CN1972995A - Binder resin composition, paste, and green sheet - Google Patents

Abstract

A binder resin composition which shows no 'stringing' when used in printing and can disappear without leaving any residue upon burning at a relatively low temperature; a glass paste; and a ceramic paste. The binder resin composition contains as a matrix resin a copolymer (A) comprising a segment derived from an alkyl (meth)acrylate monomer and a polyalkylene oxide segment composed of repeating units represented by the following chemical formula (1). -(OR)n- (1) R is C3 or higher alkylene and n is an integer.

Description

Adhesive resin composition, paste and green sheet

technical field

The present invention relates to an adhesive resin composition, a paste, and a green sheet (Darinsite) that can be removed without generating residue during firing at a relatively low temperature.

Background technique

In recent years, moldings have been produced in which, after molding a paste in which inorganic powders such as ceramic powders or glass powders are dispersed in a binder resin composition, they are fired to obtain precise moldings containing ceramics or glass. body.

For example, multilayer ceramic capacitors are usually manufactured through the following steps.

After adding a plasticizer, a dispersant, etc. to a solution in which a binder resin is dissolved in an organic solvent, the ceramic raw material powder is added, and mixed uniformly by a mixing device such as a three-roller, bead mill, or ball mill. The obtained mixture is defoamed to obtain a pasty ceramic paste composition with a certain viscosity. The resulting paste composition is cast on a release-treated polyethylene terephthalate film or a support such as a stainless steel plate using a coating device such as a doctor blade or a reverse roll coater, and formed into a sheet. Next, the molded body is heated to distill off volatile components such as a solvent, and then peeled off from the support to obtain a ceramic green sheet.

Next, a conductive paste to be an internal electrode is applied on the obtained ceramic green sheet by screen printing or the like. Several ceramic green sheets coated with the conductive paste were laminated alternately, and heated and pressed to obtain a laminated body. The conductive paste used at this time is mainly composed of a metal material such as palladium or nickel constituting the electrodes, an organic solvent compatible with the surface of the ceramic green sheet, and a binder resin such as ethyl cellulose.

Next, the binder component etc. contained in the laminated body which is a constituent component of a ceramic green sheet and a conductive paste is thermally decomposed by heating, a removal process (so-called degreasing process) is performed, and firing is performed to obtain a fired ceramic product. A multilayer ceramic capacitor is obtained through the step of sintering the external electrodes on the end faces of the ceramic fired product.

In addition, for example, the basic structure of a plasma display panel (hereinafter also referred to as PDP) includes a pair of glass substrates as a panel body, a phosphor layer, an enclosed gas mainly composed of neon and/or xenon, a dielectric layer, partitions and electrodes. Materials such as Ag paste or Cu-Al alloy are used in the electrodes. The electrodes can be obtained by, for example, forming a metal film on a glass substrate by thick-film printing or vapor deposition, followed by patterning. Among PDPs, there are AC type driven by alternating voltage or pulse voltage, and DC type driven by direct voltage. An AC-type PDP has a structure in which electrodes are covered with a dielectric layer, while a DC-type PDP has a structure in which electrodes are exposed in a discharge space. A method of forming a dielectric layer by firing a binder resin composition in which a low-melting glass is dispersed can also be employed.

In addition, in a DC type PDP, it is necessary to use a glass substrate having partition walls. Conventionally, as a method of manufacturing a glass substrate with partitions, a paste formed by mixing ceramic powder, an organic binder, and a solvent, etc., is applied on a glass substrate by a thick-film printing method to form a pattern, followed by drying and firing to form partition walls. method (the so-called thick film printing method, such as Patent Document 1); a paste formed by mixing ceramic powder, an organic binder, a solvent, etc. with a predetermined film thickness is flatly printed on a glass substrate, and then, the light A method in which the patterned part is masked with a resist, and then dry-etched by a sandblasting method. After the pattern is formed, the resist is removed, and then fired to form a partition (so-called sandblasting method, for example, Patent Document 2 )wait.

However, in the thick film printing method, the thickness that can be formed by one printing is at most about tens of μm, and it is necessary to repeat printing about 10 times in order to achieve the height of 100 μm or more necessary for the partition wall. It is difficult or impossible to obtain high precision, so there is a problem of poor yield. In addition, in the sandblasting method, since a photoresist is used, steps such as exposure, development, and resist removal are necessary, and the process becomes complicated, and there are cases where the side walls of the partition walls are etched to be smaller than the width of the mask, or There is a problem that it is difficult to form a partition wall with high precision, such as the expansion of the bottom (leg) of the partition wall.

In this case, a predetermined pattern made of a light-shielding material is formed on the surface, and the light-transmitting substrate on which the photosensitive material layer is formed is exposed from the back surface of the substrate, and developed after exposure. Next, using the master mold (pattern) for the transfer gravure of the partition wall formed by forming the convex part of the desired pattern on the substrate, the transfer gravure for the partition wall is produced, and the concave part of the gravure for transfer is filled with the partition wall material and transferred. Printed on substrates for plasma display panels. Patent Document 3 discloses a method of forming a partition wall of a plasma display panel including these various steps. In this method, a resin containing glass powder is poured into a master mold in which a desired pattern of concave parts is formed, a substrate is superimposed on it, and the prototype is turned over and removed, thereby forming protrusions made of resin containing glass powder on the substrate. part, and then by firing it to integrate the glass component and the substrate to form a partition wall method (so-called transfer method). By the transfer method, compared with the sandblasting method or the thick film printing method, the glass substrate which has partition walls can be manufactured easily and simply.

As a binder resin composition used in the manufacture of such laminated ceramic capacitors or PDPs, for example, ethyl cellulose, methyl cellulose, polyvinyl butyral, polyethylene Alcohol, polyethylene glycol etc. are the composition of main component. However, the thermal decomposition temperature of the binder resin composition mainly composed of these resins is high. The problem of resin decomposition residue components.

In response to such circumstances, low-temperature firing adhesive resin compositions containing acrylic resins as main components have been studied. Patent Document 4 discloses a methacrylic resin containing 90% by weight or more of an alkyl methacrylate component having a weight average molecular weight of 200,000 or more and a glass transition temperature of -20 to 60°C. This methacrylic resin has a low thermal decomposition temperature and is easy to degrease during firing. In addition, when a mixture containing ceramic powder is molded into a tape shape to form a ceramic green sheet, excellent tape strength is exhibited. However, since the molecular weight is large, when it is used for purposes such as conductive paste and is printed by screen printing or the like, there is a problem that the paste sometimes becomes a thread from the printing plate and hangs down, which is called "stringing" (系引き)The phenomenon.

Patent Document 5 discloses a ceramic green sheet using an acrylic resin having an average molecular weight of 200,000 or more, an acid value of 2.4 to 7.2, and a glass transition temperature of 50 to 90°C. However, when this acrylic resin is used in applications such as conductive pastes and printed by screen printing or the like, a phenomenon of "stringing" sometimes occurs.

Patent Document 6 discloses an acrylic resin composition containing an alkyl (meth)acrylate, an unsaturated carboxylic acid, a hydroxyl group-containing (meth)acrylate, and other copolymerizable monomers. A solid acrylic resin as the adhesive component. When this acrylic resin composition is printed by screen printing or the like, since the paste does not hang down in a thread form from the printing plate but is cut off, a phenomenon called "slitting" occurs, so there is little stringing. , can be fired at low temperature. However, in fact, compared with conventional ethyl cellulose or polyvinyl butyral, although it can be fired at a lower temperature, the firing temperature suitable for degreasing is still as high as 450°C. Therefore, it is difficult to degrease satisfactorily under the lower firing conditions of the currently studied firing temperature, and residues may remain during firing.

In Patent Document 7, Patent Document 8, Patent Document 9, Patent Document 10, and Patent Documents 14 and 15, photosensitive resin binders using metal powder, phosphor, and glass powder together are disclosed. etc., and include (meth)acrylic polymers having polyethylene oxide chains as side chains and containing (methyl) ) repeating units of acrylate monomers.

Patent Document 11 discloses a photopolymerizable resin binder that uses metal powder, glass powder, ceramic powder, etc., and contains a (meth)acrylic polymer. The base) acrylic polymer has a polyethylene oxide chain as a side chain, and contains a repeating unit derived from a methacrylate monomer having a carboxyl group at the end of the side chain.

However, a (meth)acrylic polymer having a polyethylene oxide chain in its side chain has high water absorption and may absorb moisture in a high-humidity environment. The moisture-absorbing paste has a problem that the thickness of the sheet tends to be uneven when the paste is dried after being printed and applied in a sheet form. In addition, the firing temperature suitable for degreasing is 450° C., but there is still a problem of high firing temperature.

In Patent Document 12, a photopolymerizable material is disclosed, which uses inorganic powders such as insulators, dielectrics, resistors, conductors, etc. to form inorganic structures, and contains polyethylene oxide chains The polyfunctional (meth)acrylate of the main chain is used as a polyfunctional polymerizable monomer component. This material is used as a material for forming a resin adhesive.

In Patent Document 13, a material having anaerobic polymerizability is disclosed, which uses ceramic powder and contains hexaethylene glycol diacrylate, tetraethylene glycol dimethacrylate, etc. A polyfunctional (meth)acrylate having a polyethylene oxide chain as the main chain serves as a polyfunctional polymerizable monomer component. This material is used as a material for forming a resin adhesive.

Patent Documents 12 to 15 disclose a resin binder which is a (meth)acrylate polymer containing a polyethylene oxide chain as a main chain or a side chain.

However, in acrylic resin adhesives containing polyoxyethylene chains as the main chain, the resin adhesive tends to contain water due to the presence of polyoxyethylene chains, and when moisture is absorbed in a high-humidity environment, there is a problem that the viscosity of the paste is difficult to stabilize. . In addition, the firing temperature suitable for degreasing is 450° C., but there is still a problem of high firing temperature.

Patent Document 1: Japanese Patent Publication No. 58-150248

Patent Document 2: Japanese Unexamined Patent Publication No. 5-182592

Patent Document 3: JP-A-2000-11865

Patent Document 4: JP-A-2004-59358

Patent Document 5: Japanese Unexamined Patent Publication No. 9-142941

Patent Document 6: JP-A-2001-49070

Patent Document 7: Japanese Unexamined Patent Publication No. 5-132692

Patent Document 8: Japanese Unexamined Patent Publication No. 5-194548

Patent Document 9: Japanese Unexamined Patent Publication No. 5-194551

Patent Document 10: Japanese Unexamined Patent Publication No. 5-208640

Patent Document 11: JP-A-2000-290314

Patent Document 12: JP-A-7-316456

Patent Document 13: Japanese Unexamined Patent Publication No. 5-157035

Patent Document 14: JP-A-2004-315719

Patent Document 15: JP-A-2004-142964

Contents of the invention

The object of the present invention is to provide a low-temperature fired adhesive resin composition, glass paste, ceramic paste, phosphor paste, conductive paste, etc. piece.

In a broad aspect, the present invention is characterized in that the adhesive resin composition contains a copolymer (A) containing a copolymer (A) derived from an alkyl (meth)acrylate unit as a base resin, and other components. A segment of a body, and a polyalkylene oxide segment comprising a repeating unit represented by the following chemical formula (1).

-(OR) _n - ...(1)

R: an alkylene group having 3 or more carbon atoms, and n is an integer.

In addition, the integer n in the above chemical formula is preferably 5 or more.

In addition, the adhesive resin composition more preferably has a segment derived from an alkyl (meth)acrylate monomer, and a chain segment selected from polypropylene oxide, polymethyl oxirane, polyethylene oxide, The copolymer (A) of at least one polyalkylene oxide segment in polyoxetane and polytetrahydrofuran is used as the matrix resin.

In a specific aspect of the present invention, an adhesive resin composition is provided, the resin composition uses a copolymer (A) as a matrix resin, and the copolymer (A) has The chain segment of the alkyl acrylate monomer is derived from the chain segment of the alkyl (meth)acrylate monomer whose glass transition temperature of the homopolymer is 30° C. or higher, and the polyalkylene oxide described in the above chemical formula (1). chain segment.

In another specific aspect of the adhesive resin composition according to the present invention, the copolymer (A) is an alkyl (meth)acrylate monomer having a homopolymer-derived glass transition temperature of 0° C. or lower The segment of the copolymer (A1) as the copolymerization component.

In still another specific aspect of the adhesive resin composition according to the present invention, the copolymer (A) copolymerizes a copolymerizable monomer having a functional group capable of forming a hydrogen bond with a hydroxyl group.

In yet another specific aspect of the adhesive resin composition according to the present invention, the copolymerizable monomer having a functional group capable of forming a hydrogen bond with a hydroxyl group is a hydroxyl group-containing (meth)acrylate monomer.

In yet another specific aspect of the adhesive resin composition according to the present invention, the copolymer (A) contains a long-chain alkyl (meth)acrylate as a copolymerization component.

In a further limitation of the binder resin composition according to the present invention, the long-chain alkyl group is a long-chain alkyl group having 8 or more carbon atoms.

In yet another specific aspect of the adhesive resin composition according to the present invention, the content of the long-chain alkyl (meth)acrylate in 100% by weight of the copolymer (A) is 1 to 30% by weight.

In still another specific aspect of the adhesive resin composition according to the present invention, the above-mentioned copolymer (A) further contains 1 to 80% by weight of (meth)acrylate having a functional group capable of forming a hydrogen bond with a hydroxyl group. as a copolymer component.

In the adhesive resin composition according to the present invention, it is preferable to further contain polyalkylene oxide (B).

In the case of a further limitation of the adhesive resin composition according to the present invention, an oligomer (C) which is liquid at 23° C. is further added.

A preferable binder resin composition is characterized in that the resin oligomer (C) has an SP value of 10×10 ^-3 to 8.5×10 ^-3 (J/m ³ ) ^0.5 as determined by Hoy's method.

In the binder resin composition according to the present invention, it is preferable to further contain an organic compound (D) having three or more hydroxyl groups.

As the above-mentioned organic compound (D), it is more preferable to use a compound that is liquid at normal temperature.

In another specific aspect of the adhesive resin composition according to the present invention, the above-mentioned compound having three or more hydroxyl groups (D ).

In the binder resin composition according to the present invention, it is preferable to further contain a nonionic surfactant.

Moreover, in the binder resin composition concerning this invention, it is more preferable to contain the organic solvent whose boiling point is 150 degreeC or more.

In yet another specific aspect of the adhesive resin composition according to the present invention, when a film having a thickness of 5 mm is formed, the haze value obtained from the total light transmittance of the film is 20 or more.

In yet another specific aspect of the adhesive resin composition according to the present invention, the above-mentioned copolymer (A) contains a (meth)acrylate having a functional group capable of forming a hydrogen bond with a hydroxyl group, and a (meth)acrylic acid long Alkyl ester is used as a monomer component, and in 100% by weight of the copolymer (A), it contains 1 to 80% by weight of the above-mentioned (meth)acrylate having a functional group capable of forming a hydrogen bond with a hydroxyl group, 1 to 80% by weight. 30% by weight of the aforementioned long-chain alkyl (meth)acrylate also contains an organic compound having three or more hydroxyl groups.

In another specific aspect of the adhesive resin composition according to the present invention, the aforementioned adhesive resin composition contains a long-chain alkyl (meth)acrylate as a constituent monomer of the polymer (A).

In a further limitation of the adhesive resin composition according to the present invention, the long-chain alkyl (meth)acrylate is a long-chain alkyl (meth)acrylate having 8 or more carbon atoms.

The method for producing a fired body according to the present invention is characterized in that a ceramic green sheet is produced using a ceramic paste containing ceramic powder and the binder resin composition according to the present invention, and then a plurality of the ceramic green sheets are laminated to form The laminated body is fired at a temperature below 300°C.

The glass paste according to the present invention is characterized by comprising the binder resin composition according to the present invention and glass powder dispersed in the binder resin composition.

The ceramic paste according to the present invention is characterized by comprising the binder resin composition according to the present invention and ceramic powder dispersed in the binder resin composition.

The phosphor paste according to the present invention is characterized by comprising the binder resin composition according to the present invention and phosphor powder dispersed in the binder resin composition.

The conductive paste according to the present invention is characterized by comprising the binder resin composition according to the present invention and conductive powder dispersed in the binder resin composition.

The green sheet according to the present invention contains the binder resin composition according to the present invention, and glass powder or ceramic powder dispersed in the binder resin composition.

Hereinafter, the present invention will be described in detail.

As a result of in-depth studies by the present inventors, it has been found that the polymer containing the polyalkylene oxide segment described in the chemical formula (1) is effective in forming ceramic green sheets, conductive pastes, partition walls of PDP, dielectric layers, and phosphor layers. The present invention has been accomplished because of the fact that the adhesive composition exhibits high abatement (destroyability) at a relatively low temperature of 400° C. or lower.

The above-mentioned copolymer (A) has a polyalkylene oxide segment represented by the chemical formula (1). Owing to having a polyalkylene oxide segment, the content of the oxygen component in the entire resin increases, and it is possible to prevent the binder resin from remaining as carbonized residue during firing.

-(OR) _n - ...(1)

R: an alkylene group having 3 or more carbon atoms, and n is an integer.

The content of the polyalkylene oxide segment in the copolymer (A) is not particularly limited, but the lower limit is preferably 1% by weight, the upper limit is preferably 80% by weight, and the upper limit is more preferably 60% by weight. A preferable upper limit is 50% by weight. When it is less than 1% by weight, it may not be possible to suppress the residue of carbonized residue, and when it exceeds 80% by weight, when the polypropylene oxide segment with relatively weak cohesive force is the polyalkylene oxide segment of the chemical formula (1) represented, sometimes It exhibits adhesiveness in the resin, easily causes blocking, and makes handling difficult. A more preferable lower limit is 3% by weight, an especially preferable upper limit is 40% by weight, and a more preferable upper limit is 30% by weight.

The integer n in the above chemical formula (1) is preferably 5 or more. When n is less than 5, decomposition at a relatively low temperature may become difficult depending on the firing time. More preferably, n is 5-1000, still more preferably 5-500, particularly preferably 5-200. When n exceeds 1000, it may be difficult to express thixotropy.

More specifically, it is preferred to have a segment derived from an alkyl (meth)acrylate monomer, and to be selected from the group consisting of polypropylene oxide, polymethylethylene oxide, polyethylene oxide, polyoxetane Copolymer (A) of at least one polyalkylene oxide segment in alkanes and polytetrahydrofuran. In addition, polypropylene oxide, polymethylethylene oxide, polyethylene oxide, and polytetrahydrofuran are particularly preferable because they are easily fired at low temperatures. In addition, the term "alkyl (meth)acrylate" is a generic term for alkyl acrylate and alkyl methacrylate. Among these, the alkyl (meth)acrylate is preferably an alkyl methacrylate since residues are less likely to remain after firing when it is an alkyl methacrylate.

In the above-mentioned copolymer (A), the chain segment from the alkyl (meth)acrylate monomer and the bonding position of the polyoxyalkylene oxide chain segment can be covalently bonded to the (meth)acrylate-containing alkyl Either the side chain of the poly(meth)acrylic acid alkyl ester chain segment, any one of the end, or the positional relationship between the two, can also be a chain segment and a polyalkylene oxide chain from the (meth)acrylic acid alkyl ester monomer A copolymer of alternating block copolymers.

FIG. 1 shows a schematic view showing how a segment derived from an alkyl (meth)acrylate monomer and a polyalkylene oxide segment are bonded. As the linking method of the segments, for example, (A) to (G) can be mentioned.

The above-mentioned copolymer (A) preferably has a segment derived from an alkyl (meth)acrylate monomer whose glass transition temperature of the homopolymer is 30° C. or higher. The alkyl (meth)acrylate component whose glass transition temperature of the above-mentioned homopolymer is 30° C. or higher imparts excellent adhesion to inorganic powders such as glass powder or ceramic powder to the copolymer (A), and makes the coating Components that are non-sticky on the film surface and easily inhibit the adhesion of dirt. When the temperature is lower than 30° C., stickiness tends to be generated on the coating film surface, and adhesion or blocking of dust and dirt tends to occur easily. Preferably it is 40°C or higher.

The alkyl (meth)acrylate having a glass transition temperature of 30° C. or higher as the homopolymer is not particularly limited, and examples thereof include methyl methacrylate, ethyl methacrylate, and propyl methacrylate. , tert-butyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, n-octadecyl methacrylate, benzyl methacrylate, isobornyl acrylate, Benzyl acrylate, etc.

The above-mentioned copolymer (A) may be a copolymer (A1) having, as a copolymerization component, a segment derived from an alkyl (meth)acrylate monomer whose glass transition temperature of a homopolymer is 0° C. or lower. In such a copolymer (A1), the viscosity of the adhesive resin composition of the present invention can be easily adjusted by adjusting the content of the segment derived from the above-mentioned alkyl (meth)acrylate monomer.

The alkyl (meth)acrylate monomer whose glass transition temperature of the homopolymer is 0°C or lower is not particularly limited, and examples thereof include ethyl acrylate, n-butyl acrylate, tert-butyl acrylate, acrylic acid Isopentyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, isononyl acrylate, isomyristyl acrylate, lauryl methacrylate, isodecyl methacrylate, decamethacrylate Trialkyl esters, 2-ethylhexyl methacrylate, etc. Among them, lauryl methacrylate and 2-ethylhexyl methacrylate are preferable because of their excellent decomposability.

In the above-mentioned copolymer (A1), as a segment of an alkyl (meth)acrylate monomer having a glass transition temperature derived from the above-mentioned homopolymer of 30° C. or higher and a glass transition temperature derived from the homopolymer of 0° C. The ratio of the segments of the following alkyl (meth)acrylate monomers is not particularly limited and can be appropriately selected as needed, but is preferably 100:0 to 50:50 by weight ratio. When the segment ratio of the alkyl methacrylate monomer derived from the homopolymer having a glass transition temperature of 30° C. or higher is lower than this range, stickiness tends to occur on the coating film surface, which tends to cause adhesion of dust and dirt. or adhesions. More preferably 100:0 to 70:30.

In order to sufficiently express the thixotropy of the adhesive resin composition and perform "filament breaking" well, it is more preferable that the copolymer (A) is a copolymer having a functional group capable of forming a hydrogen bond with a hydroxyl group.

The said copolymer (A) can be obtained by copolymerizing the (meth)acrylate monomer containing the functional group etc. which contain a hydroxyl group, a carboxyl group, a nitrogen atom, etc., for example. In addition, the (meth)acrylate monomer is preferably an alkyl methacrylate since there are few decomposition residues after firing. As the methacrylate monomer containing a hydroxyl group, for example, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxypropyl methacrylate, Butyl ester, cyclohexanedimethanol monomethacrylate, neopentyl glycol monomethacrylate, glycerin monomethacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, etc.

Examples of the carboxyl group-containing methacrylate monomer include methacrylic acid, 2-carboxyethyl methacrylate, 2-methacryloyloxyethylsuccinic acid, and the like.

Examples of methacrylate monomers having functional groups containing nitrogen atoms include methacrylamide, methacrylonitrile, N-vinylpyrrolidone, N-methacryloylmorpholine, 2-N,N-di Methylaminoethyl methacrylate, 2-N,N-diethylaminoethyl methacrylate, etc.

Among the above, methacrylates containing a hydroxyl group are preferable because there are few decomposition residues after firing.

The preferred content of the hydroxyl group-containing (meth)acrylate monomer in the copolymer (A) is preferably 30% by weight or less in 100% by weight of the copolymer (A). When this ratio is exceeded, water absorption becomes easy, and when the glass powder is dispersed and gelatinized, it may be difficult to obtain a composition with a long-term stable viscosity. More preferably, it is 1-15 weight part.

Although it does not specifically limit as molecular weight of the said copolymer (A), the preferable lower limit of a number average molecular weight is 500, and a preferable upper limit is 200,000. If it is less than 500, although it can be handled, the obtained polymer has a low molecular weight, and therefore, a paste having a viscosity suitable for printing may not be obtained. In addition, sometimes the full cohesion cannot be obtained. When it exceeds 200,000, since the complexing effect of polymer molecules becomes stronger, it may be difficult to suppress "stringiness" during coating. A more preferable upper limit is 150,000, and a more preferable lower limit is 10,000.

As a method for producing the above-mentioned copolymer (A), for example, conventional methods such as radical polymerization, living radical polymerization, initiator-transfer-termination polymerization, anionic polymerization, and living anionic polymerization can be used. known methods.

As an example of a method for obtaining the copolymer shown in Fig. 1, in the presence of a chain transfer agent having a carboxyl group, an alkyl (meth)acrylate monomer is polymerized so that the carboxyl group introduced into the terminal and the terminal of the polyalkylene oxide Hydroxyl reaction to bind. Thus, a (meth)acrylic resin having a polyalkylene oxide introduced into the main chain was obtained.

In addition, as a method of introducing into the side chain, polyalkylene oxide having a copolymerizable functional group that can be copolymerized with an alkyl (meth)acrylate is copolymerized with an alkyl (meth)acrylate to obtain a compound introduced into the side chain. Acrylic resin containing polyalkylene oxide.

The above-mentioned compound having a copolymerizable functional group and polyalkylene oxide copolymerizable with alkyl (meth)acrylate is not particularly limited, and examples thereof include polymers represented by the following general formulas (2) to (13). A compound having a (meth)acryloyl group at the terminal of an alkylene oxide, etc.

[chemical 1]

CH ₂ ＝CH-C(O)O-[CH ₂ CH(CH ₃ )O] _n -H...(2)

(n=1～12)

CH ₂ ＝C(CH ₃ )-C(O)O-[CH ₂ CH(CH ₃ )O] _n -H...(3)

(n=1～12)

CH ₂ =C(CH ₃ )-C(O)O-(CH ₂ CH ₂ O) _n- [CH ₂ CH(CH ₃ )O] _m -H...(4)

(n=1～12, m=1～12)

CH ₂ ＝CH-C(O)O-(CH ₂ CH ₂ O) _n- [CH ₂ CH(CH ₃ )O] _m -H...(5)

(n=1～12, m=1～12)

CH ₂ =C(CH ₃ )-C(O)O-(CH ₂ CH ₂ O) _n -(CH ₂ CH ₂ CH ₂ CH ₂ O) _m -H...(6)

(n=1～12, m=1～12)

CH ₂ ＝CH-C(O)O-(CH ₂ CH ₂ O) _n -(CH ₂ CH ₂ CH ₂ CH ₂ O) _m -H...(7)

(n=1～12, m=1～12)

CH ₂ ＝CH-C(O)O-[CH ₂ CH(CH ₃ )O] _n -CH ₃ ...(8)

(n=1～10)

CH ₂ ＝C(CH ₃ )-C(O)O-[CH ₂ CH(CH ₃ )O] _n -CH ₃ ...(9)

(n=1～10)

CH ₂ =C(CH ₃ )-C(O)O-(CH ₂ CH ₂ O) _n- [CH ₂ CH(CH ₃ )O] _m -CH ₃ ...(10)

(n=1～10, m=1～10)

CH ₂ =CH-C(O)O-(CH ₂ CH ₂ O) _n- [CH ₂ CH(CH ₃ )O] _m -CH ₃ ...(11)

(n=1～10, m=1～10)

CH ₂ =CH-C(O)O-[CH ₂ CH(CH ₃ )O] _n -C(O)-CH=CH ₂ ...(12)

(n=1～20)

CH ₂ =C(CH ₃ )-C(O)O-[CH ₂ CH(CH ₃ )O] _n -C(O)-C(CH ₃ )=CH ₂ ...(13)

(n=1～20)

The said copolymer (A) may have a crosslinkable functional group in a side chain or a terminal. Since the above-mentioned copolymer (A) has a crosslinkable functional group at the side chain or terminal, the adhesive resin composition of the present invention can exhibit the function of forming a PDP by the transfer method mentioned as an example of the use of the present invention. Excellent moldability and transferability in the partition wall.

In this specification, the so-called cross-linkable functional group refers to a group that undergoes a cross-linking reaction by light irradiation and/or heating, wherein it can be easily cured due to ultraviolet irradiation and the like, and there is no residual heat in the binder resin. Because of concerns about history and the like, a crosslinkable functional group that causes a crosslinking reaction by light irradiation is preferred.

The above-mentioned crosslinkable functional group is not particularly limited, and examples thereof include hydrolyzable silyl groups, isocyanate groups, epoxy groups, oxetanyl groups, acid anhydride groups, carboxyl groups, hydroxyl groups, polymerizable unsaturated Hydrocarbyl etc. Among them, preferably at least one selected from hydrolyzable silyl groups, isocyanate groups, epoxy groups, oxetanyl groups, acid anhydride groups, carboxyl groups, hydroxyl groups, and polymerizable unsaturated hydrocarbon groups, more preferably selected from hydrolyzed At least one of a hydrolyzable silyl group, an epoxy group, and an oxetanyl group, more preferably a hydrolyzable silyl group. These crosslinkable functional groups may be used alone or in combination of two or more.

When the said copolymer (A) has a crosslinkable functional group in a side chain or a terminal, it is preferable that the adhesive resin composition of this invention contains the crosslinking agent which crosslinks the said crosslinkable functional group.

As the above-mentioned cross-linking agent, there are, for example, cross-linking agents that react with the cross-linkable functional groups that the above-mentioned copolymer (A) has and that themselves enter into the structure of the cross-linked body (hereinafter also referred to as reactive type). cross-linking agent), and a cross-linking agent having a catalytic action for making the cross-linkable functional groups of the copolymer (A) react with each other (hereinafter also referred to as a catalytic cross-linking agent). In addition, there is also a crosslinking agent having both the functions of the above-mentioned reactive crosslinking agent and catalytic crosslinking agent (hereinafter referred to as a reaction-catalytic crosslinking agent).

There are no particular limitations on the reactive crosslinking agent, but when the crosslinkable functional group of the copolymer (A) is an oxetanyl group, for example, a photocation-initiated crosslinking agent that generates an acid by ultraviolet light or visible light can be mentioned. agent, thermal cationic initiator, etc.

In addition, as the above-mentioned reactive crosslinking agent, when the crosslinkable functional group of the above-mentioned copolymer (A) is an isocyanate group, for example, a compound having a plurality of hydroxyl groups or a compound having a plurality of amino groups, etc. active hydrogen compounds, etc.

Examples of the above compound having a plurality of hydroxyl groups include ethylene glycol, butylene glycol, glycerin, neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, pentaerythritol , Polyester polyol, etc. Examples of the compound having a plurality of amino groups include hexamethylenediamine, tetramethylenediamine, α,ω-diaminopropylene glycol, and the like.

The catalytic crosslinking agent is not particularly limited, and when the crosslinkable functional group of the copolymer (A) is a hydrolyzable silyl group, for example, a functional group represented by the following general formula (14) Photoreactive catalysts, photocationic initiators that generate acids through ultraviolet or visible light, organometallic compounds, amine compounds, acid phosphates, tetraalkylammonium halides (halides: fluoride, chloride, bromide, iodine Compounds), organic acids such as carboxyl groups, inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid, etc. Among them, a photoreactive catalyst having a functional group represented by the following general formula (14) is preferable.

[Chem 2]

In the above general formula (14), m represents an integer of 2 to 5, Y (m) represents an atom of the IVB group, VB group or VIB group of the periodic table, and Z represents a hydrogen group, a hydrocarbon group, a mercapto group, an amino group, a halogen atom group , Alkoxy, alkylthio, carbonyloxy or bridging oxygen (Okiso group).

The photoreaction catalyst having the functional group represented by the above general formula (14) may have different functional groups among the functional groups represented by the above general formula (14).

As the functional group represented by the above general formula (14), for example, a compound in which two carbonyl groups are bonded to an atom represented by Y(m) selected from oxygen, sulfur, nitrogen, phosphorus and carbon, corresponding to Y The valence of the atom represented by (m) suitably has a functional group represented by Z as a hydrocarbon group or an oxy group.

Examples of the hydrocarbon group represented by Z above include aliphatic hydrocarbon groups, unsaturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups and the like. These hydrocarbon groups may have substituents such as amino groups, hydroxyl groups, ether groups, epoxy groups, polymerizable unsaturated groups, urethane groups, ureido groups, imino groups, and ester groups within the range that does not impair the object of the present invention. In addition, different hydrocarbon groups can also be used in combination.

The photoreaction catalyst having the functional group represented by the above general formula (14) may also be a cyclic compound. Such cyclic compounds include, for example, compounds having one or two or more of the same or different functional groups represented by the above general formula (14) in the cyclic chain. In addition, it is also possible to use a compound in which a plurality of the above-mentioned cyclic compounds of the same or different types are bonded to an appropriate organic group, or a bicyclic compound containing at least one or more of the above-mentioned cyclic compounds of the same or different types as a unit. compounds etc.

As a photoreaction catalyst having a functional group represented by the above general formula (14), when the atom represented by Y(m) is an oxygen atom, for example, acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride , 2-methylbutyric anhydride, trimethylacetic anhydride, caproic anhydride, heptanoic anhydride, capric anhydride, lauric anhydride, myristic anhydride, palmitic anhydride, stearic anhydride, docosanoic anhydride, crotonic anhydride, acrylic anhydride, methyl Acrylic anhydride, oleic anhydride, linolenic acid, chloroacetic anhydride, iodoacetic anhydride, dichloroacetic anhydride, trifluoroacetic anhydride, monochlorodifluoroacetic anhydride, trichloroacetic anhydride, pentafluoropropionic anhydride, heptafluorobutyric anhydride, amber Anhydride, Methylsuccinic Anhydride, 2,2-Dimethylsuccinic Anhydride, Isobutylsuccinic Anhydride, 1,2-Cyclohexanedicarboxylic Anhydride, Hexahydro-4-Methylphthalic Anhydride, Itaconic Anhydride , 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, maleic anhydride, 2-methylmaleic anhydride, 2,3-di Methylmaleic anhydride, 1-cyclopentene-1,2-dicarboxylic anhydride, glutaric anhydride, 1-naphthylacetic anhydride, benzoic anhydride, phenylsuccinic anhydride, phenylmaleic anhydride, 2,3- Diphenyl maleic anhydride, phthalic anhydride, 4-methylphthalic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 4,4'-(hexa Fluoropropylene) diphthalic anhydride, 1,2,4,5-benzenetetracarboxylic anhydride, 1,8-naphthalene dicarboxylic anhydride, 1,4,5,8-naphthalene tetracarboxylic anhydride, etc.; as horse Copolymers of maleic anhydride and compounds having radically polymerizable double bonds include, for example, copolymers of maleic anhydride and (meth)acrylic acid esters, copolymers of maleic anhydride and styrene, maleic anhydride and Copolymers of vinyl ethers, etc. Among these, commercially available products include, for example, Adeka Hadona-EH-700, Adeka Hadona-EH-703, and Adeka Hadona-EH-705A manufactured by Asahi Denka Co., Ltd.; TH, RIKASHID HT-1, RIKASHID HH, RIKASHID MH-700, RIKASHID MH-700H, RIKASHID MH, RIKASHID SH, RIKARAGINTMEG; HN-5000, HN-2000 manufactured by Hitachi Chemical Co., Ltd.; 134A, ェピキュァ YH306, ェピキュァ YH307, ェピキュァ YH308H; SUMIKUA-MS manufactured by Sumitomo Chemical Co., Ltd., etc.

As a photoreaction catalyst having a functional group represented by the above general formula (14), when the atom represented by Y(m) is a nitrogen atom, for example, succinimide, N-methylsuccinimide, α , α-Dimethyl-β-methylsuccinimide, α-methyl-α-propylsuccinimide, maleimide, N-methylmaleimide, N-ethyl Maleimide, N-propylmaleimide, N-tert-butylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-benzene phenylmaleimide, N-(2-chlorophenyl)maleimide, N-benzylmaleimide, N-(1-pyrenyl)maleimide, 3-methyl -N-phenylmaleimide, N,N'-1,2-phenylene bismaleimide, N,N'-1,3-phenylene bismaleimide, N , N'-1,4-phenylene bismaleimide, N,N'-(4-methyl-1,3-phenylene) bismaleimide, 1,1'-( Methylenebis-1,4-phenylene)bismaleimide, phthalimide, N-methylphthalimide, N-ethylphthalimide Amines, N-propylphthalimide, N-phenylphthalimide, N-benzylphthalimide, pyromellitic acid diimide, and the like.

As a photoreaction catalyst having a functional group represented by the above general formula (14), when the atom represented by Y(m) is a phosphorus atom, for example, bis(2,6-dimethoxybenzoyl)- 2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethoxybenzoyl)phenylphosphine oxide, and the like.

As a photoreaction catalyst having a functional group represented by the above general formula (14), when the atom represented by Y(m) is a carbon atom, for example, 2,4-pentanedione, 3-methyl-2, 4-pentanedione, 3-ethyl-2,4-pentanedione, 3-chloro-2,4-pentanedione, 1,1,1-trifluoro-2,4-pentanedione, 1, 1,1,5,5,5-hexafluoro-2,4-pentanedione, 2,2,6,6-tetramethyl-3,5-pentanedione, 1-benzoylacetone, diphenyl Diketones such as formylmethane; dimethylmalonate, diethylmalonate, dimethylmethylmalonate, tetraethyl-1,1,2,2-ethane tetracarboxylate Polycarboxylic acid esters such as acid; α-carbonyl acetate such as methyl acetylacetone, ethyl acetylacetone, methyl propionoacetate, etc.

Among the photoreaction catalysts having a functional group represented by the above general formula (14), diacylphosphine oxide is particularly preferably used because there is very little residue after cleaning.

The preferable usage amount of the compounding quantity of the photoreaction catalyst which has the functional group represented by the said General formula (14) is 0.01 weight part with respect to 100 weight part of said copolymer (A), and a preferable upper limit is 30 weight part. When it is less than 0.01 parts by weight, it may not show photoreactivity, and when it exceeds 30 parts by weight, the light transmittance of the composition containing the binder resin of the present invention having a hydrolyzable silyl group decreases, and even if it is irradiated with light , Sometimes it is only cross-linked and cured on the surface, and it is not cross-linked and cured in the deep part. A more preferable lower limit is 0.1 parts by weight, and a more preferable upper limit is 20 parts by weight.

As the organometallic compound used as the above-mentioned catalytic crosslinking agent, for example, dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, bis(dibutyltin laurate) oxide Dibutyltin bisacetylacetonate, bis(monoester malate) dibutyltin, tin octoate, dibutyltin octoate, tin oxide such as dioctoate, tetra-n-butoxy titanate, tetraiso Alkoxy titanate such as propoxy titanate, etc.

In addition, as the above-mentioned catalytic type crosslinking agent, when the crosslinkable functional group of the above-mentioned copolymer (A) is a polymerizable unsaturated group, for example, thermal radical type such as peroxide and azo compound Initiators; photoradical initiators generated by ultraviolet light or visible light; initiator systems formed by combining thermal or photoradical initiators and compounds with multiple mercapto groups, etc.

As the above-mentioned thermal radical initiator, for example, dicumyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, tert-hexyl peroxide Hydrogen, hydroperoxides such as tert-butyl hydroperoxide, α,α'-bis(tert-butylperoxy-m-isopropyl)benzene, dicumyl peroxide, 2,5-dimethyl- 2,5-bis(tert-butyl peroxy)hexane, tert-butyl cumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butyl peroxide Dialkyl peroxides such as oxy)hexene-3, ketone peroxides, peroxyacetals, diacyl peroxides, peroxydicarbonates, peroxyesters and other organic peroxides , or 2,2'-azobisisobutyronitrile, 1,1'-(cyclohexane-1-carbonitrile), 2,2'-azobis(2-cyclopropylpropionitrile), 2,2 Azo compounds such as '-azobis(2,4-dimethylvaleronitrile), etc.

Examples of photoradical initiators include 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone, α-hydroxy-α,α'-dimethyl Acetophenone derivatives such as acetophenone, methoxyacetophenone, and 2,2-dimethoxy-2-phenylacetophenone; benzoin ethers such as benzoin ethyl ether and benzoin propyl ether ketal derivatives such as benzyl dimethyl ketal; halogenated ketones; acyl phosphine oxides; acyl phosphonates; 2-methyl-1-[4-(methylthio)phenyl]-2 -Morpholinopropan-1-one, 2-benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)-1-butanone; bis(2,4,6 -Trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; bis(η5-cyclopentadiene base) bis(pentafluorophenyl)titanium, bis(η5-cyclopentadienyl)bis[2,6-difluoro-3-(1H-pyrido-1-yl)phenyl]titanium; anthracene, perylene , coronene, naphthacene, benzanthracene, phenothiazine, flavin, acridine, oxocoumarin, thioxanthene derivatives, benzophenone, acetophenone, 2-chlorothioxanthane, 2, 4-Di-methylthioxanthene, 2,4-diethylthioxanthene, 2,4-diisopropylthioxanthene, isopropylthioxanthene, etc. These may be used alone or in combination of two or more.

In addition, as the above-mentioned catalytic type crosslinking agent, when the crosslinkable functional group possessed by the above-mentioned copolymer (A) is an epoxy group, for example, photocation initiators that generate acids by ultraviolet rays or visible light, thermal Cationic initiators, amine compound curing agents, amide curing agents, acid anhydride curing agents, mercapto curing agents, thermal latent curing agents such as ketimine or DICY, photoamine generators containing carbamoyloxyimino groups, etc. wait.

As the above-mentioned photocation catalyst, for example, iron-allene complexes, aromatic disazoonium salts, aromatic iodonium salts, aromatic sulfonium salts, pyridinium salts, aluminum complexes/silane Alkoxides, trichloromethyltriazine derivatives, etc. Among these, as the counter anion of onium salt or pyridinium salt, for example, SbF ₆ ^- , PF ₆ ^- , AsF ₆ ^- , BF ₄ ^- , tetrakis(pentafluoro)borate, trifluoromethanesulfonic acid Salt, methanesulfonate, trifluoroacetate, acetate, sulfonate, p-toluenesulfonate, nitrate, etc. Among these photocation catalysts, commercially available ones include, for example, Irgakiyua-261 (manufactured by Chibagaigi Corporation), Optoma-SP-150 (manufactured by Asahi Denka Industries), Optoma-SP-151 (manufactured by Asahi Denka Industries, Ltd.) company), Optoma-SP-170 (manufactured by Asahi Denka Kogyo Co., Ltd.), Optoma-SP-171 (manufactured by Asahi Denka Kogyo Co., Ltd.), UVE-1014 (manufactured by Zenerale Rectronix Co., Ltd.), CD-1012 (manufactured by Saitoma Co., Ltd. Manufactured), Suned SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.), Suned SI-80L (manufactured by Sanshin Chemical Industry Co., Ltd.), Suned SI-100L (manufactured by Sanshin Chemical Industry Co., Manufactured), CI-2639 (manufactured by Nippon Soda Co., Ltd.), CI-2624 (manufactured by Nippon Soda Co., Ltd.), CI2481 (manufactured by Nippon Soda Co., Ltd.), RHODORSIL PHOTOINITIATOR 2074 (manufactured by Roichi プ プ ラン Co., Ltd.), UVI -6990 (manufactured by Yunoka Bird), BBI-103 (manufactured by Midori), MPI-103 (manufactured by Midori), TPS-103 (manufactured by Midori), MDS-103 (manufactured by Midori), DTS-103 ( Midori Co.), NAT-103 (Midori Co., Ltd.), NDS-103 (Midori Co., Ltd.) and the like. These photocation catalysts may be used alone or in combination of two or more.

Examples of the thermal cationic curing agent include ammonium salts having at least one alkyl group, sulfonium salts, iodonium salts, diazonium salts, and boron trifluoride/triethylamine complexes. Examples of counter anions of these salts include SbF ₆ ^- , PF ₆ ^- , AsF ₆ ^- , BF ₄ ^- , tetrakis(pentafluoro)borate, trifluoromethanesulfonate, methanesulfonate , trifluoroacetate, acetate, sulfonate, p-toluenesulfonate, nitrate, etc.

Examples of the above-mentioned photoamine generating agent include compounds having a carbamoyloxyimino group, cobalamin complexes, o-nitrobenzyl carbamate, o-acyl oxime, and the like.

The reaction-catalyzed crosslinking agent is not particularly limited, and examples thereof include α,ω-diaminopolyoxypropylene and the like.

Examples of compounds having a copolymerizable functional group and a crosslinkable functional group that can be copolymerized with the above-mentioned alkyl (meth)acrylate include, for example, 3-methacryloxypropyltrimethoxysilane, 3-methyl Acryloxypropyldimethoxysilane, glycidyl methacrylate, 3-methacryloxypropyl isocyanate, etc.

The compound having a functional group capable of forming a bond with a compound of a copolymerizable functional group and a crosslinkable functional group is not particularly limited, and examples thereof include 2-hydroxyethyl (meth)acrylate, 3-hydroxyethyl (meth)acrylate, Propyl ester, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, (meth) ) 6-hydroxyhexyl acrylate, 3-hydroxy-3-methylbutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-[(meth)acryloyl Oxygen] ethyl-2-hydroxyethyl phthalic acid, 2-[(meth)acryloyloxy] ethyl-2-hydroxypropyl phthalic acid, etc., the copolymerizable functional group can be combined with A copolymerizable functional group for copolymerization of the above-mentioned alkyl (meth)acrylate.

When the functional group of the compound having a functional group capable of forming a bond with a compound having a copolymerizable functional group and a crosslinkable functional group is a hydroxyl group, examples include 3-(trimethoxysilyl)propyl isocyanate, 3-(triethoxymethyl Silyl)propyl isocyanate maleic acid, etc., wherein the copolymerizable functional group is a functional group that can be copolymerized with the above-mentioned alkyl (meth)acrylate.

In addition, when the functional group of the compound having a functional group capable of forming a bond with a compound having a copolymerizable functional group and a crosslinkable functional group is a carboxyl group, glycidyl (meth)acrylate, bisphenol A type epoxy resin, bisphenol F Type epoxy resin, hydrogenated bisphenol A type epoxy resin, etc., the copolymerizable functional group is a functional group that can be copolymerized with the above-mentioned alkyl (meth)acrylate.

In order to lower the firing temperature, the binder resin composition of the present invention preferably further contains polyalkylene oxide (B).

The above-mentioned polyalkylene oxide (B) is not particularly limited, and examples thereof include polyethylene glycol, polypropylene glycol, poly-1,3-propylene glycol, poly-1,4-butylene glycol, poly(ethyl)ethylene glycol, and poly(ethyl)ethylene glycol. Glycols, poly(benzyl)glycols and their copolymers, etc.

The number average molecular weight of the polyalkylene oxide (B) is not particularly limited, and may be appropriately selected according to the viscosity of the intended binder resin composition of the present invention. In addition, the number average molecular weight is preferably 300 to 100,000. More preferably, it is 1,000 to 50,000.

As a compounding quantity of the said polyalkylene oxide (B), the preferable upper limit with respect to 100 weight part of copolymers (A) is 200 weight part. When it exceeds 200 parts by weight, although the polyalkylene oxide (B) exhibits the so-called "low-temperature firing property" that is easy to fire at a low temperature, the combination of the copolymer (A) and the polyalkylene oxide (B) However, phase separation becomes easy, and it may be difficult to obtain a paste with a stable viscosity. A preferable upper limit is 100 parts by weight, more preferably 50 parts by weight.

In order to further suppress "stringing", it is preferable to further add a resin oligomer (C) that is liquid at normal temperature, that is, at 23° C., to the adhesive resin composition of the present invention. In addition, in order to avoid phase separation with the binder resin composition, it is preferable that the SP value of the oligomer (C) obtained by the Hoy method is 10×10 ^-3 8.5×10 ^-3 (J/m ³ ) ^0.5 Oligomer. For example, polypropylene glycol (SP value: 8.65×10 ^-3 (J/m ³ ) ^0.5 ), polyester polyol oligomer, butyl acrylate oligomer (SP Value: 9.77×10 ^-3 (J/m ³ ) ^0.5 ), 2-ethylhexyl acrylate oligomer (SP value: 9.22×10 ^-3 (J/m ³ ) ^0.5 ), polyisoprene low Polymer (SP value: 8.75×10 ^-3 (J/m ³ ) ^0.5 ), polybutadiene oligomer (SP value: 8.73×10 ^-3 (J/m ³ ) ^0.5 ), lauryl methacrylate Oligomers (SP value: 8.81×10 ^-3 (J/m ³ ) ^0.5 ) and the like.

It is preferable to further contain a decomposition accelerator in the binder resin composition of the present invention. By containing a decomposition accelerator, it can be removed more quickly during firing.

The above-mentioned decomposition accelerator is not particularly limited, and examples thereof include azo compounds; heavy metal compounds such as iron sulfate, sodium nitrate, and cobalt naphthenate; carboxylic acids such as oxalic acid, linolenic acid, and ascorbic acid; hydroquinone, peroxide, tin oxide, etc. Among them, the above-mentioned peroxides are preferable because they can also suppress the decomposition residue due to the decomposition accelerator to a low level. In addition, the above-mentioned azo compound can promote volatilization of the decomposed product by the nitrogen gas generated by the decomposition of the azo compound while exerting the effect of accelerating the decomposition by the decomposition accelerator, so it is preferable.

The above-mentioned peroxide is not particularly limited, and may be an inorganic peroxide or an organic peroxide.

Examples of the inorganic peroxide include potassium persulfate, sodium persulfate, ammonium persulfate, potassium perchlorate, sodium perchlorate, ammonium perchlorate, potassium periodate and the like.

烷、过氧化氢二异丙苯、过氧化氢1，1，3，3-四甲基丁基、过氧化氢异丙苯、过氧化氢叔己基、过氧化氢叔丁基等氢过氧化物；过氧化二异丙苯、α，α’-双(叔丁基过氧间异丙苯)、2，5-二甲基-2，5-双(叔丁基过氧)己烷、叔丁基异丙苯基过氧化物、过氧化二叔丁基、2，5-二甲基-2，5-双(叔丁基过氧)己烯-3等二烷基过氧化物；1，l-双(叔己基过氧)-3，3，5-三甲基环己烷、1，1-双(叔己基过氧)环己烷、l，1-双(叔丁基过氧)-3，3，5-三甲基环己烷、1，1-双(叔丁基过氧)环己烷、1，1-双(叔丁基过氧)环十二烷、2，2-双(叔丁基过氧)丁烷、4，4-双(叔丁基过氧)戊酸正丁酯、2，2-双(4，4-二叔丁基过氧环己基)丙烷等过氧化缩酮；过氧化异丙基单碳酸叔己酯、叔丁基过氧化马来酸、过氧化3，5，5-三甲基己酸叔丁酯、过氧化月桂酸叔丁酯、2，5-二甲基-2，5-双(间甲苯酰过氧)己烷、过氧化异丙基单碳酸叔丁酯、过氧化苯甲酸叔己酯、2，5-二甲基-2，5-双(间苯甲酰过氧)己烷、过氧化乙酸叔丁酯、过氧化苯甲酸叔丁酯、双叔丁基过氧化间苯二甲酸酯、过氧化烯丙基单碳酸叔丁酯等过氧化酯等。As the organic peroxide, an organic peroxide having a 10-hour half-life temperature of 100° C. or higher is preferable from the viewpoint of storage stability. As an organic peroxide having a half-life temperature of 100° C. or higher in 10 hours, for example, hydrogen peroxide is

Alkanes, dicumyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, tert-hexyl hydroperoxide, tert-butyl hydroperoxide and other hydroperoxides substances; dicumyl peroxide, α,α'-bis(tert-butylperoxym-cumene), 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, Dialkyl peroxides such as tert-butylcumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexene-3; 1, l-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-hexylperoxy)cyclohexane, l,1-bis(tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)cyclododecane, 2,2 - Bis(tert-butylperoxy)butane, n-butyl 4,4-bis(tert-butylperoxy)pentanoate, 2,2-bis(4,4-di-tert-butylperoxycyclohexyl)propane Isoperoxyketal; tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxymaleic acid, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxylaurate , 2,5-dimethyl-2,5-bis(m-toluoylperoxy)hexane, tert-butyl peroxyisopropyl monocarbonate, tert-hexyl peroxybenzoate, 2,5-dimethyl -2,5-bis(isobenzoylperoxy)hexane, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, bis-tert-butylperoxyisophthalate, allyl peroxide Peroxyesters such as tert-butyl monocarbonate, etc.

The above-mentioned azo compound is not particularly limited, and examples thereof include azodicarbonamide, azobisisobutyronitrile (AIBN), 2,2-azobis(4-methoxy-2,4- Dimethylvaleronitrile), 2,2-azobis(2-cyclopropylpropionitrile), 2,2-azobis(2-methylbutyronitrile), 1,1-azobis(cyclohexane Alkane-1-carbonitrile), etc.

The binder resin composition of the present invention may further contain a decomposition retarder for the purpose of improving handleability and the like. It does not specifically limit as said decomposition retarder, For example, a mercapto compound, an amine compound, organotin, organoboron etc. are mentioned.

The above-mentioned mercapto compound is not particularly limited, and examples thereof include propanethiol, butanethiol, pentanethiol, 1-octanethiol, dodecanethiol, cyclopentanethiol, cyclohexanethiol, 1 , 3-propanedithiol, etc.

The amine compound is not particularly limited, and examples thereof include propylamine, butylamine, hexylamine, dodecylamine, isopropylamine, hexamethylenediamine, cyclohexylamine, benzylamine, aniline, and methylaniline. wait.

The organotin mentioned above is not particularly limited, and examples thereof include dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dioctoate, dibutyltin diacetate, bis(2,4-pentanedione)di Butyl tin, dilauryl tin dilaurate, etc.

The organic boron is not particularly limited, and examples thereof include trimethyl borate, tripropyl borate, tributyl borate, trimethoxyboroxane, trimethylene borate, etc. .

The content of the decomposition accelerator or decomposition retarder in the binder resin composition of the present invention is not particularly limited, but the lower limit is preferably 1% by weight, and the upper limit is preferably 10% by weight.

The adhesive resin composition of the present invention may further contain a gas generating agent that generates gas by light irradiation and/or heating. By containing a gas generating agent, when the adhesive resin composition of the present invention is cured in the transfer method of the PDP partition wall cited as an example of the use of the present invention, gas is generated from the surface, and the pressure is promoted to form a template. stripping. As such a gas generating agent, an azo compound, an azide compound, etc. are mentioned, for example.

The adhesive resin composition of the present invention may further contain a liquid resin. By containing the liquid resin, the removal start temperature of the adhesive resin composition of the present invention can be lowered, and the viscosity can also be adjusted. In addition, it can be removed quickly even at a temperature of about 150°C. The above-mentioned liquid resin is not particularly limited as long as it is a compound having a boiling point of 100° C. or higher, and examples thereof include polyethylene glycol oligomers, polypropylene oligomers, polytetramethylene glycol oligomers substances, dioctyl phthalate, dibutyl phthalate, glycerol monooleate, etc.

The low-temperature-decomposable adhesive resin composition of the present invention may further contain a filler in order to improve cohesion. However, since the filler inevitably becomes an inorganic residue, its content should be suppressed to the necessary minimum.

The above-mentioned filler is not particularly limited, and examples thereof include titanium oxide, aluminum oxide, colloidal calcium carbonate, ground calcium carbonate, barium carbonate, magnesium carbonate, silica, surface-treated silica, calcium silicate, Hydrous silicon, hydrous silicon, mica, surface treated mica, talc, clay, surface treated talc, boron nitride, aluminum nitride, carbon nitride, carbon black, silica, glass short fiber, glass beads, glass spheres, natural Vitreous hollow microspheres (silas balls), acrylic beads, polyethylene beads, etc.

The adhesive resin composition of the present invention may further contain a silane coupling agent. Examples of the aforementioned silane coupling agents include vinyltrimethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, tetramethoxysilane, Ethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane Ethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N,N' -Bis[3-(trimethoxysilyl)propyl]ethylenediamine, N,N'-bis[3-(triethoxysilyl)propyl]ethylenediamine, N,N'- Bis[3-(trimethoxysilyl)propyl]hexaethylenediamine, N,N'-bis[3-(triethoxysilyl)propyl]hexaethylenediamine, etc. .

The adhesive resin composition of the present invention may further contain a titanium coupling agent. As the above-mentioned titanium coupling agent, for example, isopropyl triisostearyl titanate, isopropyl n-dodecylbenzenesulfonyl titanate, isopropyl tris(dioctyl pyrophosphate) ) titanate, tetraisopropyl bis (dioctyl phosphate) titanate, tetraisopropyl bis (two (tridecyl) phosphate) titanate, tetrakis (2,2-diene Propoxymethyl-1-butyl)bis(di(trilauryl))phosphate titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate) ) Ethylene titanate, isopropyl tris(N-aminoethylaminoethyl) titanate, etc.

As the components combined by the binder resin composition of the present invention, for example, borosilicate lead glass, lead glass, CaO·Al ₂ O ₃ ·SiO ₂ -based inorganic glass, MgO· Al ₂ O ₃ SiO ₂ inorganic glass, Li ₂ O Al ₂ O ₃ SiO ₂ inorganic glass and other low melting point glass; ZnS:Ag, Al, ZnS:Cu, Al, Y ₂ O ₂ S:Eu, (SrCaBaMg) ₅ (PO ₄ ) ₃ Cl:Eu, LaPO ₄ :Ce, Tb, Y ₂ O ₃ :Eu, Ca ₁₀ (PO ₄ ) ₆ FCl:Sb, Mn, BaMgAl ₁₀ O ₁₇ :Eu, Zn ₂ SiO ₄ : Phosphors such as Mn, (Y, Gd)BO ₃ :Eu, CaWO ₄ , Gd ₂ O ₂ S:Tb, (Y, Sr)TaO ₄ :Nb; aluminum, gold, platinum, silver, copper, nickel, etc. Metal powder; suitable glass, ceramic powder or metal oxide powder such as silver oxide, aluminum oxide, titanium oxide, zirconium oxide, indium oxide, indium tin oxide, magnesium oxide, and zinc oxide.

In a specific aspect of the present invention, there is provided a method for producing a fired body using a ceramic paste containing ceramic powder and a binder resin having acrylic polymer chains and polyalkylene oxide chains. A ceramic green sheet is produced, and a laminated body in which a plurality of the above-mentioned ceramic green sheets are stacked is fired at 300° C. or lower.

As a binder resin that can degrease ceramic green sheets at low temperatures, the inventors of the present invention have developed a polyolefin resin that decomposes and removes at about 300°C as disclosed in the previous Japanese Patent Application Laid-Open No. 2004-256788. Binder resin with oxide resin as the main component. However, since this binder resin has a high ratio of oxygen atoms present in the resin molecules, it is difficult to control the burning rate when heated to about 300° C., and burning cracks may occur due to violent burning. In addition, since the viscosity is low, it is difficult to produce ceramic green sheets using a ceramic paste prepared by mixing a ceramic material and a solvent or the like.

Therefore, as a result of further studies by the present inventors, it has been found that by using a binder resin having an acrylic polymer segment and a polyalkylene oxide segment as described above, it is possible to carry out the process at a low temperature of about 300°C. Degreasing and controlling it, and can be made to higher viscosity.

In the method for producing a fired body using the binder resin composition of the present invention, first, a binder resin containing ceramic powder and the above-mentioned binder resin having an acrylic polymer segment and a polyalkylene oxide segment is produced. ceramic paste.

The ceramic powder is not particularly limited as long as it can be fired at a low temperature of 300°C or lower _. For example, it is preferably selected from CaO- _{Al2O3 - SiO2} - _B2O3 , MgO- _Al2 A mixture of O ₃ -SiO ₂ -B ₂ O ₃ , and at least one glass material of CaO-MgO-Al ₂ O ₃ -SiO ₂ -B ₂ O ₃ , and Al ₂ O ₃ .

The content of CaO and/or MgO in the glass material as the ceramic powder is not particularly limited, but the lower limit is preferably 10% by weight, and the upper limit is preferably 55% by weight.

The content of Al ₂ O ₃ in the glass material as the ceramic powder is not particularly limited, but the upper limit is preferably 30% by weight.

The content of SiO ₂ in the glass material as the ceramic powder is not particularly limited, but the lower limit is preferably 45% by weight, and the upper limit is preferably 75% by weight.

The content of B ₂ O ₃ in the glass material as the ceramic powder is not particularly limited, but the upper limit is preferably 30% by weight.

The mixing ratio of the glass material and Al ₂ O ₃ contained in the ceramic powder is not particularly limited, but is preferably 50:50 to 65:35 in weight ratio.

The content of the ceramic powder in the ceramic paste is not particularly limited, but the lower limit is preferably 5 parts by weight relative to 100 parts by weight of the binder resin having an acrylic polymer segment and a polyalkylene oxide segment. , the preferred upper limit is 50 parts by weight. When the amount is less than 5 parts by weight, a fired body with sufficient strength may not be obtained, and when it exceeds 50 parts by weight, molding of ceramic green sheets may not be performed.

The above-mentioned ceramic paste may further contain an organic solvent. As the above-mentioned organic solvent, a solvent having a boiling point of 150° C. or higher is preferable from the viewpoint of stability of solid content and viscosity stability during printing. Such an organic solvent is not particularly limited, and examples thereof include terpineol, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, butyl carbitol, butyl carbitol, and butyl carbitol. Butyl alcohol acetate, isophorone, butyl lactate, dioctyl phthalate, dioctyl adipate, benzyl alcohol, phenylpropylene glycol, cresol, etc.

The method for producing the above-mentioned ceramic paste is not particularly limited, and examples thereof include adding ceramic powder or an organic solvent to a binder resin, followed by uniform mixing with a ball mill, and defoaming.

In this production method, next, a ceramic green sheet is produced using the above-mentioned ceramic paste.

The film thickness of the above-mentioned ceramic green sheet is not particularly limited, but a preferable lower limit is 20 μm, and a preferable upper limit is 150 μm. When the thickness is less than 20 μm, cracks may occur in the ceramic green sheet, and when the thickness exceeds 150 μm, the layered laminate becomes too thick and is not practical.

The method for producing the above-mentioned ceramic green sheet is not particularly limited, and examples thereof include applying the above-mentioned ceramic paste to a release-treated polyethylene terephthalate film using a doctor blade, a reverse roll coater, or the like. Or a method of tape-casting on the surface of a support such as a SUS plate, and then removing volatile components such as a solvent by heating or the like, and then peeling off from the support.

Via holes may also be formed in the above ceramic green sheet. By forming a through hole, a metal or the like can be bonded to the through hole to be used as a multilayer film capacitor or the like.

The above-mentioned metal is not particularly limited, but it is preferable to use a highly conductive metal, for example, Cu, Ni, Ag, Au, Al, and the like.

Since the fired body produced by this production method can be fired at 300° C. or lower, Cu, which has been easily oxidized and difficult to handle in the past, can also be used.

In this production method, next, a laminate is produced.

The method for producing the above-mentioned laminate is not particularly limited, and examples thereof include a method of laminating and compressing a plurality of the above-mentioned ceramic green sheets.

In this manufacturing method, next, the above-mentioned ceramic green sheet is fired. By firing, the binder resin or volatile resin can be decomposed and the ceramic green sheet can be cured.

The above-mentioned firing method is not particularly limited, and examples thereof include a method in which the temperature is raised to 300° C. using a firing furnace such as an electric muffle furnace, and the firing is carried out.

In addition, when firing, it may be carried out in the air, or may be carried out under anaerobic conditions such as a reducing atmosphere.

The fired body obtained by this production method can be fired in a very low temperature environment of 300° C. or lower by using the above-mentioned binder resin, and is particularly excellent in terms of production time and production cost.

Since the adhesive resin composition of the present invention has the above-mentioned constitution, when it is used as an adhesive resin composition for forming various materials such as ceramic green sheets, conductive pastes, PDP partition walls, dielectric layers, phosphor layers, etc. , can be fired at a relatively low temperature, and even if it is printed, it is not easy to draw. In addition, the applications of the adhesive resin composition of the present invention are not limited to these. In addition, the adhesive resin composition of the present invention is preferably used for forming a partition wall of a PDP as an example of its use by a transfer method. That is, when the partition walls of the PDP are formed by the transfer method, according to the present invention, basic performances such as the fillability of the recesses can be satisfied. In addition, by having a polyether component, high scavenging properties can be exhibited at a relatively low temperature without generating residue. In addition, by having a crosslinkable functional group at the side chain or terminal, excellent moldability and transferability can be exhibited when forming PDP partition walls by a transfer method.

Moreover, the glass paste containing the adhesive resin composition of this invention and the glass powder dispersed in this adhesive resin composition is also one of this invention.

In addition, a ceramic paste comprising the binder resin composition of the present invention and ceramic powder dispersed in the binder resin composition is also one of the present invention.

In addition, a phosphor paste comprising the binder resin composition of the present invention and phosphor powder dispersed in the binder resin composition is also one of the present invention.

Moreover, the electrically conductive paste containing the adhesive resin composition of this invention and the electrically conductive powder dispersed in this adhesive resin composition is also one of this invention.

In addition, a green sheet comprising the binder resin composition of the present invention and glass powder or ceramic powder dispersed in the binder resin composition is also one of the present invention.

In the case of the ceramic paste, at least one layer of the ceramic paste film is printed by screen printing or the like and fired to obtain a film or a laminated sintered body including a ceramic sintered body.

As an organic compound having three or more hydroxyl groups (OH groups) used in the present invention, for example, glycerin, diglycerol, trimethylolpropane, pentaerythritol, mesoerythritol, L-sreitol, D-slaytol, DL-slacketol, 2-hydroxymethyl-1,3-propanediol, 1,1,1-trimethylolethane, 1,2,4-butanetriol, 1, 2,6-hexanetriol, etc.

The compounding quantity of the organic compound which has 3 or more hydroxyl groups is 20-200 weight part with respect to 100 weight part of (meth)acrylates of the functional group which can form a hydrogen bond with a hydroxyl group. Within this range, it is possible to provide an adhesive resin composition that rarely causes misalignment during screen printing. It is preferably 30 to 150 parts by weight, and within this range, it becomes a binder resin composition with less occurrence of misalignment defects during screen printing.

The adhesive resin composition of the present invention is made to contain 1 to 30 parts by weight of a long-chain alkyl (meth)acrylate with respect to 100 parts by weight of the above-mentioned (meth)acrylate having a functional group capable of forming a hydrogen bond with a hydroxyl group. , and a mixture of 20 to 200 parts by weight of an organic compound having 3 or more hydroxyl groups, the (meth)acrylate in the mixture is (co)polymerized to produce a polymer.

The above-mentioned organic compound having three or more hydroxyl groups may be added after polymerizing (meth)acrylate in advance, or may be allowed to coexist during polymerization to obtain an adhesive resin composition.

Content of the organic compound which has 3 or more hydroxyl groups used in this invention is 20-200 weight part with respect to 100 weight part of the (meth)acrylate polymer of the functional group which can form a hydrogen bond with a hydroxyl group. Within this range, it is possible to provide an adhesive resin composition that has excellent screen printability, improved storage stability at high temperature, improved "stringing" phenomenon, and less occurrence of silky paste on the surface of the printing plate. . More preferably 30 to 150 parts by weight, within this range, it is possible to provide more excellent screen printability, further improved storage stability at high temperature, further improved "stringing" phenomenon, and suppressed "filamentous dirt" resulting adhesive resin composition.

In addition, the binder resin composition according to the present invention preferably has a haze value calculated from the total light transmittance of 20 or more when formed into a film having a thickness of 5 mm.

The haze value can be measured using a haze meter on a dried sheet obtained from the paste.

The binder resin composition according to the present invention preferably contains a nonionic surfactant. In particular, in a specific aspect of the present invention, there is provided an adhesive resin composition preferably containing 0.01 to 10 parts by weight of a nonionic surfactant with respect to 100 parts by weight of the above-mentioned copolymer (A). More preferably, the polymer (A) has a functional group capable of hydrogen bonding.

Although it does not specifically limit as said nonionic surfactant, Polyoxyethylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene isodecyl ether etc. are mentioned.

Therefore, in the present invention, it is possible to provide an adhesive resin composition which is excellent in screen printability, has improved storage stability at high temperature, and has improved "stringing" Occurrence of "filamentous dust" that hangs down in a thread-like paste and cuts off the fly.

In another particular aspect of the invention, it is preferred that the copolymer (A) is a polymer containing long-chain alkyl (meth)acrylates. The long-chain alkyl (meth)acrylate contained in 100% by weight of the polymer (A) is preferably 1 to 30% by weight. In other words, the copolymer (A) is preferably 100 parts by weight of a (meth)acrylate having a functional group capable of forming a hydrogen bond with a hydroxyl group, and 1 to 30 parts by weight of a long-chain alkyl (meth)acrylate, and A copolymer obtained by polymerizing the above-mentioned (meth)acrylate after mixing organic compounds having three or more hydroxyl groups.

Accordingly, it is possible to provide an acrylic-based low-temperature-fireable binder resin composition that rarely causes misalignment during continuous printing by screen printing.

In addition, it is further preferred that the polymer (A) is preferably a copolymer (A2) having a functional group capable of forming a hydrogen bond with a hydroxyl group. Thereby, since thixotropy can fully be expressed, it is preferable.

When the copolymerization ratio of the long-chain alkyl (meth)acrylate monomer used in the present invention decreases, the release property decreases, and when it increases, the screen printability decreases. Therefore, the polymer (A) (preferably polymer (A2 The ratio of the long-chain alkyl (meth)acrylate in 100% by weight of )) is preferably 1 to 30% by weight.

In addition, it is preferable that the above-mentioned long-chain alkyl (meth)acrylate is a long-chain alkyl (meth)acrylate having 8 or more carbon atoms, whereby it is possible to provide an adhesive with less occurrence of misalignment during continuous screen printing. mixture.

As the (meth)acrylate monomer having a long-chain alkyl chain having 8 or more carbon atoms, for example, 2-ethylhexyl methacrylate, octyl methacrylate, stearyl methacrylate, methyl Isomyristyl acrylate, lauryl methacrylate, behenyl methacrylate, etc.

In this invention, it is preferable to add 100 weight part or less of organic solvents with respect to 100 weight part of solid content, and it is set as an adhesive resin composition. In addition, the term "solid content" refers to polymer components other than organic solvents.

In addition, it is preferable to further contain an organic solvent having a boiling point of 150° C. or higher at 500 parts by weight or less, more preferably at most 100 parts by weight. More preferably 300 parts by weight or less, still more preferably 100 parts by weight or less, particularly preferably 30 to 80 parts by weight. Thereby, the viscosity required for screen printing etc. can also be adjusted easily.

The binder resin composition of the present invention preferably contains 500 parts by weight or less of an organic solvent (C) having a boiling point of 150° C. or higher relative to 100 parts by weight of the copolymer (A) having a functional group capable of forming a hydrogen bond with a hydroxyl group, and more preferably It is preferably 300 parts by weight or less, more preferably 100 parts by weight or less, and particularly preferably 30 to 80 parts by weight.

The adhesive resin composition of the present invention further contains an organic solvent. The organic solvent preferably has a boiling point of 150° C. or higher in terms of solid content stability and viscosity stability during printing. Such an organic solvent is not particularly limited, and examples thereof include terpineol, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, butyl carbitol, butyl carbitol, and butyl carbitol. Butyl alcohol acetate, isophorone, butyl lactate, dioctyl phthalate, dioctyl adipate, benzyl alcohol, phenylpropylene glycol, cresol, etc. Among these solvents, solvents not containing an aromatic ring that hardly leave organic residues are preferable.

According to the present invention, it is possible to provide a low-temperature decomposing adhesive resin composition, glass paste, ceramic paste, phosphor paste, conductive paste, and raw piece.

In addition, it is possible to obtain a paste that is less prone to "stringing" even during printing.

In the case of an adhesive resin composition containing a polymer obtained by polymerizing (meth)acrylate, it is possible to provide an acrylic with excellent screen printability, and especially less occurrence of misalignment during continuous printing of screen printing A kind of adhesive that can be fired at low temperature, the (meth)acrylate is a copolymer (A) containing 100 parts by weight of a functional group that can form a hydrogen bond with a hydroxyl group, and 1 to 30 parts by weight of (methyl) A mixture of long-chain alkyl acrylate and 20-200 parts by weight of an organic compound having 3 or more hydroxyl groups.

In the present invention, 100 parts by weight of a copolymer (A) having a functional group capable of forming a hydrogen bond with a hydroxyl group, 20 to 200 parts by weight of an organic compound having 3 or more hydroxyl groups, and 0.01 to 10 parts by weight of a nonionic surface active In the case of an additive, the screen printability is improved, the storage stability at high temperature is improved, and "stringing" and "filamentous dirt" are less likely to occur.

(An example of a preferred use of the present invention)

For example, the manufacturing method of the glass substrate for plasma display panels using the binder resin composition of this invention is demonstrated. In this case, as said copolymer (A), the copolymer which has a crosslinkable functional group in a side chain or a terminal is used.

FIG. 2 is a schematic diagram showing the outline of a method for manufacturing a glass substrate for a plasma display panel using the binder resin composition of the present invention.

In the manufacturing method of the glass substrate for plasma display panels of this embodiment, first, the process of filling the binder resin composition of this invention which dispersed the glass powder in the recessed part of the template which formed the recessed part of a predetermined pattern (hereinafter , also referred to as "Step 1").

By using the binder resin composition of the present invention, in addition to being excellent in the filling properties of the above-mentioned template, the shape of the molded body can be sufficiently maintained until the time of sintering, and in the firing process, it is possible to prevent generation of residue.

The recesses of the template are formed corresponding to the intervals of the electrodes formed (or to be formed) on the glass substrate, and the recesses are in a pattern in the middle of the electrodes on the glass substrate.

The width or interval of the recesses of the template varies depending on the screen size or the number of pixels of the PDP to be fabricated, but generally the width of the recesses is about 20 to 100 μm, and the interval of the recesses is about 50 to 300 μm.

In addition, since the depth of the concave portion of the template corresponds to the height of the partition walls to be formed, it is usually about 100 to 300 μm.

The above-mentioned glass powder has the function of being integrated with the substrate by firing in a step described later to form a partition wall. The above-mentioned glass powder is not particularly limited, and examples thereof include lead borosilicate glass, lead glass, CaO·Al ₂ O ₃ ·SiO ₂ -based inorganic glass, MgO·Al ₂ O ₃ ·SiO ₂ -based inorganic glass, Low melting point glass such as Li ₂ O·Al ₂ O ₃ ·SiO ₂ -based inorganic glass, etc.

In addition, the preferable lower limit of the particle diameter of the said glass powder is 0.1 micrometer, and a preferable upper limit is 10 micrometers. When it is less than 0.1 μm, it may be difficult to sufficiently disperse in the low-temperature firing resin composition of the copolymer (A), and when it exceeds 10 μm, the precision of formed partition walls may be poor.

As the compounding ratio of the binder resin composition of the present invention and glass powder, it can be appropriately selected according to the type of binder resin composition or glass powder to be used, but the binder of the present invention relative to 100 parts by weight of glass powder The preferable lower limit of the compounding quantity of a resin composition is 1 weight part, and a preferable upper limit is 20 weight parts. When the amount is less than 1 part by weight, the binder resin composition of the present invention may not sufficiently function as an adhesive, and when it exceeds 20 parts by weight, the partition walls may not be formed or may be formed with poor precision.

In step 1, glass powder dispersed in the binder resin composition of the present invention is filled into the concave portion of the template ( FIG. 2 a ). As the filling amount, it is preferable to fill the adhesive resin composition of the present invention containing glass powder above the edge of the recess when filling the laminated glass substrate after filling, so that the adhesive resin composition of the present invention containing glass powder can be reliably contacted with the glass substrate, and it can also be filled to overflow the recess and make the adhesive resin composition containing The binder resin composition of the present invention of the glass powder spreads on the surface of the form to form a thin film. When the adhesive resin composition of the present invention containing glass powder is filled into the recess just at the edge (FIG. 2b1), a glass substrate having a partition wall directly formed on the glass substrate can be obtained (FIG. 2f1), On the other hand, when the binder resin composition of the present invention containing glass powder is filled into the overflow recess (FIG. 262), a glass substrate having a partition wall formed on the glass substrate by a thin film can be obtained ( Figure 2f2).

In the method for manufacturing a glass substrate for a plasma display panel according to the present embodiment, a step of laminating a template filled with the binder resin composition of the present invention containing the above-mentioned glass powder and a glass substrate to obtain a laminate is then performed ( Hereinafter, it is also referred to as step 2). The obtained laminate is shown in Fig. 2c1 and Fig. 2c2.

When the electrodes are formed on the glass substrate in advance, care should be taken that the electrodes are located between the recesses of the template during lamination.

In the method for manufacturing a glass substrate for a plasma display panel according to this embodiment, next, a stimulus for curing the binder resin composition of the present invention is applied to the laminate obtained in step 2, and the glass powder containing the above-mentioned The step of curing the binder resin composition of the present invention (hereinafter also referred to as step 3).

In this embodiment, since the above-mentioned copolymer (A) contained in the adhesive resin composition of the present invention has a crosslinkable functional group that undergoes a crosslinking reaction by light irradiation and/or heating, it can be irradiated with light and/or heat. Or heat is easily cured (Figure 2d1 and Figure 2d2).

In the method for manufacturing a glass substrate for a plasma display panel according to this embodiment, next, the template is released from the above-mentioned laminate to obtain the adhesive of the present invention formed on the substrate by solidified glass powder. A step of forming a partition wall precursor formed of a resin composition (hereinafter also referred to as step 4).

In step 3, by curing the binder resin composition of the present invention containing the above-mentioned glass powder, the cured binder resin composition of the present invention containing glass powder adheres to the above-mentioned glass substrate, and at the same time causes some Curing shrinks and, therefore, the formwork can be demoulded extremely easily. In addition, since the cured product has sufficient strength, it will not be deformed or chipped when it is released from the mold.

In this way, a partition wall precursor to form partition walls by firing in a step described later was formed on the glass substrate corresponding to the shape and size of the concave portion of the template ( FIGS. 2e1 and 2e2 ).

In the method for manufacturing a glass substrate for a plasma display panel according to this embodiment, next, the molded body obtained in the above-mentioned step 4 is fired to reduce the binder resin composition of the present invention, and at the same time, the above-mentioned glass powder and the glass substrate A step of integrally forming partition walls (hereinafter also referred to as step 5).

The above-mentioned firing is carried out under the conditions that the binder resin composition of the present invention is completely removed, the glass powder is fired, and the glass substrate is not warped or deformed. In the method for manufacturing a glass substrate for a plasma display panel according to this embodiment, since the adhesive resin composition of the present invention is used as an adhesive, no residue, etc., can be generated by heating at a relatively low temperature for a short time. Definitely remove adhesive. In addition, especially when the firing is performed in an atmosphere with a high oxygen concentration, the binder can be completely removed even under conditions of a lower temperature and a shorter time. Through step 5, an integrated partition wall is formed on the glass substrate (FIG. 2f1 and FIG. 2f2).

In the method for manufacturing a glass substrate for a plasma display panel according to the present embodiment, by using the binder resin composition of the present invention, it is possible to manufacture glass substrates with shape precision without deformation or chipping through significantly simplified and simplified steps. Very high partition glass substrate. In addition, since the firing is performed at a relatively low temperature for a short period of time, the glass substrate does not deform, and it does not take too much time to let it cool down.

Description of drawings

[ Fig. 1] Fig. 1 is a schematic diagram showing a bonding mode between segments in a polymer (A) used in the adhesive resin composition of the present invention.

[ Fig. 2] Fig. 2 is a schematic schematic view showing an example of a method for producing a glass substrate for a plasma display panel using the binder resin composition of the present invention.

[ Fig. 3] Fig. 3 is a schematic view showing a bonding mode between segments in a binder resin.

Symbol Description

1...template

2...Heat subtractive curable resin composition containing glass powder

3…Glass substrate

4…Septoid precursor

5…next door

Detailed ways

Hereinafter, although an Example is given and this invention is demonstrated in more detail, this invention is not limited to these Examples.

(Synthesis Example 1)

Into a 0.5L separable flask equipped with a stirrer, a cooler, a thermometer, and a nitrogen inlet, 100 g of 2-ethylhexyl acrylate, 3 g of dodecyl mercaptan (manufactured by Wako Pure Chemical Industries, Ltd.) and 100 g of ethyl acetate were charged and carried out. Mix to obtain a monomer mixed solution. Dissolved oxygen was removed by bubbling the obtained monomer mixed solution with nitrogen gas for 20 minutes, and then, the inside of the separable flask was replaced with nitrogen gas, and the temperature was raised to reflux while stirring. After refluxing, a solution obtained by diluting 0.024 g of 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane as a polymerization initiator with 1 g of ethyl acetate was charged into the polymerization system. One hour later, a solution obtained by diluting 0.036 g of 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane with 1 g of ethyl acetate was added. Moreover, the solution which diluted 0.048g of bis(3,5,5-trimethylhexanoyl) peroxides with 1g of ethyl acetate was injected|thrown-in after 2, 3, and 4 hours after polymerization start. After 7 hours from the first injection of the polymerization initiator, it was cooled to room temperature to complete the polymerization. Thus, an ethyl acetate solution of a 2-ethylhexyl acrylate oligomer was obtained.

When the obtained oligomer was analyzed by gel permeation chromatography, the number average molecular weight was about 5,000 in terms of polystyrene.

(Synthesis Example 2)

In a 0.5 L separable flask, 0.1 moles of tripropylene glycol, 0.1 moles of methacrylic anhydride were mixed in anhydrous tetrahydrofuran. After the mixture was stirred for a while, the inside of the container was reduced in pressure to volatilize the contents, and the raw material was distilled off to obtain tripropylene glycol monomethacrylate.

(Synthesis Example 3)

Polypropylene glycol monomethacrylate was obtained in the same manner as in Synthesis Example 2, except that tripropylene glycol in Synthesis Example 2 was changed to polypropylene glycol having a polymerization degree of 7.

(Example 1)

As shown in Table 1, in a 0.5L separable flask with a stirrer, a cooler, a thermometer, and a nitrogen inlet, 95g of methyl methacrylate (manufactured by Nippon Shokubai), 5g of polypropylene glycol monomethacrylate (NOF (Blenmer-PP-1000), 1 g of dodecanethiol (manufactured by Wako Pure Chemical Industries, Ltd.), and 100 g of ethyl acetate were mixed to obtain a monomer mixed solution. Dissolved oxygen was removed by bubbling the obtained monomer mixed solution with nitrogen gas for 20 minutes, and then, the inside of the separable flask was replaced with nitrogen gas, and the temperature was raised to reflux while stirring. After refluxing, a solution obtained by diluting 0.024 g of 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane as a polymerization initiator with 1 g of ethyl acetate was charged into the polymerization system. One hour later, a solution obtained by diluting 0.036 g of 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane with 1 g of ethyl acetate was added. Moreover, the solution which diluted 0.048g of bis(3,5,5-trimethylhexanoyl) peroxides with 1g of ethyl acetate was injected|thrown-in after 2, 3, and 4 hours after polymerization start. After 7 hours from the first injection of the polymerization initiator, it was cooled to room temperature to complete the polymerization. Thus, an ethyl acetate solution of a copolymer (A) having a polyalkylene oxide side chain was obtained.

When the obtained copolymer (A) was analyzed by gel permeation chromatography, the number average molecular weight in terms of polystyrene was about 30,000.

After removing ethyl acetate with a rotary evaporator, terpineol (manufactured by Yasuhara Chemical Co., Ltd., terpineol) was added and dissolved in the compounding ratio shown in Table 2. Glass powder (manufactured by Tokan Material Technology Co., Ltd., ABX169F: melting point 464° C., particle diameter 2.5 μm) was mixed in the compounding ratio shown in Table 2 using a three-roll machine to prepare a glass paste.

(Examples 2-46, and Examples 56-77, Comparative Examples 1, 2, 4-7, 9-21)

In Examples 2-77 and Comparative Examples 1-21, it is the same as Example 1 except the content shown in following Table 1-Table 26. That is, polymer (A) was prepared according to the composition of each monomer, and in Examples 2 to 29, Examples 34 to 36, and Examples 45, 46, and 56 to 77, glass powder was mixed in the compounding ratio in the following table to obtain glass paste. On the other hand, in Examples 31, 38, and 42, phosphor particles (BaMgAl ₁₀ O ₁₇ :Eu, manufactured by Nichia Chemical Industries, Ltd.) were mixed instead of glass powder to obtain phosphor paste. In addition, in Examples 32, 39, and 43, nickel particles (manufactured by Aldo Rich, with an average particle diameter of 3 μm) were mixed in the same manner instead of glass powder to obtain a nickel paste. In addition, in Examples 30, 37, and 41, similarly, alumina particles (manufactured by Wako Pure Chemical Industries, Ltd., with an average particle diameter of 1 μm) were mixed instead of glass powder to obtain ceramic pastes. In addition, in Examples 33, 40, and 44, similarly, silver powder (manufactured by Wako Pure Chemical Industries, Ltd., average particle size: 1 μm) was mixed instead of glass powder to obtain an electrically conductive paste. Mix using a three-roll machine.

Similarly, pastes having the compositions shown in Comparative Examples 1, 2, 4-7, and 9-21 were obtained.

(comparative example 3)

A 10% terpineol solution of ethyl cellulose (48% ethoxy content) manufactured by Aldrich Co. was prepared, and glass powder was mixed in the compounding ratio shown in Table 1 to obtain a glass paste.

(evaluate)

Pastes such as glass pastes, phosphor pastes, and conductive pastes prepared in Examples 1 to 46, Examples 56 to 77, and Comparative Examples 1, 2, 4 to 7, and 9 to 21 were evaluated according to the following methods. The evaluation results are shown in Tables 1-26.

(1) Evaluation of "drawing"

A material in which two spacers of 350 μm were arranged in parallel at an interval of 100 mm on a glass substrate was prepared. After excessively applying the obtained glass paste between the separators, the coating film was spread using a squeegee, and the presence or absence of "stringing" at the edge of the coating film was observed visually.

(2) Determination of 95% decomposition temperature

Using TGA/DTA (manufactured by TA Instruments Co., Ltd.), the measurement was performed in an air atmosphere at a temperature increase rate of 10° C./minute, and the temperature and weight change of the binder resin composition were measured. The temperature at which 95% of the initial weight is reduced is taken as the 95% decomposition temperature. In addition, the temperature at which the initial weight is reduced by 99% is defined as the 99% decomposition temperature.

On the other hand, the temperature increase rate was changed to 30° C./minute for measurement, and the temperature at which the initial weight was reduced by 95% was defined as the 95% decomposition temperature.

(3) Evaluation of whether there is blackening

Apply a glass paste on a glass substrate to a thickness of 350 μm, dry it at 150° C. for 10 minutes, and use an electric muffle furnace (manufactured by ADVANTEC, FUW230PA) to degrease the resin at 450° C. for 5 minutes. Observe the black coloration.

(4) Evaluation of stickiness

The glass paste was applied on a glass substrate to a thickness of 350 μm, dried at 150° C. for 10 minutes, cooled to room temperature, and evaluated for stickiness by finger stickiness.

(5) Determination of water content

The amount of water in the paste was measured at room temperature for 7 days after preparation of the paste using a Karl Fischer moisture meter.

(6) Determination of solvent content

Adjustment of paste for measurement

The paste was poured into a frame surrounded by a height of 1 mm on a glass plate, left to stand for 6 hours, and whether peeling occurred on the surface of the paste was observed.

Then, 0.5 g of the paste taken out from the frame was weighed on an aluminum dish, heated in an oven at 150° C. for 15 minutes, and the decrease in paste weight was measured.

The viscosity ratio and release property of the pastes obtained in Examples 28 to 32 and Comparative Examples 9 to 12 were evaluated by the following evaluation methods.

(7) Screen printability (viscosity ratio)

Viscosities at room temperature at 5 rpm and 30 rpm were measured for the obtained glass paste using a B-type viscometer, and the viscosity ratio (viscosity at 30 rpm/viscosity at 5 rpm) was calculated from the viscosity measurement results.

When this viscosity ratio is 1.5 or more, it judges that screen printability is favorable.

Above 1.5 is good

Less than 1.5 is bad

(8) Off-print

The ease of screen printing release was evaluated from the sensory evaluation of the printed matter when screen printing was performed 1000 times continuously.

○: Detached from the board smoothly

×: Cannot be detached from the board smoothly

About Examples 61-68 and Comparative Examples 13-16, the screen printability and storage stability were evaluated in the following procedure.

1) Screen printability (viscosity ratio)

The viscosities of the obtained glass paste were measured at room temperature using a B-type viscometer at rotation speeds of 5 rpm and 30 rpm. The viscosity ratio (viscosity at 30 rpm/viscosity at 5 rpm) was calculated|required from the obtained viscosity. 1.5 or more was regarded as excellent in screen printability.

Above 1.5 means good screen printability

Less than 1.5 is poor screen printing

2) Storage stability

After the obtained adhesive resin composition was stored at 50° C. for 2 months, whether or not phase separation occurred in the solution was evaluated visually.

○: No phase separation

△: Slight phase separation

×: complete phase separation

Examples 69 to 77 and Comparative Examples 17 to 22 were evaluated for the following low-temperature sinterability, screen printability, occurrence of filamentous grime, solution stability, and haze value.

1) Low temperature decomposition

Using TGA/DTA (manufactured by TA Instruments Co., Ltd.), the glass paste obtained above was measured in an air atmosphere at a temperature increase rate of 10° C./minute, and temperature and weight changes were measured. The temperature at which the weight decreased by 99.5% from the initial weight was defined as the 99.5% decomposition temperature, and the temperature below 400°C was evaluated as ○, and 400°C or higher was evaluated as ×.

2) Screen printability

The viscosity of the above-obtained glass paste was measured using a B-type viscometer while changing the rotational speed. The screen printing property represented by the easiness of passing through the mesh (high speed and low viscosity) and release/dripping property (low speed and high viscosity) was evaluated from the viscosity ratio (thixotropic ratio) at room temperature at rotation speeds of 5 rpm and 30 rpm. Here, a viscosity ratio of 1.5 or more was defined as ◯ and less than 1.5 was defined as ×.

3) Is there any occurrence of filamentous dirt?

A material in which two spacers with a thickness of 350 μm were arranged in parallel at an interval of 100 mm on a glass substrate was prepared. After excessively applying the above-obtained glass paste between the separators, it was evaluated whether or not fine thread-like dirt was generated when the coating film was stretched at a speed of 3 m/min with a squeegee. Here, when no filamentous dirt was generated, it was rated as ◯, and when filamentous dirt was generated, it was rated as x.

4) Solution stability

After the vehicle solution obtained above was stored at room temperature for 4 weeks, the solution was visually observed for phase separation. The case where phase separation did not occur was rated as ◯, and the case where phase separation occurred was rated as x.

5) Haze value

The vehicle obtained above was made into a film with a thickness of 5 mm, and the haze value was measured according to the following formula using a haze meter (TC-HIIIDPK) manufactured by Tokyo Denshoku Co., Ltd.

Haze value = Td/Tt

Here, Tt represents the total light transmittance (%), and Td represents the diffuse transmittance (%).

When the compounding range of Examples 56-60 and stearyl methacrylate (SMA) which are long-chain alkyl (meth)acrylates were 1-30 weight part, each evaluation was a favorable evaluation. On the contrary, in Comparative Example 9, since SMA was not copolymerized, the release property was poor. In Comparative Example 10, since there was little SMA, the release property was poor. In Comparative Example 11, since there were many SMAs, the viscosity ratio fell and the screen printability deteriorated. In Comparative Examples 11 and 12, since there were many SMAs, the viscosity ratio fell and the screen printability deteriorated.

All evaluations of Examples 61 to 68 in which 0.01 to 10 parts by weight of polyethylene oxides were added as nonionic surfactants were good. On the other hand, in Comparative Example 13, since no nonionic surfactant (polyethylene oxide) was added, phase separation occurred and screen printability deteriorated. In Comparative Example 14, since there were few nonionic surfactants, phase separation occurred and the screen printability deteriorated. In Comparative Example 15, since there were many nonionic surfactants, the viscosity ratio decreased, and the screen printability deteriorated. In Comparative Example 16, since there were many nonionic surfactants, the viscosity ratio decreased, and the screen printability deteriorated.

(Example 47)

(1) Preparation of crosslinkable binder resin

In a 0.5L separable flask with a stirrer, a cooler, a thermometer, and a nitrogen gas introduction port, 92g of isobutyl methacrylate (manufactured by Nippon Shokubai), 5g of polypropylene glycol monomethacrylate (manufactured by NOF, ブレンマ-PP -1000), 3 g of 3-methacryloxypropyltrimethoxysilane, 3 g of dodecanethiol (manufactured by Wako Pure Chemical Industries, Ltd.), and 100 g of ethyl acetate were mixed to prepare a monomer mixed solution. Dissolved oxygen was removed by bubbling the obtained monomer mixed solution with nitrogen gas for 20 minutes, and then, the inside of the separable flask was replaced with nitrogen gas, and the temperature was raised to reflux while stirring. After refluxing, a solution obtained by diluting 0.024 g of 1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane as a polymerization initiator with 1 g of ethyl acetate was put into the polymerization system . One hour later, a solution obtained by diluting 0.036 g of 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane with 1 g of ethyl acetate was added. In addition, 2, 3, and 4 hours after the start of polymerization, solutions obtained by diluting 0.048 g and 0.12 g of bis(3,5,5-trimethylhexanoyl) peroxide with 1 g of ethyl acetate were added. . After 7 hours from the first injection of the polymerization initiator, it was cooled to room temperature to complete the polymerization. Thus, an ethyl acetate solution of a copolymer (A) having a polyalkylene oxide side chain was obtained.

When the obtained copolymer (A) was analyzed by gel permeation chromatography, the number average molecular weight in terms of polystyrene was about 6,000.

50 g of polypropylene glycol (manufactured by Asahi Galas Co., Ltd., Exsenol 3020) was added to the obtained ethyl acetate solution of the copolymer (A), and ethyl acetate was removed by a rotary evaporator to obtain a liquid curable binder resin.

(2) Preparation of glass paste

With respect to 100 parts by weight of the obtained liquid curable binder resin, add 3 parts by weight of a diacylphosphine oxide compound (manufactured by Chiba Specialty Kumical Co., Ltd., Ilgakyua 819), heat to 50° C. under light-shielding, and mix with a stirring rod Until it is uniform, a pasty adhesive resin composition is obtained.

75 parts by weight of glass powder (manufactured by Tocan Materi Al Technology Co., Ltd., ABX169F: melting point 464° C., particle diameter 2.5 μm) was mixed with 25 parts by weight of the obtained paste binder resin composition, and the glass powder was made by a ball mill. Fully disperse to prepare glass paste.

(3) Manufacture of glass substrates for plasma display panels

A template was prepared in which a plurality of recesses with a width of 50 μm and a depth of 150 μm were formed at intervals of 160 μm on the surface of a plate-shaped object made of silicone rubber. The obtained glass paste is filled in the recesses of the template, overflows the recesses, and spreads to a thin film on the surface of the template. A glass substrate was laminated thereon to obtain a laminate.

Next, ultraviolet rays of 365 nm were irradiated from the side of the glass substrate for 60 seconds using a high-pressure mercury lamp and adjusting the irradiation intensity to an illumination intensity of 10 mW/cm ² . After irradiating ultraviolet rays, maintain at 80° C. for 30 minutes.

After the maintenance, the glass substrate was slowly picked up. At this time, the template was easily detached, and a molded body in which a partition wall precursor composed of a cured glass-containing heat-absorbent curable resin composition was formed on the substrate was obtained. This molded body was degreased at 260° C. for 10 minutes, and then fired at 460° C. for 5 minutes. As a result, the heat-subtractive resin composition was completely removed, and partition walls with extremely high shape accuracy without deformation or chipping were formed on the glass substrate.

(Example 48)

A paste-like binder resin composition was obtained in the same manner as in Example 47, except that 2 parts by weight of cumene hydroperoxide was added as a decomposition accelerator.

A glass paste was prepared in the same manner as in Example 17 except that the obtained binder resin composition was used, and a glass substrate for a plasma display panel was produced. The obtained partition walls were partition walls with extremely high shape accuracy without deformation or chipping.

(Example 49)

A pasty binder resin composition was obtained in the same manner as in Example 47, except that 2 parts by weight of azobisisobutyronitrile (AIBN) was added as a decomposition accelerator.

A glass paste was prepared in the same manner as in Example 17 except that the obtained binder resin composition was used, and a glass substrate for a plasma display panel was produced. The obtained partition walls were partition walls with extremely high shape accuracy without deformation or chipping.

(Example 50)

Except having added 4 weight part of tin oxides as a decomposition accelerator, it carried out similarly to Example 47, and obtained the adhesive resin composition of paste form.

A glass paste was prepared in the same manner as in Example 47 except that the obtained binder resin composition was used, and a glass substrate for a plasma display panel was produced. The obtained partition walls were partition walls with extremely high shape accuracy without deformation or chipping.

(Example 51)

A paste-like binder resin composition was obtained in the same manner as in Example 47, except that 3 parts by weight of dodecanethiol was added as a decomposition retarder.

A glass paste was prepared in the same manner as in Example 47 except that the obtained binder resin composition was used, and a glass substrate for a plasma display panel was produced. The obtained partition walls were partition walls with extremely high shape accuracy without deformation or chipping.

(Example 52)

A paste-like binder resin composition was obtained in the same manner as in Example 47, except that 2 parts by weight of 1,6-hexamethylenediamine was added as a decomposition retarder.

A glass paste was prepared in the same manner as in Example 47 except that the obtained binder resin composition was used, and a glass substrate for a plasma display panel was produced. The obtained partition walls were partition walls with extremely high shape accuracy without deformation or chipping.

(Example 53)

A pasty binder resin composition was obtained in the same manner as in Example 47, except that 2 parts by weight of dibutyltin dilaurate was added as a decomposition retarder.

A glass paste was prepared in the same manner as in Example 47 except that the obtained binder resin composition was used, and a glass substrate for a plasma display panel was produced. The obtained partition walls were partition walls with extremely high shape accuracy without deformation or chipping.

(Example 54)

Except having added 3 weight part of tributyl borates as a decomposition retarder, it carried out similarly to Example 47, and obtained the adhesive resin composition of paste form.

A glass paste was prepared in the same manner as in Example 47 except that the obtained binder resin composition was used, and a glass substrate for a plasma display panel was produced. The obtained partition walls were partition walls with extremely high shape accuracy without deformation or chipping.

(comparative example 8)

In a 0.2L beaker, 75 parts by weight of lead borosilicate glass powder (manufactured by Tokan Material Technology Co., Ltd., ABX169F: melting point 464° C., particle size 2.5 μm) was mixed with 100 parts by weight of polyvinyl butyral (product (manufactured by Water Chemical Co., Ltd.) in a 25% toluene solution was stirred with a stirring bar until uniform, and a glass paste was prepared.

A template was prepared in which a plurality of recesses with a width of 50 μm and a depth of 150 μm were formed at intervals of 160 μm on the surface of a plate-shaped object made of silicone rubber. The obtained glass paste is filled in the recesses of the template, overflows the recesses, and spreads to a thin film on the surface of the template. A glass substrate was laminated thereon to obtain a laminate. The glass substrate was picked up slowly, and at this time, the glass paste remained in some recesses and did not come to the side of the glass substrate. Next, the obtained molded body was degreased at 400° C. for 20 minutes, and then fired at 460° C. for 5 minutes. As a result, although the resin composition was reduced to obtain partition walls, some partition walls collapsed laterally, and when observed with a microscope, deformation or chipping of some partition walls was confirmed. It was also confirmed that part of the glass substrate was deformed.

(Example 55)

In a 0.5L separable flask with a stirrer, a cooler, a thermometer, and a nitrogen inlet, 95g of isobutyl methacrylate (manufactured by Nippon Shokubai), 5g of polypropylene glycol monomethacrylate (manufactured by NOF, ブレンマ-PP -1000), 1 g of dodecanethiol (manufactured by Wako Pure Chemical Industries, Ltd.), and 100 g of ethyl acetate were mixed to obtain a monomer mixed solution.

Dissolved oxygen was removed by bubbling the obtained monomer mixed solution with nitrogen gas for 20 minutes, and then, the inside of the separable flask system was replaced with nitrogen gas, and the temperature was raised to reflux while stirring.

After refluxing, a solution obtained by diluting 0.024 g of 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane as a polymerization initiator with 1 g of ethyl acetate was charged into the polymerization system. One hour later, a solution obtained by diluting 0.036 g of 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane with 1 g of ethyl acetate was added. Moreover, the solution which diluted 0.048g of bis(3,5,5-trimethylhexanoyl) peroxides with 1g of ethyl acetate was injected|thrown-in after 2, 3, and 4 hours after polymerization start. After 7 hours from the first injection of the polymerization initiator, it was cooled to room temperature to complete the polymerization. Thus, an ethyl acetate solution of a binder resin having a polyether side chain was obtained.

When the obtained binder resin was analyzed by gel permeation chromatography, the number average molecular weight in terms of polystyrene was about 30,000.

Ethyl acetate was removed from the obtained ethyl acetate solution of the binder resin with a rotary evaporator, and then terpineol (manufactured by Yasuhara Chemical Co., Ltd., terpineol) was added and dissolved. A mixture of CaO-Al ₂ O ₃ -SiO ₂ -B ₂ O ₃ and Al ₂ O ₃ as ceramic powder was added to the obtained solution in an amount of 15% by weight relative to the entire solution, and kneaded with a three-roll mill, A ceramic paste was produced by further mixing with a ball mill for 48 hours.

Coat the obtained ceramic paste on the mold-release-treated polyester film, and make the dried thickness about 5 μm, air-dry at room temperature for 1 hour, dry at 80°C for 3 hours with a hot air dryer, and then dry at 120°C Dry for 2 hours to obtain a ceramic green sheet.

The ceramic green sheet was cut into a size of 5 cm square, and 100 sheets of the material obtained by screen-printing the conductive paste for screen printing were superimposed on it, and hot-pressed at a temperature of 70°C and a pressure of 150kg/cm ² for 10 minutes. Pressing is carried out under the same conditions to obtain a laminated body of ceramic green sheets.

The obtained ceramic green sheet laminate was heated up to 300° C. at a temperature increase rate of 10° C./minute to obtain a ceramic fired body.

(evaluate)

In the same manner as in Example 1, the "stringiness" and 95% decomposition temperature of the fired ceramic body obtained in Example 55 were evaluated. As a result, "stringiness" was not confirmed visually. In addition, the 95% decomposition temperature is 300°C.

Table 1

Example 1 2 3 4 5 6 7 8 9 monomer composition Methyl methacrylate 95 Isobutyl methacrylate 95 90 80 80 60 80 80 Stearyl methacrylate 95 Polypropylene glycol monomethacrylate trade name "Buren Ma-PP-1000", degree of polymerization 16, manufactured by NOF Corporation 5 5 5 10 20 20 40 Polypropylene glycol monomethacrylate trade name "Blenma-PP-500", degree of polymerization 9, manufactured by NOF Co., Ltd. 20 Polypropylene glycol monomethacrylate trade name "Burenma PP-800", degree of polymerization 13, manufactured by NOF Corporation 20 chain transfer agent Dodecanethiol 1 1 1 1 1 1 1 1 1 Polymerization solvent Ethyl acetate 100 100 100 100 100 100 100 100 100 Number average molecular weight (Mn) (×10,000) 3 3.5 3.2 3.4 3.6 3.6 3.3 3.5 3.4

Table 2

Example 1 2 3 4 5 6 7 8 9 additive Polypropylene glycol (number-average molecular weight 3000) trade name "Excel 3020", manufactured by Asahi Glass Co., Ltd. Polypropylene glycol (number-average molecular weight: 10,000) trade name "Pureminol 4011", manufactured by Asahi Glass Co., Ltd. Polytetramethylene glycol (number average molecular weight 1000) trade name "PTMG1000", manufactured by Mitsubishi Chemical Corporation 2-ethylhexyl acrylate oligomer (number average molecular weight 5000), synthesis example 1 Ethyl cellulose decomposition accelerator cumene hydroperoxide tert-butanol peroxide Azobisisobutyronitrile tin oxide Dodecanethiol 1,6-Hexamethylenediamine Dibutyltin laurate Tributyl borate solvent Terpineol (boiling point 218°C) 100 100 100 100 100 100 100 100 Butyl Carbitol (boiling point 230°C) 1-Hexanol (boiling point 156°C) 100 Butyl acetate (boiling point 125°C) Inorganic powder glass powder 300 300 300 300 300 300 300 300 300 Aluminum oxide powder Phosphor nickel powder silver powder

table 3

Example 1 2 3 4 5 6 7 8 9 Evaluation results drawing none none none none none none none none none 95% decomposition temperature (℃) 370 350 400 340 330 330 320 330 330 Whether there is blackening none none none none none none none none none Stickiness none none none none none none none none none After 7 days, moisture content (ppm) 4800 3900 2500 4000 4000 4200 4800 5300 5000 Solvent content just after gelatinization (weight%) 20 20 20 20 20 20 20 20 20 After gelatinization, the solvent content after 23°C×6 hours (weight %) 19 18 18 19 19 17 19 19 19 After gelatinization, the state after 23℃×6 hours No peeling No peeling No peeling No peeling No peeling No peeling No peeling No peeling No peeling 99% decomposition temperature (°C) (TGA device, heating rate 10°C/min) 400 380 420 380 380 360 350 350 360 95% decomposition temperature (°C) (TGA device, heating rate 30°C/min) 370 360 400 360 350 340 340 350 340 Viscosity ratio 1.8 1.9 2.4 2.2 2.1 1.9 2.7 1.8 1.9

Table 4

Example 10 11 12 13 14 15 16 17 18 monomer composition Methyl methacrylate Isobutyl methacrylate 80 60 80 80 95 95 95 95 95 stearyl methacrylate n-Butyl methacrylate lauryl methacrylate Glyceryl methacrylate Hydroxyethyl Methacrylate 3-Methacryloxypropyltrimethoxysilane Polypropylene glycol monomethacrylate trade name "Blenma-PP-1000", degree of polymerization 16, manufactured by NOF Co., Ltd. 5 5 5 5 5 Polypropylene glycol monomethacrylate trade name "Blenmer-PP-500", degree of polymerization 9, manufactured by NOF Corporation Polypropylene glycol monomethacrylate trade name "Blenma-PP-800", degree of polymerization 13, manufactured by NOF Corporation Monomethacrylate modified product of polypropylene glycol-polytetramethylene glycol copolymer, trade name "Blenma-70PPT-800", manufactured by NOF Corporation 20 40 The monomethacrylate modified product of polypropylene glycol/poly-1,2-butylene oxide copolymer is named "Blenma-10PPB-500B", the degree of polymerization of poly-1,2-butylene oxide is 6, NOF Corporation manufacture 20 Polyethylene glycol monomethacrylate trade name "Blenma-PE-350", degree of polymerization 8, manufactured by NOF Co., Ltd. Tripropylene glycol methacrylate (synthesis example 2) Polypropylene glycol monomethacrylate (synthesis example 3), degree of polymerization 7, number average molecular weight 400 20 chain transfer agent Dodecanethiol 1 1 1 1 1 1 1 1 1 Polymerization solvent ethyl acetate 100 100 100 100 100 100 100 100 100 Number average molecular weight (Mn) (×10,000) 3.5 3 3.6 3.6 18 3.5 3.5 3.5 3.4

table 5

Example 10 11 12 13 14 15 16 17 18 additive Polypropylene glycol (number average molecular weight 3000) trade name "EXENOL 3020", manufactured by Asahi Glass Co., Ltd. 30 Polypropylene glycol (number-average molecular weight: 10,000), trade name "Preminol 4011", manufactured by Asahi Glass Co., Ltd. 30 Polytetramethylene glycol (number average molecular weight 1000) trade name "PTMG1000", manufactured by Mitsubishi Chemical Corporation 30 2-ethylhexyl acrylate oligomer (number average molecular weight 5000), synthesis example 1 Ethyl cellulose decomposition accelerator cumene hydroperoxide tert-butanol peroxide Azobisisobutyronitrile tin oxide Dodecanethiol 1,6-Hexamethylenediamine Dibutyltin laurate Tributyl borate solvent Terpineol (boiling point 218°C) 100 100 100 100 100 100 100 100 Butyl Carbitol (boiling point 230°C) 100 1-Hexanol (boiling point 156°C) Butyl acetate (boiling point 125°C) Inorganic powder glass powder 300 300 300 300 300 300 300 300 300 Aluminum oxide powder Phosphor nickel powder silver powder

Table 6

Example 10 11 12 13 14 15 16 17 18 Evaluation results drawing none none none none none none none none none 95% decomposition temperature (℃) 330 310 320 320 350 350 350 350 330 Whether there is blackening none none none none none none none none none stickiness none none none none none none none none none After 7 days, moisture content (ppm) 3500 5100 4600 4800 4000 4800 5100 5500 5300 Solvent content just after gelatinization (weight%) 20 20 20 20 20 20 19 19 19 After gelatinization, the solvent content after 23°C×6 hours (weight %) 18 18 19 18 19 19 18 18 17 After gelatinization, the state after 23℃×6 hours No peeling No peeling No peeling No peeling No peeling No peeling No peeling No peeling No peeling 99% decomposition temperature (°C) (TGA device, heating rate 10°C/min) 350 340 350 360 370 370 390 380 370 95% decomposition temperature (°C) (TGA device, heating rate 30°C/min) 340 330 330 340 360 360 370 360 350 Viscosity ratio 2.3 2.6 2.4 2 1.7 2 2.4 2.6 2.7

Table 7

Example 19 20 twenty one twenty two twenty three twenty four 25 26 27 28 monomer composition Methyl methacrylate 30 Isobutyl methacrylate 95 80 80 80 80 80 80 80 80 60 stearyl methacrylate n-Butyl methacrylate lauryl methacrylate Glyceryl methacrylate 5 Hydroxyethyl Methacrylate 3-Methacryloxypropyltrimethoxysilane Polypropylene glycol monomethacrylate trade name "Blenma-PP-1000", degree of polymerization 16, manufactured by NOF Corporation 5 20 20 20 20 20 20 20 20 5 Polypropylene glycol monomethacrylate trade name "Buren Mar-PP-500", degree of polymerization 9, manufactured by NOF Co., Ltd. Polypropylene glycol monomethacrylate trade name "Blenma-PP-800", degree of polymerization 13, manufactured by NOF Corporation Monomethacrylate modified product of polypropylene glycol-polytetramethylene glycol copolymer, trade name "Bumma-70PPT-800", manufactured by NOF Corporation The monomethacrylate modified product of polypropylene glycol/poly-1,2-butylene oxide copolymer is named "Blens-10PPB-500B", the degree of polymerization of poly-1,2-butylene oxide is 6, NOF Corporation manufacture Polyethylene glycol monomethacrylate trade name "Blenma-PE-350", degree of polymerization 8, manufactured by NOF Co., Ltd. Tripropylene glycol methacrylate (synthesis example 2) Polypropylene glycol monomethacrylate (synthesis example 3), degree of polymerization 7, number average molecular weight 400 chain transfer agent Dodecanethiol 1 1 1 1 1 1 1 1 1 1 Polymerization solvent ethyl acetate 100 100 100 100 100 100 100 100 100 100 Number average molecular weight (Mn) (×10,000) 3.4 3.4 3.4 3.4 3.4 3.4 3.4 3.4 3.4 4.5

Table 8

Example 19 20 twenty one twenty two twenty three twenty four 25 26 27 28 additive Polypropylene glycol (number average molecular weight 3000) trade name "EXENOL 3020", manufactured by Asahi Glass Co., Ltd. Polypropylene glycol (number-average molecular weight: 10,000), trade name "Preminol 4011", manufactured by Asahi Glass Co., Ltd. Polytetramethylene glycol (number average molecular weight 1000) trade name "PTMG1000", manufactured by Mitsubishi Chemical Corporation 2-ethylhexyl acrylate oligomer (number average molecular weight 5000), synthesis example 1 30 Ethyl cellulose decomposition accelerator cumene hydroperoxide 2 tert-butanol peroxide 3 Azobisisobutyronitrile 2 tin oxide 4 Dodecanethiol 3 1,6-Hexamethylenediamine 2 Dibutyltin laurate 3 Tributyl borate 3 solvent Terpineol (boiling point 218°C) 100 100 100 100 100 100 100 100 100 100 Butyl Carbitol (boiling point 230°C) 1-Hexanol (boiling point 156°C) Butyl acetate (boiling point 125°C) Inorganic powder glass powder 300 300 300 300 300 300 300 300 300 300 Aluminum oxide powder Phosphor nickel powder silver powder

Table 9

Example 19 20 twenty one twenty two twenty three twenty four 25 26 27 28 Evaluation results drawing none none none none none none none none none none 95% decomposition temperature (℃) 330 310 300 330 320 320 330 330 330 380 Whether there is blackening none none none none none none none none none none Stickiness none none none none none none none none none none After 7 days, moisture content (ppm) 5400 4100 3800 3800 4200 4000 4000 4200 4100 5200 Solvent content just after gelatinization (weight%) 19 20 20 20 20 20 20 20 20 20 After gelatinization, the solvent content after 23°C×6 hours (weight %) 17 18 18 18 18 19 19 19 18 18 After gelatinization, the state after 23℃×6 hours No peeling No peeling No peeling No peeling No peeling No peeling No peeling No peeling No peeling No peeling 99% decomposition temperature (°C) (TGA device, heating rate 10°C/min) 370 330 330 350 350 360 360 350 350 400 95% decomposition temperature (°C) (TGA device, heating rate 30°C/min) 350 330 330 340 330 340 340 340 330 380 Viscosity ratio 2.4 1.8 1.9 2 2 1.8 2.1 2 2 3.5

Table 10

Example 29 30 31 32 33 34 35 36 37 38 monomer composition Methyl methacrylate 30 30 30 30 30 30 Isobutyl methacrylate 60 60 60 60 60 60 55 90 90 90 stearyl methacrylate n-Butyl methacrylate lauryl methacrylate 45 Glyceryl methacrylate 5 5 5 5 5 5 Hydroxyethyl Methacrylate 5 3-Methacryloxypropyltrimethoxysilane Polypropylene glycol monomethacrylate trade name "Bresoma-PP-1000", degree of polymerization 16, manufactured by NOF Co., Ltd. 5 5 5 5 5 5 5 10 10 10 Polypropylene glycol monomethacrylate trade name "Bresoma-PP-500", degree of polymerization 9, manufactured by NOF Corporation Polypropylene glycol monomethacrylate trade name "Blenma-PP-800", degree of polymerization 13, manufactured by NOF Corporation Monomethacrylate modified product of polypropylene glycol-polytetramethylene glycol copolymer, trade name "Bresoma-70PPT-800", manufactured by NOF Corporation The monomethacrylate modified product of polypropylene glycol/poly-1,2-butylene oxide copolymer is named "Buresoma-10PPB-500B", the degree of polymerization of poly-1,2-butylene oxide is 6, NOF Corporation manufacture Polyethylene glycol monomethacrylate trade name "Blenma-PE-350", degree of polymerization 8, manufactured by NOF Co., Ltd. Tripropylene glycol methacrylate (synthesis example 2) Polypropylene glycol monomethacrylate (synthesis example 3), degree of polymerization 7, number average molecular weight 400 chain transfer agent Dodecanethiol 1 1 1 1 1 1 1 0.4 0.4 0.4 Polymerization solvent ethyl acetate 100 100 100 100 100 100 100 100 100 100 Number average molecular weight (Mn) (×10,000) 4.5 4.5 4.5 4.5 4.5 4.5 4 9.1 9.1 9.1

Table 11

Example 29 30 31 32 33 34 35 36 37 38 additive Polypropylene glycol (number-average molecular weight: 10,000), trade name "Preminol 4011", manufactured by Asahi Glass Co., Ltd. Polytetramethylene glycol (number average molecular weight 1000) trade name "PTMG1000", manufactured by Mitsubishi Chemical Corporation 2-ethylhexyl acrylate oligomer (number average molecular weight 5000), synthesis example 1 Ethyl cellulose decomposition accelerator cumene hydroperoxide tert-butanol peroxide Azobisisobutyronitrile tin oxide Dodecanethiol 1,6-Hexamethylenediamine Dibutyltin laurate Tributyl borate solvent Terpineol (boiling point 218°C) 100 100 100 100 100 100 100 100 100 100 Butyl Carbitol (boiling point 230°C) 1-Hexanol (boiling point 156°C) Butyl acetate (boiling point 125°C) Inorganic powder glass powder 300 300 300 300 Aluminum oxide powder 300 300 Phosphor 300 300 nickel powder 300 silver powder 300

Table 12

Example 29 30 31 32 33 34 35 36 37 38 Evaluation results drawing none none none none none none none none none 95% decomposition temperature (℃) 380 380 380 380 380 400 380 370 370 360 Whether there is blackening none none none none none none none none none Stickiness none none none none none none none none none After 7 days, moisture content (ppm) 5400 5400 5300 5200 5300 5000 3100 4400 4500 4300 Solvent content just after gelatinization (weight%) 20 20 20 20 20 20 20 20 20 20 After gelatinization, the solvent content after 23°C×6 hours (weight %) 19 19 19 19 18 18 19 19 19 18 After gelatinization, the state after 23℃×6 hours No peeling No peeling No peeling No peeling No peeling No peeling No peeling No peeling No peeling No peeling 99% decomposition temperature (°C) (TGA device, heating rate 10°C/min) 390 400 400 390 400 400 390 390 400 390 95% decomposition temperature (°C) (TGA device, heating rate 30°C/min) 380 380 390 380 380 400 380 380 380 370 Viscosity ratio 3.4 3 3.1 3.1 3.1 2.8 3.4 1.8 2.3 2.2

Table 13

Example 39 40 41 42 43 44 45 46 monomer composition Methyl methacrylate Isobutyl methacrylate 90 90 95 95 95 95 95 stearyl methacrylate n-Butyl methacrylate 95 lauryl methacrylate Glyceryl methacrylate Hydroxyethyl Methacrylate 3-Methacryloxypropyltrimethoxysilane Polypropylene glycol monomethacrylate trade name "Blenma-PP-1000", degree of polymerization 16, manufactured by NOF Co., Ltd. 10 10 5 5 5 5 5 5 Polypropylene glycol monomethacrylate trade name "Blenmer-PP-500", degree of polymerization 9, manufactured by NOF Corporation Polypropylene glycol monomethacrylate trade name "Blenma-PP-800", degree of polymerization 13, manufactured by NOF Corporation Monomethacrylate modified product of polypropylene glycol-polytetramethylene glycol copolymer, trade name "Blenma-70PPT-800", manufactured by NOF Corporation The monomethacrylate modified product of polypropylene glycol/poly-1,2-butylene oxide copolymer is named "Blenma-10PPB-500B", the degree of polymerization of poly-1,2-butylene oxide is 6, NOF Corporation manufacture Polyethylene glycol monomethacrylate trade name "Buren Ma-PE-350", degree of polymerization 8, manufactured by NOF Co., Ltd. Tripropylene glycol methacrylate (synthesis example 2) Polypropylene glycol monomethacrylate (synthesis example 3), degree of polymerization 7, number average molecular weight 400 chain transfer agent Dodecanethiol 0.4 0.4 1 1 1 1 1 1 Polymerization solvent ethyl acetate 100 100 100 100 100 100 100 100 Number average molecular weight (Mn) (×10,000) 9.1 9.1 3.6 3.6 3.6 3.6 10.7 3.2

Table 14

Example 39 40 41 42 43 44 45 46 additive Polypropylene glycol (number average molecular weight 3000) trade name "EXENOL 3020", manufactured by Asahi Glass Co., Ltd. Polypropylene glycol (number-average molecular weight: 10,000), trade name "Preminol 4011", manufactured by Asahi Glass Co., Ltd. Polytetramethylene glycol (number average molecular weight 1000) trade name "PTMG1000", manufactured by Mitsubishi Chemical Corporation 2-ethylhexyl acrylate oligomer (number average molecular weight 5000), synthesis example 1 Ethyl cellulose decomposition accelerator cumene hydroperoxide tert-butanol peroxide Azobisisobutyronitrile tin oxide Dodecanethiol 1,6-Hexamethylenediamine Dibutyltin laurate Tributyl borate solvent Terpineol (boiling point 218°C) 100 100 100 100 100 100 100 100 Butyl Carbitol (boiling point 230°C) 1-Hexanol (boiling point 156°C) Butyl acetate (boiling point 125°C) Inorganic powder glass powder 300 300 Aluminum oxide powder 300 Phosphor 300 nickel powder 300 300 silver powder 300 300

Table 15

Example 39 40 41 42 43 44 45 46 Evaluation results drawing none none none none none none none none 95% decomposition temperature (℃) 370 370 350 360 350 350 300 400 Whether there is blackening none none none none none none none none Stickiness none none none none none none none After 7 days, moisture content (ppm) 4800 4700 4600 4200 4400 4500 4300 4700 Solvent content just after gelatinization (weight%) 20 20 20 20 20 20 20 20 After gelatinization, the solvent content after 23°C×6 hours (weight %) 19 18 18 19 18 18 18 18 After gelatinization, the state after 23℃×6 hours No peeling No peeling No peeling No peeling No peeling No peeling No peeling No peeling 99% decomposition temperature (°C) (TGA device, heating rate 10°C/min) 380 370 380 380 370 390 340 400 95% decomposition temperature (°C) (TGA device, heating rate 30°C/min) 370 370 370 360 360 360 320 400 Viscosity ratio 2.1 2.4 2.1 1.8 1.9 2 1.7 1.8

Table 16

Example 47 48 49 50 51 52 53 54 55 monomer composition Methyl methacrylate Isobutyl methacrylate 92 92 92 92 92 92 92 92 95 stearyl methacrylate n-Butyl methacrylate lauryl methacrylate Glyceryl methacrylate Hydroxyethyl Methacrylate 3-Methacryloxypropyltrimethoxysilane 3 3 3 3 3 3 3 3 Polypropylene glycol monomethacrylate trade name "Zurens-PP-1000", degree of polymerization 16, manufactured by NOF Corporation 5 5 5 5 5 5 5 5 5 Polypropylene glycol monomethacrylate trade name "Blenmer-PP-500", degree of polymerization 9, manufactured by NOF Corporation Polypropylene glycol monomethacrylate trade name "Buren Mar-PP-800", degree of polymerization 13, manufactured by NOF Co., Ltd. Monomethacrylate modified product of polypropylene glycol-polytetramethylene glycol copolymer, trade name "Blens-70PPT-800", manufactured by NOF Corporation The monomethacrylate modified product of polypropylene glycol/poly-1,2-butylene oxide copolymer is named "Blens-10PPB-500B", the degree of polymerization of poly-1,2-butylene oxide is 6, NOF Corporation manufacture Polyethylene glycol monomethacrylate trade name "Blenma-PE-350", degree of polymerization 8, manufactured by NOF Co., Ltd. Tripropylene glycol methacrylate (synthesis example 2) Polypropylene glycol monomethacrylate (synthesis example 3), degree of polymerization 7, number average molecular weight 400 chain transfer agent Dodecanethiol 3 3 3 3 3 3 3 3 Polymerization solvent ethyl acetate Number average molecular weight (Mn) (×10,000) 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6

Table 17

Example 47 48 49 50 51 52 53 54 55 additive Polypropylene glycol (number average molecular weight 3000) trade name "EXENOL 3020", manufactured by Asahi Glass Co., Ltd. Polypropylene glycol (number-average molecular weight: 10,000), trade name "Preminol 4011", manufactured by Asahi Glass Co., Ltd. Polytetramethylene glycol (number average molecular weight 1000) trade name "PTMG1000", manufactured by Mitsubishi Chemical Corporation 2-ethylhexyl acrylate oligomer (number average molecular weight 5000), synthesis example 1 Ethyl cellulose decomposition accelerator cumene hydroperoxide 2 tert-butanol peroxide Azobisisobutyronitrile 2 tin oxide 4 Dodecanethiol 3 1,6-Hexamethylenediamine 2 Dibutyltin laurate 3 Tributyl borate 3 solvent Terpineol (boiling point 218°C) Butyl Carbitol (boiling point 230°C) 1-Hexanol (boiling point 156°C) Butyl acetate (boiling point 125°C) Inorganic powder glass powder Aluminum oxide powder Phosphor nickel powder silver powder

Table 18

Example 47 48 49 50 51 52 53 54 55 Evaluation results drawing 95% decomposition temperature (℃) 300 Whether there is blackening stickiness After 7 days, moisture content (ppm) Solvent content just after gelatinization (weight %) After gelatinization, the solvent content after 23°C×6 hours (weight %) After gelatinization, the state after 23℃×6 hours 99% decomposition temperature (°C) (TGA device, heating rate 10°C/min) 95% decomposition temperature (°C) (TGA device, heating rate 30°C/min) Viscosity ratio

Table 19

Comparative example 1 2 3 4 5 6 7 monomer composition Methyl methacrylate 80 Isobutyl methacrylate 95 99.5 100 80 80 stearyl methacrylate n-Butyl methacrylate lauryl methacrylate Glyceryl methacrylate Hydroxyethyl Methacrylate 3-Methacryloxypropyltrimethoxysilane Polypropylene glycol monomethacrylate trade name "Blenma-PP-1000", degree of polymerization 16, manufactured by NOF Co., Ltd. 5 0.5 20 Polypropylene glycol monomethacrylate trade name "Buren Mar-PP-500", degree of polymerization 9, manufactured by NOF Co., Ltd. Polypropylene glycol monomethacrylate trade name "Blenma-PP-800", degree of polymerization 13, manufactured by NOF Corporation Monomethacrylate modified product of polypropylene glycol-polytetramethylene glycol copolymer, trade name "Blenma-70PPT-800", manufactured by NOF Corporation The monomethacrylate modified product of polypropylene glycol/poly-1,2-butylene oxide copolymer is named "Buren Ma-10PPB-500B", the degree of polymerization of poly-1,2-butylene oxide is 6, NOF Corporation Made by the company Polyethylene glycol monomethacrylate trade name "Buren Mar-PE-350", degree of polymerization 8, manufactured by NOF Co., Ltd. 20 Tripropylene glycol methacrylate (synthesis example 2) 20 Polypropylene glycol monomethacrylate (synthesis example 3), degree of polymerization 7, number average molecular weight 400 chain transfer agent Dodecanethiol 1.2 1 1 1 1 1 Polymerization solvent ethyl acetate Number average molecular weight (Mn) (×10,000) twenty three 3.1 3.1 3.5 3.5 3.5

Table 20

Comparative example 1 2 3 4 5 6 7 additive Polypropylene glycol (number-average molecular weight: 3000), trade name "Exonolure 3020", manufactured by Asahi Glass Co., Ltd. Polypropylene glycol (number-average molecular weight: 10,000), trade name "Preminol 4011", manufactured by Asahi Glass Co., Ltd. Polytetramethylene glycol (number average molecular weight 1000) trade name "PTMG1000", manufactured by Mitsubishi Chemical Corporation 2-ethylhexyl acrylate oligomer (number average molecular weight 5000), synthesis example 1 Ethyl cellulose 10 decomposition accelerator cumene hydroperoxide tert-butanol peroxide Azobisisobutyronitrile tin oxide Dodecanethiol 1,6-Hexamethylenediamine Dibutyltin laurate Tributyl borate solvent Terpineol (boiling point 218°C) 100 90 100 100 100 Butyl Carbitol (boiling point 230°C) 1-Hexanol (boiling point 156°C) Butyl acetate (boiling point 125°C) 100 Inorganic powder glass powder 300 300 300 300 300 300 300 Aluminum oxide powder Phosphor nickel powder silver powder

Table 21

Comparative example 1 2 3 4 5 6 7 Evaluation results drawing have none none have have have have 95% decomposition temperature (℃) 350 400 450 410 430 410 330 Whether there is blackening none have have none have have none Stickiness none none none none none none none After 7 days, moisture content (ppm) 4100 4200 4300 4100 25000 4300 3700 Solvent content just after gelatinization (weight %) 20 20 twenty three 20 20 20 20 After gelatinization, the solvent content after 23°C×6 hours (weight %) 19 18 twenty two 18 19 19 13 After gelatinization, the state after 23℃×6 hours Has peeling Has peeling Has peeling Has peeling Has peeling No peeling Has peeling 99% decomposition temperature (°C) (TGA device, heating rate 10°C/min) 420 450 580 460 470 450 380 95% decomposition temperature (°C) (TGA device, heating rate 30°C/min) 400 430 470 440 460 440 350 Viscosity ratio 1.4 1.2 2.8 1.1 1.4 1.3 1.1

Table 22

Example Comparative example 56 57 58 59 60 9 10 11 12 monomer composition Isobutyl methacrylate 84 75 55 75 75 85 84.5 50 35 2-Ethylhexyl methacrylate 10 stearyl methacrylate 1 10 30 0.5 35 50 lauryl methacrylate 10 Polypropylene glycol methacrylate trade name "Buren Mar PP-1000", manufactured by NOF Co., Ltd. 5 5 5 5 5 5 5 5 5 Glyceryl methacrylate trade name "Buren Ma-GLM" 10 10 10 10 10 10 10 10 10 chain transfer agent Dodecanethiol 2 2 2 2 2 2 2 2 2 Number average molecular weight (Mn) (×10,000) 1.8 1.8 1.5 1.8 1.6 1.8 1.8 1.8 1.8 Additives polytetramethylene glycol 100 100 100 100 100 100 100 100 100 Solvent Terpineol 100 100 100 100 100 100 100 100 100 Viscosity ratio 2 2 2 2 2 2 2 1.3 1 Out of print ○ ○ ○ ○ ○ × × × ×

Table 23

Example 61 62 63 64 65 66 67 68 monomer composition Isobutyl methacrylate 85 85 85 85 85 85 85 85 Polypropylene glycol methacrylate trade name "Buren Mar PP-1000", manufactured by NOF Co., Ltd. 5 5 5 5 5 5 5 5 Glyceryl methacrylate trade name "Buren Ma-GLM" 10 10 10 10 10 10 10 10 Dodecanethiol 2 2 2 2 2 2 2 2 Number average molecular weight (Mn) (×10,000) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 additive polytetramethylene glycol 100 100 100 glycerin 100 100 100 100 100 solvent Terpineol 100 100 100 100 100 100 100 100 additive polyoxyethylene decyl ether 0.01 1 10 polyoxyethylene lauryl ether 4 10 20 polyoxyethylene oleyl ether 10 Polyoxyethylene isodecyl ether 10 Screen printability (viscosity ratio) 2 2 2 2 2 2 2 2 storage stability ○ ○ ○ ○ ○ ○ ○ ○

Table 24

Comparative example 13 14 15 16 monomer composition Isobutyl methacrylate 85 85 85 85 Polypropylene glycol methacrylate trade name "Blenmer PP-1000", manufactured by Honyu Co., Ltd. 5 5 5 5 Glyceryl methacrylate trade name "Blenma-GLM" 10 10 10 10 Dodecanethiol 2 2 2 2 Number average molecular weight (Mn) (×10,000) 1.8 1.8 1.8 1.8 additive polytetramethylene glycol 100 100 100 100 glycerin solvent Terpineol 100 100 100 100 additive polyoxyethylene decyl ether 0 0.005 15 30 polyoxyethylene lauryl ether polyoxyethylene oleyl ether Polyoxyethylene isodecyl ether Screen printability (viscosity ratio) 2 2 1.5 1 storage stability × △ △ ×

Table 25

Example 69 70 71 72 73 74 75 76 77 monomer composition Isobutyl methacrylate 85 85 85 85 85 85 85 85 85 Polypropylene glycol methacrylate trade name "Blens-PP-1000", manufactured by NOF Corporation 5 5 5 5 5 5 5 5 5 Glyceryl methacrylate trade name "Buren Mar-GLM", manufactured by NOF Co., Ltd. 10 10 10 10 10 10 10 2-Hydroxyethyl methacrylate 10 1,6-Hexanediol monomethacrylate 10 chain transfer agent Dodecanethiol 2 2 2 2 2 2 2 2 2 Number average molecular weight (Mn) (×10,000) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.9 1.7 Solvent Terpineol 30 100 30 100 30 100 100 100 100 additive glycerin 20 20 100 100 200 200 100 100 polytetramethylene glycol 100 Evaluation results low temperature decomposability ○ ○ ○ ○ ○ ○ ○ ○ ○ screen printability ○ ○ ○ ○ ○ ○ ○ ○ ○ Viscosity ratio 2 2 2 2 2 2 2 2 2 Whether there is filamentous dust ○ ○ ○ ○ ○ ○ ○ ○ ○ solution stability ○ ○ ○ ○ ○ ○ ○ ○ ○ Haze value 20 20 80 80 95 95 95 70 65

Table 26

Comparative example 17 18 19 20 twenty one twenty two monomer composition Isobutyl methacrylate 85 85 85 85 95 100 Polypropylene glycol methacrylate trade name "Blenmer PP-1000", manufactured by NOF Corporation 5 5 5 5 5 Glyceryl methacrylate trade name "Blenma-GLM", manufactured by NOF Co., Ltd. 10 10 10 10 2-Hydroxyethyl methacrylate 1. 6-Hexanediol monomethacrylate chain transfer agent Dodecanethiol 2 2 2 2 2 0.5 Number average molecular weight (Mn) (×10,000) 1.8 1.8 1.8 1.8 1.8 5.8 Solvent Terpineol 100 100 120 100 100 220 additive glycerin 5 220 200 100 polytetramethylene glycol Evaluation results low temperature decomposability ○ ○ ○ ○ ○ ○ screen printability × ○ × × × ○ Viscosity ratio 1.1 2 1.4 1.1 1.1 2 Whether there is filamentous dust × ○ ○ × × × solution stability ○ ○ ○ × ○ Haze value 10 Can't be determined 15 5 Can't be determined 2

Claims (28)

1. adhesive resin composition, it comprises multipolymer (A) and other compositions as matrix resin, described multipolymer (A) comprises from the segment of (methyl) alkyl acrylate monomer and comprises the polyalkylene oxide segment of the repeating unit shown in the following chemical formula (1)

-(OR) _n- …(1)

R: the alkylidene group of carbonatoms more than 3, n are integer.

2. the described adhesive resin composition of claim 1, wherein, the Integer n of above-mentioned chemical formula (1) is more than 5.

3. claim 1 or 2 described adhesive resin compositions, wherein, to comprise from the segment of (methyl) alkyl acrylate monomer and the multipolymer (A) that is selected from least a polyalkylene oxide segment in poly(propylene oxide), poly-methyl oxirane, poly-ethyl oxyethane, polyoxy heterocycle butane, the polytetrahydrofuran as matrix resin.

4. each described adhesive resin composition in the claim 1～3 wherein, is that second-order transition temperature from homopolymer is the segment of (methyl) alkyl acrylate monomer more than 30 ℃ from the segment of (methyl) alkyl acrylate monomer.

5. each described adhesive resin composition in the claim 1～4, wherein, multipolymer (A) is that the second-order transition temperature that comprises from homopolymer is the multipolymer (A1) of the segment of (methyl) alkyl acrylate monomer below 0 ℃ as copolymer composition.

6. each described adhesive resin composition in the claim 1～5, wherein, in multipolymer (A), copolymerization comprise the co-polymerized monomer that can form the functional group of hydrogen bond with hydroxyl.

7. the described adhesive resin composition of claim 6, wherein, above-mentioned to comprise the co-polymerized monomer that can form the functional group of hydrogen bond with hydroxyl be (methyl) acrylate monomer that contains hydroxyl.

8. each described adhesive resin composition in the claim 1～7, wherein, multipolymer (A) contains (methyl) long-chain aliphatic acrylate as copolymer composition.

9. the described adhesive resin composition of claim 8, wherein, above-mentioned chain alkyl is the chain alkyl of carbonatoms more than 8.

10. claim 8 or 9 described adhesive resin compositions, wherein, the content of (methyl) long-chain aliphatic acrylate among multipolymer (A) the 100 weight % is 1～30 weight %.

11. the described adhesive resin composition of claim 10, wherein, above-mentioned multipolymer (A) also contains can form (methyl) acrylate of functional group of hydrogen bond as copolymer composition with hydroxyl comprising of 1～80 weight % scope.

12. each described adhesive resin composition in the claim 1～11 wherein, also contains polyalkylene oxide (B).

13. each described adhesive resin composition in the claim 1～12 wherein, also is added in 23 ℃ and is liquid resin oligomers (C).

14. the described adhesive resin composition of claim 13, wherein, the SP value that above-mentioned resin oligomers (C) is obtained according to the Hoy method is 10 * 10 ^-3～8.5 * 10 ^-3(J/m ³) ^0.5

15. each described adhesive resin composition in the claim 1～14 wherein, also contains the organic compound (D) that comprises 3 above hydroxyls.

16. the described adhesive resin composition of claim 15, wherein, the above-mentioned organic compound (D) that comprises 3 above hydroxyls is liquid compound at normal temperatures.

17. claim 15 or 16 described adhesive resin compositions wherein, with respect to the above-mentioned multipolymer of 100 weight parts (A), contain the above-mentioned compound (D) that comprises 3 above hydroxyls with the ratio of 20～200 weight parts.

18. each described adhesive resin composition in the claim 1～17 wherein, also contains nonionogenic tenside.

19. each described adhesive resin composition in the claim 13～18, wherein, the haze value of being tried to achieve by total light penetration of this film when forming thickness and be the film of 5mm is more than 20.

20. each described adhesive resin composition in the claim 1～19 wherein, also contains boiling point and is the organic solvent more than 150 ℃.

21. each described adhesive resin composition in the claim 1～20 wherein, also contains decomposition accelerating agent.

22. the described adhesive resin composition of claim 21, wherein, decomposition accelerating agent is an organo-peroxide.

23. the manufacture method of a sintered body, this method uses the ceramic size that contains each described adhesive resin composition in ceramic powder and the claim 1～22 to make ceramic green sheet, and the multilayer body that many above-mentioned ceramic green sheet laminations are formed is burnt till in the temperature below 300 ℃ again.

24. a glass paste is comprising each described adhesive resin composition in the claim 1～22 and the glass powder that is dispersed in this adhesive resin composition.

25. a pottery is stuck with paste, comprising each described adhesive resin composition in the claim 1～22 and the ceramic powder that is dispersed in this adhesive resin composition.

26. a phosphor paste is comprising each described adhesive resin composition in the claim 1～22 and the fluorophor powder that is dispersed in this adhesive resin composition.

27. a conduction is stuck with paste, comprising each described adhesive resin composition in the claim 1～22 and the electroconductive powder that is dispersed in this adhesive resin composition.

28. a raw cook is comprising each described adhesive resin composition in the claim 1～22 and the glass powder or the ceramic powder that are dispersed in this adhesive resin composition.

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