TW201900695A - Polymer, paste composition containing polymer, adhesive resin for conductive paste, conductive paste composition, ceramic binder resin, ceramic composition, and ceramic molded body - Google Patents

Polymer, paste composition containing polymer, adhesive resin for conductive paste, conductive paste composition, ceramic binder resin, ceramic composition, and ceramic molded body Download PDF

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TW201900695A
TW201900695A TW107117576A TW107117576A TW201900695A TW 201900695 A TW201900695 A TW 201900695A TW 107117576 A TW107117576 A TW 107117576A TW 107117576 A TW107117576 A TW 107117576A TW 201900695 A TW201900695 A TW 201900695A
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monomer
mol
binder resin
ceramic
parts
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TWI774774B (en
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長澤敦
円山圭一
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日商日油股份有限公司
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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Abstract

This invention provides a binder resin which is composed of a polymer of a monomer (A), having a molar ratio of 10 to 100 mol%, represented by a general formula (1) and another monomer (B), having a molar ratio of 0 to 90 mol%, copolymerizable with the monomer (A), wherein the polymer has a weight average molecular weight of 10,000 to 1,000,000. R1 represents a hydrogen atom or a methyl group, R2 represents a hydrogen atom, a methyl group or an ethyl group, R3 represents an alkyl group having 1 to 18 carbon atoms, and X and Y each independently represent NH or O.

Description

聚合物、包含聚合物而成的膏組合物、導電膏用黏結劑樹脂、導電膏組合物、陶瓷用黏結劑樹脂、陶瓷組合物及陶瓷成型體Polymer, polymer-containing paste composition, adhesive resin for conductive paste, conductive paste composition, adhesive resin for ceramics, ceramic composition, and ceramic molded body

本發明涉及一種觸變性及熱分解性優異的、特別適合作為黏結劑樹脂的聚合物以及包含其而成的膏組合物。The present invention relates to a polymer having excellent thixotropy and thermal decomposition properties, and particularly suitable as a binder resin, and a paste composition containing the polymer.

此外，本發明涉及一種成型體強度及熱分解性優異的、特別適合作為陶瓷用黏結劑樹脂的聚合物。In addition, the present invention relates to a polymer having excellent strength and thermal decomposition properties of a molded body, which is particularly suitable as a binder resin for ceramics.

層疊陶瓷電容器等層疊型電子部件的內部電極層的形成或太陽能電池的導電層的形成等中使用的金屬膏主要由鎳或銅等金屬顆粒、溶劑及黏結劑樹脂組成，利用絲網印刷等方法將其印刷在片材上。如專利文獻1所示，作為黏結劑樹脂，使用了觸變性高、在印刷時沒有拉絲（糸引き）或滲出（にじみ）、適於印刷的乙基纖維素樹脂。然而，由於乙基纖維素的熱分解性低，在燒成時殘存有碳成分，因此存在加熱殘留成分多，從而導致電極的缺陷的問題。另一方面，雖然丙烯酸樹脂具有熱分解性優異的性能，但觸變性低，存在若進行高黏度化則拉絲變強，若為了降低拉絲而進行低黏度化則印刷時產生滲出等不適於印刷的技術問題。Metal pastes used in the formation of internal electrode layers of laminated electronic components such as laminated ceramic capacitors or the formation of conductive layers in solar cells are mainly composed of metal particles such as nickel or copper, solvents, and binder resins, and screen printing is used. It is printed on a sheet. As shown in Patent Document 1, as the binder resin, an ethyl cellulose resin having high thixotropy and no drawing or bleeding during printing, and suitable for printing is used. However, since ethylcellulose has low thermal decomposition properties and carbon components remain during firing, there is a problem that there are many residual components during heating, which causes defects in the electrodes. On the other hand, although acrylic resins have excellent thermal decomposability, they have low thixotropy, and there are cases where drawing becomes stronger if the viscosity is increased, and if the viscosity is lowered in order to reduce the drawing, bleeding occurs during printing, which is not suitable for printing. technical problem.

此處，金屬膏的觸變性是指在剪切速度快的狀態下，表觀黏度變低，且在剪切速度慢的狀態及未剪切的狀態下，表觀黏度變高的性質。Here, the thixotropy of the metal paste refers to a property that the apparent viscosity becomes low in a state where the shear rate is fast, and the apparent viscosity becomes high in a state where the shear rate is slow and in an unsheared state.

近年來，出於小型化的目的，層疊陶瓷電容器等層疊設備的生片的薄層化與多層化得到推行。然而，若進行薄層化，則由燒成時電極層中的殘存碳成分引起的缺陷的影響變大的問題變得顯著。因此，尋求一種觸變性優異、沒有印刷時的拉絲及滲出、具有適於印刷的性質且熱分解性更優異、殘存碳成分少的黏結劑樹脂。In recent years, for the purpose of miniaturization, thinning and multilayering of green sheets of multilayer equipment such as multilayer ceramic capacitors have been promoted. However, if the thickness is reduced, the problem that the influence of defects caused by the residual carbon component in the electrode layer during firing becomes large becomes significant. Therefore, there is a need for a binder resin which is excellent in thixotropy, has no drawing and bleeding during printing, has properties suitable for printing, has better thermal decomposition properties, and has less residual carbon components.

此外，乙基纖維素存在熱分解性低、燒成時加熱殘留成分多，從而導致電極的缺陷的問題。進而，使用了乙基纖維素的導電膏還存在對片材的接著性低、因電極的剝離導致在層疊時產生不良情況的問題。In addition, ethyl cellulose has a problem that the thermal decomposition property is low, and there are many heating residual components during firing, which causes defects in the electrode. Furthermore, the conductive paste using ethylcellulose also has the problems of low adhesion to a sheet, and problems such as occurrence of defects during lamination due to electrode peeling.

因此，如專利文獻2所示，雖然研究了藉由向乙基纖維素添加聚乙烯醇縮丁醛來提高片材密著性，但存在熱分解性的降低及無法獲得充分的接著性的技術問題。Therefore, as shown in Patent Document 2, although a technique for improving the adhesion of a sheet by adding polyvinyl butyral to ethyl cellulose has been studied, there is a reduction in thermal decomposition properties and a failure to obtain sufficient adhesiveness. problem.

此外，層疊陶瓷電容器等層疊型電子部件的介電層的形成等的片材形成等中使用的陶瓷漿料主要由如鈦酸鋇或氧化鋁等金屬氧化物、氮化矽等氮化物這樣的陶瓷顆粒、溶劑及黏結劑樹脂構成，利用刮刀法等方法進行片材成型。對已片材成型的生片要求強度以使在處理片材時沒有尺寸變化或破損。In addition, ceramic pastes used in sheet formation, such as formation of dielectric layers of laminated electronic components such as laminated ceramic capacitors, are mainly composed of metal oxides such as barium titanate or alumina, and nitrides such as silicon nitride. It is composed of ceramic particles, solvent, and binder resin, and is formed into a sheet by a method such as a doctor blade method. The formed green sheet is required to have strength so that there is no dimensional change or breakage when the sheet is processed.

因此，如專利文獻3所示，作為黏結劑樹脂，使用了強度優異的聚乙烯醇縮丁醛樹脂。然而，由於聚乙烯醇縮丁醛樹脂的熱分解性低、燒成時殘存有碳成分，因此存在加熱殘留成分多，從而導致片材內的缺陷的問題。另一方面，雖然丙烯酸樹脂具有熱分解性優異的性能，但片材強度低，特別是在薄層化時，存在片材強度之低變得顯著，不適於作為黏結劑樹脂的技術問題。Therefore, as shown in Patent Document 3, as the binder resin, a polyvinyl butyral resin having excellent strength is used. However, since the polyvinyl butyral resin has low thermal decomposability and carbon components remain during firing, there is a problem in that there are many residual components during heating, which causes defects in the sheet. On the other hand, although acrylic resins have excellent thermal decomposability, sheet strength is low, and particularly when the layer is thinned, there is a technical problem that sheet strength is significantly reduced, which is not suitable as a binder resin.

現有技術文獻 專利文獻 專利文獻1：日本特開2012-181988 專利文獻2：日本特開2016-033998 專利文獻3：日本特開2006-089354Prior Art Literature Patent Literature Patent Literature 1: Japanese Patent Laid-Open No. 2012-181988 Patent Literature 2: Japanese Patent Laid-Open No. 2016-033998 Patent Literature 3: Japanese Patent Laid-Open No. 2006-089354

本發明要解決的技術問題Technical problem to be solved by the present invention

為了解決這樣的技術問題，尋求一種觸變性優異、熱分解性優異、加熱殘留成分少的黏結劑樹脂。除此以外，尋求一種沒有印刷時的拉絲及滲出的、具有高印刷適性的黏結劑樹脂及導電膏組合物。In order to solve such a technical problem, a binder resin having excellent thixotropy, excellent thermal decomposability, and low heating residual components is sought. In addition, there is a demand for a binder resin and a conductive paste composition having high printability without drawing and bleeding during printing.

近年來，層疊陶瓷電容器經小型及大容量化，多層化與薄層化得到推行。然而，若進行薄層化，則由少許的加熱殘留成分導致的缺陷引起的絕緣性降低的問題、由成為多層而導致的接著性低引發的層疊錯位或層間的剝離的問題變得顯著，尋求一種熱分解性與接著性更優異的黏結劑樹脂。In recent years, multilayer ceramic capacitors have been reduced in size and capacity, and multilayered and thinner layers have been promoted. However, if the thickness is reduced, the problem of reduced insulation due to defects due to a small amount of heating residual components, and the problems of lamination dislocation or interlayer peeling due to low adhesion caused by multilayering are prominent. A binder resin with better thermal decomposition and adhesion.

為了解決這樣的問題，尋求一種觸變性及熱分解性優異、加熱殘留成分少且接著性也優異的黏結劑樹脂。In order to solve such a problem, a binder resin which is excellent in thixotropy and thermal decomposability, has few heating residual components, and is also excellent in adhesiveness is sought.

近年來，出於使層疊陶瓷電容器等層疊設備小型化的目的，陶瓷生片的薄層化與多層化得到推行。然而，若進行薄層化，則由燒成時介電層中的殘存碳成分引起的缺陷的影響變大，引起絕緣擊穿等的問題變得日益顯著。In recent years, for the purpose of miniaturizing multilayer equipment such as multilayer ceramic capacitors, thinning and multilayering of ceramic green sheets have been promoted. However, if the thickness is reduced, the effect of defects caused by the residual carbon components in the dielectric layer during firing becomes large, and problems such as insulation breakdown become increasingly prominent.

為了解決這樣的問題，尋求一種能夠提高陶瓷成型體的強度、熱分解性優異的陶瓷用黏結劑樹脂。In order to solve such problems, a ceramic binder resin capable of improving the strength of a ceramic molded body and having excellent thermal decomposition properties has been sought.

第一發明的技術問題在於提供一種觸變性優異、熱分解性也優異的黏結劑樹脂。The technical problem of the first invention is to provide a binder resin which is excellent in thixotropy and excellent in thermal decomposition properties.

此外，本發明的技術問題在於進一步提供一種沒有印刷時的拉絲或滲出的黏結劑樹脂及利用了該黏結劑樹脂的具有高印刷適性的導電組合物。In addition, the technical problem of the present invention is to further provide a binder resin without drawing or bleeding during printing, and a conductive composition having high printability using the binder resin.

第二發明的技術問題在於提供一種觸變性及熱分解性、接著性優異的導電膏用黏結劑樹脂。The technical problem of the second invention is to provide a binder resin for a conductive paste having excellent thixotropy and thermal decomposability, and excellent adhesion.

第三發明的技術問題在於提供一種能夠提高陶瓷成型體的強度、熱分解性也優異的陶瓷用黏結劑樹脂。The technical problem of the third invention is to provide a ceramic binder resin which can improve the strength of a ceramic molded body and also has excellent thermal decomposition properties.

解決技術問題的技術手段Technical means to solve technical problems

本申請的發明人為了解決上述技術問題進行了研究，結果發現，由具有脲結構或氨基甲酸酯結構的特定結構的聚合物構成的黏結劑樹脂能夠解決上述技術問題。The inventors of the present application conducted research in order to solve the above-mentioned technical problems, and as a result, found that a binder resin composed of a polymer having a specific structure having a urea structure or a urethane structure can solve the above-mentioned technical problems.

即，第一發明為以下的發明。That is, the first invention is the following invention.

[1] 一種黏結劑樹脂，其由下述通式（1）表示的單體（A）的莫耳比為10莫耳%～100莫耳%、可與單體（A）共聚的其他單體（B）的莫耳比為0～90莫耳%、重量平均分子量為10,000～1,000,000的聚合物構成。・・・（1） 通式（1）中， R1 表示氫原子或甲基， R2 表示氫原子、甲基或乙基， R3 表示碳原子數為1～18的烷基， X及Y各自獨立地表示NH或O。[1] A binder resin having a molar ratio of a monomer (A) represented by the following general formula (1) of 10 mol% to 100 mol% and other monomers copolymerizable with the monomer (A) The polymer (B) has a mole ratio of 0 to 90 mole% and a polymer having a weight average molecular weight of 10,000 to 1,000,000. (1) In the general formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 represents a hydrogen atom, a methyl group, or an ethyl group, R 3 represents an alkyl group having 1 to 18 carbon atoms, X and Y each independently represents NH or O.

[2] 一種導電膏組合物，其中含有所述黏結劑樹脂、有機溶劑及金屬顆粒。[2] A conductive paste composition containing the binder resin, an organic solvent, and metal particles.

[3] 根據所述導電膏組合物，其中相對於金屬顆粒100重量份，含有0.5～30重量份的黏結劑樹脂，10～200重量份的有機溶劑。[3] According to the conductive paste composition, it contains 0.5 to 30 parts by weight of a binder resin and 10 to 200 parts by weight of an organic solvent with respect to 100 parts by weight of the metal particles.

第一發明的聚合物除了觸變性優異、熱分解性也優異以外，在用於印刷用途時沒有印刷時的拉絲或滲出。其結果，將本發明的聚合物用作黏結劑樹脂的膏、尤其是金屬膏，除了在燒成時殘存碳成分少以外，在用於印刷用途時印刷適性也高。The polymer of the first invention is excellent in thixotropy and excellent in thermal decomposition properties, and when used in printing applications, there is no drawing or bleeding during printing. As a result, a paste, particularly a metal paste, in which the polymer of the present invention is used as a binder resin has low residual carbon content during firing and high printability when used in printing applications.

此外，本申請的發明人為了解決上述技術問題進行了研究，結果發現，由具有脲結構或氨基甲酸酯結構的特定結構的聚合物構成的黏結劑樹脂能夠解決上述技術問題。In addition, the inventors of the present application conducted research to solve the above-mentioned technical problems, and as a result, found that a binder resin composed of a polymer having a specific structure having a urea structure or a urethane structure can solve the above-mentioned technical problems.

即，第二發明為以下的發明。That is, the second invention is the following invention.

[4] 一種導電膏用黏結劑樹脂，其由下述通式（1）表示的單體（A）的莫耳比為10莫耳%～90莫耳%、下述通式（2）表示的（甲基）丙烯酸烷基酯（D）的莫耳比為10～90莫耳%、可與所述單體（A）及所述（甲基）丙烯酸烷基酯（D）共聚的其他單體的莫耳比為0～30莫耳%、重量平均分子量為10,000～1,000,000的聚合物構成。・・・（1） 通式（1）中， R1 表示氫原子或甲基， R2 表示氫原子、甲基或乙基， R3 表示碳原子數為1～18的烷基， X及Y各自獨立地表示NH或O。・・・（2） 通式（2）中， R4 表示氫原子或甲基， R5 表示碳原子數為1～18的烷基。[4] A binder resin for conductive paste, which has a molar ratio of the monomer (A) represented by the following general formula (1) of 10 mol% to 90 mol%, and is represented by the following general formula (2) The molar ratio of the (meth) acrylic acid alkyl ester (D) is 10 to 90 mol%, and other copolymerizable with the monomer (A) and the (meth) acrylic acid alkyl ester (D) The polymer has a molar ratio of a monomer of 0 to 30 mol% and a weight average molecular weight of 10,000 to 1,000,000. (1) In the general formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 represents a hydrogen atom, a methyl group, or an ethyl group, R 3 represents an alkyl group having 1 to 18 carbon atoms, X and Y each independently represents NH or O. (2) In the general formula (2), R 4 represents a hydrogen atom or a methyl group, and R 5 represents an alkyl group having 1 to 18 carbon atoms.

[5] 根據[4]的導電膏用黏結劑樹脂，其中所述其他單體為丙烯腈或烷基丙烯醯胺。[5] The adhesive resin for conductive paste according to [4], wherein the other monomer is acrylonitrile or alkyl acrylamide.

[6] 一種導電膏組合物，其中含有[4]或[5]的黏結劑樹脂、有機溶劑及金屬顆粒。[6] A conductive paste composition containing the binder resin of [4] or [5], an organic solvent, and metal particles.

[7] 根據[6]的導電膏組合物，其中相對於所述金屬顆粒100質量份，所述黏結劑樹脂的質量比為0.5～30質量份，所述有機溶劑的質量比為10～200質量份。[7] The conductive paste composition according to [6], wherein the mass ratio of the binder resin is 0.5 to 30 parts by mass with respect to 100 parts by mass of the metal particles, and the mass ratio of the organic solvent is 10 to 200 Parts by mass.

第二發明的聚合物的觸變性及熱分解性、接著性優異。其結果，將本發明的聚合物用作黏結劑樹脂的導電膏的印刷適性及接著性高，且在燒成時殘存碳量少。The polymer of the second invention is excellent in thixotropy, thermal decomposition, and adhesion. As a result, the conductive paste using the polymer of the present invention as a binder resin has high printability and adhesion, and has a small amount of residual carbon during firing.

本申請的發明人為瞭解決上述技術問題進行了研究，結果發現，由具有脲結構或氨基甲酸酯結構的特定結構的聚合物構成的黏結劑樹脂能夠解決上述技術問題。The inventors of the present application conducted research in order to solve the above-mentioned technical problems, and as a result, found that a binder resin composed of a polymer having a specific structure having a urea structure or a urethane structure can solve the above-mentioned technical problems.

即，第三發明為以下的發明。That is, the third invention is the following invention.

[8] 一種陶瓷用黏結劑樹脂，其由下述通式（1）表示的單體（A）的莫耳比為10莫耳%～100莫耳%、可與所述單體（A）共聚的其他單體（E）的莫耳比為0～90莫耳%、重量平均分子量為10,000～1,000,000的聚合物構成。・・・（1） 通式（1）中， R1 表示氫原子或甲基， R2 表示氫原子、甲基或乙基， R3 表示碳原子數為1～18的烷基， X及Y各自獨立地表示NH或O。[8] A binder resin for ceramics, in which the molar ratio of the monomer (A) represented by the following general formula (1) is 10 mol% to 100 mol% and is compatible with the monomer (A) The copolymerized other monomer (E) is a polymer having a molar ratio of 0 to 90 mol% and a weight average molecular weight of 10,000 to 1,000,000. (1) In the general formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 represents a hydrogen atom, a methyl group, or an ethyl group, R 3 represents an alkyl group having 1 to 18 carbon atoms, X and Y each independently represents NH or O.

[9] 一種陶瓷組合物，其中含有[8]的黏結劑樹脂、有機溶劑及陶瓷顆粒。[9] A ceramic composition containing the binder resin of [8], an organic solvent, and ceramic particles.

[10] 根據[9]的陶瓷組合物，其中相對於所述陶瓷顆粒100質量份，含有0.5～30質量份的所述黏結劑樹脂以及10～200質量份的所述有機溶劑。[10] The ceramic composition according to [9], which contains 0.5 to 30 parts by mass of the binder resin and 10 to 200 parts by mass of the organic solvent with respect to 100 parts by mass of the ceramic particles.

[11] 一種陶瓷成型體，其由[9]或[10]的陶瓷組合物形成。[11] A ceramic molded body formed of the ceramic composition of [9] or [10].

發明效果Invention effect

使用了第三發明的陶瓷用黏結劑樹脂的陶瓷組合物的強度優異、熱分解性也優異。其結果，使用了本發明的陶瓷用黏結劑樹脂組合物的陶瓷成型體的強度（尤其是片材強度）優異，且在燒成時殘存碳成分少。The ceramic composition using the ceramic binder resin of the third invention has excellent strength and excellent thermal decomposition properties. As a result, the ceramic molded body using the ceramic binder resin composition of the present invention has excellent strength (especially sheet strength) and has a small amount of residual carbon components during firing.

[單體（A）][Monomer (A)]

本發明中使用的單體（A）以下述通式（1）表示。・・・（1）The monomer (A) used in the present invention is represented by the following general formula (1). ···(1)

通式（1）中，R1 為氫原子或甲基，從聚合的難易度的角度出發，特佳為甲基。In the general formula (1), R 1 is a hydrogen atom or a methyl group, and is particularly preferably a methyl group from the viewpoint of the ease of polymerization.

R2 表示氫原子、甲基或乙基，但從與胺或醇的反應性的角度出發，特佳為氫原子。R 2 represents a hydrogen atom, a methyl group, or an ethyl group, but is particularly preferably a hydrogen atom from the viewpoint of reactivity with an amine or an alcohol.

R3 是碳原子數為1～18的烷基。作為碳原子數為1～18的烷基，例如可列舉出甲基、乙基、丙基、異丙基、正丁基、異丁基、叔丁基、正己基、正辛基、2-乙基己基、癸基、十二烷基、十八烷基等，從合成的難易度及觸變性的角度出發，R3 的碳原子數較佳為2～12，更佳為3～6。R 3 is an alkyl group having 1 to 18 carbon atoms. Examples of the alkyl group having 1 to 18 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, n-octyl, 2- Ethylhexyl, decyl, dodecyl, octadecyl, and the like, from the standpoint of ease of synthesis and thixotropy, the number of carbon atoms of R 3 is preferably 2 to 12, and more preferably 3 to 6.

X與Y為氧原子（-O-）或NH基，從觸變性的角度出發，較佳為X與Y中的至少一者為NH基，更佳為X及Y這兩者均為NH基。X and Y are oxygen atoms (-O-) or NH groups. From the viewpoint of thixotropy, it is preferred that at least one of X and Y is an NH group, and more preferably, both X and Y are NH groups. .

單體（A）可以單獨使用一種，也可以同時使用兩種以上。The monomer (A) may be used singly or in combination of two or more kinds.

第一發明及第二發明中，將構成聚合物的單體整體設為100莫耳%時，單體（A）的莫耳比為10莫耳%以上。若單體（A）的莫耳比過低，則觸變性可能下降，因此設為10mol%以上，但較佳為15mol%以上，更佳為20mol%以上。In the first invention and the second invention, when the entire monomer constituting the polymer is 100 mole%, the mole ratio of the monomer (A) is 10 mole% or more. If the molar ratio of the monomer (A) is too low, thixotropy may decrease. Therefore, it is set to 10 mol% or more, but it is preferably 15 mol% or more, and more preferably 20 mol% or more.

第一發明中，將構成聚合物的單體中的單體（A）的莫耳比設為100莫耳%以下。單體（A）的莫耳比為100莫耳%時，本發明的聚合物為均聚物，單體（A）的莫耳比小於100莫耳%時，本發明的聚合物為共聚物。藉由將單體（A）的莫耳比設為50mol%以下，聚合物的熱分解性進一步提高，從該角度出發，更佳為設為40莫耳%以下。In the first invention, the molar ratio of the monomer (A) in the monomers constituting the polymer is 100 mol% or less. When the mole ratio of the monomer (A) is 100 mole%, the polymer of the present invention is a homopolymer, and when the mole ratio of the monomer (A) is less than 100 mole%, the polymer of the present invention is a copolymer . By setting the molar ratio of the monomer (A) to 50 mol% or less, the thermal decomposability of the polymer is further improved. From this viewpoint, the molar ratio is more preferably 40 mol% or less.

第二發明中，將構成聚合物的單體整體設為100莫耳%時，單體（A）的莫耳比為90莫耳%以下。藉由將單體（A）的莫耳比設為50mol%以下，聚合物的熱分解性進一步提高，從該角度出發，更佳為設為40莫耳%以下。In the second invention, when the entire monomer constituting the polymer is 100 mol%, the molar ratio of the monomer (A) is 90 mol% or less. By setting the molar ratio of the monomer (A) to 50 mol% or less, the thermal decomposability of the polymer is further improved. From this viewpoint, the molar ratio is more preferably 40 mol% or less.

第三發明中，將構成聚合物的單體整體設為100莫耳%時，單體（A）的莫耳比為100莫耳%以下。單體（A）的莫耳比為100莫耳%時，本發明的聚合物為均聚物，單體（A）的莫耳比小於100莫耳%時，本發明的聚合物為共聚物。藉由將單體（A）的莫耳比設為50mol%以下，聚合物的熱分解性進一步提高，從該角度出發，更佳為設為40莫耳%以下。In the third invention, when the entire monomer constituting the polymer is 100 mol%, the molar ratio of the monomer (A) is 100 mol% or less. When the mole ratio of the monomer (A) is 100 mole%, the polymer of the present invention is a homopolymer, and when the mole ratio of the monomer (A) is less than 100 mole%, the polymer of the present invention is a copolymer . By setting the molar ratio of the monomer (A) to 50 mol% or less, the thermal decomposability of the polymer is further improved. From this viewpoint, the molar ratio is more preferably 40 mol% or less.

[第一發明：單體（B）][First invention: monomer (B)]

作為第一發明中的單體（B），為可與單體（A）共聚的乙烯類單體，例如可列舉出（甲基）丙烯酸酯化合物或芳香族烯基化合物、氰化乙烯基化合物、丙烯醯胺化合物等。The monomer (B) in the first invention is a vinyl-based monomer copolymerizable with the monomer (A), and examples thereof include (meth) acrylate compounds, aromatic alkenyl compounds, and vinyl cyanide compounds. , Acrylamide compounds and so on.

作為（甲基）丙烯酸酯化合物，例如可列舉出（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸正丁酯、（甲基）丙烯酸異丁酯、（甲基）丙烯酸叔丁酯、（甲基）丙烯酸正己酯、（甲基）丙烯酸正辛酯、（甲基）丙烯酸2-乙基己酯、（甲基）丙烯酸癸酯、（甲基）丙烯酸十二酯、（甲基）丙烯酸十八酯等。Examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and (meth) ) Tert-butyl acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, twelve (meth) acrylate Esters, stearyl (meth) acrylate, and the like.

作為芳香族烯基化合物，例如可列舉出苯乙烯、α-甲基苯乙烯、對甲基苯乙烯、對甲氧基苯乙烯等。Examples of the aromatic alkenyl compound include styrene, α-methylstyrene, p-methylstyrene, and p-methoxystyrene.

作為氰化乙烯基化合物，例如可列舉出丙烯腈、甲基丙烯腈等。Examples of the cyanidated vinyl compound include acrylonitrile and methacrylonitrile.

作為丙烯醯胺化合物，例如可列舉出丙烯醯胺、甲基丙烯醯胺等。Examples of the acrylamide compound include acrylamide, methacrylamide, and the like.

單體（B）可單獨使用一種，也可同時使用兩種以上。其中，從溶劑溶解性與熱分解性的角度出發，特佳為（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸正丁酯、（甲基）丙烯酸異丁酯。The monomer (B) may be used singly or in combination of two or more kinds. Among them, from the viewpoints of solvent solubility and thermal decomposition properties, particularly preferred are methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. .

單體混合物中，將單體（A）與單體（B）的合計量設為100莫耳%。因此，單體（B）的莫耳比為0～90莫耳%。In the monomer mixture, the total amount of the monomer (A) and the monomer (B) is 100 mol%. Therefore, the mole ratio of the monomer (B) is 0 to 90 mole%.

[第二發明：（甲基）丙烯酸烷基酯（D）][Second invention: alkyl (meth) acrylate (D)]

第二發明中使用的（甲基）丙烯酸烷基酯（D）以下述通式（2）表示。 ・・・（2）The alkyl (meth) acrylate (D) used in the second invention is represented by the following general formula (2). ···(2)

通式（2）中，R4 為氫原子或甲基。In the general formula (2), R 4 is a hydrogen atom or a methyl group.

R5 是碳原子數為1～18的烷基。作為碳原子數為1～18的烷基，例如可列舉出甲基、乙基、丙基、異丙基、正丁基、異丁基、叔丁基、正己基、正辛基、2-乙基己基、癸基、十二烷基、十八烷基等，從聚合性和聚合物的玻璃化轉變溫度的角度出發，R5 的碳原子數較佳為1～12，更佳為1～8。R 5 is an alkyl group having 1 to 18 carbon atoms. Examples of the alkyl group having 1 to 18 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, n-octyl, 2- Ethylhexyl, decyl, dodecyl, octadecyl and the like. From the viewpoint of polymerizability and glass transition temperature of the polymer, the number of carbon atoms of R 5 is preferably 1 to 12, and more preferably 1 ~ 8.

（甲基）丙烯酸烷基酯（D）可單獨使用一種，也可同時使用兩種以上。從強度與接著性的角度出發，較佳為同時使用R4 為氫原子的單體（b1）與R4 為甲基的單體（b2）。相對於（b1）與（b2）的合計量的（b1）的比，即（b1）/｛（b1）+（b2）｝較佳為1～50莫耳%，更佳為5～30莫耳%。The alkyl (meth) acrylate (D) may be used singly or in combination of two or more kinds. From the viewpoint of strength and adhesiveness, it is preferable to use a monomer (b1) in which R 4 is a hydrogen atom and a monomer (b2) in which R 4 is a methyl group at the same time. The ratio of (b1) to the total amount of (b1) and (b2), that is, (b1) / ｛(b1) + (b2)｝ is preferably 1-50 mol%, more preferably 5-30 mol. ear%.

將構成聚合物的單體整體設為100莫耳%時，將（甲基）丙烯酸烷基酯（D）的莫耳比設為10莫耳%以上。若（甲基）丙烯酸烷基酯（D）的莫耳比過低，則作為黏結劑樹脂的強度或熱分解性可能降低，因此設為10莫耳%以上，但較佳為30莫耳%以上，特佳為50莫耳%以上。When the entire monomer constituting the polymer is 100 mol%, the molar ratio of the alkyl (meth) acrylate (D) is 10 mol% or more. If the molar ratio of the alkyl (meth) acrylate (D) is too low, the strength or thermal decomposition properties of the binder resin may be reduced. Therefore, the molar ratio is 10 mol% or more, but 30 mol% is preferred. Above, especially preferred is 50 mol% or more.

此外，將構成聚合物的單體整體設為100莫耳%時，將（甲基）丙烯酸烷基酯（D）的莫耳比設為90莫耳%以下。若（甲基）丙烯酸烷基酯（D）的莫耳比過高，則觸變性可能降低，因此設為90莫耳%以下，但較佳為85莫耳%，特佳為80莫耳%以下。When the entire monomer constituting the polymer is 100 mol%, the molar ratio of the alkyl (meth) acrylate (D) is 90 mol% or less. If the molar ratio of the alkyl (meth) acrylate (D) is too high, thixotropy may be reduced. Therefore, the molar ratio is set to 90 mol% or less, but 85 mol% is preferred, and 80 mol% is particularly preferred. the following.

作為（甲基）丙烯酸酯化合物（D），例如可列舉出（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸正丁酯、（甲基）丙烯酸異丁酯、（甲基）丙烯酸叔丁酯、（甲基）丙烯酸正己酯、（甲基）丙烯酸正辛酯、（甲基）丙烯酸2-乙基己酯、（甲基）丙烯酸癸酯、（甲基）丙烯酸十二酯、（甲基）丙烯酸十八酯等。Examples of the (meth) acrylate compound (D) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, Tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, (meth) Dodecyl acrylate, stearyl (meth) acrylate and the like.

第二發明的聚合物可以由單體（A）及（甲基）丙烯酸烷基酯（D）構成，或者進一步含有30莫耳%以下的可與它們共聚的其他單體。將其他單體的比率設為30莫耳%以下，但更佳為15莫耳%以下，也可以為0莫耳%。The polymer of the second invention may be composed of the monomer (A) and the alkyl (meth) acrylate (D), or may further contain 30 mol% or less of other monomers copolymerizable with them. Although the ratio of other monomers is 30 mol% or less, it is more preferably 15 mol% or less, and may be 0 mol%.

作為這樣的其他單體，可列舉出丙烯醯胺、二甲基丙烯醯胺或二乙基丙烯醯胺等烷基丙烯醯胺、丙烯腈等。Examples of such other monomers include alkyl acrylamide, acrylonitrile, acrylonitrile, acrylonitrile, and the like.

[第三發明：單體（E）][Third invention: monomer (E)]

第三發明中的單體（E）為可與單體（A）共聚的乙烯基類單體，例如可列舉出（甲基）丙烯酸酯化合物或芳香族烯基化合物、氰化乙烯基化合物、丙烯醯胺化合物等。The monomer (E) in the third invention is a vinyl-based monomer copolymerizable with the monomer (A), and examples thereof include (meth) acrylate compounds or aromatic alkenyl compounds, vinyl cyanide compounds, Acrylamide compounds and the like.

作為（甲基）丙烯酸酯化合物，例如可列舉出（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸正丁酯、（甲基）丙烯酸異丁酯、（甲基）丙烯酸叔丁酯、（甲基）丙烯酸正己酯、（甲基）丙烯酸正辛酯、（甲基）丙烯酸2-乙基己酯、（甲基）丙烯酸癸酯、（甲基）丙烯酸十二酯、（甲基）丙烯酸十八酯等。Examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and (meth) ) Tert-butyl acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, twelve (meth) acrylate Esters, stearyl (meth) acrylate, and the like.

作為芳香族烯基化合物，例如可列舉出苯乙烯、α-甲基苯乙烯、對甲基苯乙烯、對甲氧基苯乙烯等。Examples of the aromatic alkenyl compound include styrene, α-methylstyrene, p-methylstyrene, and p-methoxystyrene.

作為氰化乙烯基化合物，例如可列舉出丙烯腈、甲基丙烯腈等。Examples of the cyanidated vinyl compound include acrylonitrile and methacrylonitrile.

作為丙烯醯胺化合物，例如可列舉出丙烯醯胺、二甲基丙烯醯胺、甲基丙烯醯胺等。Examples of the acrylamide compound include acrylamide, dimethylacrylamide, and methacrylamide.

其中，從樹脂強度與熱分解性的角度出發，較佳為（甲基）丙烯酸酯化合物，更佳為甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸異丁酯，更佳為甲基丙烯酸甲酯、甲基丙烯酸異丁酯。Among these, from the viewpoint of resin strength and thermal decomposition properties, (meth) acrylate compounds are preferred, and methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and isomethacrylate are more preferred. Butyl, more preferably methyl methacrylate and isobutyl methacrylate.

單體（E）可單獨使用一種，也可同時使用兩種以上，但較佳為同時使用兩種以上。該情況下，將單體（A）與單體（E）的合計量設為100莫耳%時，特佳為使用5～25莫耳%的甲基丙烯酸甲酯。The monomer (E) may be used singly or in combination of two or more kinds, but it is preferable to use two or more kinds in combination. In this case, when the total amount of the monomer (A) and the monomer (E) is 100 mol%, it is particularly preferable to use 5 to 25 mol% of methyl methacrylate.

此外，由於將單體（A）與單體（E）的合計量設為100莫耳%，因此單體（E）的莫耳比為單體（A）的剩餘部分，即為0～90莫耳%。In addition, since the total amount of the monomer (A) and the monomer (E) is 100 mol%, the molar ratio of the monomer (E) is the remainder of the monomer (A), that is, 0 to 90. Mohr%.

[第一發明及第二發明：聚合物][First invention and second invention: polymer]

第一發明及第二發明的聚合物的重量平均分子量可以使用凝膠層析儀（GPC）以聚苯乙烯換算而求得，為10,000～1,000,000，較佳為10,000～800,000，更佳為30,000～300,000。若聚合物的重量平均分子量過低，則聚合物的強度或黏度不足，若重量平均分子量過高，則可能產生溶劑溶解性或印刷適性的降低。The weight average molecular weights of the polymers of the first invention and the second invention can be calculated in terms of polystyrene using a gel chromatograph (GPC), and are 10,000 to 1,000,000, preferably 10,000 to 800,000, and more preferably 30,000 to 300,000. If the weight average molecular weight of the polymer is too low, the strength or viscosity of the polymer is insufficient, and if the weight average molecular weight is too high, there may be a decrease in solvent solubility or printability.

[第三發明：聚合物][Third invention: polymer]

第三發明的聚合物的重量平均分子量可以使用凝膠層析儀（GPC）以聚苯乙烯換算而求得，為10,000～1,000,000，較佳為30,000～800,000，更佳為50,000～500,000。若聚合物的重量平均分子量過低，則片材強度不足，若重量平均分子量過高，則漿料增黏，可能對塗布性產生不良影響。The weight-average molecular weight of the polymer of the third invention can be determined in terms of polystyrene using a gel chromatography (GPC), and is 10,000 to 1,000,000, preferably 30,000 to 800,000, and more preferably 50,000 to 500,000. If the weight average molecular weight of the polymer is too low, the strength of the sheet will be insufficient. If the weight average molecular weight is too high, the slurry will thicken, which may adversely affect the coatability.

[單體（A）的製造方法][Manufacturing method of monomer (A)]

本發明的單體（A）為具有脲鍵或氨基甲酸酯鍵的單體。The monomer (A) of the present invention is a monomer having a urea bond or a urethane bond.

上述單體（A）例如能夠藉由含異氰酸酯基單體與胺化合物或醇化合物的反應、含羥基單體與異氰酸烷基酯的反應而得到。The monomer (A) can be obtained, for example, by a reaction of an isocyanate group-containing monomer with an amine compound or an alcohol compound, or a reaction of a hydroxyl group-containing monomer with an alkyl isocyanate.

作為所述含異氰酸酯基單體，較佳為2-（甲基）丙烯醯氧乙基異氰酸酯，從聚合穩定性的角度出發，更佳為2-甲基丙烯醯氧乙基異氰酸酯。The isocyanate group-containing monomer is preferably 2- (meth) acryloxyethyl isocyanate, and more preferably 2-methacryloxyethyl isocyanate from the viewpoint of polymerization stability.

所述胺化合物較佳為伯胺化合物或仲胺化合物，更佳為伯胺化合物。The amine compound is preferably a primary amine compound or a secondary amine compound, and more preferably a primary amine compound.

作為上述伯胺化合物，例如可列舉出乙胺、正丙胺、異丙胺、正丁胺、仲丁胺、叔丁胺、正戊胺、正己胺、正辛胺、2-乙基己胺、癸胺、十二胺、十八胺、環己胺、苄胺、苯胺等，它們可單獨使用或組合使用兩種以上。其中，從黏結劑樹脂組合物的觸變性的角度出發，較佳為正丁胺、正戊胺、正己胺、正辛胺、2-乙基己胺、癸胺、十二胺，更佳為正丁胺。Examples of the primary amine compound include ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-octylamine, 2-ethylhexylamine, decylamine, Dodecylamine, octadecylamine, cyclohexylamine, benzylamine, aniline, etc. can be used alone or in combination of two or more. Among these, from the viewpoint of thixotropy of the binder resin composition, n-butylamine, n-pentylamine, n-hexylamine, n-octylamine, 2-ethylhexylamine, decylamine, and dodecylamine are more preferable, N-Butylamine.

此外，作為所述仲胺化合物，例如可列舉出二乙胺、二丙胺、二丁胺、二異丙胺、二辛胺（二正辛胺）、二-2-乙基己胺、呱啶、嗎啉等，它們可單獨使用或組合使用兩種以上。Examples of the secondary amine compound include diethylamine, dipropylamine, dibutylamine, diisopropylamine, dioctylamine (di-n-octylamine), di-2-ethylhexylamine, pyridine, Morpholine and the like can be used alone or in combination of two or more.

此外，作為所述醇化合物，例如可列舉出甲醇、乙醇、丙醇、丁醇、戊醇、己醇、環己醇、庚醇、辛醇、壬醇、癸醇、十一醇、十二醇、十三醇、十四醇、十五醇、十六醇、十七醇、十八醇等，它們可單獨使用或組合使用兩種以上。其中，從反應時的穩定性的角度出發，較佳為上述醇化合物是碳原子數為2～8的醇。作為該碳原子數為2～8的烷醇，可列舉出乙醇、丙醇、丁醇、戊醇、己醇、環己醇、庚醇、正辛醇、2-乙基-1-己醇等，其中，優選乙醇、丙醇、丁醇。Examples of the alcohol compound include methanol, ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, heptanol, octanol, nonanol, decanol, undecanol, and twelve Alcohols, tridecanols, tetradecanols, pentadecanols, cetyl alcohols, heptadecyl alcohols, stearyl alcohols, etc., which can be used alone or in combination of two or more. Among these, from the viewpoint of stability during the reaction, it is preferable that the alcohol compound is an alcohol having 2 to 8 carbon atoms. Examples of the alkanol having 2 to 8 carbon atoms include ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, heptanol, n-octanol, and 2-ethyl-1-hexanol. Among others, ethanol, propanol, and butanol are preferred.

作為所述含羥基單體，例如可列舉出（甲基）丙烯酸2-羥基乙酯、（甲基）丙烯酸2-羥基丙酯、（甲基）丙烯酸3-羥基丙酯、（甲基）丙烯酸4-羥基丁酯等（甲基）丙烯酸與碳原子數為2～8的二元醇的單酯化物。其中，從與異氰酸酯基的反應性的角度出發，較佳為甲基丙烯酸2-羥基乙酯。Examples of the hydroxyl-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth) acrylic acid. Monoesters of (meth) acrylic acid, such as 4-hydroxybutyl ester, and glycols having 2 to 8 carbon atoms. Among these, 2-hydroxyethyl methacrylate is preferable from the viewpoint of reactivity with an isocyanate group.

作為所述異氰酸烷基酯，例如可列舉出異氰酸乙酯、異氰酸正丁酯、異氰酸異丁酯、異氰酸叔丁酯、異氰酸己酯、異氰酸正辛酯、異氰酸2-乙基己酯、異氰酸環己酯等，從共聚物的觸變性的角度出發，較佳為異氰酸正丁酯。Examples of the alkyl isocyanate include ethyl isocyanate, n-butyl isocyanate, isobutyl isocyanate, tert-butyl isocyanate, hexyl isocyanate, and isocyanate. From the viewpoint of the thixotropy of the copolymer, n-octyl, 2-ethylhexyl isocyanate, cyclohexyl isocyanate, and the like are preferably n-butyl isocyanate.

所述含異氰酸酯基單體與胺化合物或醇化合物的反應、以及含羥基單體與異氰酸烷基酯的反應，能夠藉由將兩者混合、根據所需提高溫度並利用習知的方法而實施。此外，也可以根據需要添加催化劑，例如，可以使用辛酸亞錫、二月桂酸二丁基錫等錫類催化劑，三亞乙基二胺等胺類催化劑等習知的催化劑。該反應理想在5～100℃、較佳為在20～80℃的溫度下進行。此外，上述反應可以使用溶劑，例如能夠在丙酮、甲基異丁基酮、乙酸乙酯、乙酸丁酯、甲苯、二甲苯、四氫呋喃等的存在下進行。The reaction of the isocyanate group-containing monomer with an amine compound or an alcohol compound, and the reaction of a hydroxyl group-containing monomer with an alkyl isocyanate can be performed by mixing the two, raising the temperature as required, and using a conventional method. While implementing. In addition, a catalyst may be added as necessary. For example, conventional catalysts such as tin-based catalysts such as stannous octoate and dibutyltin dilaurate, and amine-based catalysts such as triethylenediamine can be used. This reaction is preferably carried out at a temperature of 5 to 100 ° C, preferably 20 to 80 ° C. The above reaction can be carried out using a solvent, for example, it can be performed in the presence of acetone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene, xylene, tetrahydrofuran, and the like.

[第一、第二及第三發明：聚合物的製造方法][First, Second, and Third Inventions: Production Method of Polymer]

接著，對製造第一、第二及第三發明的聚合物的方法進行說明。Next, methods for producing the polymers of the first, second, and third inventions will be described.

第一發明中的聚合物能夠藉由使至少含有單體（A）的單體混合物進行自由基聚合而得到。聚合可以利用習知的方法進行。例如可列舉出溶液聚合、懸浮聚合、乳液聚合等，從易於將共聚物的重量平均分子量調整在上述範圍內的方面考慮，較佳為溶液聚合或懸浮聚合。The polymer in the first invention can be obtained by subjecting a monomer mixture containing at least the monomer (A) to radical polymerization. Polymerization can be performed by a conventional method. Examples include solution polymerization, suspension polymerization, and emulsion polymerization. From the viewpoint of easily adjusting the weight average molecular weight of the copolymer within the above range, solution polymerization or suspension polymerization is preferred.

第二發明中的聚合物能夠藉由使至少含有單體（A）及（甲基）丙烯酸烷基酯（D）的單體混合物進行自由基聚合而得到。聚合可以利用習知的方法進行。例如可列舉出溶液聚合、懸浮聚合、乳液聚合等，從易於將共聚物的重量平均分子量調整在上述範圍內的方面考慮，較佳為溶液聚合或懸浮聚合。The polymer in the second invention can be obtained by radical polymerization of a monomer mixture containing at least the monomer (A) and the alkyl (meth) acrylate (D). Polymerization can be performed by a conventional method. Examples include solution polymerization, suspension polymerization, and emulsion polymerization. From the viewpoint of easily adjusting the weight average molecular weight of the copolymer within the above range, solution polymerization or suspension polymerization is preferred.

第三發明中的聚合物能夠藉由使至少含有單體（A）的單體混合物進行自由基聚合而得到。聚合可以利用習知的方法進行。例如可列舉出溶液聚合、懸浮聚合、乳液聚合等，從易於將共聚物的重量平均分子量調整在上述範圍內的方面考慮，較佳為溶液聚合或懸浮聚合。The polymer in the third invention can be obtained by subjecting a monomer mixture containing at least the monomer (A) to radical polymerization. Polymerization can be performed by a conventional method. Examples include solution polymerization, suspension polymerization, and emulsion polymerization. From the viewpoint of easily adjusting the weight average molecular weight of the copolymer within the above range, solution polymerization or suspension polymerization is preferred.

各發明中，聚合引發劑可使用習知的聚合引發劑。例如可列舉出二（4-叔丁基環己基）過氧化二碳酸酯、1,1,3,3-四甲基丁基過氧化-2-乙基己酸酯等有機過氧化物，2,2’-偶氮二異丁腈等偶氮類聚合引發劑等。這些聚合引發劑可以僅使用一種，也可以同時使用兩種以上。In each invention, a conventional polymerization initiator can be used as a polymerization initiator. Examples include organic peroxides such as bis (4-tert-butylcyclohexyl) peroxydicarbonate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2 , 2'-azobisisobutyronitrile and other azo polymerization initiators. These polymerization initiators may be used alone or in combination of two or more thereof.

聚合引發劑的使用量可根據使用的單體的組合或反應條件等進行適當設定。The amount of the polymerization initiator used can be appropriately set according to the combination of the monomers used, the reaction conditions, and the like.

另外，在投入聚合引發劑時，例如可以一次性加入全部，也可以將一次性加入一部分並將剩餘部分滴下，或者也可以將全部滴下。此外，若將聚合引發劑與所述單體一起滴下，則反應的控制變得容易故而較佳，若在單體滴下後仍進一步添加聚合引發劑，則能夠減少殘存單體故而較佳。In addition, when the polymerization initiator is added, for example, the entire amount may be added all at once, or a part may be added at a time and the remaining part may be dropped, or the entire amount may be dropped. In addition, if the polymerization initiator is dropped together with the monomer, it is preferable to control the reaction, and if the polymerization initiator is further added after the monomer is dropped, it is preferable to reduce the residual monomer.

作為在溶液聚合時使用的聚合溶劑，可使用溶解單體與聚合引發劑的聚合溶劑，具體而言，可列舉出甲醇、乙醇、1-丙醇、丙酮、甲基乙基酮、丙二醇單甲醚等。As a polymerization solvent used in solution polymerization, a polymerization solvent that dissolves a monomer and a polymerization initiator can be used. Specific examples include methanol, ethanol, 1-propanol, acetone, methyl ethyl ketone, and propylene glycol monomethyl. Ether, etc.

相對於聚合溶劑的單體（合計量）的濃度較佳為10～60質量%，特佳為20～50質量%。若單體混合物的濃度過低，則單體容易殘存，得到的共聚物的分子量可能降低，若單體的濃度過高，則可能變得難以控制發熱。The concentration of the monomer (total amount) with respect to the polymerization solvent is preferably from 10 to 60% by mass, and particularly preferably from 20 to 50% by mass. If the concentration of the monomer mixture is too low, the monomers tend to remain, and the molecular weight of the obtained copolymer may decrease. If the concentration of the monomer is too high, it may become difficult to control heat generation.

在投入單體時，例如可以一次性加入全部，也可以一次性加入一部分並將剩餘部分滴下，或者也可以將全部滴下。從控制發熱的難易度出發，較佳為一次性加入一部分並將剩餘部分滴下，或者將全部滴下。When the monomer is charged, for example, the whole may be added all at once, or one part may be added at a time and the remaining part may be dropped, or the whole may be dropped. From the viewpoint of controlling the difficulty of heat generation, it is preferable to add a part at a time and drip the remaining part, or drip all.

聚合溫度依賴於聚合溶劑的種類等，例如為50℃～110℃。聚合時間依賴於聚合引發劑的種類與聚合溫度，例如將二（4-叔丁基環己基）過氧化二碳酸酯用作聚合引發劑時，若將聚合溫度設為70℃而進行聚合，則聚合時間適宜為6小時左右。The polymerization temperature depends on the type of the polymerization solvent, and is, for example, 50 ° C to 110 ° C. The polymerization time depends on the type of polymerization initiator and the polymerization temperature. For example, when bis (4-tert-butylcyclohexyl) peroxydicarbonate is used as the polymerization initiator, if the polymerization temperature is set to 70 ° C and the polymerization is performed, The polymerization time is preferably about 6 hours.

藉由進行以上的聚合反應，能夠得到第一、第二及第三發明的樹脂組合物涉及的共聚物。所得到的共聚物可以直接使用，也可以藉由對聚合反應後的反應液實施過濾或純化而分離。By performing the above-mentioned polymerization reaction, copolymers according to the resin composition of the first, second, and third inventions can be obtained. The obtained copolymer may be used as it is, or may be isolated by filtering or purifying the reaction solution after the polymerization reaction.

[第一及第二發明：導電膏][First and second inventions: conductive paste]

可以使用攪拌機或三輥研磨機等混煉裝置，將黏結劑樹脂與由鎳、鈀、鉑、金、銀、銅或它們的合金等組成的金屬顆粒、松油醇或丁基溶纖劑等有機溶劑、以及根據需要的表面活性劑或抗氧化劑等其他成分摻合，製成含有金屬顆粒的導電膏（以下，也稱為金屬膏）。由於本申請發明的黏結劑樹脂的觸變性及熱分解性優異，因此藉由利用絲網印刷等將該金屬膏印刷成片狀並進行燒成，能夠適宜地形成層疊型電子部件的內部電極層或太陽能電池的導電層等。A kneading device such as a mixer or a three-roll mill can be used to mix the binder resin with metal particles composed of nickel, palladium, platinum, gold, silver, copper, or their alloys, organic solvents such as terpineol or butyl cellosolve And other components such as a surfactant or an antioxidant, if necessary, to form a conductive paste containing metal particles (hereinafter, also referred to as a metal paste). Since the binder resin of the present invention is excellent in thixotropy and thermal decomposition properties, by printing the metal paste into a sheet shape by screen printing or the like and firing, the internal electrode layer of a multilayer electronic component can be suitably formed Or the conductive layer of a solar cell.

[第一發明：金屬膏][First invention: metal paste]

第一發明的聚合物特別適合作為金屬膏的黏結劑樹脂。金屬膏除了本發明的聚合物以外，還含有金屬顆粒及溶劑。The polymer of the first invention is particularly suitable as a binder resin for a metal paste. The metal paste contains metal particles and a solvent in addition to the polymer of the present invention.

作為這樣的金屬顆粒，可例示出鉑、金、銀、銅、鎳、錫、鈀、鋁及這些金屬的合金。金屬顆粒的中心粒徑（D50）、即利用激光衍射散射式粒度分佈測定裝置而測定的體積累積粒徑D50較佳為0.05μm～50.0μm。Examples of such metal particles include platinum, gold, silver, copper, nickel, tin, palladium, aluminum, and alloys of these metals. The center particle diameter (D50) of the metal particles, that is, the volume cumulative particle diameter D50 measured by a laser diffraction scattering particle size distribution measuring device, is preferably 0.05 μm to 50.0 μm.

此外，作為有機溶劑，可列舉出甲苯、二甲苯等烴類溶劑，乙酸乙酯、乙酸丁酯等酯類溶劑，甲醇、乙醇、異丙醇、異丁醇、1-丁醇、雙丙酮醇等醇類溶劑，乙二醇單丁醚、丙二醇單甲醚、丙二醇單乙醚等二醇醚類溶劑，二乙二醇單乙醚乙酸酯、二乙二醇單丁醚乙酸酯、丙二醇單甲醚乙酸酯等二醇醚乙酸酯類溶劑，松油醇、二氫松油醇、二氫松油醇乙酸酯等松油醇類溶劑，丙酮、甲基乙基酮、甲基異丁基酮等酮類溶劑等，它們可以作為單體使用，或者可以混合使用兩種以上。Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate and butyl acetate, methanol, ethanol, isopropanol, isobutanol, 1-butanol, and diacetone alcohol. Other alcohol solvents, glycol ether solvents such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and propylene glycol monoethyl ether; Glycol ether acetate solvents such as methyl ether acetate, terpineol solvents such as terpineol, dihydroterpineol, and diterpineol acetate, acetone, methyl ethyl ketone, and methyl isopropyl alcohol Ketone solvents such as butyl ketone, etc., may be used as a monomer, or two or more of them may be used in combination.

將金屬顆粒的重量設為100重量份時，金屬膏中的黏結劑樹脂的含量較佳為0.1～50重量份，更佳為0.5～30重量份。此外，將金屬顆粒的重量設為100重量份時，金屬膏中的溶劑的含量較佳為10～200重量份，更佳為30～150重量份。此外，除此以外，可根據需要摻合表面活性劑或抗氧化劑等其他成分。When the weight of the metal particles is 100 parts by weight, the content of the binder resin in the metal paste is preferably 0.1 to 50 parts by weight, and more preferably 0.5 to 30 parts by weight. When the weight of the metal particles is 100 parts by weight, the content of the solvent in the metal paste is preferably 10 to 200 parts by weight, and more preferably 30 to 150 parts by weight. In addition, other components such as a surfactant and an antioxidant may be blended as necessary.

對它們的混合物進行攪拌、分散從而得到金屬膏。攪拌沒有特別限制，可使用習知的手段，較佳為例如可使用PD攪拌機或行星式混煉機，特佳為使用行星式混煉機。分散沒有特別限制，可使用習知的手段，較佳為例如可使用捏合機、珠磨機或三輥研磨機，特佳為使用三輥研磨機。The mixture is stirred and dispersed to obtain a metal paste. There is no particular limitation on the stirring, and conventional means can be used. For example, a PD mixer or a planetary mixer can be used, and a planetary mixer is particularly preferred. Dispersion is not particularly limited, and conventional means can be used. For example, a kneader, a bead mill, or a three-roll mill can be used, and a three-roll mill is particularly preferred.

金屬膏藉由絲網印刷等方法而印刷在片材上。The metal paste is printed on the sheet by a method such as screen printing.

[第二發明：導電膏組合物][Second invention: conductive paste composition]

除了本發明的聚合物以外，第二發明的導電膏組合物進一步含有金屬顆粒及有機溶劑。In addition to the polymer of the present invention, the conductive paste composition of the second invention further contains metal particles and an organic solvent.

作為這樣的金屬顆粒，能夠例示出鉑、金、銀、銅、鎳、錫、鈀、鋁及這些金屬的合金。金屬顆粒的中心粒徑（D50）、即利用激光衍射散射式粒度分佈測定裝置而測定的體積累積粒徑D50較佳為0.05μm～50.0μm。Examples of such metal particles include platinum, gold, silver, copper, nickel, tin, palladium, aluminum, and alloys of these metals. The center particle diameter (D50) of the metal particles, that is, the volume cumulative particle diameter D50 measured by a laser diffraction scattering particle size distribution measuring device, is preferably 0.05 μm to 50.0 μm.

此外，作為有機溶劑，可列舉出甲苯、二甲苯等烴類溶劑，乙酸乙酯、乙酸丁酯等酯類溶劑，甲醇、乙醇、異丙醇、異丁醇、1-丁醇、雙丙酮醇等醇類溶劑，乙二醇單丁醚、丙二醇單甲醚、丙二醇單乙醚等二醇醚類溶劑，二乙二醇單乙醚乙酸酯、二乙二醇單丁醚乙酸酯、丙二醇單甲醚乙酸酯等二醇醚乙酸酯類溶劑，松油醇、二氫松油醇、二氫松油醇乙酸酯等松油醇類溶劑，丙酮、甲基乙基酮、甲基異丁基酮等酮類溶劑等，它們可以作為單體使用，或者可以混合使用兩種以上。Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate and butyl acetate, methanol, ethanol, isopropanol, isobutanol, 1-butanol, and diacetone alcohol. Other alcohol solvents, glycol ether solvents such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and propylene glycol monoethyl ether; Glycol ether acetate solvents such as methyl ether acetate, terpineol solvents such as terpineol, dihydroterpineol, and diterpineol acetate, acetone, methyl ethyl ketone, and methyl isopropyl alcohol Ketone solvents such as butyl ketone, etc., may be used as a monomer, or two or more of them may be used in combination.

在將金屬顆粒的質量設為100質量份時，導電膏組合物中的黏結劑樹脂的含量的質量比較佳為0.5～30質量份，更佳為1～15質量份。此外，在將金屬顆粒的質量設為100質量份時，導電膏中的溶劑的含量的質量比較佳為10～200質量份，更佳為50～150質量份。此外，除此以外，也可以根據需要摻合表面活性劑或抗氧化劑等其他成分。When the mass of the metal particles is set to 100 parts by mass, the mass of the content of the binder resin in the conductive paste composition is preferably 0.5 to 30 parts by mass, and more preferably 1 to 15 parts by mass. In addition, when the mass of the metal particles is set to 100 parts by mass, the mass of the content of the solvent in the conductive paste is preferably 10 to 200 parts by mass, and more preferably 50 to 150 parts by mass. In addition, other components such as a surfactant and an antioxidant may be blended if necessary.

對它們的混合物進行攪拌、分散從而得到導電膏。攪拌沒有特別限制，可使用習知的手段，較佳為例如可使用PD攪拌機或行星式混煉機，特佳為使用行星式混煉機。分散沒有特別限制，可使用習知的手段，較佳為例如可使用捏合機、珠磨機或三輥研磨機，特佳為使用三輥研磨機。The mixture is stirred and dispersed to obtain a conductive paste. There is no particular limitation on the stirring, and conventional means can be used. For example, a PD mixer or a planetary mixer can be used, and a planetary mixer is particularly preferred. Dispersion is not particularly limited, and conventional means can be used. For example, a kneader, a bead mill, or a three-roll mill can be used, and a three-roll mill is particularly preferred.

導電膏可藉由絲網印刷等方法而印刷在片材上。The conductive paste can be printed on the sheet by a method such as screen printing.

[第三發明：陶瓷組合物][Third invention: ceramic composition]

第三發明的聚合物特別適合作為陶瓷組合物用的黏結劑樹脂。陶瓷組合物除了本發明的聚合物以外，還含有陶瓷顆粒及有機溶劑。The polymer of the third invention is particularly suitable as a binder resin for a ceramic composition. The ceramic composition contains ceramic particles and an organic solvent in addition to the polymer of the present invention.

作為這樣的陶瓷顆粒，可以例示出氧化鋁或鈦酸鋇等金屬氧化物、氮化矽或氮化鋁等氮化物。Examples of such ceramic particles include metal oxides such as alumina and barium titanate, and nitrides such as silicon nitride and aluminum nitride.

陶瓷顆粒的中心粒徑（D50）、即利用激光衍射散射式粒度分佈測定裝置而測定的體積累積粒徑D50較佳為0.05μm～50.0μm。The central particle diameter (D50) of the ceramic particles, that is, the volume cumulative particle diameter D50 measured by a laser diffraction scattering particle size distribution measurement device, is preferably 0.05 μm to 50.0 μm.

此外，作為有機溶劑，可列舉出甲苯、二甲苯等烴類溶劑，乙酸乙酯、乙酸丁酯等酯類溶劑，甲醇、乙醇、異丙醇、異丁醇、1-丁醇、雙丙酮醇等醇類溶劑，乙二醇單丁醚、丙二醇單甲醚、丙二醇單乙醚等二醇醚類溶劑，二乙二醇單乙醚乙酸酯、二乙二醇單丁醚乙酸酯、丙二醇單甲醚乙酸酯等二醇醚乙酸酯類溶劑，丙酮、甲基乙基酮、甲基異丁基酮等酮類溶劑等，它們可以作為單體使用，或者可以混合使用兩種以上。Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate and butyl acetate, methanol, ethanol, isopropanol, isobutanol, 1-butanol, and diacetone alcohol. Other alcohol solvents, glycol ether solvents such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and propylene glycol monoethyl ether Glycol ether acetate solvents, such as methyl ether acetate, and ketone solvents, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, can be used as a monomer, or two or more of them can be used in combination.

將陶瓷顆粒的重量設為100質量份時，陶瓷組合物中的本發明的黏結劑樹脂的含量較佳為0.5～30質量份。此外，將陶瓷顆粒的重量設為100質量份時，陶瓷組合物中的溶劑的含量較佳為10～200質量份。除此以外，可以根據需要摻合表面活性劑或抗氧化劑等其他成分。When the weight of the ceramic particles is 100 parts by mass, the content of the binder resin of the present invention in the ceramic composition is preferably 0.5 to 30 parts by mass. When the weight of the ceramic particles is 100 parts by mass, the content of the solvent in the ceramic composition is preferably 10 to 200 parts by mass. In addition, other components such as a surfactant and an antioxidant may be blended as necessary.

對它們的混合物進行攪拌、分散從而得到陶瓷組合物。攪拌沒有特別限制，可使用習知的手段，較佳為例如可使用球磨機、珠磨機、或行星式混煉機等，特佳為使用球磨機。The mixture is stirred and dispersed to obtain a ceramic composition. The stirring is not particularly limited, and conventional means can be used, and for example, a ball mill, a bead mill, or a planetary kneader can be preferably used, and a ball mill is particularly preferred.

陶瓷組合物較佳為漿料的形態，藉由利用刮刀法等方法將漿料載體膜上成型，從而得到陶瓷生片。然而，也可藉由利用鑄塑成型、加壓成型等將陶瓷組合物成型為片狀等從而得到成型體。The ceramic composition is preferably in the form of a slurry, and the slurry carrier film is formed by a method such as a doctor blade method to obtain a ceramic green sheet. However, it is also possible to obtain a molded body by molding a ceramic composition into a sheet or the like by casting molding, pressure molding, or the like.

實施例Examples

第一發明的實施例Embodiment of the first invention

以下，列舉出實施例及比較例對本發明進行進一步具體的說明。Hereinafter, the present invention will be described more specifically with examples and comparative examples.

將單體（A）的結構與縮寫符號示於下述的表1中。The structure and abbreviated symbols of the monomer (A) are shown in Table 1 below.

[表1] 式（1）表示的單體（A）的結構 ・・・（1）[Table 1] Structure of monomer (A) represented by formula (1) ···(1)

（合成例1：單體A1）(Synthesis Example 1: Monomer A1)

向安裝有攪拌機、溫度計、冷卻器、滴液漏斗及空氣導入管的300mL燒瓶中添加了2-甲基丙烯醯氧乙基異氰酸酯（SHOWA DENKO K.K.製造“Karenz MOI”）51.2g、四氫呋喃40g、對甲氧基苯酚0.012g。向燒瓶內導入空氣，將內溫保持為40℃，同時經1小時滴下了正丁胺24.1g。然後，使其於40℃熟化2小時後，於60℃減壓餾去四氫呋喃，得到了單體A1（收率92%）。A 300 mL flask equipped with a stirrer, a thermometer, a cooler, a dropping funnel and an air introduction tube was charged with 51.2 g of 2-methacryloxyethyl isocyanate ("Karenz MOI" manufactured by SHOWA DENKO KK), 40 g of tetrahydrofuran, and 0.012 g of methoxyphenol. Air was introduced into the flask, and 24.1 g of n-butylamine was dropped over 1 hour while keeping the internal temperature at 40 ° C. Then, after aging at 40 ° C for 2 hours, tetrahydrofuran was distilled off under reduced pressure at 60 ° C to obtain monomer A1 (yield 92%).

（合成例2：單體A2）(Synthesis Example 2: Monomer A2)

向安裝有攪拌機、溫度計、冷卻器、滴液漏斗及空氣導入管的300mL燒瓶中添加了2-甲基丙烯醯氧乙基異氰酸酯（SHOWA DENKO K.K.製造“Karenz MOI”）51.2g、對甲氧基苯酚0.012g、二月桂酸二丁基錫0.034g。向燒瓶內導入空氣，將內溫保持為60℃，同時經1小時滴下了正丁醇。然後，升溫至80℃，並使其熟化6小時後，於60℃減壓餾去四氫呋喃，得到了單體A2（收率95%）。To a 300 mL flask equipped with a stirrer, thermometer, cooler, dropping funnel, and air introduction tube was added 51.2 g of 2-methacryloxyethyl isocyanate ("Karenz MOI" manufactured by SHOWA DENKO KK) and p-methoxy 0.012 g of phenol and 0.034 g of dibutyltin dilaurate. Air was introduced into the flask, and the internal temperature was maintained at 60 ° C. At the same time, n-butanol was dropped over 1 hour. Then, the temperature was raised to 80 ° C, and the mixture was aged for 6 hours. Then, tetrahydrofuran was distilled off under reduced pressure at 60 ° C to obtain a monomer A2 (yield: 95%).

（合成例3：單體A3）(Synthesis Example 3: Monomer A3)

向安裝有攪拌機、溫度計、冷卻器、滴液漏斗及空氣導入管的300mL燒瓶中添加了甲基丙烯酸2-羥基乙酯（NOF CORPORATION製造“Blemmer E”）、對甲氧基苯酚0.012g。向燒瓶內導入空氣，將內溫保持為60℃，同時經1小時滴下了異氰酸正丁酯。然後，升溫至80℃，使其熟化6小時後，冷卻至40℃後加入離子交換水100mL，進行攪拌、靜置。提出下層的單體A3層，於80℃進行減壓並脫水，得到了單體A3（收率70%）。A 300 mL flask equipped with a stirrer, a thermometer, a cooler, a dropping funnel, and an air introduction tube was charged with 2-hydroxyethyl methacrylate ("Blemmer E" manufactured by NOF CORPORATION) and 0.012 g of p-methoxyphenol. Air was introduced into the flask, and the n-butyl isocyanate was dropped over 1 hour while maintaining the inner temperature at 60 ° C. Then, the temperature was raised to 80 ° C, and the mixture was aged for 6 hours. After cooling to 40 ° C, 100 mL of ion-exchanged water was added, and the mixture was stirred and left to stand. The monomer A3 layer of the lower layer was put out, and decompressed and dehydrated at 80 ° C to obtain monomer A3 (yield 70%).

（合成例4：單體A4）(Synthesis Example 4: Monomer A4)

向安裝有攪拌機、溫度計、冷卻器、滴液漏斗及空氣導入管的300mL燒瓶中添加了2-丙烯醯氧基乙基異氰酸酯（SHOWA DENKO K.K.製造“Karenz AOI”）46.6g、四氫呋喃40g、對甲氧基苯酚0.012g。向燒瓶內導入空氣，將內溫保持於40℃，同時經1小時滴下了正丁胺24.1g。然後，使其於40℃熟化2小時後，於60℃減壓餾去四氫呋喃，得到了單體A4（收率90%）。To a 300 mL flask equipped with a stirrer, thermometer, cooler, dropping funnel, and air introduction tube were added 46.6 g of 2-propenyloxyethyl isocyanate ("Karenz AOI" manufactured by SHOWA DENKO KK), 40 g of tetrahydrofuran, p-formyl 0.012 g of oxyphenol. Air was introduced into the flask, and 24.1 g of n-butylamine was dropped over 1 hour while keeping the internal temperature at 40 ° C. Then, after aging at 40 ° C for 2 hours, tetrahydrofuran was distilled off under reduced pressure at 60 ° C to obtain monomer A4 (yield 90%).

（合成例5：單體A5）(Synthesis Example 5: Monomer A5)

向安裝有攪拌機、溫度計、冷卻器、滴液漏斗及空氣導入管的300mL燒瓶中添加了2-丙烯醯氧基乙基異氰酸酯（SHOWA DENKO K.K.製造“Karenz AOI”）46.6g、四氫呋喃40g、對甲氧基苯酚0.012g。向燒瓶內導入空氣，將內溫保持為40℃，同時經1小時滴下了正十二胺61.1g。然後，使其於40℃熟化2小時後，於60℃減壓餾去四氫呋喃，得到了單體A5（收率90%）。To a 300 mL flask equipped with a stirrer, thermometer, cooler, dropping funnel, and air introduction tube were added 46.6 g of 2-propenyloxyethyl isocyanate ("Karenz AOI" manufactured by SHOWA DENKO KK), 40 g of tetrahydrofuran, p-formyl 0.012 g of oxyphenol. Air was introduced into the flask, and while maintaining the internal temperature at 40 ° C., 61.1 g of n-dodecylamine was dropped over 1 hour. Then, after aging at 40 ° C for 2 hours, tetrahydrofuran was distilled off under reduced pressure at 60 ° C to obtain monomer A5 (yield 90%).

（聚合例1：共聚物A）(Polymerization Example 1: Copolymer A)

向安裝有攪拌機、溫度計、冷卻器、滴液漏斗及氮氣導入管的1L可分離式燒瓶中添加異丙醇250g，對燒瓶內進行氮氣置換，使其處在氮氣氛圍下。分別製備了將66.2g的甲基丙烯酸異丁酯（產品名稱：Acryester IB（MITSUBISHI RAYON CO., LTD.製造））與233.8g的單體A1混合而成的單體溶液、及將異丙醇50g與2,2’-偶氮雙（2,4-二甲基戊腈）（產品名稱：V-65（Wako Pure Chemical Industries, Ltd.製造））0.6g混合而成的聚合引發劑溶液。To a 1-liter separable flask equipped with a stirrer, a thermometer, a cooler, a dropping funnel, and a nitrogen introduction tube, 250 g of isopropyl alcohol was added, and the inside of the flask was replaced with nitrogen to be placed under a nitrogen atmosphere. A monomer solution prepared by mixing 66.2 g of isobutyl methacrylate (product name: Acryester IB (manufactured by MITSUBISHI RAYON CO., LTD.)) With 233.8 g of monomer A1, and isopropyl alcohol A polymerization initiator solution prepared by mixing 50 g with 0.6 g of 2,2'-azobis (2,4-dimethylvaleronitrile) (product name: V-65 (manufactured by Wako Pure Chemical Industries, Ltd.)).

將反應容器內升溫至75℃，同時分別經3小時滴下了單體溶液及聚合引發劑溶液。然後，使其於75℃反應3小時得到了共聚物A的異丙醇溶液。接著，在60℃減壓下經180分鐘進行脫溶劑，得到了共聚物A。While the temperature in the reaction vessel was raised to 75 ° C., the monomer solution and the polymerization initiator solution were dropped over 3 hours, respectively. Then, it was made to react at 75 degreeC for 3 hours, and the isopropyl alcohol solution of the copolymer A was obtained. Then, the solvent was removed under reduced pressure at 60 ° C for 180 minutes to obtain a copolymer A.

（聚合例2：共聚物B）(Polymerization Example 2: Copolymer B)

除了將甲基丙烯酸異丁酯的使用量變更為177.7g、將單體A1的使用量變更為122.3g以外，利用與聚合例1相同的手法得到了共聚物B。Copolymer B was obtained in the same manner as in Polymerization Example 1 except that the amount of isobutyl methacrylate was changed to 177.7 g and the amount of monomer A1 was changed to 122.3 g.

（聚合例3：共聚物C）(Polymerization Example 3: Copolymer C)

除了將甲基丙烯酸異丁酯的使用量變更為115.1g、將單體A1的使用量變更為184.9g以外，利用與聚合例1相同的手法得到了共聚物C。Copolymer C was obtained in the same manner as in Polymerization Example 1 except that the amount of isobutyl methacrylate was changed to 115.1 g and the amount of monomer A1 was changed to 184.9 g.

（聚合例4：共聚物D）(Polymerization Example 4: Copolymer D)

除了將甲基丙烯酸異丁酯的使用量變更為177.4g、將單體A1變更為單體A2並使用了122.6g以外，利用與聚合例1相同的手法得到了共聚物D。Copolymer D was obtained in the same manner as in Polymerization Example 1 except that the amount of isobutyl methacrylate was changed to 177.4 g, and monomer A1 was changed to monomer A2, and 122.6 g was used.

（聚合例5：共聚物E）(Polymerization Example 5: Copolymer E)

除了將甲基丙烯酸異丁酯的使用量變更為177.4g、將單體A1變更為單體A3並使用了122.6g以外，利用與聚合例1相同的手法得到了共聚物E。Copolymer E was obtained in the same manner as in Polymerization Example 1 except that the amount of isobutyl methacrylate was changed to 177.4 g, the monomer A1 was changed to monomer A3, and 122.6 g was used.

（聚合例6：共聚物F）(Polymerization Example 6: Copolymer F)

除了將甲基丙烯酸異丁酯的使用量變更為182.3g、將單體A1變更為單體A4並使用了117.7g以外，利用與聚合例1相同的手法得到了共聚物F。Copolymer F was obtained in the same manner as in Polymerization Example 1, except that the amount of isobutyl methacrylate was changed to 182.3 g, the monomer A1 was changed to monomer A4, and 117.7 g was used.

（聚合例7：共聚物G）(Polymerization Example 7: Copolymer G)

除了將甲基丙烯酸異丁酯的使用量變更為151.2g、將單體A1變更為單體A5並使用了148.8g以外，利用與聚合例1相同的手法得到了共聚物G。Copolymer G was obtained in the same manner as in Polymerization Example 1 except that the used amount of isobutyl methacrylate was changed to 151.2 g, the monomer A1 was changed to monomer A5, and 148.8 g was used.

（聚合例8：共聚物H）(Polymerization Example 8: Copolymer H)

除了將甲基丙烯酸異丁酯的使用量變更為133.6g、將單體A1的使用量變更為128.7g，並使用了37.7g的甲基丙烯酸甲酯以外，利用與聚合例1相同的手法得到了共聚物H。Except that the used amount of isobutyl methacrylate was changed to 133.6 g, the used amount of monomer A1 was changed to 128.7 g, and 37.7 g of methyl methacrylate was used, the same method as in Polymerization Example 1 Copolymer H.

（聚合例9：共聚物I）(Polymerization Example 9: Copolymer I)

除了將甲基丙烯酸異丁酯的使用量變更為133.0g、將單體A1的使用量變更為128.1g，並使用了38.9g的苯乙烯以外，利用與聚合例1相同的手法得到了共聚物I。A copolymer was obtained in the same manner as in Polymerization Example 1 except that the amount of isobutyl methacrylate was changed to 133.0 g, the amount of monomer A1 was changed to 128.1 g, and 38.9 g of styrene was used. I.

（聚合例10：共聚物J）(Polymerization Example 10: Copolymer J)

除了將甲基丙烯酸異丁酯的使用量變更為160.9g、將單體A1的使用量變更為129.1g，並使用了10.0g的丙烯腈以外，利用與聚合例1相同的手法得到了共聚物J。A copolymer was obtained in the same manner as in Polymerization Example 1 except that the amount of isobutyl methacrylate was changed to 160.9 g, the amount of monomer A1 was changed to 129.1 g, and 10.0 g of acrylonitrile was used. J.

（聚合例11：共聚物K）(Polymerization Example 11: Copolymer K)

除了將甲基丙烯酸異丁酯的使用量變更為159.1g、將單體A1的使用量變更為127.7g，並使用了13.2g的丙烯醯胺以外，利用與聚合例1相同的手法得到了共聚物K。A copolymer was obtained in the same manner as in Polymerization Example 1 except that the amount of isobutyl methacrylate was changed to 159.1 g, the amount of monomer A1 was changed to 127.7 g, and 13.2 g of acrylamide was used.物 K。 Matter K.

（聚合例12：共聚物L）(Polymerization Example 12: Copolymer L)

除了將甲基丙烯酸異丁酯的使用量變更為276.6g、將單體A1的使用量變更為23.4g以外，利用與聚合例1相同的手法得到了共聚物L。Copolymer L was obtained in the same manner as in Polymerization Example 1 except that the amount of isobutyl methacrylate was changed to 276.6 g and the amount of monomer A1 was changed to 23.4 g.

（聚合例13：共聚物M）(Polymerization Example 13: Copolymer M)

除了將甲基丙烯酸異丁酯的使用量設為215.5g、使用了84.5g的甲基丙烯酸2-羥基乙酯代替單體A1以外，利用與聚合例1相同的手法得到了共聚物M。Copolymer M was obtained in the same manner as in Polymerization Example 1 except that the amount of isobutyl methacrylate used was 215.5 g, and 84.5 g of 2-hydroxyethyl methacrylate was used instead of monomer A1.

[重量平均分子量的測定][Measurement of weight average molecular weight]

使用凝膠層析儀（GPC）並利用以下的條件求出了共聚物A～M的重量平均分子量。The weight average molecular weights of the copolymers A to M were determined using a gel chromatography (GPC) under the following conditions.

裝置：Tosoh Corporation製造、HLC-8220Device: manufactured by Tosoh Corporation, HLC-8220

層析柱：shodex公司製造、LF-804Chromatographic column: manufactured by Shodex, LF-804

標準物質：聚苯乙烯Standard substance: polystyrene

洗脫液：THF（四氫呋喃）Eluent: THF (tetrahydrofuran)

流量：1.0ml/minFlow: 1.0ml / min

層析柱溫度：40℃Column temperature: 40 ° C

檢測器：RI（示差折射率檢測器）Detector: RI (differential refractive index detector)

[觸變性的評估][Assessment of thixotropy]

將共聚物20重量份、二氫松油醇80重量份混合，一邊於60℃加熱一邊攪拌2小時得到完全溶解而成的溶液，利用流變儀在1s-1至1,000s-1的範圍測定了該溶液的黏度的剪切速度依賴性。算出了1s-1與1,000s-1時的黏度的比作為TI值。20 parts by weight of copolymer and 80 parts by weight of dihydroterpineol were mixed and heated at 60 ° C for 2 hours to obtain a completely dissolved solution. The solution was measured using a rheometer in the range of 1s-1 to 1,000s-1. The shear rate dependence of the viscosity of the solution is given. The ratio of the viscosity at 1s-1 to 1,000s-1 was calculated as the TI value.

[熱分解性的評估][Evaluation of Thermal Decomposability]

將共聚物5mg加入鋁鍋中，利用TG/DTA在空氣氛圍下以升溫速度10℃/分鐘升溫至500℃，並測定了樣品的殘存量。5 mg of the copolymer was added to an aluminum pan, and the temperature was increased to 500 ° C. at a heating rate of 10 ° C./min by using TG / DTA in an air atmosphere, and the remaining amount of the sample was measured.

[印刷適性的評估][Evaluation of printability]

相對於Ni粉（JFE MINERAL Co., LTD.製造：NFP201S）100重量份，加入油醯肌氨酸（NOF CORPORATION製造：ESLEAM 221P）1重量份、各例的黏結劑樹脂3重量份、二氫松油醇90重量份。使用行星式混煉機對這些混合物進行攪拌後，利用三輥研磨機進行混煉得到了Ni膏。To 100 parts by weight of Ni powder (manufactured by JFE MINERAL Co., LTD .: NFP201S), 1 part by weight of oleosine sarcosine (NOF CORPORATION: ESLEAM 221P) was added, 3 parts by weight of the binder resin of each example, and dihydrogen Terpineol is 90 parts by weight. These mixtures were stirred with a planetary mixer, and then kneaded with a three-roll mill to obtain a Ni paste.

對得到的Ni膏進行絲網印刷，利用光學顯微鏡確認得到的印刷體，目視確認了是否觀察到滲出或拉絲的痕跡。若沒有觀察到滲出或拉絲則記為○（良好），觀察到了滲出或拉絲時記為×（不良）。The obtained Ni paste was screen-printed, and the obtained printed body was confirmed with an optical microscope, and it was visually confirmed whether traces of bleeding or drawing were observed. When no bleeding or drawing was observed, it was marked as ○ (good), and when bleeding or drawing was observed, it was marked as × (bad).

[表2] 評估結果 [Table 2] Evaluation results

[表3] 評估結果 [Table 3] Evaluation results

[表4] 評估結果 [Table 4] Evaluation results

實施例1～11中，觸變值變高，此外，加熱殘留成分變少，且印刷適性變高。In Examples 1 to 11, the thixotropic value was increased, and the heating residual component was reduced, and the printability was increased.

比較例1中，單體1的比率小於10莫耳%，加熱殘留成分變少，但觸變值低、印刷適性也變低。In Comparative Example 1, although the ratio of the monomer 1 was less than 10 mol%, the heating residual component was reduced, but the thixotropic value was low, and the printability was also low.

比較例2中，使用了不含有本發明的單體的共聚物，加熱殘留成分變少，但觸變值低、印刷適性也變低。In Comparative Example 2, a copolymer not containing the monomer of the present invention was used, and the heating residual component was reduced, but the thixotropic value was low and the printability was also low.

比較例3中，使用了乙基纖維素，觸變值大且印刷適性高，但加熱殘留成分變多。In Comparative Example 3, although ethyl cellulose was used, the thixotropic value was large and the printability was high, but the heating residual component was increased.

第二發明的實施例Embodiment of the second invention

將單體（A）的結構與縮寫符號示於下述的表5中 [表5] 式（1）表示的單體（A）的結構 ・・・（1）The structure and abbreviation of the monomer (A) are shown in Table 5 below. [Table 5] Structure of the monomer (A) represented by the formula (1) ···(1)

（合成例1：單體A1）(Synthesis Example 1: Monomer A1)

向安裝有攪拌機、溫度計、冷卻器、滴液漏斗及空氣導入管的300mL燒瓶中添加了2-丙烯醯氧基乙基異氰酸酯（SHOWA DENKO K.K.製造“Karenz AOI”）46.6g、四氫呋喃40g、對甲氧基苯酚0.012g。向燒瓶內導入空氣，將內溫保持為40℃，同時經1小時滴下了正丁胺24.1g。然後，使其於40℃熟化2小時後，於60℃減壓餾去四氫呋喃，得到了單體A1（收率90%）。To a 300 mL flask equipped with a stirrer, thermometer, cooler, dropping funnel, and air introduction tube were added 46.6 g of 2-propenyloxyethyl isocyanate ("Karenz AOI" manufactured by SHOWA DENKO KK), 40 g of tetrahydrofuran, p-formyl 0.012 g of oxyphenol. Air was introduced into the flask, and 24.1 g of n-butylamine was dropped over 1 hour while keeping the internal temperature at 40 ° C. Then, after aging at 40 ° C for 2 hours, tetrahydrofuran was distilled off under reduced pressure at 60 ° C to obtain monomer A1 (yield 90%).

（合成例2：單體A2）(Synthesis Example 2: Monomer A2)

向安裝有攪拌機、溫度計、冷卻器、滴液漏斗及空氣導入管的300mL燒瓶中添加了2-甲基丙烯醯氧乙基異氰酸酯（SHOWA DENKO K.K.製造“Karenz MOI”）51.2g、四氫呋喃40g、對甲氧基苯酚0.012g。向燒瓶內導入空氣，將內溫保持為40℃，同時經1小時滴下了正丁胺24.1g。然後，使其於40℃熟化2小時後，於60℃減壓餾去四氫呋喃，得到了單體A2（收率92%）。A 300 mL flask equipped with a stirrer, a thermometer, a cooler, a dropping funnel and an air introduction tube was charged with 51.2 g of 2-methacryloxyethyl isocyanate ("Karenz MOI" manufactured by SHOWA DENKO KK), 40 g of tetrahydrofuran, and 0.012 g of methoxyphenol. Air was introduced into the flask, and 24.1 g of n-butylamine was dropped over 1 hour while keeping the internal temperature at 40 ° C. Then, after aging at 40 ° C for 2 hours, tetrahydrofuran was distilled off under reduced pressure at 60 ° C to obtain monomer A2 (yield: 92%).

（合成例3：單體A3）(Synthesis Example 3: Monomer A3)

向安裝有攪拌機、溫度計、冷卻器、滴液漏斗及空氣導入管的300mL燒瓶中添加了2-甲基丙烯醯氧乙基異氰酸酯（SHOWA DENKO K.K.製造“Karenz MOI”）51.2g、對甲氧基苯酚0.012g、二月桂酸二丁基錫0.034g。向燒瓶內導入空氣，將內溫保持為60℃，同時經1小時滴下了正丁醇。然後，升溫至80℃，並使其熟化6小時後，於60℃減壓餾去四氫呋喃，得到了單體A3（收率95%）。To a 300 mL flask equipped with a stirrer, thermometer, cooler, dropping funnel, and air introduction tube was added 51.2 g of 2-methacryloxyethyl isocyanate ("Karenz MOI" manufactured by SHOWA DENKO KK) and p-methoxy 0.012 g of phenol and 0.034 g of dibutyltin dilaurate. Air was introduced into the flask, and the internal temperature was maintained at 60 ° C. At the same time, n-butanol was dropped over 1 hour. Then, the temperature was raised to 80 ° C. and the mixture was aged for 6 hours, and then tetrahydrofuran was distilled off under reduced pressure at 60 ° C. to obtain a monomer A3 (yield: 95%).

（合成例4：單體A4）(Synthesis Example 4: Monomer A4)

向安裝有攪拌機、溫度計、冷卻器、滴液漏斗及空氣導入管的300mL燒瓶中添加了甲基丙烯酸2-羥基乙酯（NOF CORPORATION製造“Blemmer E”）、對甲氧基苯酚0.012g。向燒瓶內導入空氣，將內溫保持為60℃，同時經1小時滴下了異氰酸正丁酯。然後，升溫至80℃，使其熟化6小時後，冷卻至40℃後加入離子交換水100mL，進行攪拌、靜置。提出下層的單體A3層，於80℃進行減壓並脫水，得到了單體A4（收率70%）。A 300 mL flask equipped with a stirrer, a thermometer, a cooler, a dropping funnel, and an air introduction tube was charged with 2-hydroxyethyl methacrylate ("Blemmer E" manufactured by NOF CORPORATION) and 0.012 g of p-methoxyphenol. Air was introduced into the flask, and the n-butyl isocyanate was dropped over 1 hour while maintaining the inner temperature at 60 ° C. Then, the temperature was raised to 80 ° C, and the mixture was aged for 6 hours. After cooling to 40 ° C, 100 mL of ion-exchanged water was added, and the mixture was stirred and left to stand. The monomer A3 layer of the lower layer was put out, and decompressed and dehydrated at 80 ° C to obtain monomer A4 (yield 70%).

（聚合例1：共聚物A）(Polymerization Example 1: Copolymer A)

向安裝有攪拌機、溫度計、冷卻器及氮氣導入管的500mL可分離式燒瓶中添加異丙醇210g、甲基丙烯酸異丁酯（產品名稱：Acryester IB（MITSUBISHI RAYON CO., LTD.製造））47.3g與丙烯酸丁酯（產品名稱：丙烯酸丁酯（NIPPON SHOKUBAI CO., LTD.製造））7.1g與35.6g的單體A1混合而成的單體溶液及2,2’-偶氮雙（2,4-二甲基戊腈）（產品名稱：V-65（Wako Pure Chemical Industries, Ltd.製造））0.2g，對燒瓶內進行氮氣置換後，將反應容器內升溫至75℃，並使其反應6小時，得到了共聚物A的異丙醇溶液。接著，在60℃減壓下經180分鐘進行脫溶劑，得到了共聚物A。To a 500 mL separable flask equipped with a stirrer, a thermometer, a cooler, and a nitrogen introduction tube was added 210 g of isopropanol and isobutyl methacrylate (product name: Acryester IB (manufactured by MITSUBISHI RAYON CO., LTD.)) 47.3 g monomer solution with butyl acrylate (product name: butyl acrylate (manufactured by NIPPON SHOKUBAI CO., LTD.)) 7.1g and 35.6g monomer A1 and 2,2'-azobis (2 , 4-dimethylvaleronitrile) (product name: V-65 (manufactured by Wako Pure Chemical Industries, Ltd.)) 0.2 g. After replacing nitrogen in the flask, the temperature in the reaction vessel was raised to 75 ° C. After 6 hours of reaction, an isopropanol solution of copolymer A was obtained. Then, the solvent was removed under reduced pressure at 60 ° C for 180 minutes to obtain a copolymer A.

（聚合例2：共聚物B）(Polymerization Example 2: Copolymer B)

除了將甲基丙烯酸異丁酯的使用量變更為69.2g、將丙烯酸丁酯的使用量變更為7.8g、將單體A1的使用量變更為13.0g以外，利用與聚合例1相同的手法得到了共聚物B。Except that the amount of isobutyl methacrylate used was changed to 69.2 g, the amount of butyl acrylate used was changed to 7.8 g, and the amount of monomer A1 was changed to 13.0 g, it was obtained by the same method as in Polymerization Example 1. Copolymer B.

（聚合例3：共聚物C）(Polymerization Example 3: Copolymer C)

除了將甲基丙烯酸異丁酯的使用量設為46.1g、將丙烯酸丁酯的使用量設為6.9g、使用了37.0g的單體A2代替單體A1以外，利用與聚合例1相同的手法得到了共聚物C。Except that the amount of isobutyl methacrylate used was 46.1 g, the amount of butyl acrylate used was 6.9 g, and 37.0 g of monomer A2 was used instead of monomer A1, the same method as in Polymerization Example 1 was used. Copolymer C was obtained.

（聚合例4：共聚物D）(Polymerization Example 4: Copolymer D)

除了將甲基丙烯酸異丁酯的使用量設為46.0g、將丙烯酸丁酯的使用量設為6.9g、使用了37.1g的單體A3代替單體A1以外，利用與聚合例1相同的手法得到了共聚物D。Except that the amount of isobutyl methacrylate used was 46.0 g, the amount of butyl acrylate used was 6.9 g, and 37.1 g of monomer A3 was used instead of monomer A1, the same method as in Polymerization Example 1 was used. Copolymer D was obtained.

（聚合例5：共聚物E）(Polymerization Example 5: Copolymer E)

除了將甲基丙烯酸異丁酯的使用量設為46.0g、將丙烯酸丁酯的使用量設為6.9g、使用了37.0g的單體A4代替單體A1以外，利用與聚合例1相同的手法得到了共聚物E。Except that the amount of isobutyl methacrylate used was 46.0 g, the amount of butyl acrylate used was 6.9 g, and 37.0 g of monomer A4 was used instead of monomer A1, the same method as in Polymerization Example 1 was used. Copolymer E was obtained.

（聚合例6：共聚物F）(Polymerization Example 6: Copolymer F)

除了使用11.7g的甲基丙烯酸甲酯（產品名稱：Acryester M（MITSUBISHI RAYON CO., LTD.製造））、將甲基丙烯酸異丁酯的使用量變更為33.2g、將丙烯酸丁酯的使用量變更為7.5g、將單體A1的使用量變更為37.0g以外，利用與聚合例1相同的手法得到了共聚物F。In addition to using 11.7 g of methyl methacrylate (product name: Acryester M (manufactured by MITSUBISHI RAYON CO., LTD.)), Changing the amount of isobutyl methacrylate to 33.2 g, and the amount of butyl acrylate Copolymer F was obtained in the same manner as in Polymerization Example 1 except that the amount was changed to 7.5 g and the amount of monomer A1 was changed to 37.0 g.

（聚合例7：共聚物G）(Polymerization Example 7: Copolymer G)

除了使用20.6g的甲基丙烯酸2-乙基己酯（產品名稱：Acryester EH（MITSUBISHI RAYON CO., LTD.製造））、將甲基丙烯酸異丁酯的使用量變更為29.5g、將丙烯酸丁酯的使用量變更為6.6g、將單體A1的使用量變更為33.3g以外，利用與聚合例1相同的手法得到了共聚物G。In addition to using 20.6 g of 2-ethylhexyl methacrylate (product name: Acryester EH (manufactured by MITSUBISHI RAYON CO., LTD.)), The amount of isobutyl methacrylate was changed to 29.5 g, and butyl acrylate was changed. Copolymer G was obtained in the same manner as in Polymerization Example 1 except that the amount of ester used was changed to 6.6 g and the amount of monomer A1 was changed to 33.3 g.

（聚合例8：共聚物H）(Polymerization Example 8: Copolymer H)

除了使用11.6g的丙烯酸乙酯（產品名稱：丙烯酸乙酯（NIPPON SHOKUBAI CO., LTD.製造））、將甲基丙烯酸異丁酯的使用量變更為41.2g、將單體A1的使用量變更為37.2g以外，利用與聚合例1相同的手法得到了共聚物H。In addition to using 11.6 g of ethyl acrylate (product name: ethyl acrylate (manufactured by NIPPON SHOKUBAI CO., LTD.)), Changing the amount of isobutyl methacrylate to 41.2 g, and changing the amount of monomer A1 Copolymer H was obtained in the same manner as in Polymerization Example 1 except for 37.2 g.

（聚合例9：共聚物I）(Polymerization Example 9: Copolymer I)

除了使用5.6g的二甲基丙烯醯胺（產品名稱：DMAA（KJ CHEMICALS CORPORATION製造））、將甲基丙烯酸異丁酯的使用量變更為40.5g、將丙烯酸丁酯的使用量變更為7.3g、將單體A1的使用量變更為36.6g以外，利用與聚合例1相同的手法得到了共聚物I。In addition to using 5.6 g of methacrylamide (product name: DMAA (manufactured by KJ CHEMICALS CORPORATION)), the amount of isobutyl methacrylate used was changed to 40.5 g, and the amount of butyl acrylate used was changed to 7.3 g Copolymer I was obtained in the same manner as in Polymerization Example 1 except that the amount of monomer A1 was changed to 36.6 g.

（聚合例10：共聚物J）(Polymerization Example 10: Copolymer J)

除了使用3.1g的丙烯腈（產品名稱：丙烯腈（Tokyo Chemical Industry Co., Ltd.製造））、將甲基丙烯酸異丁酯的使用量變更為41.7g、將丙烯酸丁酯的使用量變更為7.5g、將單體A1的使用量變更為37.7g以外，利用與聚合例1相同的手法得到了共聚物J。In addition to using 3.1 g of acrylonitrile (product name: acrylonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.)), the amount of isobutyl methacrylate used was changed to 41.7 g, and the amount of butyl acrylate used was changed to Copolymer J was obtained in the same manner as in Polymerization Example 1 except that 7.5 g and the used amount of monomer A1 were changed to 37.7 g.

（聚合例11：共聚物K）(Polymerization Example 11: Copolymer K)

除了將甲基丙烯酸異丁酯的使用量變更為29.0g、將丙烯酸丁酯的使用量變更為6.5g、將單體A1的使用量變更為54.5g以外，利用與聚合例1相同的手法得到了共聚物K。Except that the amount of isobutyl methacrylate used was changed to 29.0 g, the amount of butyl acrylate used was changed to 6.5 g, and the amount of monomer A1 was changed to 54.5 g, it was obtained by the same method as in Polymerization Example 1. Copolymer K.

（聚合例12：共聚物L）(Polymerization Example 12: Copolymer L)

除了將甲基丙烯酸異丁酯的使用量變更為83.4g、將單體A1的使用量變更為6.6g以外，利用與聚合例1相同的手法得到了共聚物L。Copolymer L was obtained in the same manner as in Polymerization Example 1 except that the amount of isobutyl methacrylate was changed to 83.4 g and the amount of monomer A1 was changed to 6.6 g.

（聚合例13：共聚物M）(Polymerization Example 13: Copolymer M)

除了將甲基丙烯酸異丁酯的使用量變更為64.7g、使用了25.3g的甲基丙烯酸2-羥基乙酯（產品名稱：Blemmer E（NOF CORPORATION製造））以外，利用與聚合例1相同的手法得到了共聚物M。Except that the amount of isobutyl methacrylate was changed to 64.7 g and 25.3 g of 2-hydroxyethyl methacrylate (product name: Blemmer E (manufactured by NOF CORPORATION)) was used, the same procedure as in Polymerization Example 1 was used. Copolymer M was obtained by a method.

[重量平均分子量的測定][Measurement of weight average molecular weight]

使用凝膠層析儀（GPC）並利用以下的條件求出了共聚物A～M的重量平均分子量。The weight average molecular weights of the copolymers A to M were determined using a gel chromatography (GPC) under the following conditions.

裝置：Tosoh Corporation製造、HLC-8220Device: manufactured by Tosoh Corporation, HLC-8220

層析柱：shodex公司製造、LF-804Chromatographic column: manufactured by Shodex, LF-804

標準物質：聚苯乙烯Standard substance: polystyrene

洗脫液：THF（四氫呋喃）Eluent: THF (tetrahydrofuran)

流量：1.0ml/minFlow: 1.0ml / min

層析柱溫度：40℃Column temperature: 40 ° C

檢測器：RI（示差折射率檢測器）Detector: RI (differential refractive index detector)

[觸變性的評估][Assessment of thixotropy]

將共聚物20質量份、二氫松油醇80質量份混合，一邊於60℃加熱一邊攪拌2小時得到完全溶解而成的溶液，利用流變儀在1s-1至1,000s-1的範圍測定了該溶液的黏度的剪切速度依賴性。算出了1s-1與1,000s-1時的黏度的比作為TI值。20 parts by mass of copolymer and 80 parts by mass of dihydroterpineol were mixed, and heated at 60 ° C with stirring for 2 hours to obtain a completely dissolved solution. The rheometer was used to measure from 1s-1 to 1,000s-1. The shear rate dependence of the viscosity of the solution is given. The ratio of the viscosity at 1s-1 to 1,000s-1 was calculated as the TI value.

[熱分解性的評估][Evaluation of Thermal Decomposability]

將共聚物5mg加入鋁鍋中，利用TG/DTA在空氣氛圍下以升溫速度10℃/分鐘升溫至500℃，並測定了樣品的殘存量。5 mg of the copolymer was added to an aluminum pan, and the temperature was increased to 500 ° C. at a heating rate of 10 ° C./min by using TG / DTA in an air atmosphere, and the remaining amount of the sample was measured.

[密著性的評估][Assessment of adhesion]

相對於鈦酸鋇粉末（Sakai Chemical Industry Co.,Ltd.製造：BT-03）100質量份，將高分子多元羧酸類分散劑（NOF CORPORATION製造：MALIALIM AKM-0531）0.8質量份、甲苯18質量份、乙醇18質量份、粒徑1mm的氧化鋯球100質量份加入球磨機中，混合8小時後，加入聚乙烯醇縮丁醛（SEKISUI CHEMICAL CO.,LTD.製造：S-LEC. BM-2）8質量份、甲苯10質量份、乙醇10質量份，進一步混合12小時後，將氧化鋯球過濾，製備了陶瓷漿料。然後，利用刮刀法將陶瓷漿料在作為載體片材的PET膜上塗布成厚度為5μm的片狀後，使其於90℃乾燥10分鐘，製作了生片。Based on 100 parts by mass of barium titanate powder (manufactured by Sakai Chemical Industry Co., Ltd .: BT-03), 0.8 parts by mass of polymer polycarboxylic acid dispersant (manufactured by NOF CORPORATION: MALIALIM AKM-0531) and 18 parts by mass of toluene Parts, 18 parts by mass of ethanol, and 100 parts by mass of zirconia balls with a particle diameter of 1 mm were added to a ball mill, and after 8 hours of mixing, polyvinyl butyral (SEKISUI CHEMICAL CO., LTD. Made: S-LEC. BM-2 ) 8 parts by mass, 10 parts by mass of toluene, and 10 parts by mass of ethanol. After further mixing for 12 hours, the zirconia balls were filtered to prepare a ceramic slurry. Then, a ceramic slurry was applied on a PET film as a carrier sheet into a sheet shape having a thickness of 5 μm by a doctor blade method, and then dried at 90 ° C. for 10 minutes to produce a green sheet.

相對於Ni粉（JFE MINERAL Co., LTD.製造：NFP201S）100質量份，加入油醯肌氨酸（NOF CORPORATION製造：ESLEAM 221P）1質量份、黏結劑樹脂3質量份、二氫松油醇90質量份。使用行星式混煉機對這些混合物進行攪拌後，利用三輥研磨機進行混煉得到了Ni膏。利用絲網印刷將得到的Ni膏印刷在所製作的生片上，並於90℃乾燥10分鐘後，進一步在其上疊加生片，在50℃、100kg/cm2、5秒鐘的條件下使其壓接。利用拉伸試驗機將壓接的片材剝離，測定了剝離所需的力。Based on 100 parts by mass of Ni powder (manufactured by JFE MINERAL Co., LTD .: NFP201S), 1 part by mass of oleosine sarcosine (NOF CORPORATION: ESLEAM 221P), 3 parts by mass of binder resin, and dihydroterpineol are added. 90 parts by mass. These mixtures were stirred with a planetary mixer, and then kneaded with a three-roll mill to obtain a Ni paste. The obtained Ni paste was printed on the produced green sheet by screen printing, and dried at 90 ° C for 10 minutes, and then the green sheet was further superimposed thereon, and it was allowed to stand at 50 ° C, 100 kg / cm2, and 5 seconds Crimp. The pressure-bonded sheet was peeled using a tensile tester, and the force required for peeling was measured.

[表6] [TABLE 6]

[表7] [TABLE 7]

[表8] [TABLE 8]

實施例1～11中，觸變值變高，此外，加熱殘留成分少，且對片材的接著性變高。In Examples 1 to 11, the thixotropic value was increased, and the heating residual component was small, and the adhesiveness to the sheet was increased.

比較例1中，單體（A）的比率小於10莫耳%，加熱殘留成分變少，但觸變值變低。In Comparative Example 1, the ratio of the monomer (A) was less than 10 mol%, and the heating residual component was reduced, but the thixotropic value was reduced.

比較例2中，使用不含有本發明的單體的共聚物，加熱殘留成分變少，但觸變值變低。In Comparative Example 2, a copolymer not containing the monomer of the present invention was used, and the residual amount of heating was reduced, but the thixotropic value was reduced.

比較例3中，使用乙基纖維素，觸變值大，但加熱殘留成分多、接著性變低。In Comparative Example 3, although ethyl cellulose was used, the thixotropic value was large, but there were many heating residual components and the adhesiveness was low.

第三發明的實施例Embodiment of the third invention

將單體（A）的結構與縮寫符號示於下述的表9中。 [表9] 式（1）表示的單體（A）的結構 ・・・（1）The structure and abbreviation of the monomer (A) are shown in Table 9 below. [Table 9] Structure of monomer (A) represented by formula (1) ···(1)

（合成例1：單體A1）(Synthesis Example 1: Monomer A1)

向安裝有攪拌機、溫度計、冷卻器、滴液漏斗及空氣導入管的300mL燒瓶中添加了2-甲基丙烯醯氧乙基異氰酸酯（SHOWA DENKO K.K.製造“Karenz MOI”）51.2g、四氫呋喃40g、對甲氧基苯酚0.012g。向燒瓶內導入空氣，將內溫保持為40℃，同時經1小時滴下了正丁胺24.1g。然後，使其於40℃熟化2小時後，於60℃減壓餾去四氫呋喃，得到了單體A1（收率92%）。A 300 mL flask equipped with a stirrer, a thermometer, a cooler, a dropping funnel and an air introduction tube was charged with 51.2 g of 2-methacryloxyethyl isocyanate ("Karenz MOI" manufactured by SHOWA DENKO KK), 40 g of tetrahydrofuran, and 0.012 g of methoxyphenol. Air was introduced into the flask, and 24.1 g of n-butylamine was dropped over 1 hour while keeping the internal temperature at 40 ° C. Then, after aging at 40 ° C for 2 hours, tetrahydrofuran was distilled off under reduced pressure at 60 ° C to obtain monomer A1 (yield 92%).

（合成例2：單體A2）(Synthesis Example 2: Monomer A2)

向安裝有攪拌機、溫度計、冷卻器、滴液漏斗及空氣導入管的300mL燒瓶中添加了2-甲基丙烯醯氧乙基異氰酸酯（SHOWA DENKO K.K.製造“Karenz MOI”）51.2g、對甲氧基苯酚0.012g、二月桂酸二丁基錫0.034g。向燒瓶內導入空氣，將內溫保持為60℃，同時經1小時滴下了正丁醇。然後，升溫至80℃，並使其熟化6小時後，於60℃減壓餾去四氫呋喃，得到了單體A2（收率95%）。To a 300 mL flask equipped with a stirrer, thermometer, cooler, dropping funnel, and air introduction tube was added 51.2 g of 2-methacryloxyethyl isocyanate ("Karenz MOI" manufactured by SHOWA DENKO KK) and p-methoxy 0.012 g of phenol and 0.034 g of dibutyltin dilaurate. Air was introduced into the flask, and the internal temperature was maintained at 60 ° C. At the same time, n-butanol was dropped over 1 hour. Then, the temperature was raised to 80 ° C, and the mixture was aged for 6 hours. Then, tetrahydrofuran was distilled off under reduced pressure at 60 ° C to obtain a monomer A2 (yield: 95%).

（合成例3：單體A3）(Synthesis Example 3: Monomer A3)

向安裝有攪拌機、溫度計、冷卻器、滴液漏斗及空氣導入管的300mL燒瓶中添加了甲基丙烯酸2-羥基乙酯（NOF CORPORATION製造“Blemmer E”）、對甲氧基苯酚0.012g。向燒瓶內導入空氣，將內溫保持為60℃，同時經1小時滴下了異氰酸正丁酯。然後，升溫至80℃，並使其熟化6小時後，冷卻至40℃後加入離子交換水100mL，進行攪拌、靜置。提出下層的單體A3層，於80℃進行減壓並脫水，得到了單體A3（收率70%）。A 300 mL flask equipped with a stirrer, a thermometer, a cooler, a dropping funnel, and an air introduction tube was charged with 2-hydroxyethyl methacrylate ("Blemmer E" manufactured by NOF CORPORATION) and 0.012 g of p-methoxyphenol. Air was introduced into the flask, and the n-butyl isocyanate was dropped over 1 hour while maintaining the inner temperature at 60 ° C. Then, the temperature was raised to 80 ° C, and the mixture was aged for 6 hours. After cooling to 40 ° C, 100 mL of ion-exchanged water was added, and the mixture was stirred and left to stand. The monomer A3 layer of the lower layer was put out, and decompressed and dehydrated at 80 ° C to obtain monomer A3 (yield 70%).

（合成例4：單體A4）(Synthesis Example 4: Monomer A4)

向安裝有攪拌機、溫度計、冷卻器、滴液漏斗及空氣導入管的300mL燒瓶中添加了2-丙烯醯氧基乙基異氰酸酯（SHOWA DENKO K.K.製造“Karenz AOI”）46.6g、四氫呋喃40g、對甲氧基苯酚0.012g。向燒瓶內導入空氣，將內溫保持為40℃，同時經1小時滴下了正丁胺24.1g。然後，使其於40℃熟化2小時後，於60℃減壓餾去四氫呋喃，得到了單體A4（收率90%）。To a 300 mL flask equipped with a stirrer, thermometer, cooler, dropping funnel, and air introduction tube were added 46.6 g of 2-propenyloxyethyl isocyanate ("Karenz AOI" manufactured by SHOWA DENKO KK), 40 g of tetrahydrofuran, p-formyl 0.012 g of oxyphenol. Air was introduced into the flask, and 24.1 g of n-butylamine was dropped over 1 hour while keeping the internal temperature at 40 ° C. Then, after aging at 40 ° C for 2 hours, tetrahydrofuran was distilled off under reduced pressure at 60 ° C to obtain monomer A4 (yield 90%).

（合成例5：單體A5）(Synthesis Example 5: Monomer A5)

向安裝有攪拌機、溫度計、冷卻器、滴液漏斗及空氣導入管的300mL燒瓶中添加了2-丙烯醯氧基乙基異氰酸酯（SHOWA DENKO K.K.製造“Karenz AOI”）46.6g、四氫呋喃40g、對甲氧基苯酚0.012g。向燒瓶內導入空氣，將內溫保持為40℃，同時經1小時滴下了正十二胺61.1g。然後，使其於40℃熟化2小時後，於60℃減壓餾去四氫呋喃，得到了單體A5（收率90%）。To a 300 mL flask equipped with a stirrer, thermometer, cooler, dropping funnel, and air introduction tube were added 46.6 g of 2-propenyloxyethyl isocyanate ("Karenz AOI" manufactured by SHOWA DENKO KK), 40 g of tetrahydrofuran, p-formyl 0.012 g of oxyphenol. Air was introduced into the flask, and while maintaining the internal temperature at 40 ° C., 61.1 g of n-dodecylamine was dropped over 1 hour. Then, after aging at 40 ° C for 2 hours, tetrahydrofuran was distilled off under reduced pressure at 60 ° C to obtain monomer A5 (yield 90%).

（聚合例1：共聚物A）(Polymerization Example 1: Copolymer A)

向安裝有攪拌機、溫度計、冷卻器、滴液漏斗及氮氣導入管的1L可分離式燒瓶中添加異丙醇250g，對燒瓶內進行氮氣置換，使其處在氮氣氛圍下。分別製備了將212.1g的甲基丙烯酸異丁酯（iBMA：產品名稱：Acryester IB（MITSUBISHI RAYON CO., LTD.製造））、19.9g的甲基丙烯酸甲酯（MMA：產品名稱：Acryester M（MITSUBISHI RAYON CO., LTD.製造）與68.0g的單體A1混合而成的單體溶液、及將異丙醇50g與2,2’-偶氮雙（2,4-二甲基戊腈）（產品名稱：V-65（Wako Pure Chemical Industries, Ltd.製造））0.3g混合而成的聚合引發劑溶液。To a 1-liter separable flask equipped with a stirrer, a thermometer, a cooler, a dropping funnel, and a nitrogen introduction tube, 250 g of isopropyl alcohol was added, and the inside of the flask was replaced with nitrogen to be placed under a nitrogen atmosphere. 212.1 g of isobutyl methacrylate (iBMA: product name: Acryester IB (manufactured by MITSUBISHI RAYON CO., LTD.)) And 19.9 g of methyl methacrylate (MMA: product name: Acryester M ( Monomer solution made by MITSUBISHI RAYON CO., LTD.) And 68.0 g of monomer A1, and 50 g of isopropanol and 2,2'-azobis (2,4-dimethylvaleronitrile) (Product name: V-65 (manufactured by Wako Pure Chemical Industries, Ltd.)) 0.3 g of a polymerization initiator solution.

將反應容器內升溫至75℃，同時經3小時分別滴下了單體溶液及聚合引發劑溶液。然後，使其於75℃反應3小時得到了共聚物A的異丙醇溶液。接著，在60℃減壓下經180分鐘進行脫溶劑，得到了共聚物A。While the temperature in the reaction vessel was raised to 75 ° C., the monomer solution and the polymerization initiator solution were dropped respectively over 3 hours. Then, it was made to react at 75 degreeC for 3 hours, and the isopropyl alcohol solution of the copolymer A was obtained. Then, the solvent was removed under reduced pressure at 60 ° C for 180 minutes to obtain a copolymer A.

（聚合例2：共聚物B）(Polymerization Example 2: Copolymer B)

除了將甲基丙烯酸異丁酯的使用量變更為156.3g、將甲基丙烯酸甲酯的使用量變更為18.3g、將單體A1的使用量變更為125.3g以外，利用與聚合例1相同的手法得到了共聚物B。Except that the used amount of isobutyl methacrylate was changed to 156.3 g, the used amount of methyl methacrylate was changed to 18.3 g, and the used amount of monomer A1 was changed to 125.3 g, the same use as in Polymerization Example 1 Copolymer B was obtained by a method.

（聚合例3：共聚物C）(Polymerization Example 3: Copolymer C)

除了將甲基丙烯酸異丁酯的使用量變更為94.3g、將甲基丙烯酸甲酯的使用量變更為16.6g、將單體A1的使用量變更為189.1g以外，利用與聚合例1相同的手法得到了共聚物C。Except that the used amount of isobutyl methacrylate was changed to 94.3 g, the used amount of methyl methacrylate was changed to 16.6 g, and the used amount of monomer A1 was changed to 189.1 g, the same use as in Polymerization Example 1 was used. Copolymer C was obtained by a method.

（聚合例4：共聚物D）(Polymerization Example 4: Copolymer D)

除了將甲基丙烯酸異丁酯的使用量變更為155.8g、將甲基丙烯酸甲酯的使用量變更為18.3g、將單體A1變更為單體A2並使用了126.0g以外，利用與聚合例1相同的手法得到了共聚物D。Except changing the use amount of isobutyl methacrylate to 155.8 g, changing the use amount of methyl methacrylate to 18.3 g, changing monomer A1 to monomer A2, and using 126.0 g, examples of use and polymerization Copolymer D was obtained in the same manner as in 1.

（聚合例5：共聚物E）(Polymerization Example 5: Copolymer E)

除了將單體A2變更為單體A3以外，利用與聚合例4相同的手法得到了共聚物E。A copolymer E was obtained in the same manner as in Polymerization Example 4 except that the monomer A2 was changed to the monomer A3.

（聚合例6：共聚物F）(Polymerization Example 6: Copolymer F)

除了將甲基丙烯酸異丁酯的使用量變更為160.4g、將甲基丙烯酸甲酯的使用量變更為18.8g、將單體A1變更為單體A4並使用了120.8g以外，利用與聚合例1相同的手法得到了共聚物F。Except changing the use amount of isobutyl methacrylate to 160.4 g, changing the use amount of methyl methacrylate to 18.8 g, changing monomer A1 to monomer A4, and using 120.8 g, examples of use and polymerization Copolymer F was obtained in the same manner as in 1.

（聚合例7：共聚物G）(Polymerization Example 7: Copolymer G)

除了將甲基丙烯酸異丁酯的使用量變更為132.4g、將甲基丙烯酸甲酯的使用量變更為15.5g、將單體A1變更為單體A5並使用了152.0g以外，利用與聚合例1相同的手法得到了共聚物G。Except changing the use amount of isobutyl methacrylate to 132.4 g, changing the use amount of methyl methacrylate to 15.5 g, changing monomer A1 to monomer A5, and using 152.0 g, examples of use and polymerization Copolymer G was obtained in the same manner as in 1.

（聚合例8：共聚物H）(Polymerization Example 8: Copolymer H)

除了將甲基丙烯酸異丁酯的使用量變更為133.7g、將甲基丙烯酸甲酯的使用量變更為37.7g、將單體A1的使用量變更為128.6g以外，利用與聚合例1相同的手法得到了共聚物H。Except that the use amount of isobutyl methacrylate was changed to 133.7 g, the use amount of methyl methacrylate was changed to 37.7 g, and the use amount of the monomer A1 was changed to 128.6 g, the same use was made as in Polymerization Example 1. Copolymer H was obtained by a method.

（聚合例9：共聚物I）(Polymerization Example 9: Copolymer I)

除了將甲基丙烯酸異丁酯的使用量變更為109.3g、將甲基丙烯酸甲酯的使用量變更為19.2g、將單體A1的使用量變更為131.4g、並使用了40.0g的苯乙烯以外，利用與聚合例1相同的手法得到了共聚物I。In addition to changing the amount of isobutyl methacrylate to 109.3 g, the amount of methyl methacrylate to 19.2 g, the amount of monomer A1 to 131.4 g, and 40.0 g of styrene Other than that, copolymer I was obtained in the same manner as in Polymerization Example 1.

（聚合例10：共聚物J）(Polymerization Example 10: Copolymer J)

除了將甲基丙烯酸異丁酯的使用量變更為137.8g、將甲基丙烯酸甲酯的使用量變更為19.4g、將單體A1的使用量變更為132.5g、並使用了10.3g的丙烯腈以外，利用與聚合例1相同的手法得到了共聚物J。In addition to changing the use amount of isobutyl methacrylate to 137.8 g, changing the use amount of methyl methacrylate to 19.4 g, changing the use amount of monomer A1 to 132.5 g, and using 10.3 g of acrylonitrile Other than that, copolymer J was obtained in the same manner as in Polymerization Example 1.

（聚合例11：共聚物K）(Polymerization Example 11: Copolymer K)

除了將甲基丙烯酸異丁酯的使用量變更為136.2g、將甲基丙烯酸甲酯的使用量變更為19.2g、將單體A1的使用量變更為131.0g、並使用了13.6g的丙烯醯胺以外，利用與聚合例1相同的手法得到了共聚物K。In addition to changing the amount of isobutyl methacrylate to 136.2 g, the amount of methyl methacrylate to 19.2 g, the amount of monomer A1 to 131.0 g, and 13.6 g of propylene used Copolymer K was obtained in the same manner as in Polymerization Example 1 except for the amine.

（聚合例12：共聚物L）(Polymerization Example 12: Copolymer L)

除了將甲基丙烯酸異丁酯的使用量變更為276.6g、將單體A1的使用量變更為23.4g以外，利用與聚合例1相同的手法得到了共聚物L。Copolymer L was obtained in the same manner as in Polymerization Example 1 except that the amount of isobutyl methacrylate was changed to 276.6 g and the amount of monomer A1 was changed to 23.4 g.

（聚合例13：共聚物M）(Polymerization Example 13: Copolymer M)

除了將甲基丙烯酸異丁酯的使用量設為215.5g、使用了84.5g的甲基丙烯酸2-羥基乙酯（HEMA）代替單體A1以外，利用與聚合例1相同的手法得到了共聚物M。A copolymer was obtained in the same manner as in Polymerization Example 1 except that the amount of isobutyl methacrylate was 215.5 g and 84.5 g of 2-hydroxyethyl methacrylate (HEMA) was used instead of the monomer A1. M.

[重量平均分子量的測定][Measurement of weight average molecular weight]

使用凝膠層析儀（GPC）並利用以下的條件求出了共聚物A～M的重量平均分子量。The weight average molecular weights of the copolymers A to M were determined using a gel chromatography (GPC) under the following conditions.

裝置：Tosoh Corporation製造、HLC-8220Device: manufactured by Tosoh Corporation, HLC-8220

層析柱：shodex公司製造、LF-804Chromatographic column: manufactured by Shodex, LF-804

標準物質：聚苯乙烯Standard substance: polystyrene

洗脫液：THF（四氫呋喃）Eluent: THF (tetrahydrofuran)

流量：1.0ml/minFlow: 1.0ml / min

層析柱溫度：40℃Column temperature: 40 ° C

檢測器：RI（示差折射率檢測器）Detector: RI (differential refractive index detector)

[樹脂強度的評估][Evaluation of resin strength]

使黏結劑樹脂30質量份溶解於甲苯35質量份、乙醇35質量份的混合溶劑中從而得到溶液，利用刮棒塗布機No.32將得到的溶液塗布於PET膜上，於100℃乾燥1小時後，使其剝離，得到了厚度為30μm的樹脂片。將得到的樹脂片裁切成1cm×5cm的大小，利用拉伸試驗機以10mm/min的拉伸速度測定樹脂強度，並使用了五次測定的平均值。30 parts by mass of the binder resin was dissolved in a mixed solvent of 35 parts by mass of toluene and 35 parts by mass of ethanol to obtain a solution. The obtained solution was applied to a PET film using a bar coater No. 32, and dried at 100 ° C for 1 hour. Then, it peeled, and the resin sheet with a thickness of 30 micrometers was obtained. The obtained resin sheet was cut into a size of 1 cm × 5 cm, and the resin strength was measured at a tensile speed of 10 mm / min using a tensile tester, and an average of five measurements was used.

[片材強度的評估][Evaluation of sheet strength]

相對於鈦酸鋇顆粒（Sakai Chemical Industry Co.,Ltd.製造：BT-03）100質量份，將高分子多元羧酸類分散劑（NOF CORPORATION製造：MALIALIM AKM-0531）0.8質量份、甲苯18質量份、乙醇18質量份、粒徑1mm的氧化鋯球100質量份加入球磨機中，混合8小時後，加入黏結劑樹脂8質量份、甲苯10質量份、乙醇10質量份，進一步混合12小時後，將氧化鋯球過濾，製備了陶瓷漿料。然後，利用刮刀法將陶瓷漿料在作為載體片材的PET膜上塗布成厚度為20μm的片狀後，使其於90℃乾燥10分鐘，製作了生片。利用拉伸試驗機以10mm/min的拉伸速度測定製作的生片的強度，並使用了五次測定的平均值。Based on 100 parts by mass of barium titanate particles (manufactured by Sakai Chemical Industry Co., Ltd .: BT-03), 0.8 parts by mass of polymer polycarboxylic acid dispersant (manufactured by NOF CORPORATION: MALIALIM AKM-0531) and 18 parts by mass of toluene Parts, 18 parts by mass of ethanol, and 100 parts by mass of zirconia balls with a particle diameter of 1 mm were added to a ball mill, and after mixing for 8 hours, 8 parts by mass of a binder resin, 10 parts by mass of toluene, and 10 parts by mass of ethanol were added. The zirconia balls were filtered to prepare a ceramic slurry. Then, a ceramic slurry was applied on a PET film as a carrier sheet into a sheet shape having a thickness of 20 μm by a doctor blade method, and then dried at 90 ° C. for 10 minutes to produce a green sheet. The strength of the green sheet produced was measured with a tensile tester at a tensile speed of 10 mm / min, and an average of five measurements was used.

[熱分解性的評估][Evaluation of Thermal Decomposability]

將共聚物5mg加入鋁鍋中，利用TG/DTA在空氣氛圍下以升溫速度10℃/分鐘升溫至500℃，並測定了樣品的殘存量。5 mg of the copolymer was added to an aluminum pan, and the temperature was increased to 500 ° C. at a heating rate of 10 ° C./min by using TG / DTA in an air atmosphere, and the remaining amount of the sample was measured.

[表10] [TABLE 10]

[表11] [TABLE 11]

[表12] [TABLE 12]

PVB：聚乙烯醇縮丁醛樹脂“S-LEC. BL-2H”(SEKISUI CHEMICAL CO.,LTD .製造)PVB: polyvinyl butyral resin "S-LEC. BL-2H" (manufactured by SEKISUI CHEMICAL CO., LTD.)

實施例1～11中，陶瓷生片的片材強度變高，此外，加熱殘留成分變少。In Examples 1 to 11, the sheet strength of the ceramic green sheet was increased, and the heating residual component was reduced.

比較例1中，單體A1的比率小於10莫耳%，加熱殘留成分變少，但片材強度變低。In Comparative Example 1, the ratio of the monomer A1 was less than 10 mol%, and the heating residual component was reduced, but the sheet strength was reduced.

比較例2中，使用了不含有本發明的單體（A）的共聚物，加熱殘留成分變少，但片材強度變低。In Comparative Example 2, a copolymer that did not contain the monomer (A) of the present invention was used, and the heating residual component was reduced, but the sheet strength was reduced.

比較例3中，使用聚乙烯醇縮丁醛樹脂，片材強度高，但加熱殘留成分變多。In Comparative Example 3, a polyvinyl butyral resin was used, and the sheet strength was high, but the heating residual component was increased.

Claims (11)

一種黏結劑樹脂，其由下述通式（1）表示的單體（A）的莫耳比為10莫耳%～100莫耳%、可與該單體（A）共聚的其他單體（B）的莫耳比為0～90莫耳%、重量平均分子量為10,000～1,000,000的聚合物構成，・・・（1） 通式（1）中， R1 表示氫原子或甲基， R2 表示氫原子、甲基或乙基， R3 表示碳原子數為1～18的烷基， X及Y各自獨立地表示NH或O。A binder resin having a molar ratio of a monomer (A) represented by the following general formula (1) of 10 mol% to 100 mol% and other monomers (copolymerizable with the monomer (A)) ( B) a polymer having a molar ratio of 0 to 90 mol% and a weight average molecular weight of 10,000 to 1,000,000, (1) In the general formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 represents a hydrogen atom, a methyl group, or an ethyl group, R 3 represents an alkyl group having 1 to 18 carbon atoms, X and Y each independently represents NH or O. 一種導電膏組合物，其含有如申請專利範圍第1項所述的黏結劑樹脂、有機溶劑及金屬顆粒。A conductive paste composition includes the binder resin, the organic solvent, and the metal particles according to item 1 of the scope of patent application. 如申請專利範圍第2項所述的導電膏組合物，其中相對於該金屬顆粒100重量份，含有0.5～30重量份的該黏結劑樹脂，10～200重量份的該有機溶劑。The conductive paste composition according to item 2 of the scope of patent application, which contains 0.5 to 30 parts by weight of the binder resin and 10 to 200 parts by weight of the organic solvent with respect to 100 parts by weight of the metal particles. 一種導電膏用黏結劑樹脂，其由下述通式（1）表示的單體（A）的莫耳比為10莫耳%～90莫耳%、下述通式（2）表示的（甲基）丙烯酸烷基酯（D）的莫耳比為10～90莫耳%、可與該單體（A）及該（甲基）丙烯酸烷基酯（D）共聚的其他單體的莫耳比為0～30莫耳%、重量平均分子量為10,000～1,000,000的聚合物構成，・・・（1） 通式（1）中， R1 表示氫原子或甲基， R2 表示氫原子、甲基或乙基， R3 表示碳原子數為1～18的烷基， X及Y各自獨立地表示NH或O；・・・（2） 通式（2）中， R4 表示氫原子或甲基， R5 表示碳原子數為1～18的烷基。A binder resin for conductive paste, wherein the molar ratio of the monomer (A) represented by the following general formula (1) is 10 mol% to 90 mol%, and (A Mole ratio of the alkyl acrylate (D) is 10 to 90 mol%, and the mol of other monomers copolymerizable with the monomer (A) and the (meth) acrylic acid alkyl ester (D) A polymer having a ratio of 0 to 30 mol% and a weight average molecular weight of 10,000 to 1,000,000, (1) In the general formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 represents a hydrogen atom, a methyl group, or an ethyl group, R 3 represents an alkyl group having 1 to 18 carbon atoms, X and Y each independently represents NH or O; (2) In the general formula (2), R 4 represents a hydrogen atom or a methyl group, and R 5 represents an alkyl group having 1 to 18 carbon atoms. 如申請專利範圍第4項所述的導電膏用黏結劑樹脂，其中該其他單體為丙烯腈或烷基丙烯醯胺。The adhesive resin for conductive paste according to item 4 of the patent application scope, wherein the other monomer is acrylonitrile or alkyl acrylamide. 一種導電膏組合物，其含有如申請專利範圍第4項或第5項所述的黏結劑樹脂、有機溶劑及金屬顆粒。A conductive paste composition containing the binder resin, the organic solvent, and the metal particles according to item 4 or item 5 of the scope of patent application. 如申請專利範圍第6項所述的導電膏組合物，其中相對於該金屬顆粒100質量份，該黏結劑樹脂的質量比為0.5～30質量份，該有機溶劑的質量比為10～200質量份。The conductive paste composition according to item 6 of the scope of patent application, wherein the mass ratio of the binder resin is 0.5 to 30 parts by mass and the mass ratio of the organic solvent is 10 to 200 parts by mass relative to 100 parts by mass of the metal particles. Serving. 一種陶瓷用黏結劑樹脂，其由下述通式（1）表示的單體（A）的莫耳比為10莫耳%～100莫耳%、可與該單體（A）共聚的其他單體（E）的莫耳比為0～90莫耳%、重量平均分子量為10,000～1,000,000的聚合物構成，・・・（1） 通式（1）中， R1 表示氫原子或甲基， R2 表示氫原子、甲基或乙基， R3 表示碳原子數為1～18的烷基， X及Y各自獨立地表示NH或O。A binder resin for ceramics, in which the molar ratio of the monomer (A) represented by the following general formula (1) is 10 mol% to 100 mol%, and other monomers copolymerizable with the monomer (A) The polymer (E) has a molar ratio of 0 to 90 mol% and a weight average molecular weight of 10,000 to 1,000,000. (1) In the general formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 represents a hydrogen atom, a methyl group, or an ethyl group, R 3 represents an alkyl group having 1 to 18 carbon atoms, X and Y each independently represents NH or O. 一種陶瓷組合物，其含有如申請專利範圍第8項所述的黏結劑樹脂、有機溶劑及陶瓷顆粒。A ceramic composition includes the binder resin, the organic solvent, and the ceramic particles according to item 8 of the patent application scope. 如申請專利範圍第9項所述的陶瓷組合物，其中相對於該陶瓷顆粒100質量份，含有0.5～30質量份的該黏結劑樹脂以及10～200質量份的該有機溶劑。The ceramic composition according to item 9 of the scope of the patent application, wherein it contains 0.5 to 30 parts by mass of the binder resin and 10 to 200 parts by mass of the organic solvent with respect to 100 parts by mass of the ceramic particles. 一種陶瓷成型體，其由如申請專利範圍第9項或第10項所述的陶瓷組合物形成。A ceramic molded body is formed from the ceramic composition as described in item 9 or 10 of the scope of patent application.
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