust the Tg of polyvinyl acetate, thereby improving the moldability of the compositions of the present invention.

[0073] In the compositions of the present invention, the adhesive resin is preferably contained in an emulsion state.

[0074] In this case, the inorganic powder in the composition of the present invention is not locally dense and is easily dispersed.

[0075] The composition of the present invention preferably contains 5 to 50 parts by weight of binder resin relative to 100 parts by weight of inorganic powder, more preferably 10 to 30 parts by weight, and even more preferably 10 to 20 parts by weight.

[0076] When the amount of binder resin is less than 5 parts by weight relative to 100 parts by weight of inorganic powder, the content of binder resin is relatively low, making it difficult to fully bond the inorganic powder together. As a result, the molded article is prone to damage when the composition is molded into a specified shape.

[0077] When the content of inorganic powder is less than 50 parts by weight compared to 100 parts by weight of binder resin, the dimensional changes during calcination are greater, and the stress caused by shrinkage is greater, which makes it easier to crack.

[0078] (Glass transition temperature regulator)

[0079] In the compositions of the present invention, the structure represented by general formula (1) has R 1 It can be a linear or branched hydrocarbon group with 1 to 12 carbon atoms. Additionally, R... 1 It may contain unsaturated bonds or consist only of saturated bonds, preferably consisting only of saturated bonds.

[0080] R 1 When unsaturated bonds are present, intramolecular rotation is restricted, and the portions with unsaturated bonds form a rigid planar structure. On the other hand, R 1 When the molecules consist solely of saturated bonds, intramolecular rotation is unrestricted, resulting in a slower increase in temperature (Tg) compared to the case containing unsaturated bonds. The presence or absence of unsaturated bonds can be chosen based on the desired Tg. It should be noted that, aside from the Tg considerations, substances consisting solely of saturated bonds are more stable and easier to preserve as materials compared to those containing unsaturated bonds.

[0081] It should be noted that R 1 Preferably, it is 2-ethylhexyl.

[0082] In the compositions of the present invention, the structure represented by general formula (1) has R 2 It can be a straight-chain, branched, or cyclic hydrocarbon group with 1 to 12 carbon atoms.

[0083] R 2 When the group is a cyclic hydrocarbon group, it can also be a heterocyclic group.

[0084] Additionally, R2 The preferred component is a benzene ring.

[0085] Additionally, R 2 It can contain unsaturated bonds or consist only of saturated bonds.

[0086] In the compositions of the present invention, the structure represented by general formula (1) has R 3 It can be a linear or branched hydrocarbon group with 1 to 12 carbon atoms. Additionally, R... 3 It may contain unsaturated bonds or consist only of saturated bonds, preferably consisting only of saturated bonds.

[0087] It should be noted that R 3 Preferably, it is 2-ethylhexyl.

[0088] In the compositions of the present invention, the structure represented by general formula (1) has R 4 It can be a linear or branched hydrocarbon group with 1 to 12 carbon atoms. Additionally, R... 4 It may contain unsaturated bonds or consist only of saturated bonds, preferably consisting only of saturated bonds.

[0089] It should be noted that R 4 Preferably, it is 2-ethylhexyl.

[0090] In the compositions of the present invention, compounds having the structure represented by general formula (1) may include derivatives of tricarboxylic acids such as trimellitic acid, aconitic acid, propane-1,2,3-tricarboxylic acid, and cyclohexane-1,2,4-tricarboxylic acid.

[0091] Examples of such tricarboxylic acid derivatives include alkyl trimellitic acid, alkyl aconitate, alkyl propane-1,2,3-tricarboxylic acid, and alkyl cyclohexane-1,2,4-tricarboxylic acid.

[0092] In this case, the structure represented by general formula (1) can also be a carboxyl residue (i.e., R). 1 R 3 or R 4 (The case of hydrogen atoms).

[0093] In the compositions of the present invention, the compound having the structure represented by general formula (1) is preferably tri(2-ethylhexyl) trimellitate as shown in general formula (2) below.

[0094]

[0095] The aforementioned tricarboxylic acid alkyl esters are inexpensive, which can reduce the manufacturing cost of the compositions of the present invention.

[0096] In the composition of the present invention, relative to 100 parts by weight of inorganic powder, it preferably contains 0.01 to 5 parts by weight of glass transition temperature regulator, more preferably 0.1 to 1.0 parts by weight.

[0097] When the glass transition temperature regulator is less than 0.01 parts by weight relative to 100 parts by weight of inorganic powder, the Tg of the adhesive resin is difficult to increase sufficiently.

[0098] Compared to 100 parts by weight of inorganic powder, when the glass transition temperature regulator is more than 5 parts by weight, the effect of increasing the Tg of the adhesive resin is close to the upper limit, which is not economical.

[0099] (solvent)

[0100] The compositions of the present invention may further contain a solvent.

[0101] Examples of solvents include diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (Texanol), eugenol, terpineol, dihydroterpineol, benzyl alcohol, ethanol, isophorone, methyl ethyl ketone, and diethyl ketone.

[0102] These solvents are useful in the compositions of the present invention for uniformly mixing inorganic powders, binder resins and glass transition temperature regulators.

[0103] In the composition of the present invention, the solvent content is preferably 0.05% to 20% by weight.

[0104] (Other additives)

[0105] The compositions of the present invention may contain dispersants, plasticizers, defoamers, wetting agents as other additives.

[0106] Examples of dispersants include ammonium polycarboxylate salts and maleic anhydride-styrene copolymers.

[0107] Examples of plasticizers include diglycerides, polyglycerides, and alkyl hydroxy acids.

[0108] Examples of defoamers include polyalkylene glycol, dimethylpolysiloxane, and octadecyl alcohol.

[0109] Examples of wetting agents include polyalkylene glycols and polyglycerols.

[0110] (The proportions of each component, etc.)

[0111] In the composition of the present invention, preferably, 5 to 50 parts by weight of binder resin are contained relative to 100 parts by weight of inorganic powder, and 0.01 to 5 parts by weight of glass transition temperature regulator are contained relative to 100 parts by weight of inorganic powder; more preferably, 10 to 30 parts by weight of binder resin are contained relative to 100 parts by weight of inorganic powder, and 0.01 to 5 parts by weight of glass transition temperature regulator are contained; even more preferably, 10 to 20 parts by weight of binder resin are contained relative to 100 parts by weight of inorganic powder, and 0.1 to 1.0 parts by weight of glass transition temperature regulator are contained.

[0112] When the compositions of the present invention contain inorganic powder, binder resin, and glass transition temperature regulator in such proportions, the Tg of the binder resin is appropriately increased. Therefore, the formability of the compositions of the present invention is improved.

[0113] In the composition of the present invention, the weight percentage (wt%) of the adhesive resin relative to the weight of the glass transition temperature regulator is preferably 0.5 to 5000, more preferably 2.5 to 200.

[0114] Next, the method for manufacturing the composition of the present invention will be described.

[0115] The method for manufacturing the composition of the present invention includes: a pulverizing step of pulverizing inorganic materials into inorganic powder, and a mixing step of mixing the inorganic powder, adhesive resin and glass transition temperature regulator, wherein the glass transition temperature regulator comprises a compound having a structure represented by the following general formula (1).

[0116]

[0117] (In general formula (1), R) 1 It consists of a hydrocarbon group with 1 to 12 hydrogen and carbon atoms.

[0118] In general formula (1), R 2 It consists of hydrocarbon groups with 1 to 12 carbon atoms.

[0119] In general formula (1), R 3 It consists of a hydrocarbon group with 1 to 12 hydrogen and carbon atoms.

[0120] In general formula (1), R 4 (A hydrocarbon group consisting of 1 to 12 hydrogen and carbon atoms.)

[0121] The Tg of the adhesive resin can be increased by using a glass transition temperature regulator comprising a compound having the structure represented by the general formula (1) above. That is, the plasticity of the manufactured composition can be adjusted by using a glass transition temperature regulator.

[0122] In the method for manufacturing the composition of the present invention, in the above-mentioned mixing step, it is preferable to mix the inorganic powder, the adhesive resin, and the glass transition temperature regulator in such a way that the adhesive resin is 5 to 50 parts by weight relative to 100 parts by weight of the inorganic powder and the glass transition temperature regulator is 0.01 to 5 parts by weight. Furthermore, in the above-mentioned mixing step, it is more preferable to mix the inorganic powder, the adhesive resin, and the glass transition temperature regulator in such a way that the adhesive resin is 10 to 30 parts by weight relative to 100 parts by weight of the inorganic powder and the glass transition temperature regulator is 0.01 to 5 parts by weight. It is even more preferable to mix the inorganic powder, the adhesive resin, and the glass transition temperature regulator in such a way that the adhesive resin is 10 to 20 parts by weight relative to 100 parts by weight of the inorganic powder and the glass transition temperature regulator is 0.1 to 1.0 parts by weight.

[0123] When a composition manufactured in this proportion contains inorganic powder, binder resin, and glass transition temperature regulator, the Tg of the binder resin is appropriately increased. Therefore, the moldability of the manufactured composition is improved.

[0124] Next, a chip-type multilayer electronic device fabricated using the composition of the present invention will be described. The chip-type multilayer electronic device fabricated using the composition of the present invention is one embodiment of the present invention.

[0125] In addition, when manufacturing chip-type stacked electronic components, manufacturing sheet-like objects obtained using the composition of the present invention and stacked bodies formed by stacking the sheet-like objects are also aspects of the present invention.

[0126] Figure 1A This is a cross-sectional view schematically illustrating an example of the sheet-like material of the present invention.

[0127] Figure 1B yes Figure 1A Enlarged view of the dotted line portion.

[0128] When fabricating the chip-type stacked electronic component of the present invention, firstly, as follows: Figure 1A As shown, the composition of the present invention is shaped into a sheet to form sheet 10a.

[0129] There is no particular limitation on the method of forming the composition of the present invention into a sheet, for example, conventional methods such as using a bar coater or printing can be used.

[0130] It should be noted that when manufacturing sheet 10a, because the specific gravity of the adhesive resin is lower than that of the inorganic powder, therefore... Figure 1B As shown, the closer to the upper surface of the sheet 10a, the higher the density of the adhesive resin 11a.

[0131] After the sheet 10a is formed, through holes (not shown) can be formed on the sheet 10a as needed. Alternatively, conductor paste (not shown) can be applied to the sheet 10a.

[0132] Through-holes and conductive paste can use materials known in the past, and their formation and preparation methods can also adopt methods known in the past.

[0133] Figure 2A and Figure 2B This is a schematic diagram illustrating an example of a process for fabricating a laminate using the sheet material of the present invention.

[0134] Next, as Figure 2A As shown, prepare multiple sheet-like objects 10a.

[0135] Then, as Figure 2B The sheet material 10a is stacked and pressed together to create a master block 20a as a laminate.

[0136] There are no particular restrictions on the conditions for crimping; previously known methods can be used.

[0137] Then, the master block 20a can be cut into a specified shape to form a chip-like object.

[0138] Furthermore, the edges of the chip-like object can be chamfered as needed.

[0139] It should be noted that both the mother block 20a and the chip-like object are included in the laminate of the present invention.

[0140] These laminates are less prone to deformation because they are made using the composition of the present invention. Therefore, the deviations in appearance quality and electrical properties of the blanks produced through the processes described later are reduced.

[0141] Next, the chip-like material is degreased and calcined. Thus, the chip-like material 10a becomes a calcined sheet 10, which can be used to manufacture... Figure 3 The blank 20 shown is formed by stacking multiple calcined sheets 10.

[0142] Figure 3 This is a side view schematically showing an example of a blank composed of multiple stacked calcined sheets.

[0143] It should be noted that during this calcination, the conductive paste formed on the sheet 10a becomes the internal electrode.

[0144] In addition, during calcination, the binder resin 11a contained in the sheet 10a is thermally decomposed to form pores 11.

[0145] As described above, in the sheet 10a, the density of the adhesive resin 11a is higher closer to the top. Therefore, the density of the pores 11 in the portion of the adhesive resin 11a with higher density is also higher. Therefore, as... Figure 3 As shown, when the blank 20 is viewed from the side, the pore 11 is presented in a linear manner in a direction perpendicular to the stacking direction.

[0146] like Figure 3 As shown, the billet 20 is formed by stacking multiple calcined sheets 10. Therefore, when the billet 20 is viewed from the side, a stripe pattern perpendicular to the stacking direction is formed on the billet 20.

[0147] The blank 20 can be formed with external electrodes, etc., as needed.

[0148] The chip-type stacked electronic components of the present invention can be fabricated using this method.

[0149] It should be noted that, as described above, since a stripe pattern perpendicular to the stacking direction is formed on the blank 20 when viewed from the side, the stripe pattern can be used as a marker to identify the side of the chip-type stacked electronic component of the present invention, which includes the blank 20.

[0150] That is, when observing chip-type stacked electronic components, the observer can identify the surface with striped patterns as the side surface and the surface without striped patterns as the top or bottom surface in the blank of the chip-type stacked electronic components.

[0151] Therefore, in the chip-type stacked electronic components of the present invention, it is not necessary to form other identification marks on the side, upper surface, and lower surface of the blank.

[0152] Therefore, production costs can be reduced.

[0153] The following inventions are described in this specification.

[0154] The present invention (1) is a composition comprising an inorganic powder, a binder resin and a glass transition temperature regulator, wherein the glass transition temperature regulator comprises a compound having a structure represented by the following general formula (1).

[0155]

[0156] (In general formula (1), R) 1 It consists of a hydrocarbon group with 1 to 12 hydrogen and carbon atoms.

[0157] In general formula (1), R 2 It consists of hydrocarbon groups with 1 to 12 carbon atoms.

[0158] In general formula (1), R 3It consists of a hydrocarbon group with 1 to 12 hydrogen and carbon atoms.

[0159] In general formula (1), R 4 (A hydrocarbon group consisting of 1 to 12 hydrogen and carbon atoms.)

[0160] The present invention (2) is the composition described in the present invention (1), wherein the glass transition temperature regulator is a derivative of at least one tricarboxylic acid selected from trimellitic acid, aconitic acid, propane-1,2,3-tricarboxylic acid, and cyclohexane-1,2,4-tricarboxylic acid.

[0161] The present invention (3) is the composition described in the present invention (1) or (2), wherein the composition further contains a solvent.

[0162] The present invention (4) is a composition of any one of the present invention (1) to (3), wherein the adhesive resin comprises at least one selected from polyvinyl acetate, polyvinyl butyral, polyvinyl alcohol, acrylic acid, polyurethane, polyvinylpyrrolidone, polyethylene glycol, ethylene-vinyl acetate copolymer, and cellulose ether.

[0163] The present invention (5) is a composition according to any one of the present invention (1) to (4), wherein the inorganic powder comprises ceramic powder.

[0164] The present invention (6) is a composition of any one of the present invention (1) to (4), wherein the inorganic powder comprises at least one selected from zirconium oxide, titanium dioxide, aluminum oxide, barium titanate, ferrite, lead zirconate titanate, zinc oxide, glass, and glass ceramics.

[0165] The present invention (7) is a composition according to any one of the present invention (1) to (6), wherein, relative to 100 parts by weight of the above-mentioned inorganic powder, it contains 5 to 50 parts by weight of the above-mentioned adhesive resin and 0.01 to 5 parts by weight of the above-mentioned glass transition temperature regulator.

[0166] The present invention (8) is a sheet containing any one of the compositions of the present invention (1) to (7).

[0167] The present invention (9) is a laminate, which is formed by stacking multiple sheets of the sheet material described in the present invention (8).

[0168] The present invention (10) is a method for manufacturing a composition, comprising: a pulverizing step of pulverizing an inorganic material to form an inorganic powder, and a mixing step of mixing the inorganic powder, an adhesive resin and a glass transition temperature regulator, wherein the glass transition temperature regulator comprises a compound having a structure represented by the following general formula (1).

[0169]

[0170] (In general formula (1), R) 1 It consists of a hydrocarbon group with 1 to 12 hydrogen and carbon atoms.

[0171] In general formula (1), R 2 It consists of hydrocarbon groups with 1 to 12 carbon atoms.

[0172] In general formula (1), R 3 It consists of a hydrocarbon group with 1 to 12 hydrogen and carbon atoms.

[0173] In general formula (1), R 4 (A hydrocarbon group consisting of 1 to 12 hydrogen and carbon atoms.)

[0174] The present invention (11) is a method for manufacturing the composition described in the present invention (10). In the above mixing process, the inorganic powder, the adhesive resin and the glass transition temperature regulator are mixed in such a way that the adhesive resin is 5 to 50 parts by weight relative to 100 parts by weight of the inorganic powder and the glass transition temperature regulator is 0.01 to 5 parts by weight.

[0175] The present invention (12) is a chip-type stacked electronic component, which has a blank formed by stacking multiple ceramic calcined sheets. When the blank is viewed from the side, a stripe pattern perpendicular to the stacking direction is formed on the blank.

[0176] [Example]

[0177] The following examples illustrate more specifically the compositions of the present invention. It should be noted that the present invention is not limited to the following examples.

[0178] (Example)

[0179] Ferrite powder (inorganic powder) is prepared by mixing 50 parts by weight of pure water relative to 100 parts by weight of ferrite, 0.5 parts by weight of polycarboxylate ammonium salt (dispersant) relative to 100 parts by weight of ferrite, and pulverizing the mixture using a ball mill.

[0180] Next, ferrite powder, polyvinyl acetate (adhesive resin), and tri(2-ethylhexyl) trimellitate (glass transition temperature regulator) were mixed in the proportions shown in Table 1 to prepare the slurry composition of the example.

[0181] Next, after degassing the composition of the example, the composition is coated onto a PET film in sheet form and dried with hot air to produce the sheet of the example (thickness: about 50 μm).

[0182] (Comparative example)

[0183] When preparing the paste composition, tri(2-ethylhexyl) trimellitate (glass transition temperature regulator) was not used. Ferrite powder and polyvinyl acetate (adhesive resin) were mixed in the proportions shown in Table 1. Otherwise, the comparative example sheet (thickness: about 50 μm) was prepared in the same manner as in the examples.

[0184] (Dynamic viscoelasticity determination and Tg calculation)

[0185] Next, the sheets from the examples and comparative examples were pressed together to create a laminate with a thickness of 500 μm.

[0186] Next, the sheet material from the examples and comparative examples was cut to a width × length of 10 mm × 50 mm to serve as test samples.

[0187] Next, dynamic viscoelasticity was measured using the test samples from the examples and comparative examples.

[0188] Dynamic viscoelasticity was measured using a viscoelasticity measuring device (instrument name: DMA7000, manufacturer: Hitachi High Technology Co., Ltd.) within a measurement temperature range of -30 to 100°C.

[0189] Based on the results of dynamic viscoelasticity measurements, the Tg of the adhesive resin contained in the compositions of the examples and comparative examples was calculated.

[0190] The results are shown in Table 1.

[0191]

[0192] As shown in Table 1, the Tg of polyvinyl acetate contained in the composition increases when tris(2-ethylhexyl) trimellitate is used as a glass transition temperature regulator.

[0193] (Relationship between the amount of glass transition temperature regulator used and Tg)

[0194] Ferrite powder, polyvinyl acetate (adhesive resin), and tris(2-ethylhexyl) trimellitate (glass transition temperature regulator) were compounded in the proportions shown in Table 2. The Tg of the polyvinyl acetate for each compound was calculated using the same method as described in "Dynamic Viscoelasticity Measurement and Tg Calculation" above. Then, the extent to which the Tg of the polyvinyl acetate increased relative to the Tg of the polyvinyl acetate in the comparative examples above was evaluated according to the following criteria. The results are shown in Table 2.

[0195] (Evaluation criteria for the temperature rise of Tg)

[0196] The Tg of the polyvinyl acetate in the comparative examples above is set to "T0", and the Tg of the polyvinyl acetate in each example is set to "T". xWhen “”, evaluations A1 and A2 satisfy the following relationship.

[0197] A1: 5℃≤(T) x -T0)

[0198] A2: (T) x -T0) <5℃

[0199]

[0200] In addition, the graphs of the loss factor (Tanδ) from the dynamic viscoelasticity measurements of each embodiment were examined to confirm whether the peaks were separated.

[0201] In the case of peak separation, it means that polyvinyl acetate and tri(2-ethylhexyl) trimellitate have been separated in the composition.

[0202] The evaluation criteria are as follows. The results are shown in Table 3. B1: Peak not separated. B2: Peak separated.

[0203]

[0204] It should be noted that, as a representative example of peak separation, for an example using 10 wt% polyvinyl acetate and 1.4 wt% tris(2-ethylhexyl) trimellitate, the graph of the loss factor (Tanδ) from the above dynamic viscoelasticity determination is shown in the figure. Figure 4 .

[0205] Figure 4 This is a graph of the loss factor (Tanδ) measured by dynamic viscoelasticity in an embodiment of the present invention.

[0206] like Figure 4 As shown in the graph of the loss factor (Tanδ) from the dynamic viscoelasticity measurement of the embodiment, two peaks appear near 18°C ​​and 48°C. The peak near 48°C is considered to be the peak of polyvinyl acetate aggregates.

[0207] It is believed that when tris(2-ethylhexyl) trimellitate is present in the composition, it is less likely to align with the acetoxy groups of the polyvinyl acetate molecules, causing the polyvinyl acetate molecules to aggregate. Therefore, it is thought that the Tg of polyvinyl acetate increases.

[0208] However, it is believed that when the proportion of tri(2-ethylhexyl) trimellitate is too high, polyvinyl acetate partially aggregates with each other, forming aggregates.

[0209] It is believed that when such aggregates are generated, such as Figure 4 The peaks shown are separated.

[0210] When aggregates are formed, the strength of sheets and laminates decreases, so it is preferable that there are no such aggregates.

[0211] In the above evaluation, embodiments that simultaneously meet evaluation A1 and evaluation B1 can be rated as "Excellent", and other embodiments can be rated as "Available". The evaluation is shown in Table 4.

[0212]

[0213] As shown in Tables 2 to 4, it can be seen that by adjusting the ratio of polyvinyl acetate to tri(2-ethylhexyl) trimellitate, the Tg of polyvinyl acetate in the compositions of the examples can be adjusted, and separation of polyvinyl acetate and tri(2-ethylhexyl) trimellitate can be avoided.

Claims

1. A composition comprising an inorganic powder, a binder resin, and a glass transition temperature regulator. The glass transition temperature regulator comprises a compound having a structure represented by the following general formula (1). In general formula (1), R 1 It consists of hydrogen atoms or hydrocarbon groups having 1 to 12 carbon atoms. In general formula (1), R 2 It consists of hydrocarbon groups with 1 to 12 carbon atoms. In general formula (1), R 3 It consists of hydrogen atoms or hydrocarbon groups having 1 to 12 carbon atoms. In general formula (1), R 4 It consists of hydrogen atoms or hydrocarbon groups with 1 to 12 carbon atoms.

2. The composition according to claim 1, wherein, The glass transition temperature regulator is a derivative of at least one tricarboxylic acid selected from trimellitic acid, aconitic acid, propane-1,2,3-tricarboxylic acid, and cyclohexane-1,2,4-tricarboxylic acid.

3. The composition according to claim 1 or 2, wherein, The composition further contains a solvent.

4. The composition according to any one of claims 1 to 3, wherein, The adhesive resin comprises at least one selected from polyvinyl acetate, polyvinyl butyral, polyvinyl alcohol, acrylic acid, polyurethane, polyvinylpyrrolidone, polyethylene glycol, ethylene-vinyl acetate copolymer, and cellulose ether.

5. The composition according to any one of claims 1 to 4, wherein the inorganic powder comprises ceramic powder.

6. The composition according to any one of claims 1 to 4, wherein, The inorganic powder comprises at least one selected from zirconium oxide, titanium dioxide, aluminum oxide, barium titanate, ferrite, lead zirconate titanate, zinc oxide, glass, and glass ceramics.

7. The composition according to any one of claims 1 to 6, wherein, Relative to 100 parts by weight of the inorganic powder, it contains 5 to 50 parts by weight of the adhesive resin and 0.01 to 5 parts by weight of the glass transition temperature regulator.

8. A sheet comprising the composition according to any one of claims 1 to 7.

9. A laminated body, which is formed by stacking multiple sheets as described in claim 8.

10. A method for manufacturing a composition, comprising: The pulverization process involves crushing inorganic materials into inorganic powder, and The mixing process involves mixing the inorganic powder, binder resin, and glass transition temperature regulator. The glass transition temperature regulator comprises a compound having a structure represented by the following general formula (1). In general formula (1), R 1 It consists of hydrogen atoms or hydrocarbon groups having 1 to 12 carbon atoms. In general formula (1), R 2 It consists of hydrocarbon groups with 1 to 12 carbon atoms. In general formula (1), R 3 It consists of hydrogen atoms or hydrocarbon groups having 1 to 12 carbon atoms. In general formula (1), R 4 It consists of hydrogen atoms or hydrocarbon groups with 1 to 12 carbon atoms.

11. The method for manufacturing the composition according to claim 10, wherein, In the mixing process, the inorganic powder, the adhesive resin, and the glass transition temperature regulator are mixed in a manner that is relative to 100 parts by weight of the inorganic powder, 5 to 50 parts by weight of the adhesive resin, and 0.01 to 5 parts by weight of the glass transition temperature regulator.

12. A chip-type stacked electronic component comprising a blank formed by stacking and calcining multiple ceramic sheets. When viewed from the side, the blank has a striped pattern that is perpendicular to the stacking direction.

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