TW202128834A - Curable composition - Google Patents

Abstract

Provided is a curable composition with which it is possible to form a flexible and heat-resistant cured article. This curable composition contains a curable compound and a silicate. The silicate is preferably a flaky silicate or a lipophilic silicate. The curable compound is preferably a compound represented by formula (1). In the formula, R1 and R2 each indicate a curable functional group, and D1 and D2 each indicate a single bond or a linking group. L indicates a divalent group including the structures represented by formulas (I) and (II). Ar1 to Ar3 each indicate an arylene group, or a group in which two or more arylene groups are bonded by a single bond or a linking group. X indicates -CO-, -S-, or -SO2-, and Y may be the same as or different from each other and indicate -S-, -SO2-, -O-, -CO-, -COO-, or -CONH-.

Description

硬化性組成物Hardening composition

本發明係關於ー種硬化性組成物及其硬化物或半硬化物。本申請案主張於2019年12月19日在日本提出申請之特願2019-229223號之優先權，將其內容引用至此。The present invention relates to a curable composition and its cured or semi-cured product. This application claims the priority of Japanese Patent Application No. 2019-229223, which was filed in Japan on December 19, 2019, and the content is quoted here.

工程塑膠係提昇了耐熱性或機械特性之塑膠，重點用作各種零件之小型化、輕量化、高性能化、及高可靠性化所需之材料。但是，工程塑膠存在因熔融溫度較高、溶劑溶解性較低導致缺乏加工性之問題。Engineering plastics are plastics with improved heat resistance or mechanical properties. They are mainly used as materials for miniaturization, light weight, high performance, and high reliability of various parts. However, engineering plastics have the problem of lack of processability due to high melting temperature and low solvent solubility.

例如，專利文獻1等中所記載之聚醯亞胺雖具有卓越之耐熱性與強度特性，但由於難溶解性且難熔解性，而導致難以進行熔融成形或用作複合材料之基質樹脂。For example, although the polyimide described in Patent Document 1 and the like has excellent heat resistance and strength properties, it is difficult to be melt-formed or used as a matrix resin for composite materials due to its poor solubility and solubility.

聚醚醚酮（PEEK）亦被稱作超級工程塑膠，其係連續使用溫度為260℃、且具有耐熱性、阻燃性、及電特性優異之性能之熱塑性樹脂，但因熔點為343℃，故尤其難以熔解，且亦難以溶解於溶劑中，因此存在加工性較差之問題（例如，專利文獻2）。Polyether ether ketone (PEEK) is also known as super engineering plastic. It is a thermoplastic resin with a continuous use temperature of 260°C and excellent heat resistance, flame retardancy, and electrical properties. However, because of its melting point of 343°C, Therefore, it is particularly difficult to dissolve, and it is also difficult to dissolve in a solvent, so there is a problem of poor processability (for example, Patent Document 2).

因此，要求一種加工性優異、且可形成具有耐熱性之硬化物之硬化性組成物。 先前技術文獻 專利文獻Therefore, there is a demand for a curable composition that is excellent in processability and can be formed into a heat-resistant hardened product. Prior art literature Patent literature

專利文獻1：日本特開2000-219741號公報 專利文獻2：日本特公昭60-32642號公報Patent Document 1: Japanese Patent Application Publication No. 2000-219741 Patent Document 2: Japanese Patent Publication No. 60-32642

[發明所欲解決之課題][The problem to be solved by the invention]

因此，本發明之目的在於提供一種可形成具有耐熱性及可撓性之硬化物之硬化性組成物。 本發明之另一目的在於提供一種可形成具有低CTE（低線膨脹係數）、耐熱性及可撓性之硬化物之硬化性組成物。 本發明之另一目的在於提供一種加工性優異、且可形成具有低CTE、耐熱性及可撓性之硬化物之硬化性組成物。 本發明之另一目的在於提供一種可形成具有耐熱性及可撓性之硬化物之半硬化物。 本發明之另一目的在於提供一種可形成具有低CTE、耐熱性及可撓性之硬化物之半硬化物。 本發明之另一目的在於提供一種具有耐熱性及可撓性之硬化物。 本發明之另一目的在於提供一種具有低CTE、耐熱性及可撓性之硬化物。 本發明之另一目的在於提供一種上述硬化物積層於基板而成之積層體。 本發明之另一目的在於提供一種具備上述積層體之電子裝置。 [解決課題之技術手段]Therefore, the object of the present invention is to provide a curable composition capable of forming a cured product having heat resistance and flexibility. Another object of the present invention is to provide a curable composition that can form a curable product with low CTE (low coefficient of linear expansion), heat resistance, and flexibility. Another object of the present invention is to provide a curable composition which is excellent in processability and can be formed into a cured product with low CTE, heat resistance and flexibility. Another object of the present invention is to provide a semi-hardened product that can form a hardened product having heat resistance and flexibility. Another object of the present invention is to provide a semi-hardened product that can form a hardened product with low CTE, heat resistance and flexibility. Another object of the present invention is to provide a hardened product with heat resistance and flexibility. Another object of the present invention is to provide a hardened product with low CTE, heat resistance and flexibility. Another object of the present invention is to provide a laminate in which the above-mentioned cured product is laminated on a substrate. Another object of the present invention is to provide an electronic device including the above-mentioned laminate. [Technical means to solve the problem]

本發明人等為了解決上述課題，進行了深入研究，結果發現於硬化性化合物中添加特定量之矽酸鹽而獲得之組成物可解決上述課題。本發明係基於該等見解而完成者。The inventors of the present invention conducted intensive studies to solve the above-mentioned problems, and as a result, found that a composition obtained by adding a specific amount of silicate to a curable compound can solve the above-mentioned problems. The present invention was completed based on these findings.

即，本發明提供一種包含硬化性化合物及矽酸鹽、且上述矽酸鹽之含量相對於硬化性化合物100重量份為0.01～95重量份之硬化性組成物。That is, the present invention provides a curable composition containing a curable compound and silicate, and the content of the silicate is 0.01 to 95 parts by weight relative to 100 parts by weight of the curable compound.

又，本發明提供一種矽酸鹽為薄片狀矽酸鹽之上述硬化性組成物。In addition, the present invention provides the above-mentioned curable composition in which the silicate is a flaky silicate.

又，本發明提供一種矽酸鹽兼具下述特性1、及特性2之上述硬化性組成物。 特性1：在設置於平面上之高度5.0 mm、直徑10 mm之粉體試樣用聚氯乙烯環中填充矽酸鹽，直至距聚氯乙烯環上部平面之高度成為5.0 mm為止，並以最大加壓7 MPa進行3分鐘加壓而使聚氯乙烯環表面變得平滑，於除壓後5分鐘於聚氯乙烯環之表面產生***。 特性2：在設置於平面上之高度5.0 mm、直徑10 mm之粉體試樣用聚氯乙烯環中填充矽酸鹽，直至距聚氯乙烯環上部平面之高度成為3.0 mm為止，並以最大加壓5 MPa進行3分鐘加壓而使聚氯乙烯環表面變得平滑，於除壓後5分鐘未於聚氯乙烯環之表面產生***。In addition, the present invention provides the above-mentioned curable composition of silicate having both the following characteristics 1 and 2. Feature 1: Fill the polyvinyl chloride ring for powder samples with a height of 5.0 mm and a diameter of 10 mm on a flat surface until the height from the upper surface of the polyvinyl chloride ring becomes 5.0 mm, and the maximum Press 7 MPa for 3 minutes to smooth the surface of the polyvinyl chloride ring, and bulge on the surface of the polyvinyl chloride ring 5 minutes after depressurization. Feature 2: Fill the polyvinyl chloride ring for a powder sample with a height of 5.0 mm and a diameter of 10 mm on a flat surface until the height from the upper surface of the polyvinyl chloride ring becomes 3.0 mm, and the maximum Press 5 MPa for 3 minutes to smooth the surface of the polyvinyl chloride ring, and no bulge on the surface of the polyvinyl chloride ring 5 minutes after depressurization.

又，本發明提供一種矽酸鹽之最大直徑L₁ 、與上述最大直徑L₁ 正交之直徑L₂ 、及厚度W滿足下述式（a）、（b）之上述硬化性組成物。 0.2L₁ ≦L₂ ≦L₁ （a） 0.001L₁ ≦W≦0.08L₁ （b）Further, the present invention provides a maximum diameter of one kind of silicate of L _1, L ₁ by the orthogonal diameter L _2, and the thickness of the maximum diameter W satisfies the following formula (a), (b) of the above-described curable composition. _{0.2L 1 ≦ L 2 ≦ L 1} (a) 0.001L 1 ≦ W ≦ 0.08L 1 (b)

又，本發明提供一種矽酸鹽為親油性矽酸鹽之上述硬化性組成物。In addition, the present invention provides the above-mentioned curable composition in which the silicate is a lipophilic silicate.

又，本發明提供一種矽酸鹽包含鹼金屬之上述硬化性組成物。Furthermore, the present invention provides the above-mentioned curable composition in which the silicate contains an alkali metal.

又，本發明提供一種矽酸鹽之鎂含量為10重量%以上之上述硬化性組成物。In addition, the present invention provides the above-mentioned curable composition in which the magnesium content of the silicate is 10% by weight or more.

又，本發明提供一種矽酸鹽為薄片狀矽酸鹽、且鈉含量未達3.0重量%之上述硬化性組成物。In addition, the present invention provides the above-mentioned curable composition in which the silicate is a flaky silicate and the sodium content is less than 3.0% by weight.

又，本發明提供一種矽酸鹽為薄片狀矽酸鹽、且鉀含量為1.0重量%以上之上述硬化性組成物。In addition, the present invention provides the above-mentioned curable composition in which the silicate is a flaky silicate and the potassium content is 1.0% by weight or more.

又，本發明提供一種矽酸鹽為薄片狀矽酸鹽、且鋁含量為0.5重量%以上之上述硬化性組成物。In addition, the present invention provides the above-mentioned curable composition in which the silicate is a flaky silicate and the aluminum content is 0.5% by weight or more.

又，本發明提供一種矽酸鹽包含氟原子之上述硬化性組成物。In addition, the present invention provides the above-mentioned curable composition in which silicate contains fluorine atoms.

又，本發明提供一種矽酸鹽為雲母之上述硬化性組成物。Furthermore, the present invention provides the above-mentioned curable composition in which the silicate is mica.

又，本發明提供一種硬化性化合物為下述式（1）所表示之化合物之上述硬化性組成物，

[式中，R¹ 、R² 相同或不同，表示硬化性官能基，D¹ 、D² 相同或不同，表示單鍵或連結基。L表示具有包含下述式（I）所表示之結構、及下述式（II）所表示之結構之重複單位的2價基；

（式中，Ar¹ ～Ar³ 相同或不同，表示伸芳基、或2個以上之伸芳基經由單鍵或者連結基鍵結而成之基，X表示-CO-、-S-、或-SO₂ -，Y相同或不同，表示-S-、-SO₂ -、-O-、-CO-、-COO-、或-CONH-，n表示0以上之整數）]。Furthermore, the present invention provides the above-mentioned curable composition in which the curable compound is a compound represented by the following formula (1),

[In the formula, R ¹ and R ^{2 are the} same or different and represent a curable functional group, and D ¹ and D ^{2 are the} same or different and represent a single bond or a linking group. L represents a divalent group having a repeating unit including the structure represented by the following formula (I) and the structure represented by the following formula (II);

(In the formula, Ar ¹ to Ar ^{3 are the} same or different, and represent an aryl extension group, or a group formed by two or more aryl extension groups bonded via a single bond or a linking group, and X represents -CO-, -S-, or -SO ₂ -, Y is the same or different, represents -S-, -SO ₂ -, -O-, -CO-, -COO-, or -CONH-, n represents an integer of 0 or more)].

又，本發明提供一種式（1）中之R¹ 、R² 相同或不同且為具有環狀醯亞胺結構之硬化性官能基的上述硬化性組成物。In addition, the present invention provides ^{the above-mentioned curable composition in which R 1} and R ² in formula (1) are the same or different and are curable functional groups having a cyclic imine structure.

又，本發明提供一種式（1）中之R¹ 、R² 相同或不同且為選自下述式（r-1）～（r-6）所表示之基中之基的上述硬化性組成物。

（式中，自氮原子延伸之鍵結鍵與D¹ 或D² 鍵結）In addition, the present invention provides a ^{curable composition in which R 1} and R ² in formula (1) are the same or different and are selected from the groups represented by the following formulas (r-1) to (r-6) Things.

(In the formula, the bonding bond extending from the nitrogen atom is bonded to D ¹ or D ² )

又，本發明提供一種上述硬化性組成物之硬化物。In addition, the present invention provides a cured product of the above-mentioned curable composition.

又，本發明提供一種上述硬化性組成物之半硬化物。In addition, the present invention provides a semi-cured product of the above-mentioned curable composition.

又，本發明提供一種具有上述硬化物積層於基板之構成之積層體。In addition, the present invention provides a laminate having a structure in which the above-mentioned cured product is laminated on a substrate.

又，本發明提供一種基板為銅基板之上述積層體。In addition, the present invention provides the above-mentioned laminate in which the substrate is a copper substrate.

又，本發明提供一種電子裝置，其具有印刷基板，該印刷基板係於由上述硬化性組成物之硬化物所構成之基板上實施導體配線而成者。 [發明之效果]In addition, the present invention provides an electronic device having a printed circuit board formed by performing conductor wiring on a substrate formed of a cured product of the above-mentioned curable composition. [Effects of Invention]

本發明之硬化性組成物藉由加熱可獲得具有耐熱性及可撓性之硬化物。又，上述硬化物較佳為低CTE，且具有與銅同等程度之熱線膨脹係數。因此，對於上述硬化物積層於銅基板上而成之積層體而言，即便暴露於高溫環境下，亦可防止由於硬化物發生收縮而造成積層體捲曲之事態之發生。 因此，上述硬化性組成物例如可適宜地用作實施銅配線之電子線路基板之原料。The curable composition of the present invention can be heated to obtain a cured product having heat resistance and flexibility. In addition, the above-mentioned hardened product preferably has a low CTE and has a thermal linear expansion coefficient equivalent to that of copper. Therefore, even if the laminate formed by laminating the cured product on the copper substrate is exposed to a high-temperature environment, it is possible to prevent the laminate from curling due to shrinkage of the cured product. Therefore, the said curable composition can be suitably used as a raw material of the electronic circuit board which implements copper wiring, for example.

[硬化性組成物] 本發明之硬化性組成物係包含硬化性化合物及矽酸鹽者。[Curable composition] The curable composition of the present invention contains a curable compound and silicate.

（硬化性化合物） 上述硬化性化合物係藉由實施加熱處理而能夠形成硬化物之化合物。作為上述硬化性化合物，就熔融溫度較低、且因溶劑溶解性優異使得使用性變得優異、硬化物具有超耐熱性之方面而言，較佳為下述式（1）所表示之化合物。

(Curing compound) The above-mentioned curing compound is a compound capable of forming a cured product by performing heat treatment. As the above-mentioned curable compound, a compound represented by the following formula (1) is preferred in terms of low melting temperature, excellent solvent solubility, excellent usability, and super heat resistance of the cured product.

式（1）中，R¹ 、R² 相同或不同，表示硬化性官能基，D¹ 、D² 相同或不同，表示單鍵或連結基。L表示具有包含下述式（I）所表示之結構、及下述式（II）所表示之結構之重複單位的2價基。

（式中，Ar¹ ～Ar³ 相同或不同，表示伸芳基、或2個以上之伸芳基經由單鍵或者連結基鍵結而成之基；X表示-CO-、-S-、或-SO² -，Y相同或不同，表示-S-、-SO₂ -、-O-、-CO-、-COO-、或-CONH-；n表示0以上之整數）In the formula (1), R ¹ and R ^{2 are the} same or different and represent a curable functional group, and D ¹ and D ^{2 are the} same or different and represent a single bond or a linking group. L represents a divalent group having a repeating unit including the structure represented by the following formula (I) and the structure represented by the following formula (II).

(In the formula, Ar ¹ to Ar ^{3 are the} same or different, and represent an aryl extension group, or a group in which two or more aryl extension groups are bonded via a single bond or a linking group; X represents -CO-, -S-, or -SO ² -, Y is the same or different, representing -S-, -SO ₂ -, -O-, -CO-, -COO-, or -CONH-; n represents an integer greater than 0)

式中，R¹ 、R² 表示硬化性官能基。R¹ 、R² 分別可相同亦可不同。作為R¹ 、R² 之硬化性官能基，例如較佳為下述式（r）所表示之基等具有環狀醯亞胺結構之硬化性官能基。

（式中，自氮原子延伸之鍵結鍵與D¹ 或D² 鍵結）In the formula, R ¹ and R ² represent a curable functional group. R ¹ and R ² may be the same or different. As ^{the curable functional group of R 1} and R ² , for example, a curable functional group having a cyclic imine structure such as a group represented by the following formula (r) is preferred.

(In the formula, the bonding bond extending from the nitrogen atom is bonded to D ¹ or D ² )

上述式（r）中，Q表示C或CH。式中之2個Q經由單鍵或雙鍵鍵結。n'為0以上之整數（例如，0～3之整數，較佳為0或1）。R³ ～R⁶ 相同或不同，表示氫原子、飽和或不飽和脂肪族烴基（較佳為碳數1～10之烷基、碳數2～10之烯基、碳數2～10之炔基）、芳香族烴基（較佳為苯基、萘基等碳數6～10之芳基）、或選自上述飽和或不飽和脂肪族烴基與芳香族烴基中之2個以上之基鍵結而成之基。選自R³ ～R⁶ 中之2個基可彼此鍵結並與相鄰之碳原子共同地形成環。In the above formula (r), Q represents C or CH. The two Qs in the formula are bonded via a single bond or a double bond. n'is an integer of 0 or more (for example, an integer of 0 to 3, preferably 0 or 1). R ³ to R ^{6 are the} same or different and represent a hydrogen atom, a saturated or unsaturated aliphatic hydrocarbon group (preferably an alkyl group with 1 to 10 carbons, an alkenyl group with 2 to 10 carbons, and an alkynyl group with 2 to 10 carbons ), aromatic hydrocarbon groups (preferably aryl groups with 6 to 10 carbon atoms such as phenyl and naphthyl groups), or two or more groups selected from the above-mentioned saturated or unsaturated aliphatic hydrocarbon groups and aromatic hydrocarbon groups. Chengzhiji. Two groups selected from R ³ to R ⁶ may be bonded to each other and form a ring together with adjacent carbon atoms.

作為選自R³ ～R⁶ 中之2個基彼此鍵結並與相鄰之碳原子共同地形成的環，例如可例舉：碳數3～20之脂環、及碳數6～14之芳香環。上述碳數3～20之脂環例如包含：環丙烷環、環丁烷環、環戊烷環、環己烷環等3～20員（較佳為3～15員，特佳為5～8員）左右之環烷烴環；環戊烯環、環己烯環等3～20員（較佳為3～15員，特佳為5～8員）左右之環烯烴環；全氫萘環（Perhydronaphthalene ring）、降莰烷環、降莰烯環、金剛烷環、三環[5.2.1.0^2,6 ]癸烷環、四環[4.4.0.1^2,5 .1^7,10 ]十二烷環等橋聯環式烴基等。上述碳數6～14之芳香環包含苯環、萘環等。As a ring in which two groups selected from R ³ to R ⁶ are bonded to each other and form together with adjacent carbon atoms, for example, an alicyclic ring having 3 to 20 carbon atoms and an alicyclic ring having 6 to 14 carbon atoms may be mentioned. Aromatic ring. The alicyclic ring having 3 to 20 carbon atoms includes, for example, 3 to 20 members (preferably 3 to 15 members, particularly preferably 5 to 8 members) such as cyclopropane ring, cyclobutane ring, cyclopentane ring, and cyclohexane ring. Cycloalkane rings of about 3-20 members (preferably 3-15 members, especially 5-8 members) such as cyclopentene ring, cyclohexene ring, etc.; perhydronaphthalene ring ( Perhydronaphthalene ring), norbornane ring, norbornene ring, adamantane ring, tricyclic [5.2.1.0 ^2,6 ] decane ring, tetracyclic [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane Ring and other bridged cyclic hydrocarbon groups, etc. The aromatic ring having 6 to 14 carbon atoms includes a benzene ring, a naphthalene ring, and the like.

作為上述具有環狀醯亞胺結構之硬化性官能基，其中，較佳為具有環狀不飽和醯亞胺結構之硬化性官能基、或具有具備芳基乙炔基之環狀醯亞胺結構的硬化性官能基，特佳為選自下述式（r-1）～（r-6）所表示之基中之基，尤其較佳為下述式（r-1）或（r-5）所表示之基。

（式中，自氮原子延伸之鍵結鍵與式（1）中之D₁ 或D₂ 鍵結）As the above-mentioned curable functional group having a cyclic amide structure, among them, a curable functional group having a cyclic unsaturated amide structure or a cyclic amide structure having an arylethynyl group is preferred. The curable functional group is particularly preferably a group selected from the groups represented by the following formulas (r-1) to (r-6), and particularly preferably the following formula (r-1) or (r-5) The base expressed.

(In the formula, the bonding bond extending from the nitrogen atom is bonded to D ₁ or D ₂ in formula (1))

上述式（r-1）～（r-6）所表示之基上亦可鍵結有1種或2種以上之取代基。作為上述取代基，例如可例舉：碳數1～6之烷基、碳數1～6之烷氧基、及鹵素原子等。One type or two or more types of substituents may be bonded to the groups represented by the above formulas (r-1) to (r-6). As said substituent, a C1-C6 alkyl group, a C1-C6 alkoxy group, a halogen atom, etc. are mentioned, for example.

作為上述碳數1～6之烷基，例如可例舉：甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、戊基、己基等直鏈狀或支鏈狀烷基。Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, tertiary butyl, pentyl, and hexyl. Etc. straight-chain or branched-chain alkyl.

作為上述碳數1～6之烷氧基，例如可例舉：甲氧基、乙氧基、丁氧基、第三丁氧基等直鏈狀或支鏈狀烷氧基。Examples of the alkoxy group having 1 to 6 carbon atoms include linear or branched alkoxy groups such as a methoxy group, an ethoxy group, a butoxy group, and a tertiary butoxy group.

式（1）中，D¹ 、D² 相同或不同，表示單鍵或連結基。作為上述連結基，例如可例舉：2價烴基、2價雜環式基、羰基、醚鍵、酯鍵、碳酸酯鍵、醯胺鍵、醯亞胺鍵、及該等之複數個連結而成之基等。In formula (1), D ¹ and D ^{2 are the} same or different, and represent a single bond or a linking group. As the above-mentioned linking group, for example, a divalent hydrocarbon group, a divalent heterocyclic group, a carbonyl group, an ether bond, an ester bond, a carbonate bond, an amide bond, an imine bond, and plural of these are connected. Cheng Zhiji and so on.

上述2價烴基包含2價脂肪族烴基、2價脂環式烴基、及2價芳香族烴基。The above-mentioned divalent hydrocarbon group includes a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group.

作為上述2價脂肪族烴基，例如可例舉：碳數1～18之直鏈狀或支鏈狀伸烷基、及碳數2～18之直鏈狀或支鏈狀伸烯基等。作為碳數1～18之直鏈狀或支鏈狀伸烷基，例如可例舉：亞甲基、甲基亞甲基、二甲基亞甲基、伸乙基、伸丙基、三亞甲基等。作為碳數2～18之直鏈狀或支鏈狀伸烯基，例如可例舉：伸乙烯基、1-甲基伸乙烯基、伸丙烯基、1-伸丁烯基、2-伸丁烯基等。As said divalent aliphatic hydrocarbon group, a C1-C18 linear or branched alkylene group, and a C2-C18 linear or branched alkenylene group etc. are mentioned, for example. Examples of linear or branched alkylene groups having 1 to 18 carbon atoms include methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene. Base and so on. Examples of linear or branched alkenylene having 2 to 18 carbon atoms include vinylene, 1-methylethylene, propenylene, 1-butenylene, and 2-butene Alkenyl etc.

作為上述2價脂環式烴基，可例舉：碳數3～18之2價脂環式烴基等，例如可例舉：1,2-伸環戊基、1,3-伸環戊基、亞環戊基、1,2-伸環己基、1,3-伸環己基、1,4-伸環己基、亞環己基等伸環烷基（包含亞環烷基）等。The divalent alicyclic hydrocarbon group may, for example, be a divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms, etc., for example, 1,2-cyclopentyl, 1,3-cyclopentyl, Cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, cyclohexylene and other cycloalkylene groups (including cycloalkylene groups), etc.

作為上述2價芳香族烴基，可例舉：碳數6～14之伸芳基等，例如可例舉：1,4-伸苯基、1,3-伸苯基、4,4'-伸聯苯基、3,3'-伸聯苯基、2,6-萘二基、2,7-萘二基、1,8-萘二基、蒽二基等。The divalent aromatic hydrocarbon group may, for example, be an arylene group having 6 to 14 carbon atoms. For example, 1,4-phenylene group, 1,3-phenylene group, 4,4'-phenylene group may be mentioned. Biphenyl, 3,3'-biphenylene, 2,6-naphthalenediyl, 2,7-naphthalenediyl, 1,8-naphthalenediyl, anthracenediyl, etc.

構成上述2價雜環式基之雜環包含芳香族性雜環及非芳香族性雜環。作為此類雜環，可例舉：構成環之原子具有碳原子及至少1種雜原子（例如，氧原子、硫原子、氮原子等）之3～10員環（較佳為4～6員環）、及其等之縮合環。具體而言，可例舉：包含氧原子作為雜原子之雜環（例如，環氧乙烷環等3員環；氧雜環丁烷環等4員環；呋喃環、四氫呋喃環、

唑環、異

唑環、γ-丁內酯環等5員環；4-氧代-4H-哌喃環、四氫哌喃環、嗎福林環等6員環；苯并呋喃環、異苯并呋喃環、4-氧代-4H-

唏環、

唍環、異

唍環等縮合環；3-氧雜三環[4.3.1.1^4,8 ]十一烷-2-酮環、3-氧雜三環[4.2.1.0^4,8 ]壬烷-2-酮環等橋聯環）、包含硫原子作為雜原子之雜環（例如，噻吩環、噻唑環、異噻唑環、噻二唑環等5員環；4-氧代-4H-噻喃環等6員環；苯并噻吩環等縮合環等）、包含氮原子作為雜原子之雜環（例如，吡咯環、吡咯啶環、吡唑環、咪唑環、***環等5員環；異三聚氰酸環、吡啶環、嗒

環、嘧啶環、吡

環、哌啶環、哌

環等6員環；吲哚環、吲哚啉環、喹啉環、吖啶環、

啶環、喹唑啉環、嘌呤環等縮合環等）等。2價雜環式基係自上述雜環之結構式去除2個氫原子後之基。The heterocyclic ring constituting the above-mentioned divalent heterocyclic group includes an aromatic heterocyclic ring and a non-aromatic heterocyclic ring. Examples of such heterocyclic rings include: 3-10 membered rings (preferably 4-6 members) in which the atoms constituting the ring have carbon atoms and at least one heteroatom (for example, oxygen atom, sulfur atom, nitrogen atom, etc.) Ring), and other condensed rings. Specifically, examples include: heterocycles containing oxygen atoms as heteroatoms (for example, 3-membered rings such as oxirane ring; 4-membered rings such as oxetane ring; furan ring, tetrahydrofuran ring,

Azole ring, iso

5-membered ring such as azole ring and γ-butyrolactone ring; 6-membered ring such as 4-oxo-4H-piperan ring, tetrahydropyran ring and mophorin ring; benzofuran ring and isobenzofuran ring , 4-oxo-4H-

唏环、

Ring, different

Condensed rings such as ring; 3- ^{oxatricyclic [4.3.1.1 4,8} ] undecane-2-one ring, 3-oxatricyclic [4.2.1.0 ^4,8 ] nonane-2-one ring And other bridged rings), heterocycles containing sulfur atoms as heteroatoms (for example, 5-membered rings such as thiophene ring, thiazole ring, isothiazole ring, thiadiazole ring, etc.; 4-oxo-4H-thiopyran ring, etc. 6 members Rings; condensed rings such as benzothiophene rings, etc.), heterocycles containing nitrogen atoms as heteroatoms (for example, 5-membered rings such as pyrrole ring, pyrrolidine ring, pyrazole ring, imidazole ring, triazole ring, etc.; heterocyanuric Acid ring, pyridine ring, ta

Ring, pyrimidine ring, pyridine

Ring, piperidine ring, piper

6-membered ring such as ring; indole ring, indoline ring, quinoline ring, acridine ring,

Condensed rings such as pyridine ring, quinazoline ring, purine ring, etc.). The divalent heterocyclic group is a group obtained by removing two hydrogen atoms from the structural formula of the above heterocyclic ring.

作為上述D¹ 、D² ，其中，就獲得具有尤其優異之耐熱性之硬化物之方面而言，較佳為包含2價芳香族烴基。作為上述2價芳香族烴基，較佳為碳數6～14之2價芳香族烴基，更佳為選自下述式（d-1）～（d-4）所表示之基中之基，尤其較佳為下述式（d-1）所表示之基（1,2-伸苯基、1,3-伸苯基、或1,4-伸苯基）。

Among them, D ¹ and D ² preferably contain a divalent aromatic hydrocarbon group in terms of obtaining a cured product having particularly excellent heat resistance. The divalent aromatic hydrocarbon group is preferably a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms, and more preferably a group selected from the groups represented by the following formulas (d-1) to (d-4), Especially preferred is a group represented by the following formula (d-1) (1,2-phenylene, 1,3-phenylene, or 1,4-phenylene).

又，上述D¹ 、D² 較佳為上述2價芳香族烴基、與選自由共羰基、醚鍵、酯鍵、碳酸酯鍵、醯胺鍵、及醯亞胺鍵所組成之群中之至少1個基連結而成之基，尤其較佳為上述2價芳香族烴基連結醚鍵而成之基。Furthermore, the above D ¹ and D ^{2 are} preferably the above divalent aromatic hydrocarbon group, and at least one selected from the group consisting of a co-carbonyl group, an ether bond, an ester bond, a carbonate bond, an amide bond, and an imine bond A group formed by connecting one group is particularly preferably a group formed by connecting an ether bond to the above-mentioned divalent aromatic hydrocarbon group.

因此，式（1）中之R¹ -D¹ -基、及R² -D² -基相同或不同，較佳為包含下述式（rd-1）或（rd-2）所表示之基的基，特佳為下述式（rd-1-1）或（rd-2-1）所表示之基。

（式中，自伸苯基或氧原子延伸之鍵結鍵與式（1）中之L鍵結） ^{Therefore, the R 1} -D ¹ -group and the R ² -D ² -group in the formula (1) are the same or different, and preferably include the group represented by the following formula (rd-1) or (rd-2) The group of is particularly preferably a group represented by the following formula (rd-1-1) or (rd-2-1).

(In the formula, the bonding bond extending from the phenyl group or the oxygen atom is bonded to the L in formula (1))

式（1）中之L表示具有包含上述式（I）所表示之結構、及上述式（II）所表示之結構之重複單位的2價基。式（I）、及式（II）中之Ar¹ ～Ar³ 相同或不同，表示伸芳基、或2個以上之伸芳基經由單鍵或者連結基鍵結而成之基。X表示-CO-、-S-、或-SO₂ -，Y相同或不同，表示-S-、-SO₂ -、-O-、-CO-、-COO-、或-CONH-。n表示0以上之整數，例如0～5之整數，較佳為1～5之整數，特佳為1～3之整數。L in the formula (1) represents a divalent group having a repeating unit including the structure represented by the above formula (I) and the structure represented by the above formula (II). ^{Ar 1} to Ar ^{3 in} formula (I) and formula (II) are the same or different, and represent an aryl extension group, or a group formed by bonding two or more aryl extension groups via a single bond or a linking group. X represents -CO-, -S-, or -SO ₂ -, and Y is the same or different, and represents -S-, -SO ₂ -, -O-, -CO-, -COO-, or -CONH-. n represents an integer of 0 or more, for example, an integer of 0 to 5, preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 3.

上述伸芳基係自芳香環（＝芳香族烴環）之結構式中去除2個氫原子後之基。並且，作為上述芳香環，例如可例舉：苯、萘、蒽、菲等碳數6～14之芳香環。作為上述芳香環，其中，較佳為苯、萘等碳數6～10之芳香環，作為上述伸芳基，其中，較佳為碳數6～10之伸芳基。The above-mentioned aryl group is a group obtained by removing two hydrogen atoms from the structural formula of an aromatic ring (= aromatic hydrocarbon ring). In addition, as the above-mentioned aromatic ring, for example, an aromatic ring having 6 to 14 carbon atoms such as benzene, naphthalene, anthracene, and phenanthrene may be mentioned. As the above-mentioned aromatic ring, among them, an aromatic ring having 6 to 10 carbon atoms such as benzene and naphthalene is preferred, and as the above-mentioned arylene group, among them, an arylene group having 6 to 10 carbon atoms is preferred.

作為上述連結基，例如可例舉：碳數1～5之2價烴基、或碳數1～5之2價烴基之1個以上之氫原子被取代為鹵素原子而成之基等。As the above-mentioned linking group, for example, a divalent hydrocarbon group having 1 to 5 carbon atoms, or a divalent hydrocarbon group having 1 to 5 carbon atoms, in which one or more hydrogen atoms are substituted with halogen atoms, and the like.

上述碳數1～5之2價烴基例如包含：亞甲基、甲基亞甲基、二甲基亞甲基、二亞甲基、三亞甲基等碳數1～5之直鏈狀或支鏈狀伸烷基；伸乙烯基、1-甲基伸乙烯基、伸丙烯基等碳數2～5之直鏈狀或支鏈狀伸烯基；伸乙炔基、伸丙炔基、1-甲基伸丙炔基等碳數2～5之直鏈狀或支鏈狀伸炔基等。作為上述烴基，其中，較佳為碳數1～5之直鏈狀或支鏈狀伸烷基，特佳為碳數1～5之支鏈狀伸烷基。The above-mentioned divalent hydrocarbon group having 1 to 5 carbon atoms includes, for example, a linear or branched hydrocarbon group having 1 to 5 carbon atoms such as methylene, methylmethylene, dimethylmethylene, dimethylmethylene, trimethylene, etc. Chain alkylene; ethylene, 1-methylethylene, propylene and other linear or branched alkenylene with 2 to 5 carbon atoms; ethynylene, propynylene, 1- Linear or branched alkynylene groups with 2 to 5 carbon atoms such as methyl propynylene and the like. As the above-mentioned hydrocarbon group, among them, a linear or branched alkylene group having 1 to 5 carbon atoms is preferred, and a branched alkylene group having 1 to 5 carbon atoms is particularly preferred.

因此，上述Ar¹ ～Ar³ 相同或不同，較佳為碳數6～14之伸芳基，或2個以上之碳數6～14之伸芳基經由單鍵、碳數1～5之直鏈狀或支鏈狀伸烷基、或碳數1～5之直鏈狀或支鏈狀伸烷基之1個以上之氫原子被取代為鹵素原子而成之基鍵結而成之基，特佳為碳數6～14之伸芳基，或2個以上之碳數6～14之伸芳基經由單鍵、碳數1～5之支鏈狀伸烷基、或碳數1～5之支鏈狀伸烷基之1個以上之氫原子被取代為鹵素原子而成之基鍵結而成之基。Therefore, the above-mentioned Ar ¹ to Ar ^{3 are the} same or different, and are preferably an arylene group having 6 to 14 carbon atoms, or two or more arylene groups having 6 to 14 carbon atoms through a single bond, and a straight group having 1 to 5 carbon atoms. A group in which one or more hydrogen atoms of a chain or branched alkylene group or a linear or branched alkylene group with 1 to 5 carbon atoms are substituted with halogen atoms, Particularly preferred is an arylene group having 6 to 14 carbons, or two or more arylene groups having 6 to 14 carbons via a single bond, a branched alkylene group having 1 to 5 carbons, or a carbon number of 1 to 5 One or more hydrogen atoms of the branched alkylene group are bonded with a group formed by replacing a halogen atom.

上述Ar¹ ～Ar³ 相同或不同，尤其較佳為選自下述式（a-1）～（a-5）所表示之基中之基。再者，下述式中之鍵結鍵之鍵結位置並無特別限制。

The above-mentioned Ar ¹ to Ar ^{3 are the} same or different, and are particularly preferably a group selected from the groups represented by the following formulas (a-1) to (a-5). Furthermore, the bonding position of the bonding key in the following formula is not particularly limited.

作為式（I）中之Ar¹ 、Ar² ，其中較佳為碳數6～14之伸芳基，特佳為上述式（a-1）或（a-2）所表示之基。又，作為式（I）中之X，其中較佳為-CO-或-SO₂ -。作為式（I）所表示之結構，尤其較佳為包含來自二苯甲酮之結構。 ^{As Ar 1} and Ar ² in the formula (I), among them, an arylene group having 6 to 14 carbon atoms is preferred, and the group represented by the above formula (a-1) or (a-2) is particularly preferred. In addition, as X in the formula (I), among them, -CO- or -SO ₂ -is preferred. As the structure represented by the formula (I), it is particularly preferable to include a structure derived from benzophenone.

式（1）所表示之化合物總量中，來自芳香環之結構之比率為50重量%以上，例如為50～90重量%，較佳為60～90重量%，特佳為65～80重量%。In the total amount of the compound represented by formula (1), the ratio of the structure derived from the aromatic ring is 50% by weight or more, for example, 50 to 90% by weight, preferably 60 to 90% by weight, particularly preferably 65 to 80% by weight .

式（1）所表示之化合物總量中，來自二苯甲酮之結構單位所占之比率例如為5重量%以上，較佳為10～62重量%，特佳為15～60重量%。In the total amount of the compound represented by the formula (1), the ratio of the structural unit derived from benzophenone is, for example, 5% by weight or more, preferably 10 to 62% by weight, and particularly preferably 15 to 60% by weight.

作為式（II）中之Ar³ ，其中較佳為選自上述式（a-1）、（a-4）、及（a-5）所表示之基中之基。又，作為Y，其中較佳為-S-、-O-、或-SO₂ -。作為式（II）所表示之結構，特佳為包含來自選自對苯二酚、間苯二酚、2,6-萘二酚、2,7-萘二酚、4,4'-二羥基聯苯、4,4'-二羥基二苯醚、4,4'-二羥基二苯甲酮、4,4'-二羥基二苯硫醚、4,4'-二羥基二苯碸、及雙酚A中之至少1種化合物的結構，尤其較佳為包含來自選自對苯二酚、間苯二酚、及雙酚A中之至少1種化合物的結構。 ^{The Ar 3} in the formula (II) is preferably a group selected from the groups represented by the above formulas (a-1), (a-4), and (a-5). Moreover, as Y, among them, -S-, -O-, or -SO ₂ -is preferred. As the structure represented by the formula (II), it is particularly preferable to include a structure derived from hydroquinone, resorcinol, 2,6-naphthalenediol, 2,7-naphthalenediol, and 4,4'-dihydroxyl Biphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfide, and The structure of at least one compound in bisphenol A is particularly preferably a structure containing at least one compound selected from hydroquinone, resorcinol, and bisphenol A.

式（1）所表示之化合物總量中，來自對苯二酚、間苯二酚、2,6-萘二酚、2,7-萘二酚、4,4'-二羥基聯苯、4,4'-二羥基二苯醚、4,4'-二羥基二苯甲酮、4,4'-二羥基二苯硫醚、4,4'-二羥基二苯碸、及雙酚A之結構單位所占之比率例如為5重量%以上，較佳為10～55重量%，特佳為15～53重量%。The total amount of compounds represented by formula (1) is derived from hydroquinone, resorcinol, 2,6-naphthalenediol, 2,7-naphthalenediol, 4,4'-dihydroxybiphenyl, 4 ,4'-dihydroxydiphenyl ether, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfide, and bisphenol A The ratio of the structural unit is, for example, 5% by weight or more, preferably 10 to 55% by weight, and particularly preferably 15 to 53% by weight.

又，式（1）所表示之化合物總量中，來自對苯二酚、間苯二酚、及雙酚A之結構單位所占之比率例如為5重量%以上，較佳為10～55重量%，特佳為15～53重量%。In addition, in the total amount of the compound represented by formula (1), the ratio of structural units derived from hydroquinone, resorcinol, and bisphenol A is, for example, 5 wt% or more, preferably 10 to 55 wt% %, particularly preferably 15 to 53% by weight.

作為式（1）中之L，其中就可獲得耐熱性尤其優異之硬化物之方面而言，較佳為下述式（L-1）所表示之2價基。

Among them, L in the formula (1) is preferably a divalent group represented by the following formula (L-1) in terms of obtaining a cured product particularly excellent in heat resistance.

上述式（L-1）中之m為分子鏈（＝上述式（L-1）所表示之2價基）中所含有之圓括弧內所示之重複單位之數量、即平均聚合度，例如為2～50，較佳為3～40，更佳為4～30，特佳為5～20，最佳為5～10。於m未達2之情形時，呈現所獲得之硬化物之強度或耐熱性變得不充分之趨勢。另一方面，於m超過50之情形時，呈現熔融溫度變高之趨勢。又，亦呈現溶劑溶解性下降之趨勢。再者，m之值可藉由GPC測定或NMR之圖譜解析求出。又，上述式（L-1）中之n''表示0以上之整數，Ar¹ ～Ar³ 、X、Y與上述相同。再者，上述式（L-1）中之複數個Ar¹ 表示相同之基。Ar² 、Ar³ 亦同樣如此。The m in the above formula (L-1) is the number of repeating units shown in parentheses contained in the molecular chain (= the divalent group represented by the above formula (L-1)), that is, the average degree of polymerization, for example It is 2-50, preferably 3-40, more preferably 4-30, particularly preferably 5-20, most preferably 5-10. When m is less than 2, the strength or heat resistance of the obtained hardened product tends to become insufficient. On the other hand, when m exceeds 50, the melting temperature tends to increase. In addition, there is also a tendency for solvent solubility to decrease. In addition, the value of m can be obtained by GPC measurement or NMR spectrum analysis. In addition, n" in the above formula (L-1) represents an integer of 0 or more, and Ar ¹ to Ar ³ , X, and Y are the same as above. ^{Furthermore, the plural Ar 1} in the above formula (L-1) represent the same base. The same is true for ^{Ar 2} and Ar ^3.

作為式（1）中之L，尤其較佳為下述式（L-1-1）或（L-1-2）所表示之2價基。

As L in the formula (1), a divalent group represented by the following formula (L-1-1) or (L-1-2) is particularly preferred.

上述式中之m1、m2為分子鏈（＝上述式（L-1-1）或（L-1-2）所表示之2價基）中所含有之圓括弧內所示之重複單位之數量、即平均聚合度，例如為2～50，較佳為3～40，更佳為4～30，特佳為5～20，最佳為5～10。再者，m1、m2之值可藉由GPC測定或NMR之圖譜解析求出。In the above formula, m1 and m2 are the number of repeating units in the parentheses contained in the molecular chain (= the divalent group represented by the above formula (L-1-1) or (L-1-2)) That is, the average degree of polymerization is, for example, 2-50, preferably 3-40, more preferably 4-30, particularly preferably 5-20, most preferably 5-10. Furthermore, the values of m1 and m2 can be obtained by GPC measurement or NMR spectrum analysis.

又，式（1）所表示之化合物中，式（1）中之L為上述式（L-1-1）或（L-1-2）所表示之2價基且式中之m1、m2為5～10之化合物由於在300℃以下（250℃左右）發生熔融，故相較於PEEK等而言可於低溫下進行熔融成形，加工性尤其優異。In addition, in the compound represented by the formula (1), L in the formula (1) is the divalent group represented by the above formula (L-1-1) or (L-1-2) and m1, m2 in the formula The compound of 5 to 10 melts below 300°C (about 250°C), so it can be melt-formed at low temperature compared to PEEK, etc., and is particularly excellent in processability.

另一方面，若分子鏈之平均聚合度低於上述範圍，則呈現所獲得之硬化物變脆，機械特性下降之趨勢。又，若分子鏈之平均聚合度超過上述範圍，則呈現對溶劑之溶解性下降、或熔融黏度變高等，導致加工性下降之趨勢。On the other hand, if the average degree of polymerization of the molecular chain is lower than the above range, the obtained hardened product becomes brittle and the mechanical properties tend to decrease. Moreover, if the average degree of polymerization of the molecular chain exceeds the above-mentioned range, the solubility to the solvent will decrease, or the melt viscosity will increase, etc., leading to a tendency to decrease the processability.

上述硬化性化合物之數量平均分子量（Mn）例如為1000～15000，較佳為1000～14000，特佳為1100～12000，最佳為1200～10000。具有上述數量平均分子量之硬化性化合物不僅對於溶劑之溶解性較高，熔融黏度較低，容易進行成形加工，並且所獲得之硬化物（或者硬化後之成形體）表現出較高之韌性。若數量平均分子量低於上述範圍，則呈現所獲得之硬化物之韌性下降之趨勢。另一方面，若數量平均分子量超過上述範圍，則呈現硬化性化合物之溶劑溶解性下降，或熔融黏度變得過高，導致加工性下降之趨勢。再者，Mn係供於凝膠滲透層析法（GPC）測定（溶劑：氯仿，標準聚苯乙烯換算）求出。The number average molecular weight (Mn) of the curable compound is, for example, 1,000 to 15,000, preferably 1,000 to 14,000, particularly preferably 1,100 to 12,000, and most preferably 1,200 to 10,000. The curable compound with the above-mentioned number average molecular weight not only has high solubility in solvents, but also has low melt viscosity and is easy to form and process, and the obtained hardened product (or hardened molded body) exhibits high toughness. If the number average molecular weight is lower than the above range, the toughness of the obtained hardened product tends to decrease. On the other hand, if the number average molecular weight exceeds the above range, the solvent solubility of the curable compound will decrease, or the melt viscosity will become too high, leading to a tendency to decrease the processability. In addition, Mn is determined by gel permeation chromatography (GPC) measurement (solvent: chloroform, standard polystyrene conversion).

上述硬化性化合物具有良好之溶劑溶解性。作為上述溶劑，例如可例舉：丙酮、甲基乙基酮、甲基異丁基酮、環己酮等酮；甲醯胺、乙醯胺、N-甲基-2-吡咯啶酮（NMP）、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等醯胺；二氯甲烷、氯仿、1,2-二氯乙烷、氯苯、溴苯、二氯苯、三氟甲苯、六氟-2-丙醇等鹵代烴；二甲基亞碸（DMSO）、二乙基亞碸、苄基苯基亞碸等亞碸；二***、二異丙醚、二丁醚、四氫呋喃（THF）、二

烷、1,2-二甲氧基乙烷、環戊基甲醚等醚；乙酸乙酯等酯；乙腈、苯甲腈等腈；苯、甲苯、二甲苯等芳香族烴；及其等之2種以上之混合液等。其中，上述硬化性化合物對於選自醚、酮、醯胺、鹵代烴、及亞碸中之至少1種溶劑（尤其是選自醚、醯胺、鹵代烴、及亞碸中之至少1種溶劑）表現出優異之溶解性。The above-mentioned sclerosing compound has good solvent solubility. As the above-mentioned solvent, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; formamide, acetamide, N-methyl-2-pyrrolidone (NMP ), N,N-dimethylformamide, N,N-dimethylacetamide and other amides; dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, bromobenzene, dichloro Benzene, benzotrifluoride, hexafluoro-2-propanol and other halogenated hydrocarbons; dimethyl sulfite (DMSO), diethyl sulfite, benzyl phenyl sulfite and other sulfites; diethyl ether, diisopropyl ether , Dibutyl ether, tetrahydrofuran (THF), two

Ethers such as alkane, 1,2-dimethoxyethane, cyclopentyl methyl ether; esters such as ethyl acetate; nitriles such as acetonitrile and benzonitrile; aromatic hydrocarbons such as benzene, toluene, and xylene; and others A mixture of more than two kinds, etc. Wherein, the above-mentioned sclerosing compound is suitable for at least one solvent selected from ethers, ketones, amides, halogenated hydrocarbons, and sulfites (especially at least 1 solvents selected from ethers, amides, halogenated hydrocarbons, and sulfites). A solvent) exhibits excellent solubility.

上述硬化性化合物對於溶劑之溶解度於25℃相對於溶劑100 g，例如為1 g以上，較佳為5 g以上，特佳為10 g以上。The solubility of the above-mentioned curable compound with respect to 100 g of the solvent at 25° C. is, for example, 1 g or more, preferably 5 g or more, and particularly preferably 10 g or more.

上述硬化性化合物之氮原子含量例如為2.8～0.1重量%，較佳為2.5～0.15重量%，更佳為2.0～0.20重量%，特佳為1.8～0.40重量%，最佳為1.5～0.70重量%。氮原子含量例如可藉由CHN元素分析求出。氮原子含量為上述範圍之硬化性化合物之溶劑溶解性優異，且可形成韌性或耐熱性優異之硬化物。另一方面，若氮原子含量低於上述範圍，則呈現變得難以形成韌性或耐熱性優異之硬化物之趨勢。又，若氮原子含量超過上述範圍，則呈現溶劑溶解性下降之趨勢。The nitrogen atom content of the curable compound is, for example, 2.8 to 0.1% by weight, preferably 2.5 to 0.15% by weight, more preferably 2.0 to 0.20% by weight, particularly preferably 1.8 to 0.40% by weight, most preferably 1.5 to 0.70% by weight %. The nitrogen atom content can be determined by CHN elemental analysis, for example. The curable compound whose nitrogen atom content is in the above range has excellent solvent solubility and can form a cured product having excellent toughness or heat resistance. On the other hand, if the nitrogen atom content is less than the above range, it tends to become difficult to form a hardened product excellent in toughness or heat resistance. In addition, if the nitrogen atom content exceeds the above range, the solvent solubility tends to decrease.

上述硬化性化合物之玻璃轉移溫度（Tg）例如為280℃以下（例如，80～280℃），較佳為80～250℃，特佳為100～200℃。若上述硬化性化合物具有上述範圍之Tg，則由於熔融溫度較低（即，由於當欲使該硬化性化合物熔融時，可藉由較低溫度之加熱而使其熔融），故加工性優異。另一方面，若上述硬化性化合物之Tg超過上述範圍，則由於熔融溫度變高，故加工性呈現下降趨勢。The glass transition temperature (Tg) of the curable compound is, for example, 280°C or lower (for example, 80 to 280°C), preferably 80 to 250°C, particularly preferably 100 to 200°C. If the above-mentioned curable compound has a Tg in the above-mentioned range, the melting temperature is relatively low (that is, when the curable compound is to be melted, it can be melted by heating at a relatively low temperature), and therefore, the workability is excellent. On the other hand, if the Tg of the above-mentioned curable compound exceeds the above-mentioned range, since the melting temperature becomes higher, the workability tends to decrease.

上述式（1）所表示之化合物例如可利用Polymer 1989 p978中所記載之合成法進行製造。以下示出了上述式（1）所表示之化合物之製造方法之ー例，但上述式（1）所表示之化合物並不限定於利用該製造方法製得者。The compound represented by the above formula (1) can be produced, for example, by the synthesis method described in Polymer 1989 p978. An example of the production method of the compound represented by the above formula (1) is shown below, but the compound represented by the above formula (1) is not limited to those produced by this production method.

下述式（1a）所表示之化合物例如可經過下述步驟[1]～[3]進行製造。下述式中，Ar¹ ～Ar³ 、X、Y、n、R³ ～R⁶ 、Q、n'與上述相同。D表示連結基，Z表示鹵素原子。m為重複單位之平均聚合度，例如為3～50，較佳為4～30，特佳為5～20。上述式（1）所表示之化合物之中，下述式（1a）所表示之化合物以外之化合物亦可依據下述方法進行製造。 步驟[1]：藉由使作為反應基質之下述式（2）所表示之化合物、及下述式（3）所表示之化合物於鹼之存在下進行反應，從而獲得下述式（4）所表示之化合物。 步驟[2]：藉由使胺基醇（下述式（5）所表示之化合物）與下述式（4）所表示之化合物進行反應，從而獲得下述式（6）所表示之二胺。 步驟[3]：藉由使環狀酸酐（下述式（7）所表示之化合物）與下述式（6）所表示之二胺進行反應，從而獲得下述式（1a）所表示之化合物。The compound represented by the following formula (1a) can be produced, for example, through the following steps [1] to [3]. In the following formulae, Ar ¹ to Ar ³ , X, Y, n, R ³ to R ⁶ , Q, and n'are the same as described above. D represents a linking group, and Z represents a halogen atom. m is the average polymerization degree of the repeating unit, for example, 3-50, preferably 4-30, particularly preferably 5-20. Among the compounds represented by the above formula (1), compounds other than the compound represented by the following formula (1a) can also be produced according to the following method. Step [1]: The following formula (4) is obtained by reacting the compound represented by the following formula (2) as a reaction substrate and the compound represented by the following formula (3) in the presence of a base The compound represented. Step [2]: A diamine represented by the following formula (6) is obtained by reacting an amino alcohol (a compound represented by the following formula (5)) with a compound represented by the following formula (4) . Step [3]: A compound represented by the following formula (1a) is obtained by reacting a cyclic acid anhydride (a compound represented by the following formula (7)) with a diamine represented by the following formula (6) .

（步驟[1]） 作為上述式（2）所表示之化合物，例如可例舉：二苯甲酮、2-萘基苯基酮、及雙(2-萘基)酮等鹵化物、及其等之衍生物等。(step 1]) Examples of the compound represented by the above formula (2) include halides such as benzophenone, 2-naphthyl phenyl ketone, and bis(2-naphthyl) ketone, and derivatives thereof.

作為上述式（3）所表示之化合物，例如可例舉：對苯二酚、間苯二酚、2,6-萘二酚、2,7-萘二酚、1,5-萘二酚、4,4'-二羥基聯苯、4,4'-二羥基二苯醚、4,4'-二羥基二苯甲酮、4,4'-二羥基二苯硫醚、4,4'-二羥基二苯碸、雙酚A、雙酚F、雙酚S、2,5-二羥基聯苯、及其等之衍生物等。As the compound represented by the above formula (3), for example, hydroquinone, resorcinol, 2,6-naphthalenediol, 2,7-naphthalenediol, 1,5-naphthalenediol, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl sulfide, 4,4'- Dihydroxydiphenyl sulfide, bisphenol A, bisphenol F, bisphenol S, 2,5-dihydroxybiphenyl, and their derivatives, etc.

作為上述衍生物，例如可例舉：於上述式（2）所表示之化合物或式（3）所表示之化合物之芳香族烴基上鍵結取代基而成之化合物等。作為上述取代基，例如可例舉：碳數1～6之烷基、碳數1～6之烷氧基、及鹵素原子等。As said derivative, the compound etc. which bond a substituent to the aromatic hydrocarbon group of the compound represented by the said formula (2) or the compound represented by formula (3), etc. are mentioned, for example. As said substituent, a C1-C6 alkyl group, a C1-C6 alkoxy group, a halogen atom, etc. are mentioned, for example.

作為式（2）所表示之化合物、及式（3）所表示之化合物之使用量，通常相對於式（3）所表示之化合物1莫耳，使式（2）所表示之化合物為1莫耳以上，且較理想為根據所需之化合物（1）中之分子鏈之平均聚合度調整式（2）所表示之化合物之使用量。例如，於平均聚合度5之情形時，相對於式（3）所表示之化合物1莫耳，較佳為使用1.2莫耳左右（例如，1.18～1.22莫耳）之式（2）所表示之化合物，於平均聚合度10之情形時，較佳為使用1.1莫耳左右（例如，1.08～1.12莫耳）之式（2）所表示之化合物，於平均聚合度20之情形時，較佳為使用1.05莫耳左右（例如，1.04～1.06莫耳）之式（2）所表示之化合物。The usage amount of the compound represented by the formula (2) and the compound represented by the formula (3) is usually 1 mole of the compound represented by the formula (3), and the compound represented by the formula (2) is 1 mole The amount of the compound represented by the formula (2) is adjusted according to the required average degree of polymerization of the molecular chain in the compound (1). For example, in the case of an average degree of polymerization of 5, it is preferable to use about 1.2 mol (for example, 1.18 to 1.22 mol) represented by formula (2) relative to 1 mol of the compound represented by formula (3) For the compound, when the average degree of polymerization is 10, it is preferable to use the compound represented by formula (2) of about 1.1 mol (for example, 1.08 to 1.12 mol), and when the average degree of polymerization is 20, it is preferably The compound represented by formula (2) of about 1.05 mol (for example, 1.04 to 1.06 mol) is used.

作為式（2）所表示之化合物，較佳為至少使用二苯甲酮之鹵化物，式（2）所表示之化合物之總使用量（100莫耳%）中，二苯甲酮之鹵化物之使用量例如為10莫耳%以上，較佳為30莫耳%以上，特佳為50莫耳%以上，最佳為80莫耳%以上。再者，上限為100莫耳%。As the compound represented by the formula (2), it is preferable to use at least the halide of benzophenone. In the total usage amount (100 mol%) of the compound represented by the formula (2), the halide of benzophenone The usage amount is, for example, 10 mol% or more, preferably 30 mol% or more, particularly preferably 50 mol% or more, and most preferably 80 mol% or more. Furthermore, the upper limit is 100 mol%.

作為式（3）所表示之化合物，較佳為使用選自對苯二酚、間苯二酚、2,6-萘二酚、2,7-萘二酚、4,4'-二羥基聯苯、4,4'-二羥基二苯醚、4,4'-二羥基二苯甲酮、4,4'-二羥基二苯硫醚、4,4'-二羥基二苯碸、及雙酚A中之至少1種（尤其選自對苯二酚、間苯二酚、及雙酚A中之至少1種）化合物，上述化合物之使用量之合計為式（3）所表示之化合物之總使用量（100莫耳%）之例如10莫耳%以上，較佳為30莫耳%以上，特佳為50莫耳%以上，最佳為80莫耳%以上。再者，上限為100莫耳%。As the compound represented by the formula (3), it is preferable to use a compound selected from hydroquinone, resorcinol, 2,6-naphthalenediol, 2,7-naphthalenediol, 4,4'-dihydroxy Benzene, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfide, and double At least one compound of phenol A (especially at least one compound selected from hydroquinone, resorcinol, and bisphenol A), and the total amount of the above compounds used is that of the compound represented by formula (3) The total usage amount (100 mol%) is, for example, 10 mol% or more, preferably 30 mol% or more, particularly preferably 50 mol% or more, and most preferably 80 mol% or more. Furthermore, the upper limit is 100 mol%.

上述式（2）所表示之化合物與式（3）所表示之化合物之反應係於鹼（例如，選自氫氧化鈉、氫氧化鉀、氫氧化鈣、碳酸鈉、碳酸鉀、碳酸氫鈉等無機鹼，吡啶、三乙胺等有機鹼中之至少1種）之存在下進行。鹼之使用量可根據鹼之種類適當進行調整。例如，氫氧化鈣等二元鹼之使用量相對於式（3）所表示之化合物1莫耳，為1.0～2.0莫耳左右。The reaction between the compound represented by the above formula (2) and the compound represented by the formula (3) is based on a base (for example, selected from sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, etc.) In the presence of inorganic bases, at least one of organic bases such as pyridine and triethylamine). The amount of alkali used can be adjusted appropriately according to the type of alkali. For example, the usage amount of a binary base such as calcium hydroxide is about 1.0 to 2.0 mol with respect to 1 mol of the compound represented by formula (3).

又，該反應可於溶劑之存在下進行。作為上述溶劑，例如可使用：N-甲基-2-吡咯啶酮、二甲基甲醯胺、二甲基亞碸、丙酮、四氫呋喃、甲苯等有機溶劑、或者其等之2種以上之混合溶劑。In addition, this reaction can be carried out in the presence of a solvent. As the above-mentioned solvent, for example, organic solvents such as N-methyl-2-pyrrolidone, dimethylformamide, dimethyl sulfoxide, acetone, tetrahydrofuran, toluene, etc., or a mixture of two or more of them can be used Solvent.

作為上述溶劑之使用量，相對於反應基質之合計（重量），例如為5～20重量倍左右。若溶劑之使用量超過上述範圍，則呈現反應基質之濃度變低，反應速度下降之趨勢。The amount of the solvent used is, for example, about 5 to 20 times by weight relative to the total (weight) of the reaction substrate. If the amount of solvent used exceeds the above range, the concentration of the reaction substrate will decrease and the reaction rate will decrease.

作為反應環境，只要不妨礙反應，則無特別限定，例如可為空氣環境、氮氣環境、氬氣環境等任一環境。The reaction environment is not particularly limited as long as it does not hinder the reaction. For example, it may be any environment such as an air environment, a nitrogen environment, and an argon environment.

反應溫度例如為100～200℃左右。反應時間例如為5～24小時左右。又，該反應可利用分批式、半分批式、連續式等任一方法進行。The reaction temperature is, for example, about 100 to 200°C. The reaction time is, for example, about 5 to 24 hours. In addition, this reaction can be carried out by any method such as a batch method, a semi-batch method, and a continuous method.

該反應結束後，所獲得之反應產物可藉由例如過濾、濃縮、蒸餾、萃取、晶析、吸附、再結晶、管柱層析法等分離手段、或該等組合而成之分離手段進行分離精製。After the completion of the reaction, the obtained reaction product can be separated by separation means such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, or a combination of separation means. refined.

（步驟[2]） 作為上述式（5）所表示之化合物，例如可例舉：4-胺基苯酚、2-胺基-6-羥基萘、及其等之位置異構物或衍生物等。(Step [2]) Examples of the compound represented by the above formula (5) include 4-aminophenol, 2-amino-6-hydroxynaphthalene, and positional isomers or derivatives thereof.

上述式（5）所表示之化合物之使用量可根據所需之硬化性化合物中之分子鏈之平均聚合度適當進行調整。例如，於平均聚合度5之情形時，相對於式（3）所表示之化合物1莫耳，為0.4～0.6莫耳左右之量，於平均聚合度10之情形時，相對於式（3）所表示之化合物1莫耳，為0.2～0.4莫耳左右之量，於平均聚合度20之情形時，相對於式（3）所表示之化合物1莫耳，為0.1～0.15莫耳左右之量。The usage amount of the compound represented by the above formula (5) can be appropriately adjusted according to the average degree of polymerization of the molecular chain in the desired curable compound. For example, in the case of an average degree of polymerization of 5, relative to 1 mol of the compound represented by formula (3), the amount is about 0.4 to 0.6 mol, and in the case of an average degree of polymerization of 10, relative to formula (3) 1 mol of the compound represented is about 0.2 to 0.4 mol, and when the average degree of polymerization is 20, relative to 1 mol of the compound represented by formula (3), it is about 0.1 to 0.15 mol .

隨著該反應進行，會生成鹵化氫，故要想獲得促進反應進行之效果，較佳為在捕獲所生成之鹵化氫之鹼之存在下進行反應。作為上述鹼，例如可例舉：氫氧化鈉、氫氧化鉀、氫氧化鈣、碳酸鈉、碳酸鉀、碳酸氫鈉等無機鹼；吡啶、三乙胺等有機鹼。該等可單獨地使用1種，或組合2種以上使用。As the reaction progresses, hydrogen halide is generated. Therefore, in order to obtain the effect of accelerating the progress of the reaction, it is preferable to perform the reaction in the presence of a base that traps the generated hydrogen halide. Examples of the above-mentioned base include inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, and sodium bicarbonate; organic bases such as pyridine and triethylamine. These can be used individually by 1 type or in combination of 2 or more types.

上述鹼之使用量可根據鹼之種類適當進行調整。例如，氫氧化鈉等一元鹼之使用量相對於上述式（5）所表示之化合物1莫耳，為1.0～3.0莫耳左右。The usage amount of the above alkali can be adjusted appropriately according to the kind of alkali. For example, the usage amount of a monobasic base such as sodium hydroxide is about 1.0 to 3.0 mol with respect to 1 mol of the compound represented by the above formula (5).

又，該反應可於溶劑之存在下進行。作為溶劑，可使用與步驟[1]中所使用之溶劑相同者。In addition, this reaction can be carried out in the presence of a solvent. As the solvent, the same solvent as that used in step [1] can be used.

反應溫度例如為100～200℃左右。反應時間例如為1～15小時左右。又，該反應可利用分批式、半分批式、連續式等任一方法進行。The reaction temperature is, for example, about 100 to 200°C. The reaction time is, for example, about 1 to 15 hours. In addition, this reaction can be carried out by any method such as a batch method, a semi-batch method, and a continuous method.

該反應結束後，所獲得之反應產物可藉由例如過濾、濃縮、蒸餾、萃取、晶析、吸附、再結晶、管柱層析法等分離手段、或該等組合而成之分離手段進行分離精製。After the completion of the reaction, the obtained reaction product can be separated by separation means such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, or a combination of separation means. refined.

（步驟[3]） 作為上述環狀酸酐（上述式（7）所表示之化合物），例如可例舉：順丁烯二酸酐、2-苯基順丁烯二酸酐、4-苯基乙炔基-鄰苯二甲酸酐、4-(1-萘基乙炔基)-鄰苯二甲酸酐、二環[2.2.1]庚-5-烯-2,3-二羧酸酐、及其等之衍生物等。(Step [3]) Examples of the cyclic acid anhydride (the compound represented by the above formula (7)) include maleic anhydride, 2-phenylmaleic anhydride, and 4-phenylethynyl-phthalic anhydride , 4-(1-naphthylethynyl)-phthalic anhydride, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, and derivatives thereof.

上述環狀酸酐之使用量可根據所需之硬化性化合物中之分子鏈之平均聚合度適當進行調整。例如，於平均聚合度5之情形時，相對於式（3）所表示之化合物1莫耳，為0.4～0.8莫耳左右之量，於平均聚合度為10之情形時，相對於式（3）所表示之化合物1莫耳，為0.2～0.4莫耳左右之量，於平均聚合度20之情形時，相對於式（3）所表示之化合物1莫耳，為0.1～0.15莫耳左右之量。The amount of the cyclic acid anhydride used can be appropriately adjusted according to the average degree of polymerization of the molecular chain in the desired curable compound. For example, when the average degree of polymerization is 5, the amount is about 0.4 to 0.8 mol relative to 1 mol of the compound represented by formula (3), and when the average degree of polymerization is 10, it is relative to formula (3). 1 mol of the compound represented by) is about 0.2 to 0.4 mol. When the average degree of polymerization is 20, it is about 0.1 to 0.15 mol relative to 1 mol of the compound represented by formula (3) quantity.

該反應可於溶劑之存在下進行。作為溶劑，可使用與步驟[1]中所使用之溶劑相同者。The reaction can be carried out in the presence of a solvent. As the solvent, the same solvent as that used in step [1] can be used.

該反應較佳為於室溫（1～30℃）下進行。反應時間例如為1～30小時左右。又，該反應可利用分批式、半分批式、連續式等任一方法進行。The reaction is preferably carried out at room temperature (1-30°C). The reaction time is, for example, about 1 to 30 hours. In addition, this reaction can be carried out by any method such as a batch method, a semi-batch method, and a continuous method.

又，該反應中，要想促進反應之進行，較佳為藉由使用與水共沸之溶劑（例如，甲苯等）進行共沸、或使用脫水劑（例如，乙酸酐等）而去除副產之生成水。又，藉由使用脫水劑去除生成水較佳為於鹼性觸媒（例如，三乙胺等）之存在下進行。Furthermore, in this reaction, in order to promote the progress of the reaction, it is preferable to azeotrope by using a solvent that is azeotropic with water (for example, toluene, etc.), or use a dehydrating agent (for example, acetic anhydride, etc.) to remove by-products. It generates water. In addition, the removal of produced water by using a dehydrating agent is preferably carried out in the presence of an alkaline catalyst (for example, triethylamine, etc.).

該反應結束後，所獲得之反應產物可藉由例如過濾、濃縮、蒸餾、萃取、晶析、吸附、再結晶、管柱層析法等分離手段、或該等組合而成之分離手段進行分離精製。After the completion of the reaction, the obtained reaction product can be separated by separation means such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, or a combination of separation means. refined.

式（1）所表示之化合物之放熱峰溫依賴於硬化性官能基之種類，例如為170～450℃，較佳為200～430℃，特佳為220～420℃。例如，於式（1）所表示之化合物中，R¹ 、R² 為上述式（r-5）所表示之基之情形時，放熱峰溫為250℃左右。再者，放熱峰溫係藉由DSC測定求出。The exothermic peak temperature of the compound represented by the formula (1) depends on the type of the curable functional group, and is, for example, 170 to 450°C, preferably 200 to 430°C, and particularly preferably 220 to 420°C. For example, in the compound represented by the formula (1), when R ¹ and R ² are the groups represented by the above formula (r-5), the exothermic peak temperature is about 250°C. In addition, the exothermic peak temperature was obtained by DSC measurement.

上述硬化性組成物可單獨含有1種上述硬化性化合物，亦可組合含有2種以上之上述硬化性化合物。上述硬化性組成物總量（或者上述硬化性組成物中之不揮發分總量）中，上述硬化性化合物之含量（於含有2種以上之情形時為其總量）例如為30重量%以上，較佳為50重量%以上，特佳為70重量%以上，最佳為90重量%以上。再者，上限例如為95重量%。The curable composition may contain one type of the curable compound alone, or may contain two or more types of the curable compound in combination. In the total amount of the curable composition (or the total amount of non-volatile content in the curable composition), the content of the curable compound (in the case of containing two or more types, the total amount) is, for example, 30% by weight or more , Preferably 50% by weight or more, particularly preferably 70% by weight or more, most preferably 90% by weight or more. In addition, the upper limit is, for example, 95% by weight.

（矽酸鹽） 上述矽酸鹽例如係至少具有如下結構之化合物，即複數個由SiO₄ 四面體所組成之陰離子於平面上相連而成之Si-O四面體片結構。並且，形成上述四面體片結構之Si之一部分可被取代為Al³⁺ 、Fe³⁺ 、B³⁺ 、Ge⁴⁺ 等陽離子。又，上述矽酸鹽除了四面體片結構以外亦可具有八面體片結構，八面體片結構亦可包含Li⁺ 、Mg²⁺ 、Fe²⁺ 、Al³⁺ 、Fe³⁺ 等陽離子。又，進而上述矽酸鹽中，於四面體片結構或八面體片結構等片結構之層間亦可具有鹼金屬離子。(Silicate) The above-mentioned silicate is, for example, a compound having at least the following structure, that is, a Si-O tetrahedral sheet structure in _{which a plurality of anions composed of SiO 4 tetrahedrons are connected on a plane.} In addition, a part of Si forming the above-mentioned tetrahedral sheet structure may be substituted with ^{cations such as Al 3+} , Fe ³⁺ , B ³⁺ , Ge ⁴⁺ and the like. In addition, the above-mentioned silicate may have an octahedral sheet structure in addition to the tetrahedral sheet structure, and the octahedral sheet structure may also include ^{cations such as Li +} , Mg ²⁺ , Fe ²⁺ , Al ³⁺ , Fe ³⁺ and the like. Furthermore, in the above-mentioned silicate, an alkali metal ion may be present between the layers of the sheet structure such as a tetrahedral sheet structure or an octahedral sheet structure.

上述矽酸鹽例如包含雲母（mica）、高嶺土、滑石、二氧化矽、蒙脫石等。其中，就分散性優異之方面而言，較佳為雲母。The above-mentioned silicate includes, for example, mica, kaolin, talc, silica, montmorillonite, and the like. Among them, mica is preferred in terms of excellent dispersibility.

上述矽酸鹽之形狀包含薄片狀、粒子狀、針狀等各種形狀，其中，就分散性優異之方面而言，較佳為薄片狀矽酸鹽。The shape of the above-mentioned silicate includes various shapes such as flakes, particles, and needles. Among them, flaky silicates are preferred in terms of excellent dispersibility.

上述薄片狀矽酸鹽之厚度W例如為0.5 μm以下，較佳為0.01～0.5 μm，特佳為0.05～0.5 μm。The thickness W of the flaky silicate is, for example, 0.5 μm or less, preferably 0.01 to 0.5 μm, and particularly preferably 0.05 to 0.5 μm.

上述薄片狀矽酸鹽之最大直徑L₁ 例如為5～40 μm，較佳為6～35 μm，特佳為7～30 μm。The maximum diameter L _{1 of the} flaky silicate is, for example, 5-40 μm, preferably 6-35 μm, particularly preferably 7-30 μm.

上述薄片狀矽酸鹽之與最大直徑L₁ 正交之直徑L₂ （以下，有時稱為「交叉直徑L₂ 」）例如為3～30 μm，較佳為5～20 μm，特佳為8～15 μm。 _{The diameter L 2} (hereinafter, sometimes referred to as "cross diameter L ₂ ") orthogonal to the _{maximum diameter L 1 of the} flaky silicate is, for example, 3-30 μm, preferably 5-20 μm, and particularly preferably 8～15 μm.

上述薄片狀矽酸鹽之最大直徑L₁ 、交叉直徑L₂ 、及厚度W較佳為滿足下述式（a）、（b）。 0.2L₁ ≦L₂ ≦L₁ （a） 0.001L₁ ≦W≦0.08L₁ （b）It is preferable that the maximum diameter L ₁ , the cross diameter L ₂ , and the thickness W of the flaky silicate satisfy the following formulas (a) and (b). _{0.2L 1 ≦ L 2 ≦ L 1} (a) 0.001L 1 ≦ W ≦ 0.08L 1 (b)

上述薄片狀矽酸鹽之最大直徑L₁ 、交叉直徑L₂ 、及厚度W進而較佳為滿足下述式（a'）、（b）、（c）。 0.3L₁ ≦L₂ ≦0.9L₁ （a'） 0.001L₁ ≦W≦0.08L₁ （b） 0.005L₂ ≦W≦0.4L₂ （c）The maximum diameter L ₁ , the cross diameter L ₂ , and the thickness W of the flaky silicate further preferably satisfy the following formulas (a′), (b), and (c). _{0.3L 1 ≦ L 2 ≦ 0.9L 1} (a ') 0.001L 1 ≦ W ≦ 0.08L 1 (b) 0.005L 2 ≦ W ≦ 0.4L 2 (c)

再者，上述薄片狀矽酸鹽之直徑L₁ 、L₂ 、及厚度W例如藉由圖像解析法求出。即，使用電子顯微鏡（SEM），對足夠數量（例如，10個以上）之粒子狀物質拍攝電子顯微鏡圖像，測量該等粒子狀物質之最大直徑、交叉直徑、及厚度，算出其算術平均，從而求出上述薄片狀矽酸鹽之直徑L₁ 、L₂ 、及厚度W。In addition, the diameter L ₁ , L ₂ , and the thickness W of the flaky silicate described above are obtained by, for example, an image analysis method. That is, an electron microscope (SEM) is used to take an electron microscope image of a sufficient number (for example, 10 or more) of particulate matter, measure the maximum diameter, cross diameter, and thickness of the particulate matter, and calculate the arithmetic average. Thus, the diameter L ₁ , L ₂ , and thickness W of the flaky silicate are obtained.

又，上述矽酸鹽包含親水性矽酸鹽及親油性矽酸鹽。並且，親水性矽酸鹽為薄片狀，相較於厚膜狀者而言分散性更加優異，且具有向硬化性組成物賦予低CTE性之效果。又，親油性矽酸鹽無論粒徑如何，分散性均優異。In addition, the above-mentioned silicate includes hydrophilic silicate and lipophilic silicate. In addition, the hydrophilic silicate is in the form of flakes, which is more excellent in dispersibility than thick film, and has the effect of imparting low CTE to the curable composition. In addition, the lipophilic silicate has excellent dispersibility regardless of the particle size.

上述親油性矽酸鹽係存在於片結構之層間之鹼金屬離子之至少一部分經表現親油性之有機離子（例如，四級銨離子等）取代而成者。The above-mentioned lipophilic silicate is obtained by replacing at least a part of the alkali metal ions existing between the layers of the sheet structure with organic ions (for example, quaternary ammonium ions, etc.) exhibiting lipophilicity.

上述四級銨離子例如由下述式（d）所示。

（式中，R^a 、R^b 、R^c 及R^d 相同或不同，表示可具有羥基之碳數1～20之烷基）The quaternary ammonium ion is represented by the following formula (d), for example.

(In the formula, R ^a , R ^b , R ^c and ^{Rd are the} same or different and represent an alkyl group with 1 to 20 carbon atoms that may have a hydroxyl group)

上述親油性矽酸鹽之形狀為厚片狀或者粒子狀。親油性矽酸鹽之最大直徑L₃ 例如為1～30 μm，較佳為2～25 μm，特佳為3～20 μm。與上述最大直徑L₃ 正交之交叉直徑L₄ 為最大直徑L₃ 之0.1～0.9倍，較佳為0.2～0.8倍。又，厚度W1為最大直徑L₃ 之0.05～1.0倍，較佳為0.1～0.9倍。The shape of the lipophilic silicate is thick flake or granular. The maximum diameter L _{3 of the} lipophilic silicate is, for example, 1-30 μm, preferably 2-25 μm, particularly preferably 3-20 μm. The cross diameter L ₄ orthogonal to the above-mentioned maximum diameter L ₃ is 0.1 to 0.9 times the maximum diameter L ₃ , preferably 0.2 to 0.8 times. In addition, the thickness W1 is _{0.05 to 1.0 times the maximum diameter L 3} , preferably 0.1 to 0.9 times.

進而，上述矽酸鹽包含膨潤型矽酸鹽及非膨潤型矽酸鹽。非膨潤型矽酸鹽之耐熱性優異。另一方面，關於膨潤型矽酸鹽，當於層間含有Na⁺ ，表現親水性時，耐熱性優異，但當上述Na⁺ 經有機離子取代時，獲得親油性，但耐熱性呈下降趨勢。Furthermore, the above-mentioned silicate includes a swelling type silicate and a non-swelling type silicate. Non-swelling silicate has excellent heat resistance. On the other hand, with regard to swellable silicate, when Na ^{+ is} contained between the layers and exhibits hydrophilicity, the heat resistance is excellent, but when the Na ⁺ is substituted with organic ions, lipophilicity is obtained, but the heat resistance tends to decrease.

又，進而就分散性優異之方面而言，上述矽酸鹽較佳為具備適度之應力吸收性。並且，作為具備適度之應力吸收性之矽酸鹽，較佳為兼具下述特性1及特性2之矽酸鹽。 特性1：在設置於平面上之高度5.0 mm、直徑10 mm之粉體試樣用聚氯乙烯環中填充矽酸鹽，直至距聚氯乙烯環上部平面之高度成為5.0 mm為止，並以最大加壓7 MPa進行3分鐘加壓而使聚氯乙烯環表面變得平滑，於除壓後5分鐘於聚氯乙烯環之表面產生***。 特性2：在設置於平面上之高度5.0 mm、直徑10 mm之粉體試樣用聚氯乙烯環中填充矽酸鹽，直至距聚氯乙烯環上部平面之高度成為3.0 mm為止，並以最大加壓5 MPa進行3分鐘加壓而使聚氯乙烯環表面變得平滑，於除壓後5分鐘未於聚氯乙烯環之表面產生***。Furthermore, in terms of excellent dispersibility, the above-mentioned silicate preferably has moderate stress absorbing properties. In addition, as a silicate with moderate stress absorbing properties, a silicate having both the following characteristics 1 and 2 is preferable. Feature 1: Fill the polyvinyl chloride ring for powder samples with a height of 5.0 mm and a diameter of 10 mm on a flat surface until the height from the upper surface of the polyvinyl chloride ring becomes 5.0 mm, and the maximum Press 7 MPa for 3 minutes to smooth the surface of the polyvinyl chloride ring, and bulge on the surface of the polyvinyl chloride ring 5 minutes after depressurization. Feature 2: Fill the polyvinyl chloride ring for a powder sample with a height of 5.0 mm and a diameter of 10 mm on a flat surface until the height from the upper surface of the polyvinyl chloride ring becomes 3.0 mm, and the maximum Press 5 MPa for 3 minutes to smooth the surface of the polyvinyl chloride ring, and no bulge on the surface of the polyvinyl chloride ring 5 minutes after depressurization.

作為兼具上述特性1及特性2之矽酸鹽，可例舉：非膨潤型矽酸鹽（較佳為非膨潤型且上述直徑L₁ 、L₂ 、及厚度W滿足上述式（a）、（b）之矽酸鹽）。As a silicate having both the above-mentioned characteristics 1 and 2, for example, a non-swelling type silicate (preferably a non-swelling type and the above-mentioned diameter L ₁ , L ₂ , and thickness W satisfy the above-mentioned formula (a), (B) Silicate).

又，進而作為上述矽酸鹽，就分散性與耐熱性優異之方面而言，較佳為包含鹼金屬之矽酸鹽（更加詳細而言，於片結構之層間含有鹼金屬之矽酸鹽，即非膨潤型矽酸鹽）。Furthermore, as the above-mentioned silicate, in terms of excellent dispersibility and heat resistance, it is preferably a silicate containing an alkali metal (more specifically, a silicate containing an alkali metal between the layers of the sheet structure, That is, non-swelling silicate).

上述鹼金屬含量（於含有2種以上之情形時為其總量）例如較佳為矽酸鹽總量之7.0重量%以上，更佳為8.0重量%以上，特佳為9.0重量%以上，最佳為9.5重量%以上。再者，鹼金屬含量之上限例如為20重量%，較佳為15重量%，特佳為10重量%。The content of the alkali metal (the total amount when two or more are contained) is, for example, preferably 7.0% by weight or more of the total silicate, more preferably 8.0% by weight or more, particularly preferably 9.0% by weight or more, and most preferably Preferably, it is 9.5% by weight or more. Furthermore, the upper limit of the alkali metal content is, for example, 20% by weight, preferably 15% by weight, and particularly preferably 10% by weight.

又，鹼金屬中尤其是鉀之含量例如較佳為矽酸鹽總量之1.0重量%以上，更佳為3.0重量%以上，特佳為5.0重量%以上，最佳為7.0重量%以上。再者，鉀之含量之上限例如為20重量%，較佳為15重量%，特佳為10重量%。In addition, the content of potassium in the alkali metal is, for example, preferably 1.0% by weight or more of the total silicate, more preferably 3.0% by weight or more, particularly preferably 5.0% by weight or more, and most preferably 7.0% by weight or more. Furthermore, the upper limit of the potassium content is, for example, 20% by weight, preferably 15% by weight, and particularly preferably 10% by weight.

鹼金屬中尤其是鈉之含量例如較佳為矽酸鹽總量之5.0重量%以下，更佳為3.0重量%以下，進而較佳為未達3.0重量%，特佳為1.0重量%以下，最佳為0.5重量%以下，尤其較佳為0.1重量%以下。The content of sodium in the alkali metal is, for example, preferably 5.0% by weight or less of the total silicate, more preferably 3.0% by weight or less, still more preferably less than 3.0% by weight, particularly preferably 1.0% by weight or less, most preferably It is preferably 0.5% by weight or less, and particularly preferably 0.1% by weight or less.

含有上述範圍之鹼金屬（尤其是鉀與鈉）之矽酸鹽包含非膨潤型矽酸鹽（尤其是非膨潤型雲母）。Silicates containing alkali metals (especially potassium and sodium) in the above range include non-swelling silicates (especially non-swelling mica).

又，作為上述矽酸鹽，就分散性優異之方面而言，較佳為包含鎂之矽酸鹽（更加詳細而言，包含鎂之具有八面體片結構之矽酸鹽）。上述鎂含量較佳為矽酸鹽總量之10重量%以上（例如，10～30重量%），其中較佳為15重量%以上（例如，15～20重量%）。In addition, as the above-mentioned silicate, a silicate containing magnesium (more specifically, a silicate containing magnesium and having an octahedral sheet structure) is preferable in terms of excellent dispersibility. The above-mentioned magnesium content is preferably 10% by weight or more (for example, 10 to 30% by weight) of the total amount of silicate, and more preferably 15% by weight or more (for example, 15 to 20% by weight).

作為含有上述範圍之鎂之矽酸鹽，例如可例舉：上述薄片狀矽酸鹽或親油性矽酸鹽。As a silicate containing magnesium in the above-mentioned range, for example, the above-mentioned flaky silicate or lipophilic silicate can be mentioned.

進而，作為上述矽酸鹽，就分散性優異之方面而言，較佳為包含鋁之矽酸鹽（更加詳細而言，包含鋁之具有八面體片結構之矽酸鹽）。上述鋁含量較佳為矽酸鹽總量之0.5重量%以上，更佳為1.0重量%以上，特佳為3.0重量%以上，最佳為5.0重量%以上。再者，鋁之含量之上限例如為15重量%，較佳為10重量%，特佳為8重量%。Furthermore, as the above-mentioned silicate, in terms of excellent dispersibility, a silicate containing aluminum (more specifically, a silicate containing aluminum and having an octahedral sheet structure) is preferred. The aluminum content is preferably 0.5% by weight or more of the total amount of silicate, more preferably 1.0% by weight or more, particularly preferably 3.0% by weight or more, and most preferably 5.0% by weight or more. Furthermore, the upper limit of the aluminum content is, for example, 15% by weight, preferably 10% by weight, and particularly preferably 8% by weight.

作為含有上述範圍之鋁之矽酸鹽，例如可例舉：上述薄片狀矽酸鹽或親油性矽酸鹽。As the silicate containing aluminum in the above range, for example, the above-mentioned flaky silicate or lipophilic silicate can be mentioned.

又，進而作為上述矽酸鹽，包含氟原子之矽酸鹽於如下方面較佳，即，由於耐熱性及電特性優異（詳細而言，介電常數或介電損耗因數較低），故所獲得之硬化物可發揮優異之電特性。上述氟原子含量較佳為矽酸鹽總量之0.5重量%以上，更佳為1.0重量%以上，特佳為3.0重量%以上，最佳為5.0重量%以上。再者，氟原子之含量之上限例如為20重量%，較佳為15重量%，特佳為10重量%。Furthermore, as the above-mentioned silicate, a silicate containing fluorine atoms is preferable in that it is excellent in heat resistance and electrical characteristics (specifically, the dielectric constant or the dielectric dissipation factor is low), so The obtained hardened product can exhibit excellent electrical properties. The fluorine atom content is preferably 0.5% by weight or more of the total amount of silicate, more preferably 1.0% by weight or more, particularly preferably 3.0% by weight or more, and most preferably 5.0% by weight or more. Furthermore, the upper limit of the content of fluorine atoms is, for example, 20% by weight, preferably 15% by weight, and particularly preferably 10% by weight.

作為含有上述範圍之氟原子之矽酸鹽，可例舉：合成雲母。As the silicate containing a fluorine atom in the above range, synthetic mica can be mentioned.

矽酸鹽之含量相對於硬化性化合物100重量份，為0.01～95重量份，較佳為40～70重量份，更佳為45～65重量份，特佳為50～60重量份。上述硬化性組成物由於含有上述範圍之矽酸鹽，故可形成具有耐熱性（例如，200℃左右之耐熱性）及可撓性之硬化物。The content of the silicate is 0.01 to 95 parts by weight, preferably 40 to 70 parts by weight, more preferably 45 to 65 parts by weight, and particularly preferably 50 to 60 parts by weight relative to 100 parts by weight of the curable compound. Since the above-mentioned curable composition contains silicate in the above-mentioned range, it can be formed into a cured product having heat resistance (for example, heat resistance at about 200°C) and flexibility.

尤其是於含有上述範圍之非膨潤型矽酸鹽或親水性之膨潤型矽酸鹽、或者薄片狀矽酸鹽作為矽酸鹽之情形時，可形成具有耐熱性（例如，300℃以上之耐熱性）及可撓性（心軸試驗中，例如直徑為5 mm以下，較佳為直徑3 mm以下）之硬化物。Especially when it contains non-swelling type silicate or hydrophilic swelling type silicate, or flaky silicate as the silicate in the above range, it can be formed with heat resistance (for example, heat resistance above 300°C). Hardened products with flexibility) and flexibility (in the mandrel test, for example, a diameter of 5 mm or less, preferably a diameter of 3 mm or less).

又，於含有上述範圍之非膨潤型矽酸鹽或親油性之膨潤型矽酸鹽、或者薄片狀矽酸鹽作為矽酸鹽之情形時，可形成具有低CTE及可撓性（心軸試驗中，例如直徑5 mm以下，較佳為直徑3 mm以下）之硬化物。In addition, when the non-swelling type silicate or the lipophilic swelling type silicate or the flaky silicate is contained in the above range as the silicate, it can be formed with low CTE and flexibility (mandrel test Among them, for example, a hardened product with a diameter of 5 mm or less, preferably a diameter of 3 mm or less).

進而，於含有上述範圍之薄片狀矽酸鹽（較佳為非膨潤型薄片狀矽酸鹽）作為矽酸鹽之情形時，可形成具有低CTE、耐熱性（例如，300℃以上之耐熱性）及可撓性（心軸試驗中，例如直徑5 mm以下，較佳為直徑3 mm以下）之硬化物。Furthermore, when the flaky silicate (preferably non-swellable flaky silicate) in the above range is used as the silicate, it can be formed with low CTE and heat resistance (for example, heat resistance above 300°C). ) And flexibility (in the mandrel test, for example, the diameter is less than 5 mm, preferably less than 3 mm in diameter).

上述硬化物之CTE（線膨脹係數）例如為10×10^-6 ～50×10^-6 /℃，較佳為10×10^-6 ～30×10^-6 /℃。並且，即便溫度範圍不同，上述硬化物之CTE之變化亦較小。例如，低於Tg之溫度區域之線膨脹係數（α1）與高於Tg之溫度區域之線膨脹係數（α2）之差較小，α2/α1例如為2.0以下。The CTE (coefficient of linear expansion) of the cured product is, for example, 10×10 ^-6 to 50×10 ^-6 /°C, preferably 10×10 ^-6 to 30×10 ^-6 /°C. Moreover, even if the temperature range is different, the change in the CTE of the above-mentioned hardened product is relatively small. For example, the difference between the coefficient of linear expansion (α1) in the temperature region below Tg and the coefficient of linear expansion (α2) in the temperature region above Tg is small, and α2/α1 is, for example, 2.0 or less.

上述矽酸鹽如上所述，根據粒子形狀或性質（親水性/親油性、膨潤型/非膨潤型）之不同，可向硬化性組成物或上述硬化性組成物之硬化物所賦予之性能存在差異。因此，較佳為根據用途或所要求之特性選擇使用矽酸鹽。The above-mentioned silicate, as described above, has properties that can be imparted to the hardenable composition or the hardened substance of the above-mentioned hardenable composition according to the shape or properties of the particles (hydrophilic/lipophilic, swellable/non-swellable). difference. Therefore, it is preferable to select and use silicate according to the application or the required characteristics.

（其他成分） 上述硬化性組成物除了上述硬化性化合物及矽酸鹽以外，亦可視需要含有其他成分。作為其他成分，例如可例舉：觸媒、自由基聚合起始劑、有機樹脂（矽酮樹脂、環氧樹脂、氟樹脂等）、溶劑、穩定劑（抗氧化劑、紫外線吸收劑、耐光穩定劑、熱穩定劑等）、阻燃劑（磷系阻燃劑、鹵素系阻燃劑、無機系阻燃劑等）、阻燃助劑、補強材料、成核劑、偶合劑、潤滑劑、蠟、塑化劑、脫模劑、耐衝擊性改良劑、色相改良劑、流動性改良劑、著色劑（染料、顏料等）、分散劑、消泡劑、脫泡劑、抗菌劑、防腐劑、黏度調整劑、增黏劑等。該等可單獨地使用1種，或組合2種以上使用。(Other ingredients) In addition to the curable compound and silicate, the curable composition may also contain other components as needed. Examples of other components include: catalysts, radical polymerization initiators, organic resins (silicone resins, epoxy resins, fluororesins, etc.), solvents, stabilizers (antioxidants, ultraviolet absorbers, and light-resistant stabilizers) , Heat stabilizers, etc.), flame retardants (phosphorus flame retardants, halogen flame retardants, inorganic flame retardants, etc.), flame retardant additives, reinforcing materials, nucleating agents, coupling agents, lubricants, waxes , Plasticizers, mold release agents, impact resistance modifiers, hue modifiers, fluidity modifiers, colorants (dyes, pigments, etc.), dispersants, defoamers, defoamers, antibacterial agents, preservatives, Viscosity adjuster, tackifier, etc. These can be used individually by 1 type or in combination of 2 or more types.

其他成分（尤其是其他不揮發成分）之含量（於含有2種以上之情形時為其總量）為上述硬化性組成物總量之例如50重量%以下，較佳為40重量%以下，進而較佳為30重量%以下，特佳為20重量%以下，最佳為10重量%以下，尤其較佳為5重量%以下。The content of other components (especially other non-volatile components) (the total amount when two or more are contained) is, for example, 50% by weight or less, preferably 40% by weight or less, of the total amount of the curable composition. It is preferably 30% by weight or less, particularly preferably 20% by weight or less, most preferably 10% by weight or less, and particularly preferably 5% by weight or less.

上述硬化性組成物較佳為至少含有上述式（1）所表示之化合物作為硬化性化合物。又，亦可還含有上述式（1）所表示之化合物以外之硬化性化合物，硬化性組成物中所含有之硬化性化合物總量（100重量%）中，上述式（1）所表示之化合物所占之比率例如為70重量%以上，較佳為80重量%以上，特佳為90重量%以上。再者，上限為100重量%。因此，上述式（1）所表示之化合物以外之硬化性化合物之含量為硬化性組成物所含有之硬化性化合物總量（100重量%）之例如30重量%以下，較佳為20重量%以下，特佳為10重量%以下。The curable composition preferably contains at least the compound represented by the formula (1) as the curable compound. It may also contain a curable compound other than the compound represented by the above formula (1). Among the total amount (100% by weight) of the curable compound contained in the curable composition, the compound represented by the above formula (1) The ratio is, for example, 70% by weight or more, preferably 80% by weight or more, and particularly preferably 90% by weight or more. In addition, the upper limit is 100% by weight. Therefore, the content of the curable compound other than the compound represented by the above formula (1) is, for example, 30% by weight or less, preferably 20% by weight or less of the total amount (100% by weight) of the curable compound contained in the curable composition , Particularly preferably 10% by weight or less.

於上述硬化性組成物含有上述式（1）所表示之化合物作為硬化性化合物之情形時，由於上述式（1）所表示之化合物對於例如酮、醯胺、鹵代烴、亞碸、醚、酯、腈、芳香族烴、及其等之2種以上之混合液之溶解性優異，故可含有該等溶劑。When the curable composition contains the compound represented by the formula (1) as the curable compound, the compound represented by the formula (1) is effective for ketones, amides, halogenated hydrocarbons, sulfites, ethers, etc. A mixture of two or more kinds of esters, nitriles, aromatic hydrocarbons, and the like has excellent solubility, so these solvents can be contained.

上述硬化性組成物藉由進行加熱，可形成具有耐熱性及可撓性之硬化物。又，於含有特定之矽酸鹽之情形時，可形成具有低CTE、耐熱性、及可撓性之硬化物。進而，上述硬化性組成物之硬化物具有阻燃性、及良好之介電特性（較低之相對介電常數及介電損耗因數）。The curable composition can be heated to form a cured product having heat resistance and flexibility. In addition, when a specific silicate is contained, a hardened product with low CTE, heat resistance, and flexibility can be formed. Furthermore, the cured product of the curable composition has flame retardancy and good dielectric properties (low relative permittivity and dielectric loss factor).

又，上述硬化性組成物藉由調整加熱溫度及加熱時間，在硬化反應未結束之情況下中途停止反應，從而可形成半硬化物（B-階段）。In addition, the above-mentioned curable composition can be formed into a semi-cured product (B-stage) by adjusting the heating temperature and heating time to stop the reaction halfway when the curing reaction is not completed.

上述硬化性組成物由於具有上述特性，可較適宜地用作例如：電子資訊機器、家電、汽車、精密機械、飛行器、太空產業用機器、能源領域（油田挖掘管道/管、燃料容器）等苛刻環境溫度條件下所使用之複合材料（纖維強化塑膠、預浸體等）之成形材料（例如，上漿劑）；或遮蔽材料、傳導材料（例如，導熱材料等）、絕緣材料、接著劑（例如，耐熱性接著劑等）等功能材料。除此以外，可較好地用作：密封劑、塗料、塗佈劑、墨水、填充劑、阻劑、造形材料、形成材料[止推墊圈、濾油器、密封件、軸承、齒輪、汽缸頭罩、軸承護圈、進氣歧管、踏板等汽車零件；基材、電子線路基板（尤其是實施銅配線之電子線路基板）、電氣絕緣材料（絕緣膜等）、積層板、電子紙、觸控面板、太陽電池基板、光波導、導光板、全像記憶體、矽晶圓載具、IC晶片托盤、電解電容器托盤、絕緣膜等半導體/液晶製造裝置零件；透鏡等光學零件；泵、閥、密封件等壓縮機零件；飛行器之艙室內飾零件；滅菌器具、管柱、配管等醫療器具零件或食品/飲料製造設備零件；如個人電腦、行動電話等中所使用之殼體、以於個人電腦之內部支持鍵盤之構件即鍵盤支持體為代表之電氣/電子機器用構件等之形成材料]等。Due to the above-mentioned properties, the above-mentioned curable composition can be suitably used for demanding applications such as electronic information equipment, home appliances, automobiles, precision machinery, aircraft, space industry equipment, energy fields (oil field excavation pipelines/pipes, fuel containers), etc. Forming materials (for example, sizing agents) of composite materials (fiber reinforced plastics, prepregs, etc.) used under ambient temperature conditions; or shielding materials, conductive materials (for example, thermal conductive materials, etc.), insulating materials, adhesives ( For example, functional materials such as heat-resistant adhesives, etc.). In addition, it can be better used as: sealants, paints, coating agents, inks, fillers, resists, molding materials, forming materials [thrust washers, oil filters, seals, bearings, gears, cylinders Automotive parts such as hoods, bearing retainers, intake manifolds, pedals, etc.; substrates, electronic circuit substrates (especially electronic circuit substrates with copper wiring), electrical insulating materials (insulating films, etc.), laminates, electronic paper, Semiconductor/liquid crystal manufacturing equipment parts such as touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memory, silicon wafer carriers, IC chip trays, electrolytic capacitor trays, insulating films, etc.; optical parts such as lenses; pumps, valves , Seals and other compressor parts; aircraft cabin interior parts; sterilization equipment, pipe strings, piping and other medical equipment parts or food/beverage manufacturing equipment parts; such as shells used in personal computers, mobile phones, etc., The internal keyboard-supporting component of the personal computer, that is, the forming material of the electrical/electronic equipment components represented by the keyboard support], etc.

上述硬化性組成物由於可形成具有耐熱性、且具有與銅同等程度之低CTE之硬化物，故尤其可較好地用作實施銅配線之電子線路基板之原料。The above-mentioned curable composition can be formed into a cured product having heat resistance and a low CTE equivalent to copper, so it can be particularly preferably used as a raw material for an electronic circuit board for copper wiring.

[硬化物、半硬化物] 本發明之硬化物（或者半硬化物）係上述硬化性組成物之硬化物（或者半硬化物）。[Hardened material, semi-hardened material] The cured product (or semi-cured product) of the present invention is the cured product (or semi-cured product) of the above-mentioned curable composition.

上述硬化物（或者半硬化物）較佳為由式（1）所示，且式中之R¹ 、R² 相同或不同，為具有環狀醯亞胺結構之硬化性官能基之硬化性化合物（尤其較佳為由上述式（1）所示，且式中之R¹ 、R² 相同或不同，為選自式（r-1）～（r-6）所表示之基中之基之硬化性化合物）的硬化物（或者半硬化物）。The above-mentioned cured product (or semi-cured product) is preferably represented by formula (1), and R ¹ and R ² in the formula are the same or different, and are a curable compound having a curable functional group of a cyclic imine structure (In particular, it is preferably represented by the above formula (1), and R ¹ and R ² in the formula are the same or different, and are selected from the groups represented by the formulas (r-1) to (r-6) Hardening compound) (or semi-hardening).

上述硬化物（或者半硬化物）可藉由對上述硬化性組成物實施加熱處理（加熱溫度例如為180～250℃）而進行製造。The cured product (or semi-cured product) can be manufactured by subjecting the curable composition to heat treatment (heating temperature is, for example, 180 to 250°C).

上述加熱處理可於保持在固定溫度之狀態下進行，亦可階段性地變更溫度而進行。加熱處理溫度可根據加熱時間適當進行調整，例如，於需要縮短加熱時間之情形時，較佳為將加熱溫度設定為較高之溫度。The above-mentioned heat treatment may be carried out while keeping the temperature at a fixed temperature, or may be carried out by changing the temperature step by step. The heating temperature can be appropriately adjusted according to the heating time. For example, when the heating time needs to be shortened, it is better to set the heating temperature to a higher temperature.

上述硬化性組成物之硬化可於常壓下進行，亦可於減壓下或加壓下進行。The curing of the above-mentioned curable composition can be carried out under normal pressure, and can also be carried out under reduced pressure or under pressure.

例如，於上述硬化性組成物含有式（1）所表示之化合物作為硬化性化合物之情形時，由於式（1）所表示之化合物中來自芳香環之結構之比率較高，故儘管於高溫下進行加熱亦可於不分解之情況下形成硬化物（詳細而言，具有耐熱性之硬化物），且藉由於高溫下進行短時間之加熱，可以優異之作業性高效率地形成硬化物。又，加熱手段並無特別限制，可利用公知或慣用之手段。For example, when the above-mentioned curable composition contains the compound represented by formula (1) as the curable compound, the compound represented by formula (1) has a relatively high ratio of structures derived from the aromatic ring, so even at high temperatures Heating can also form a cured product without decomposition (specifically, a cured product with heat resistance), and by heating at a high temperature for a short time, the cured product can be formed efficiently with excellent workability. In addition, the heating means is not particularly limited, and known or customary means can be used.

並且，對於上述硬化性組成物，藉由調整加熱溫度及加熱時間而使其在硬化反應未完成之情況下中途停止反應，從而可製得半硬化物（B-階段）。上述半硬化物之硬化度例如為85%以下（例如，10～85%，較佳為15～75%，進而較佳為20～70%）。Furthermore, for the above-mentioned curable composition, by adjusting the heating temperature and heating time, the reaction is stopped halfway when the curing reaction is not completed, so that a semi-cured product (B-stage) can be obtained. The degree of hardening of the semi-cured product is, for example, 85% or less (for example, 10 to 85%, preferably 15 to 75%, and more preferably 20 to 70%).

再者，半硬化物之硬化度可藉由DSC測定硬化性組成物之放熱量、及其半硬化物之放熱量，並根據以下之式算出。 硬化度（%）=[1－（半硬化物之放熱量/硬化性組成物之放熱量）]×100Furthermore, the degree of hardening of the semi-cured product can be calculated by the following formula by measuring the heat generation amount of the curable composition and the heat generation amount of the semi-curing composition by DSC. Hardening degree (%)=[1－(heat amount of semi-hardened material/heat amount of hardenable composition)]×100

於上述半硬化物係含有式（1）所表示之化合物作為硬化性化合物之硬化性組成物之半硬化物之情形時，上述半硬化物因加熱而暫時表現流動性，可追隨階差。又，藉由實施加熱處理，可形成耐熱性優異之硬化物。When the semi-cured product is a semi-cured product of a curable composition containing the compound represented by the formula (1) as a curable compound, the semi-cured product temporarily exhibits fluidity due to heating and can follow a step difference. In addition, by applying heat treatment, a cured product with excellent heat resistance can be formed.

上述硬化物具有與銅基板同等程度之低CTE，線膨脹係數例如為10×10^-6 ～50×10^-6 /℃，較佳為10×10^-6 ～30×10^-6 /℃。並且，即便溫度範圍不同，上述線膨脹係數之變化亦較小。例如，低於Tg之溫度區域之線膨脹係數（α1）與高於Tg之溫度區域之線膨脹係數（α2）之差較小，α2/α1例如為2.0以下。因此，即便上述硬化物與銅箔之積層體暴露於高溫環境下，亦可抑制積層體之捲曲。The cured product has a low CTE equivalent to that of the copper substrate, and the coefficient of linear expansion is, for example, 10×10 ^-6 to 50×10 ^-6 /°C, preferably 10×10 ^-6 to 30×10 ^-6 /°C. Moreover, even if the temperature range is different, the change in the above-mentioned linear expansion coefficient is small. For example, the difference between the coefficient of linear expansion (α1) in the temperature region below Tg and the coefficient of linear expansion (α2) in the temperature region above Tg is small, and α2/α1 is, for example, 2.0 or less. Therefore, even if the laminate of the cured product and copper foil is exposed to a high temperature environment, curling of the laminate can be suppressed.

又，關於上述硬化物，例如5%重量減少溫度（T_d5 ）為300℃以上，於320℃供於加熱處理30分鐘之後，氮原子含量為2.8～0.1重量%。In addition, regarding the above-mentioned cured product, for example, the 5% weight reduction temperature (T _d5 ) is 300° C. or higher, and after being subjected to heat treatment at 320° C. for 30 minutes, the nitrogen atom content is 2.8 to 0.1% by weight.

關於上述硬化物，於升溫速度10℃/分鐘（氮氣中）所測得之5%重量減少溫度（T_d5 ）例如為300℃以上，較佳為400℃以上，特佳為450℃以上，最佳為500℃以上。5%重量減少溫度（T_d5 ）之上限例如為600℃，較佳為550℃，特佳為530℃。Regarding the above-mentioned cured product, the 5% weight loss temperature (T _d5 ) measured at a heating rate of 10°C/min (in nitrogen) is, for example, 300°C or higher, preferably 400°C or higher, particularly preferably 450°C or higher, most preferably Preferably, it is above 500°C. The upper limit of the 5% weight reduction temperature (T _d5 ) is, for example, 600°C, preferably 550°C, and particularly preferably 530°C.

又，將上述硬化物於320℃供於加熱處理30分鐘之後，氮原子含量例如為2.8～0.1重量%，較佳為2.5～0.15重量%，更佳為2.0～0.20重量%，特佳為1.8～0.40重量%，最佳為1.5～0.70重量%。因此，上述硬化物之韌性或耐熱性優異。另一方面，若氮原子含量低於上述範圍，則呈現硬化物之韌性或耐熱性下降之趨勢。Furthermore, after the above-mentioned cured product is subjected to heat treatment at 320°C for 30 minutes, the nitrogen atom content is, for example, 2.8 to 0.1% by weight, preferably 2.5 to 0.15% by weight, more preferably 2.0 to 0.20% by weight, particularly preferably 1.8 ～0.40% by weight, most preferably 1.5～0.70% by weight. Therefore, the above-mentioned cured product is excellent in toughness or heat resistance. On the other hand, if the nitrogen atom content is less than the above range, the toughness or heat resistance of the hardened product tends to decrease.

供於上述加熱處理後，硬化物中之氮原子含量例如可藉由CHN元素分析求出。After being subjected to the above heating treatment, the nitrogen atom content in the hardened substance can be determined by, for example, CHN elemental analysis.

上述硬化物中，除了硬化性化合物之聚合物以外，有時亦含有添加物，若將硬化物於320℃供於加熱處理30分鐘，則分解點或沸點未達320℃之添加物分解並消失，僅殘存硬化性化合物之聚合物。因此，加熱處理後之硬化物中之氮原子含量可推定為硬化性化合物之聚合物所含有之氮原子含量。再者，就熱歷程之觀點而言，亦可將硬化處理視為加熱處理。In addition to the polymer of the curable compound, the above-mentioned cured product may also contain additives. If the cured product is subjected to heat treatment at 320°C for 30 minutes, the additives with a decomposition point or boiling point below 320°C will decompose and disappear. , Only the polymer of curable compound remains. Therefore, the nitrogen atom content in the cured product after the heat treatment can be estimated as the nitrogen atom content contained in the polymer of the curable compound. Furthermore, from the viewpoint of thermal history, the hardening treatment can also be regarded as heating treatment.

又，上述硬化物於IR圖譜之1620～1750 cm^-1 之區域具有峰。上述峰來自「-C(=O)-N-C(=O)-」單元。In addition, the above-mentioned cured product has a peak in the region ^{of 1620 to 1750 cm -1 in the IR spectrum.} The above peak comes from the "-C(=O)-NC(=O)-" unit.

又，進而上述硬化物之阻燃性優異，厚度0.15 mm之硬化物利用依據UL94V之方法所測得之阻燃度為V-1等級，即具備下述1～5之條件。 （1）燃燒持續時間為30秒鐘以下； （2）5個試樣之燃燒持續時間之合計為250秒鐘以下； （3）第2次火焰接觸後之赤熱持續時間為60秒鐘以下； （4）未燃燒至固定用夾具部； （5）燃燒粒子不會掉落而點燃鋪在下方的棉紗。In addition, the above-mentioned cured product is excellent in flame retardancy, and the flame retardancy of the cured product with a thickness of 0.15 mm measured by the method based on UL94V is V-1, that is, it meets the following conditions 1 to 5. (1) The burning duration is less than 30 seconds; (2) The total burning duration of 5 samples is less than 250 seconds; (3) The duration of red heat after the second flame contact is less than 60 seconds; (4) Not burned to the fixture part for fixing; (5) The burning particles will not fall and ignite the cotton yarn laid underneath.

又，上述硬化物絕緣性優異，且相對介電常數例如為6以下（例如，1～6），較佳為5以下（例如，1～5），特佳為4以下（例如，1～4）。介電損耗因數例如為0.05以下（例如，0.0001～0.05），較佳為0.0001～0.03，特佳為0.0001～0.015。In addition, the above-mentioned cured product is excellent in insulation, and the relative dielectric constant is, for example, 6 or less (for example, 1 to 6), preferably 5 or less (for example, 1 to 5), and particularly preferably 4 or less (for example, 1 to 4). ). The dielectric loss factor is, for example, 0.05 or less (for example, 0.0001 to 0.05), preferably 0.0001 to 0.03, particularly preferably 0.0001 to 0.015.

再者，上述「相對介電常數」及「介電損耗因數」係依據JIS-C2138於測定頻率1 MHz、測定溫度23℃所測得之值，或依據ASTM D2520於頻率1 GHz、23℃所測得之值。Furthermore, the above-mentioned "relative permittivity" and "dielectric dissipation factor" are the values measured at a measurement frequency of 1 MHz and a measurement temperature of 23°C according to JIS-C2138, or according to ASTM D2520 at a frequency of 1 GHz and 23°C. The measured value.

[積層體] 本發明之積層體具有積層有上述硬化性組成物之硬化物或半硬化物、及基板之構成。上述積層體包含硬化性組成物之硬化物或半硬化物/基板、及基板/硬化性組成物之硬化物或半硬化物/基板之構成。[Layered body] The laminate of the present invention has a structure in which a cured product or a semi-cured product in which the above-mentioned curable composition is laminated, and a substrate. The above-mentioned laminate includes a cured product or semi-cured product/substrate of a curable composition, and a cured product or semi-cured product/substrate of a substrate/curable composition.

上述積層體例如可藉由將上述硬化性組成物塗佈於基板上，並實施加熱處理而進行製造。 又，上述積層體亦可藉由如下方法進行製造：將上述硬化性組成物塗佈於支持體上，實施加熱處理而使其半硬化，將如此獲得之半硬化物自支持體剝離，並將其載置於基板上，進而實施加熱處理。The laminate can be manufactured by, for example, applying the curable composition to a substrate and subjecting it to heat treatment. In addition, the laminate can also be manufactured by a method of coating the curable composition on a support, performing heat treatment to make it semi-cured, peeling the semi-cured product thus obtained from the support, and It is placed on a substrate and further subjected to heat treatment.

作為上述基板之素材，例如可例舉：半導體材料（例如，陶瓷、SiC、氮化鎵等）、紙、塗佈紙、塑膠膜、木材、布、不織布、金屬（例如，不鏽鋼、鋁合金、銅）等。As the material of the above-mentioned substrate, for example, semiconductor materials (for example, ceramics, SiC, gallium nitride, etc.), paper, coated paper, plastic film, wood, cloth, non-woven fabrics, metals (for example, stainless steel, aluminum alloy, etc.) Copper) etc.

上述硬化性組成物由於為低CTE，故即便積層於線膨脹係數較小之基材（例如，銅等金屬箔）上，亦可抑制捲曲之發生，形狀穩定性優異。Since the above-mentioned curable composition has a low CTE, even if it is laminated on a substrate with a small linear expansion coefficient (for example, a metal foil such as copper), the occurrence of curling can be suppressed and the shape stability is excellent.

於上述積層體具有硬化物/基板或基板/硬化物/基板之構成之情形時，硬化物與基板之密接性優異。上述基板與硬化物之拉伸剪切力（依據JIS K6850（1999））例如為1 MPa以上，較佳為5 MPa以上，特佳為10 MPa以上。再者，拉伸剪切力可使用拉伸試驗機（Orientec公司製造之Tensilon UCT-5T），於拉伸速度300 mm/分鐘、剝離角度180℃之條件下進行測定。In the case where the above-mentioned laminate has the structure of a cured product/substrate or a substrate/cured product/substrate, the adhesiveness between the cured product and the substrate is excellent. The tensile shear force of the substrate and the hardened product (according to JIS K6850 (1999)) is, for example, 1 MPa or more, preferably 5 MPa or more, and particularly preferably 10 MPa or more. Furthermore, the tensile shear force can be measured using a tensile testing machine (Tensilon UCT-5T manufactured by Orientec) under the conditions of a tensile speed of 300 mm/min and a peeling angle of 180°C.

又，上述積層體具有基板經由耐熱性、阻燃性、及絕緣性優異之硬化物積層之構成。因此，上述積層體例如可較好地用作電子線路基板等。In addition, the laminate has a structure in which a substrate is laminated through a cured product having excellent heat resistance, flame retardancy, and insulation. Therefore, the above-mentioned laminated body can be suitably used as an electronic circuit board etc., for example.

[印刷基板及電子裝置] 本發明之印刷基板具有於由上述硬化性組成物之硬化物所構成之基板上實施了導體配線之構成。又，上述電子裝置具有上述印刷基板。[Printed circuit board and electronic device] The printed circuit board of the present invention has a configuration in which conductor wiring is implemented on a substrate formed of a cured product of the above-mentioned curable composition. Moreover, the said electronic device has the said printed circuit board.

作為上述導體配線，包含由銅、鋁等導體形成之配線。其中，就導電性優異之方面而言，較佳為銅配線。The above-mentioned conductor wiring includes wiring formed of a conductor such as copper and aluminum. Among them, copper wiring is preferred in terms of excellent conductivity.

上述硬化性組成物耐熱性優異，且為低CTE。因此，即便將於由上述硬化性組成物之硬化物所構成之基板之表面實施線膨脹係數較小之銅或鋁等之導體配線而成者暴露在例如供於回焊步驟等之熱應力下，亦由於基板之熱膨脹率與導體配線之熱膨脹率之差極小，故可防止配線斷裂。The curable composition described above is excellent in heat resistance and has a low CTE. Therefore, even if the surface of the substrate composed of the hardened material of the above-mentioned curable composition is subjected to conductor wiring such as copper or aluminum with a small coefficient of linear expansion, it is exposed to thermal stress such as being used in the reflow step. Also, since the difference between the thermal expansion rate of the substrate and the thermal expansion rate of the conductor wiring is extremely small, the wiring can be prevented from breaking.

並且，上述電子裝置由於具備具有耐熱應力性之印刷基板，故具有較高之可靠性。In addition, the above-mentioned electronic device has a high reliability due to the printed circuit board having heat stress resistance.

以上，本發明之各構成及其等之組合等為ー例，可於不脫離本發明之主旨之範圍內適當進行構成之附加、省略、置換、及變更。又，本發明並不受實施方式限定，僅受申請專利範圍之記載所限定。 實施例As mentioned above, each configuration of the present invention and combinations thereof and the like are examples, and additions, omissions, substitutions, and changes of the configurations can be appropriately made within the scope not departing from the spirit of the present invention. In addition, the present invention is not limited by the embodiments, but is limited only by the description of the scope of the patent application. Example

以下，根據實施例，對本發明更加具體地進行說明，但本發明並不受該等實施例限定。Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited by these examples.

再者，測定係於下述條件下進行。 ＜NMR測定＞ 測定裝置：BRUKER 400 MHz/54 mm或BRUKER AVANCE 600 MHz 測定溶劑：氘代二甲基亞碸、氘氯仿、或氘氯仿/五氟苯酚（PFP）=2/1（wt/wt）之混合液 化學位移：以TMS為基準 ＜GPC測定＞ 裝置：泵「LC-20AD」（島津製作所股份有限公司製造） 檢測器：RID-10A（島津製作所股份有限公司製造）或TDA-301及UV2501（Viscotek製造） 溶劑：THF或氯仿 管柱：shodex GPC K-806L×1根＋shodex GPC K-803×1根＋shodex GPC K-801×2根 流速：1.0 mL/min 溫度：40℃ 試樣濃度：0.1%（wt/vol） 標準聚苯乙烯換算 ＜DSC測定＞ 裝置：TA Q20 升溫速度：10℃/min 環境：氮氣環境 ＜TG/DTA測定＞ 裝置：NETZSCH TG209F3 升溫速度：10℃/min 環境：氮氣環境 ＜IR測定＞ 裝置：Perkin Elmer Spectrum RX1（ATR法）In addition, the measurement was performed under the following conditions. <NMR measurement> Measuring device: BRUKER 400 MHz/54 mm or BRUKER AVANCE 600 MHz Measurement solvent: deuterated dimethyl sulfide, deuterochloroform, or a mixture of deuterochloroform/pentafluorophenol (PFP) = 2/1 (wt/wt) Chemical shift: based on TMS ＜GPC measurement＞ Device: Pump "LC-20AD" (manufactured by Shimadzu Corporation) Detector: RID-10A (manufactured by Shimadzu Corporation) or TDA-301 and UV2501 (manufactured by Viscotek) Solvent: THF or chloroform Column: shodex GPC K-806L×1 piece+shodex GPC K-803×1 piece+shodex GPC K-801×2 piece Flow rate: 1.0 mL/min Temperature: 40℃ Sample concentration: 0.1% (wt/vol) Standard polystyrene conversion ＜DSC measurement＞ Device: TA Q20 Heating rate: 10℃/min Environment: Nitrogen environment ＜TG/DTA measurement＞ Device: NETZSCH TG209F3 Heating rate: 10℃/min Environment: Nitrogen environment ＜IR measurement＞ Device: Perkin Elmer Spectrum RX1 (ATR method)

製備例1 二胺（1）之製備 於具備攪拌裝置、氮氣導入管、及迪安-斯塔克裝置之500 mL（三口）燒瓶中放入4,4'-二氟二苯甲酮27.50 g、雙酚A 23.98 g、無水碳酸鉀（K₂ CO₃ ）21.77 g、N-甲基-2-吡咯啶酮220 mL、及甲苯110 mL，於氮氣環境下一面攪拌一面進行加熱，並於130～140℃使甲苯回流4小時。其後，進而進行加熱，於170～180℃使甲苯蒸餾去除。進而，繼續於170～180℃攪拌10小時之後，恢復至室溫。Preparation Example 1 Preparation of diamine (1) Put 27.50 g of 4,4'-difluorobenzophenone in a 500 mL (three-necked) flask equipped with a stirring device, a nitrogen introduction tube, and a Dean-Stark device , Bisphenol A 23.98 g, anhydrous potassium carbonate (K ₂ CO ₃ ) 21.77 g, N-methyl-2-pyrrolidone 220 mL, and toluene 110 mL, heated under a nitrogen atmosphere while stirring, and heated at 130 Reflux toluene for 4 hours at ~140°C. After that, heating is further performed, and toluene is distilled off at 170 to 180°C. Furthermore, after continuing stirring at 170-180 degreeC for 10 hours, it returned to room temperature.

於裝入有所獲得之產物之燒瓶中添加4-胺基苯酚5.04 g、無水碳酸鉀6.39 g、N-甲基-2-吡咯啶酮30 mL、及甲苯150 mL，再次於氮氣環境下一面攪拌一面進行加熱，並於130～140℃使甲苯回流3小時。其後，進行加熱，於170～180℃使甲苯蒸餾去除，進而保持170～180℃且繼續攪拌4小時。其後，冷卻至室溫，藉由將反應液添加至3000 mL之甲醇中進行過濾，從而獲得粉末狀固體。利用甲醇及水對該粉末狀固體反覆進行洗淨之後，於100℃使其減壓乾燥8小時，從而獲得粉末狀固體（二胺（1）、下述式所表示之化合物、產率：95%）。將所獲得之粉末狀固體供於GPC測定（溶劑：THF、標準聚苯乙烯換算），所求出之數量平均分子量為2920、重量平均分子量為5100、及平均聚合度（m-2）為6.2。將所獲得之二胺（1）之¹ H-NMR圖譜示於圖1，將FTIR圖譜示於圖2。Add 5.04 g of 4-aminophenol, 6.39 g of anhydrous potassium carbonate, 30 mL of N-methyl-2-pyrrolidone, and 150 mL of toluene to the flask containing the obtained product, and place it under a nitrogen atmosphere again. Heating is performed while stirring, and toluene is refluxed at 130 to 140°C for 3 hours. After that, heating was performed to distill off toluene at 170 to 180°C, and the stirring was continued while maintaining 170 to 180°C for 4 hours. After that, it was cooled to room temperature, and the reaction liquid was added to 3000 mL of methanol and filtered to obtain a powdery solid. After washing the powdered solid repeatedly with methanol and water, it was dried under reduced pressure at 100°C for 8 hours to obtain a powdered solid (diamine (1), compound represented by the following formula, yield: 95 %). The obtained powdered solid was subjected to GPC measurement (solvent: THF, standard polystyrene conversion), and the calculated number average molecular weight was 2920, weight average molecular weight was 5100, and average degree of polymerization (m-2) was 6.2 . ^{The 1} H-NMR spectrum of the obtained diamine (1) is shown in FIG. 1, and the FTIR spectrum is shown in FIG. 2.

硬化性化合物A之製備 於具備攪拌裝置、氮氣導入管及乾燥管之1000 mL（三口）燒瓶中放入順丁烯二酸酐5.88 g、N-甲基-2-吡咯啶酮50 mL、及甲苯200 mL，進行氮氣置換。並且，添加所獲得之二胺（1）48.57 g溶解於330 mL之NMP中而成之溶液，於氮氣環境下，於室溫攪拌24小時。其後，添加對甲苯磺酸一水合物0.761 g，加熱至140℃，並繼續攪拌8小時，使甲苯回流而去除水分。將反應液恢復至室溫之後，藉由將反應液添加至3000 mL之甲醇中進行過濾，從而獲得粉末狀固體。利用甲醇及水對該粉末狀固體反覆進行洗淨之後，於100℃使其減壓乾燥8小時，從而獲得粉末狀固體（硬化性化合物A、下述式（A）所表示之化合物、來自芳香環之結構之比率：71重量%、產率：90%）。將硬化性化合物A之¹ H-NMR圖譜示於圖3，將FTIR圖譜示於圖4。¹ H-NMR (CDCl₃ ) δ: 1.71 (s), 6.87 (s), 7.02 (m), 7.09 (m), 7.17 (d, J = 8.8 Hz), 7.26 (m), 7.37 (d, J = 8.8 Hz), 7.80 (m)Preparation of sclerosing compound A: Put 5.88 g of maleic anhydride, 50 mL of N-methyl-2-pyrrolidone, and toluene into a 1000 mL (three-necked) flask equipped with a stirring device, a nitrogen introduction tube and a drying tube 200 mL, nitrogen replacement. In addition, a solution of 48.57 g of the obtained diamine (1) dissolved in 330 mL of NMP was added, and the solution was stirred at room temperature for 24 hours under a nitrogen atmosphere. After that, 0.761 g of p-toluenesulfonic acid monohydrate was added, heated to 140°C, and stirring was continued for 8 hours, and toluene was refluxed to remove water. After returning the reaction liquid to room temperature, the reaction liquid was added to 3000 mL of methanol and filtered to obtain a powdery solid. After washing the powdered solid repeatedly with methanol and water, it was dried under reduced pressure at 100°C for 8 hours to obtain a powdered solid (curable compound A, compound represented by the following formula (A), aromatic Ratio of ring structure: 71% by weight, yield: 90%). ^{The 1} H-NMR spectrum of the curable compound A is shown in FIG. 3, and the FTIR spectrum is shown in FIG. 4. ¹ H-NMR (CDCl ₃ ) δ: 1.71 (s), 6.87 (s), 7.02 (m), 7.09 (m), 7.17 (d, J = 8.8 Hz), 7.26 (m), 7.37 (d, J = 8.8 Hz), 7.80 (m)

又，藉由流變儀對硬化性化合物A於200℃、剪切速度10（1/s）之黏度進行了測定，結果為14 Pa・s。In addition, the viscosity of the curable compound A at 200°C and a shear rate of 10 (1/s) was measured by a rheometer, and the result was 14 Pa·s.

進而，藉由GPC測定（溶劑THF、標準聚苯乙烯換算）求出所獲得之硬化性化合物A之數量平均分子量、及重量平均分子量。其結果為，數量平均分子量（Mn）為3160、重量平均分子量（Mw）為5190。Furthermore, the number average molecular weight and the weight average molecular weight of the curable compound A obtained were determined by GPC measurement (solvent THF, standard polystyrene conversion). As a result, the number average molecular weight (Mn) was 3160 and the weight average molecular weight (Mw) was 5190.

又，進而藉由DSC求出所獲得之硬化性化合物A之Tg。結果為131℃。Furthermore, the Tg of the curable compound A obtained was obtained by DSC. The result was 131°C.

實施例1 如下述表1中所記載，摻合製備例中所獲得之硬化性化合物A 45重量份、甲苯55重量份、及自由基聚合起始劑（過氧化苯甲酸第三丁酯、商品名「PERBUTYL Z」、日本油脂股份有限公司製造）0.45重量份，使用自轉公轉攪拌機（商品名「去泡攪拌太郎 ARE-310」、Thinky股份有限公司製造）攪拌4小時。 其後，進而摻合雲母24重量份並攪拌5分鐘，其後，進行5分鐘脫泡處理，從而獲得硬化性組成物。Example 1 As described in Table 1 below, 45 parts by weight of the curable compound A obtained in the preparation example, 55 parts by weight of toluene, and a radical polymerization initiator (tert-butyl peroxybenzoate, trade name "PERBUTYL Z", manufactured by Nippon Oil & Fat Co., Ltd.) 0.45 parts by weight, and stirred for 4 hours using a rotating revolution mixer (trade name "Defoaming Stirring Taro ARE-310", manufactured by Thinky Co., Ltd.). After that, 24 parts by weight of mica was further blended and stirred for 5 minutes, and thereafter, a defoaming treatment was performed for 5 minutes to obtain a curable composition.

將所獲得之硬化性組成物以濕潤狀態下之厚度成為100 μm之方式，使用敷料器塗佈於銅箔（商品名「CF-T9DA-SV-18」、福田金屬箔粉工業股份有限公司製造、10 cm×10 cm）上，從而獲得塗膜/銅箔積層體。 使用加熱板將所獲得之塗膜/銅箔積層體於105℃加熱10分鐘，其後於150℃加熱10分鐘而使甲苯揮發，從而獲得乾燥塗膜/銅箔積層體。 其後，將所獲得之乾燥塗膜/銅箔積層體於真空條件下，於250℃加熱1小時而使塗膜硬化，從而獲得硬化物/銅箔積層體。The curable composition obtained was applied to a copper foil (trade name "CF-T9DA-SV-18", manufactured by Futian Metal Foil Powder Industry Co., Ltd. , 10 cm×10 cm) to obtain a coating film/copper foil laminate. The obtained coating film/copper foil laminate was heated at 105°C for 10 minutes using a hot plate, and then heated at 150°C for 10 minutes to volatilize toluene, thereby obtaining a dry coating film/copper foil laminate. Thereafter, the obtained dry coating film/copper foil laminate was heated at 250°C for 1 hour under vacuum conditions to harden the coating film, thereby obtaining a cured product/copper foil laminate.

對於所獲得之硬化物/銅箔積層體，於室溫浸漬於氯化鐵（III）水溶液（40重量%）中一晩而去除銅箔，從而獲得硬化物。對於所獲得之硬化物，根據於下述條件下所獲得之應變-溫度曲線求出α1（低於Tg之溫度區域之線膨脹係數）及α2（高於Tg之溫度區域之線膨脹係數）。 ＜TMA：拉伸＞ 測定裝置：TMA SS7100/Hitachi High-Tech Science 環境：N₂ 溫度範圍：1st heat/0℃～250℃ 2nd heat/0℃～250℃ 於開始溫度待機20分鐘 升溫速度：5℃/min 測定荷重：20 mNThe obtained hardened product/copper foil laminate was immersed in an iron (III) chloride aqueous solution (40% by weight) overnight at room temperature to remove the copper foil, thereby obtaining a hardened product. For the obtained hardened product, calculate α1 (the coefficient of linear expansion in the temperature region below Tg) and α2 (the coefficient of linear expansion in the temperature region above Tg) based on the strain-temperature curve obtained under the following conditions. <TMA: Stretching> Measuring device: TMA SS7100/Hitachi High-Tech Science Environment: N ₂ Temperature range: 1st heat/0℃～250℃ 2nd heat/0℃～250℃ Stand by at the starting temperature for 20 minutes Heating rate: 5 ℃/min Measured load: 20 mN

實施例2～4 如下述表1中所記載，變更所添加之雲母之種類，除此以外，與實施例1同樣地獲得硬化性組成物，並獲得乾燥塗膜/銅箔積層體、硬化物/銅箔積層體、及硬化物。Examples 2～4 As described in Table 1 below, except that the type of mica added was changed, a curable composition was obtained in the same manner as in Example 1, and a dry coating film/copper foil laminate and a cured product/copper foil laminate were obtained. , And hardened objects.

比較例1 未添加雲母，除此以外，與實施例同樣地獲得硬化性組成物，並獲得乾燥塗膜/銅箔積層體、硬化物/銅箔積層體、及硬化物。Comparative example 1 Except for not adding mica, a curable composition was obtained in the same manner as in the examples, and a dry coating film/copper foil laminate, a cured product/copper foil laminate, and a cured product were obtained.

對於實施例及比較例中所獲得之乾燥塗膜/銅箔積層體、及硬化物/銅箔積層體，進行以下之評價。The dry coating film/copper foil laminate and the cured product/copper foil laminate obtained in the examples and comparative examples were evaluated as follows.

（耐捲曲性評價） 將硬化物/銅箔積層體（10 cm×10 cm）以硬化物面朝上之朝向設置於平板上，並於設定為200℃之烘箱內靜置60分鐘，其後，以積層體設置於平板上之狀態自烘箱取出放置於室溫（25℃）環境下，經過5分鐘之後，測定平板之表面至積層體之四角之高度，根據平均值測得捲曲量。並且，根據下述基準，對耐捲曲性進行評價。再者，評價結果為〇表示硬化物之CTE與銅箔之CTE（約17/ppm）同等。 ＜評價基準＞ 〇（良）：平均捲曲量為2 cm以下 △（一般）：平均捲曲量超過2 cm且5 cm以下 ×（不良）：平均捲曲量超過5 cm、或捲曲成筒狀(Evaluation of curl resistance) Place the hardened product/copper foil laminate (10 cm×10 cm) on a flat plate with the hardened surface facing upwards, and place it in an oven set at 200°C for 60 minutes, and then set the laminate on The state on the plate was taken out of the oven and placed in a room temperature (25°C) environment. After 5 minutes, the height from the surface of the plate to the four corners of the laminate was measured, and the amount of curl was measured based on the average value. In addition, the curl resistance was evaluated based on the following criteria. In addition, an evaluation result of 0 means that the CTE of the cured product is equivalent to the CTE of the copper foil (about 17/ppm). <Evaluation criteria> 〇 (good): The average curl amount is less than 2 cm △(General): The average curl amount is more than 2 cm and less than 5 cm × (bad): The average amount of curl exceeds 5 cm, or curls into a cylindrical shape

（可撓性評價） 對於硬化物/銅箔積層體（10 cm×10 cm），依據JIS K5600-5-1（耐撓曲性（圓筒形心軸）），使用撓曲試驗機（商品名「心軸撓曲試驗機」、東洋精機製造作所股份有限公司製造），將積層體以硬化物層為外側之方式捲繞至直徑5 mm之心軸上，並根據下述基準對可撓性進行評價。 ＜評價基準＞ 〇（良）：無龜裂 ×（不良）：有龜裂(Flexibility evaluation) For the hardened product/copper foil laminate (10 cm×10 cm), in accordance with JIS K5600-5-1 (flexibility (cylindrical mandrel)), use a deflection tester (trade name "mandrel deflection) "Testing machine", manufactured by Toyo Seiki Seisakusho Co., Ltd.), the laminate is wound on a mandrel with a diameter of 5 mm with the hardened layer as the outside, and the flexibility is evaluated based on the following criteria. <Evaluation criteria> 〇 (good): no cracks × (bad): cracked

（耐熱性評價） 將乾燥塗膜/銅箔積層體於真空條件下於250℃加熱1小時，藉由目視對加熱前後之塗膜之顏色變化進行觀察，並根據下述基準對耐熱性進行評價。 ＜評價基準＞ 〇（良）：無變色 ×（不良）：有變色(Evaluation of heat resistance) The dry coating film/copper foil laminate was heated at 250°C under vacuum conditions for 1 hour, the color change of the coating film before and after heating was observed by visual observation, and the heat resistance was evaluated based on the following criteria. <Evaluation criteria> 〇 (good): no discoloration × (bad): discoloration

[表1] 表1    實施例1 實施例2 實施例3 實施例4 比較例1 硬化性化合物A 45 45 45 45 45 雲母 NK-8G 24 MAE 24 ME100 24 MK200 24 - 甲苯 55 55 55 55 55 自由基聚合起始劑 0.45 0.45 0.45 0.45 0.45                      耐捲曲性 〇 〇 △ △ ×^※    可撓性 〇 〇 〇 〇 〇 評價 耐熱性 〇 × 〇 〇 〇    硬化物之CTE/ppm α1 20 29 32 32 72    α2 20 - - - 175 ^※ 捲曲成筒狀。[Table 1] Table 1 Example 1 Example 2 Example 3 Example 4 Comparative example 1 Hardening compound A 45 45 45 45 45 Mica NK-8G 24 MAE 24 ME100 24 MK200 24 - Toluene 55 55 55 55 55 Free radical polymerization initiator 0.45 0.45 0.45 0.45 0.45 Curl resistance 〇 〇 △ △ × ^※ Flexibility 〇 〇 〇 〇 〇 Evaluation Heat resistance 〇 X 〇 〇 〇 CTE/ppm of hardened substance α1 20 29 32 32 72 α2 20 - - - 175 ^※ Curl into a tube shape.

NK-8G：合成雲母、商品名「NK-8G」、日本光研工業股份有限公司製造 MAE：二甲基二烷基銨改質合成雲母、商品名「somasif MAE」、Katakura & Co-op Agri股份有限公司製造 ME100：合成雲母、商品名「somasif ME100」、Katakura & Co-op Agri股份有限公司製造 MK200：合成雲母、商品名「Micromica MK200」、Katakura & Co-op Agri股份有限公司製造NK-8G: Synthetic mica, trade name "NK-8G", manufactured by Koken Kogyo Co., Ltd. MAE: Synthetic mica modified by dimethyl dialkylammonium, trade name "somasif MAE", manufactured by Katakura & Co-op Agri Co., Ltd. ME100: Synthetic mica, trade name "somasif ME100", manufactured by Katakura & Co-op Agri Co., Ltd. MK200: Synthetic mica, trade name "Micromica MK200", manufactured by Katakura & Co-op Agri Co., Ltd.

再者，將實施例中所使用之雲母供於下述試驗，確認其特性。將結果彙總示於下述表2。Furthermore, the mica used in the examples was subjected to the following test to confirm its characteristics. The results are collectively shown in Table 2 below.

（粒子形狀） 使用SEM，對10個雲母粒子拍攝電子顯微鏡圖像，藉由算術平均求出該等粒子狀物質之最大直徑L₁ 、交叉直徑L₂ 、及厚度W（圖5～8）。(Particle shape) Using SEM, take electron microscope images of 10 mica particles, and calculate the maximum diameter L ₁ , cross diameter L ₂ , and thickness W of these particulate matter by arithmetic average (Figures 5-8).

（元素分析） 藉由照射X射線，測定所產生之固有螢光X射線，從而對構成元素進行鑑定，分析上述元素之含量（重量%）。(Elemental analysis) By irradiating X-rays and measuring the inherent fluorescent X-rays generated, the constituent elements are identified and the content (weight%) of the above-mentioned elements is analyzed.

（雲母之聚氯乙烯環試驗1） 在設置於平面上之高度5.0 mm、直徑10 mm之粉體試樣用聚氯乙烯環中填充雲母，直至距聚氯乙烯環上部平面之高度成為5.0 mm為止，並以最大加壓7 MPa進行3分鐘加壓而使聚氯乙烯環表面變得平滑，藉由目視確認於除壓後5分鐘是否於聚氯乙烯環之表面產生***。於產生***之情形時，記載為「+」，於未產生***之情形時，記載為「-」。(Mica PVC ring test 1) Fill the polyvinyl chloride ring for a powder sample with a height of 5.0 mm and a diameter of 10 mm set on a flat surface with mica until the height from the upper surface of the polyvinyl chloride ring becomes 5.0 mm, and proceed with a maximum pressure of 7 MPa Press for 3 minutes to smooth the surface of the polyvinyl chloride ring, and visually confirm whether there is a bulge on the surface of the polyvinyl chloride ring 5 minutes after depressurization. When there is a bulge, it is recorded as "+", and when there is no bulge, it is recorded as "-".

（雲母之聚氯乙烯環試驗2） 在設置於平面上之高度5.0 mm、直徑10 mm之粉體試樣用聚氯乙烯環中填充雲母，直至距聚氯乙烯環上部平面之高度成為3.0 mm為止，並以最大加壓5 MPa進行3分鐘加壓而使聚氯乙烯環表面變得平滑，藉由目視確認於除壓後5分鐘是否於聚氯乙烯環之表面產生***。於產生***之情形時，記載為「+」，於未產生***之情形時，記載為「-」。(Mica PVC ring test 2) Fill the polyvinyl chloride ring for a powder sample with a height of 5.0 mm and a diameter of 10 mm set on a flat surface with mica until the height from the upper surface of the polyvinyl chloride ring becomes 3.0 mm, and carry out with a maximum pressure of 5 MPa Press for 3 minutes to smooth the surface of the polyvinyl chloride ring, and visually confirm whether there is a bulge on the surface of the polyvinyl chloride ring 5 minutes after depressurization. When there is a bulge, it is recorded as "+", and when there is no bulge, it is recorded as "-".

[表2] 表2 構成元素 NK-8G MAE ME100 MK200 C 0 29 0.9 0.8 O 44 32 45 42 F 8.1 5.8 8.0 7.8 Na 0 0.85 3.2 0 Mg 16 13 17 17 Al 6.2 0.16 0.10 0.13 Si 15 19 25 25 P 0.004 0 0 0.004 S 0.01 0.05 0 0 Cl 0 0.3 0 0 K 9.9 0.004 0.01 6.7 Ca 0.02 0.04 0.02 0.02 Ti 0.02 0 0 0 Fe 0.12 0.11 0.20 0.35 Ni 0 0.005 0 0 類型 非膨潤 膨潤 親油性 膨潤 親水性 非膨潤 形狀 薄片狀 均勻 厚片狀～粒狀 薄片狀＋粒狀 不均勻 厚片狀 最大直徑L₁ （μm） 16.5 5.7 9.8 11.6 交叉直徑L₂ （μm） 11.3 2.6 4.9 7.5 厚度W（μm） 0.3 2.0 複數層凝聚 0.6 聚氯乙烯環試驗1 5 mm×7 MPa×3 min + - - - 聚氯乙烯環試驗2 3 mm×5 MPa×3 min - - - - [Table 2] Table 2 Constituent elements NK-8G MAE ME100 MK200 C 0 29 0.9 0.8 O 44 32 45 42 F 8.1 5.8 8.0 7.8 Na 0 0.85 3.2 0 Mg 16 13 17 17 Al 6.2 0.16 0.10 0.13 Si 15 19 25 25 P 0.004 0 0 0.004 S 0.01 0.05 0 0 Cl 0 0.3 0 0 K 9.9 0.004 0.01 6.7 Ca 0.02 0.04 0.02 0.02 Ti 0.02 0 0 0 Fe 0.12 0.11 0.20 0.35 Ni 0 0.005 0 0 type Non-swelling Swelling and lipophilicity Swelling hydrophilic Non-swelling shape Thin and uniform Thick flakes ~ granular Flaky + uneven granular Thick flakes Maximum diameter L ₁ (μm) 16.5 5.7 9.8 11.6 Cross diameter L ₂ (μm) 11.3 2.6 4.9 7.5 Thickness W (μm) 0.3 2.0 Multiple layers of condensation 0.6 PVC ring test 15 mm×7 MPa×3 min + - - - PVC ring test 2 3 mm×5 MPa×3 min - - - -

對以上進行彙總，本發明之構成及其變化如下所述。 [1]一種硬化性組成物，其包含硬化性化合物及矽酸鹽，且上述矽酸鹽之含量相對於硬化性化合物100重量份為0.01～95重量份。 [2]如[1]中所記載之硬化性組成物，其中，矽酸鹽為薄片狀矽酸鹽。 [3]如[1]或[2]中所記載之硬化性組成物，其中，矽酸鹽兼具下述特性1及特性2。 特性1：在設置於平面上之高度5.0 mm、直徑10 mm之粉體試樣用聚氯乙烯環中填充矽酸鹽，直至距聚氯乙烯環上部平面之高度成為5.0 mm為止，並以最大加壓7 MPa進行3分鐘加壓而使聚氯乙烯環表面變得平滑，於除壓後5分鐘於聚氯乙烯環之表面產生***。 特性2：在設置於平面上之高度5.0 mm、直徑10 mm之粉體試樣用聚氯乙烯環中填充矽酸鹽，直至距聚氯乙烯環上部平面之高度成為3.0 mm為止，並以最大加壓5 MPa進行3分鐘加壓而使聚氯乙烯環表面變得平滑，於除壓後5分鐘未於聚氯乙烯環之表面產生***。 [4]如[1]至[3]中任一項所記載之硬化性組成物，其中矽酸鹽之最大直徑L₁ 、與上述最大直徑L₁ 正交之直徑L₂ 、及厚度W滿足下述式（a）、（b）。 0.2L₁ ≦L₂ ≦L₁ （a） 0.001L₁ ≦W≦0.08L₁ （b） [5]如[1]至[4]中任一項所記載之硬化性組成物，其中，矽酸鹽為親油性矽酸鹽。 [6]如[1]至[5]中任一項所記載之硬化性組成物，其中，矽酸鹽包含鹼金屬。 [7]如[1]至[6]中任一項所記載之硬化性組成物，其中，矽酸鹽為非膨潤型矽酸鹽。 [8]如[1]至[7]中任一項所記載之硬化性組成物，其中，矽酸鹽係最大直徑L₁ 、與上述最大直徑L₁ 正交之直徑L₂ 、及厚度W滿足下述式（a）、（b）之非膨潤型矽酸鹽。 0.2L₁ ≦L₂ ≦L₁ （a） 0.001L₁ ≦W≦0.08L₁ （b） [9]如[1]至[8]中任一項所記載之硬化性組成物，其中，矽酸鹽之鎂含量為10重量%以上。 [10]如[1]至[9]中任一項所記載之硬化性組成物，其中，矽酸鹽之鈉含量未達3.0重量%，鉀含量為1.0重量%以上。 [11]如[1]至[10]中任一項所記載之硬化性組成物，其中，矽酸鹽為薄片狀矽酸鹽，鈉含量未達3.0重量%。 [12]如[1]至[11]中任一項所記載之硬化性組成物，其中，矽酸鹽為薄片狀矽酸鹽，鉀含量為1.0重量%以上。 [13]如[1]至[12]中任一項所記載之硬化性組成物，其中，矽酸鹽為薄片狀矽酸鹽，鋁含量為0.5重量%以上。 [14]如[1]至[13]中任一項所記載之硬化性組成物，其中，矽酸鹽包含氟原子。 [15]如[1]至[14]中任一項所記載之硬化性組成物，其中，矽酸鹽係包含氟原子者，上述氟原子之含量為矽酸鹽總量之0.5重量%以上。 [16]如[1]至[15]中任一項所記載之硬化性組成物，其中，矽酸鹽為雲母。 [17]如[1]至[16]中任一項所記載之硬化性組成物，其中 硬化性化合物係下述式（1）所表示之化合物，

[式中，R¹ 、R² 相同或不同，表示硬化性官能基，D¹ 、D² 相同或不同，表示單鍵或連結基，L表示具有包含下述式（I）所表示之結構、及下述式（II）所表示之結構之重複單位的2價基；

（式中，Ar¹ ～Ar³ 相同或不同，表示伸芳基、或2個以上之伸芳基經由單鍵或者連結基鍵結而成之基，X表示-CO-、-S-、或-SO₂ -，Y相同或不同，表示-S-、-SO₂ -、-O-、-CO-、-COO-、或-CONH-，n表示0以上之整數）]。 [18]如[17]中所記載之硬化性組成物，其中，式（1）中之R¹ 、R² 相同或不同，為具有環狀醯亞胺結構之硬化性官能基。 [19]如[17]中所記載之硬化性組成物，其中，式（1）中之R¹ 、R² 為下述式（r）所表示之基。

（式中，Q表示C或CH；式中之2個Q經由單鍵或雙鍵鍵結；n'為0以上之整數；R³ ～R⁶ 相同或不同，表示氫原子、飽和或不飽和脂肪族烴基、芳香族烴基、或選自上述飽和或不飽和脂肪族烴基與芳香族烴基中之2個以上之基鍵結而成之基；選自R³ ～R⁶ 中之2個基亦可彼此鍵結並與相鄰之碳原子共同地形成環；式中，自氮原子延伸之鍵結鍵與D¹ 或D² 鍵結） [20]如[17]中所記載之硬化性組成物，其中，式（1）中之R¹ 、R² 相同或不同，為選自下述式（r-1）～（r-6）所表示之基中之基。

（式中，自氮原子延伸之鍵結鍵與D¹ 或D² 鍵結） [21]如[17]中所記載之硬化性組成物，其中，式（1）中之R¹ 、R² 相同或不同，為下述式（r-1）或（r-5）所表示之基。

（式中，自氮原子延伸之鍵結鍵與D¹ 或D² 鍵結） [22]如[17]中所記載之硬化性組成物，其中，式（1）中之R¹ -D¹ -基、及R² -D² -基相同或不同，為包含下述式（rd-1）或（rd-2）所表示之基的基。

（式中，自伸苯基延伸之鍵結鍵鍵結於式（1）中之L側） [23]如[17]中所記載之硬化性組成物，其中，式（1）中之R¹ -D¹ -基、及R² -D² -基相同或不同，為下述式（rd-1-1）或（rd-2-1）所表示之基。

（式中，自氧原子延伸之鍵結鍵與式（1）中之L鍵結） [24]如[17]至[23]中任一項所記載之硬化性組成物，其中，式（1）中之L為下述式（L-1）所表示之2價基。

（式中，Ar¹ ～Ar³ 相同或不同，表示伸芳基、或2個以上之伸芳基經由單鍵或者連結基鍵結而成之基；X表示-CO-、-S-、或-SO₂ -，Y相同或不同，表示-S-、-SO₂ -、-O-、-CO-、-COO-、或-CONH-；n''表示0以上之整數，m表示2～50之數） [25]如[17]至[23]中任一項所記載之硬化性組成物，其中，式（1）中之L為下述式（L-1-1）或（L-1-2）所表示之2價基。

（式中，m1、m2表示2～50之數） [26]如[1]至[25]中任一項所記載之硬化性組成物，其中，硬化性化合物藉由GPC測定所求出之標準聚苯乙烯換算之數量平均分子量為1000～15000。 [27]如[1]至[26]中任一項所記載之硬化性組成物，其中，硬化性化合物之玻璃轉移溫度為80～280℃。 [28]一種硬化物，其係[1]至[27]中任一項所記載之硬化性組成物之硬化物。 [29]一種半硬化物，其係[1]至[27]中任一項所記載之硬化性組成物之半硬化物。 [30]一種積層體，其具有[29]中所記載之硬化物積層於基板之構成。 [31]如[30]中所記載之積層體，其中，基板為銅基板。 [32]一種積層體之製造方法，其藉由將[1]至[27]中任一項所記載之硬化性組成物塗佈於基板上，並實施加熱處理而使上述硬化性組成物硬化，從而製得具有上述硬化性組成物之硬化物積層於基板之構成之積層體。 [33]一種積層體之製造方法，其藉由將[1]至[27]中任一項所記載之硬化性組成物之半硬化物載置於基板上，並實施加熱處理而使上述半硬化物硬化，從而製得具有上述硬化性組成物之硬化物積層於基板之構成之積層體。 [34]一種印刷基板，其係於基板上具備導體配線者，且上述基板係由[1]至[27]中任一項所記載之硬化性組成物之硬化物所構成者。 [35]一種印刷基板之製造方法，其係於基板上具備導體配線之印刷基板之製造方法，且包括如下步驟：於由如[1]至[27]中任一項所記載之硬化性組成物之硬化物所構成之基板上形成導體配線。 [36]一種電子裝置，其係具有印刷基板者，且上述印刷基板係於由[1]至[27]中任一項所記載之硬化性組成物之硬化物所構成之基板上具備導體配線者。 [37]一種電子裝置之製造方法，其係具備印刷基板之電子裝置之製造方法，且上述印刷基板係於基板上具備導體配線者，且該電子裝置之製造方法包括如下步驟：於由[1]至[27]中任一項所記載之硬化性組成物之硬化物所構成之基板上形成導體配線。 [產業上之可利用性]In summary, the constitution and changes of the present invention are as follows. [1] A curable composition comprising a curable compound and silicate, and the content of the silicate is 0.01 to 95 parts by weight relative to 100 parts by weight of the curable compound. [2] The curable composition as described in [1], wherein the silicate is a flaky silicate. [3] The curable composition as described in [1] or [2], wherein the silicate has both the following characteristics 1 and 2. Feature 1: Fill the polyvinyl chloride ring for powder samples with a height of 5.0 mm and a diameter of 10 mm on a flat surface until the height from the upper surface of the polyvinyl chloride ring becomes 5.0 mm, and the maximum Press 7 MPa for 3 minutes to smooth the surface of the polyvinyl chloride ring, and bulge on the surface of the polyvinyl chloride ring 5 minutes after depressurization. Feature 2: Fill the polyvinyl chloride ring for a powder sample with a height of 5.0 mm and a diameter of 10 mm on a flat surface until the height from the upper surface of the polyvinyl chloride ring becomes 3.0 mm, and the maximum Press 5 MPa for 3 minutes to smooth the surface of the polyvinyl chloride ring, and no bulge on the surface of the polyvinyl chloride ring 5 minutes after depressurization. [4] of [1] to [3] of curable composition according to any one of, wherein the maximum diameter of the silicate L _1, L ₁ and the maximum diameter perpendicular to the diameter L _2, W and thickness to meet the The following formulas (a) and (b). 0.2L ₁ ≦L ₂ ≦L ₁ (a) _{0.001L 1} ≦W≦0.08L ₁ (b) [5] The curable composition as described in any one of [1] to [4], wherein silicon The acid salt is a lipophilic silicate. [6] The curable composition according to any one of [1] to [5], wherein the silicate contains an alkali metal. [7] The curable composition according to any one of [1] to [6], wherein the silicate is a non-swelling silicate. [8] [1] The curable composition according to [7] according to any one of, wherein the maximum diameter of the silicate-based L _1, L ₁ and the maximum diameter perpendicular to the diameter L _2, and the thickness W A non-swelling silicate that satisfies the following formulas (a) and (b). 0.2L ₁ ≦L ₂ ≦L ₁ (a) _{0.001L 1} ≦W≦0.08L ₁ (b) [9] The curable composition as described in any one of [1] to [8], wherein silicon The magnesium content of the acid salt is more than 10% by weight. [10] The curable composition according to any one of [1] to [9], wherein the silicate has a sodium content of less than 3.0% by weight and a potassium content of 1.0% by weight or more. [11] The curable composition according to any one of [1] to [10], wherein the silicate is a flaky silicate, and the sodium content is less than 3.0% by weight. [12] The curable composition according to any one of [1] to [11], wherein the silicate is a flaky silicate, and the potassium content is 1.0% by weight or more. [13] The curable composition according to any one of [1] to [12], wherein the silicate is a flaky silicate, and the aluminum content is 0.5% by weight or more. [14] The curable composition according to any one of [1] to [13], wherein the silicate contains a fluorine atom. [15] The curable composition according to any one of [1] to [14], wherein the silicate contains fluorine atoms, and the content of the fluorine atoms is 0.5% by weight or more of the total silicate . [16] The curable composition according to any one of [1] to [15], wherein the silicate is mica. [17] The curable composition according to any one of [1] to [16], wherein the curable compound is a compound represented by the following formula (1),

[In the formula, R ¹ and R ^{2 are the} same or different, representing a curable functional group, D ¹ and D ^{2 are the} same or different, representing a single bond or a linking group, and L represents having a structure represented by the following formula (I), And the divalent group of the repeating unit of the structure represented by the following formula (II);

(In the formula, Ar ¹ to Ar ^{3 are the} same or different, and represent an aryl extension group, or a group formed by two or more aryl extension groups bonded via a single bond or a linking group, and X represents -CO-, -S-, or -SO ₂ -, Y is the same or different, represents -S-, -SO ₂ -, -O-, -CO-, -COO-, or -CONH-, n represents an integer of 0 or more)]. [18] The curable composition as described in [17], wherein R ¹ and R ² in formula (1) are the same or different, and are curable functional groups having a cyclic imine structure. [19] The curable composition as described in [17], wherein R ¹ and R ² in the formula (1) are groups represented by the following formula (r).

(In the formula, Q represents C or CH; the two Qs in the formula are bonded via a single bond or a double bond; n'is an integer greater than 0; R ³ to R ^{6 are the} same or different, and represent a hydrogen atom, saturated or unsaturated An aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group formed by bonding two or more groups selected from the above-mentioned saturated or unsaturated aliphatic hydrocarbon group and an aromatic hydrocarbon group; two groups selected from R ³ to R ⁶ are also It can be bonded to each other and form a ring with adjacent carbon atoms; in the formula, the bonding bond extending from the nitrogen atom is bonded to D ¹ or D ² ) [20] The hardenable composition as described in [17] ^{Wherein, R 1} and R ² in the formula (1) are the same or different and are selected from the groups represented by the following formulas (r-1) to (r-6).

(In the formula, the bonding bond extending from the nitrogen atom is bonded to D ¹ or D ² ) [21] The curable composition as described in [17], wherein R ¹ and R ^{2 in formula (1)} The same or different are the groups represented by the following formula (r-1) or (r-5).

(In the formula, the bonding bond extending from the nitrogen atom is bonded to D ¹ or D ² ) [22] The curable composition as described in [17], wherein R ¹ -D ^{1 in formula (1)} The-group and the R ² -D ² -group are the same or different, and are a group including a group represented by the following formula (rd-1) or (rd-2).

(In the formula, the bonding bond extending from the phenyl group is bonded to the L side in the formula (1)) [23] The curable composition as described in [17], wherein the R in the formula (1) ^{The 1-} D ¹ -group and the R ² -D ² -group are the same or different, and are groups represented by the following formula (rd-1-1) or (rd-2-1).

(In the formula, the bonding bond extending from the oxygen atom is bonded to the L in formula (1)) [24] The curable composition as described in any one of [17] to [23], wherein the formula ( 1) L is a divalent group represented by the following formula (L-1).

(In the formula, Ar ¹ to Ar ^{3 are the} same or different, and represent an aryl extension group, or a group in which two or more aryl extension groups are bonded via a single bond or a linking group; X represents -CO-, -S-, or -SO ₂ -, Y is the same or different, representing -S-, -SO ₂ -, -O-, -CO-, -COO-, or -CONH-; n'' represents an integer of 0 or more, and m represents 2～ Number of 50) [25] The curable composition as described in any one of [17] to [23], wherein L in formula (1) is the following formula (L-1-1) or (L -1-2) The divalent base indicated.

(In the formula, m1 and m2 represent a number from 2 to 50) [26] The curable composition as described in any one of [1] to [25], wherein the curable compound is determined by GPC measurement The number average molecular weight in terms of standard polystyrene is 1,000 to 15,000. [27] The curable composition according to any one of [1] to [26], wherein the glass transition temperature of the curable compound is 80 to 280°C. [28] A cured product, which is a cured product of the curable composition described in any one of [1] to [27]. [29] A semi-cured product, which is a semi-cured product of the curable composition described in any one of [1] to [27]. [30] A laminate having a structure in which the cured product described in [29] is laminated on a substrate. [31] The laminate as described in [30], wherein the substrate is a copper substrate. [32] A method for manufacturing a laminate, which hardens the curable composition by coating the curable composition as described in any one of [1] to [27] on a substrate and subjecting it to heat treatment Thus, a laminate having a structure in which the cured product of the curable composition is laminated on the substrate is obtained. [33] A method of manufacturing a laminate, which comprises placing a semi-cured material of the curable composition described in any one of [1] to [27] on a substrate, and subjecting the semi-cured material to heat treatment to make the semi-cured material The hardened product is hardened to obtain a laminate having the above-mentioned hardened composition laminated on the substrate. [34] A printed circuit board having conductor wiring on the board, and the board is made of a cured product of the curable composition described in any one of [1] to [27]. [35] A method of manufacturing a printed circuit board, which is a method of manufacturing a printed circuit board with conductor wiring on the board, and includes the following steps: a curable composition as described in any one of [1] to [27] Conductor wiring is formed on the substrate formed by the hardened material of the object. [36] An electronic device having a printed circuit board, and the printed circuit board is provided with conductor wiring on a substrate made of a cured product of the curable composition described in any one of [1] to [27] By. [37] A method of manufacturing an electronic device, which is a method of manufacturing an electronic device provided with a printed circuit board, and the above-mentioned printed circuit board is provided with conductor wiring on the substrate, and the method of manufacturing the electronic device includes the following steps: [27] Conductor wiring is formed on a substrate composed of a cured product of the curable composition described in any one of [27]. [Industrial availability]

本發明之硬化性組成物藉由加熱可獲得具有耐熱性及可撓性之硬化物。又，上述硬化物較佳為低CTE，且具有與銅同等程度之熱線膨脹係數。因此，上述硬化性組成物可較好地用作實施銅配線之電子線路基板之原料。The curable composition of the present invention can be heated to obtain a cured product having heat resistance and flexibility. In addition, the above-mentioned hardened product preferably has a low CTE and has a thermal linear expansion coefficient equivalent to that of copper. Therefore, the above-mentioned curable composition can be preferably used as a raw material of an electronic circuit board for implementing copper wiring.

無。without.

[圖1]係表示製備例中所獲得之二胺（1）之¹ H-NMR圖譜（DMSO-d₆ ）之圖。 [圖2]係表示製備例中所獲得之二胺（1）之FTIR圖譜之圖。 [圖3]係表示製備例中所獲得之硬化性化合物A之¹ H-NMR圖譜（CDCl₃ ）之圖。 [圖4]係表示製備例中所獲得之硬化性化合物A之FTIR圖譜之圖。 [圖5]係表示實施例中所使用之雲母（NK-8G）之掃描式電子顯微鏡圖像（SEM圖像）之圖。 [圖6]係表示實施例中所使用之雲母（MAE）之掃描式電子顯微鏡圖像（SEM圖像）之圖。 [圖7]係表示實施例中所使用之雲母（ME100）之掃描式電子顯微鏡圖像（SEM圖像）之圖。 [圖8]係表示實施例中所使用之雲母（MK200）之掃描式電子顯微鏡圖像（SEM圖像）之圖。 ^{[Figure 1] is a diagram showing the 1} H-NMR spectrum (DMSO-d ₆ ) of the diamine (1) obtained in the preparation example. [Figure 2] A diagram showing the FTIR spectrum of the diamine (1) obtained in the preparation example. [Fig. 3] A diagram showing the ¹ H-NMR spectrum (CDCl ₃ ) of the curable compound A obtained in the preparation example. [Fig. 4] A diagram showing the FTIR spectrum of the sclerosing compound A obtained in the preparation example. [Figure 5] is a diagram showing a scanning electron microscope image (SEM image) of the mica (NK-8G) used in the examples. [Fig. 6] is a diagram showing a scanning electron microscope image (SEM image) of the mica (MAE) used in the examples. [Fig. 7] A diagram showing a scanning electron microscope image (SEM image) of the mica (ME100) used in the examples. [Fig. 8] is a diagram showing a scanning electron microscope image (SEM image) of the mica (MK200) used in the examples.

無。without.

Claims (20)

一種硬化性組成物，其包含硬化性化合物及矽酸鹽，且上述矽酸鹽之含量相對於硬化性化合物100重量份為0.01～95重量份。A curable composition comprising a curable compound and silicate, and the content of the silicate is 0.01 to 95 parts by weight relative to 100 parts by weight of the curable compound. 如請求項1之硬化性組成物，其中，矽酸鹽為薄片狀矽酸鹽。Such as the curable composition of claim 1, wherein the silicate is a flaky silicate. 如請求項1或2之硬化性組成物，其中，矽酸鹽兼具下述特性1及特性2： 特性1：在設置於平面上之高度5.0 mm、直徑10 mm之粉體試樣用聚氯乙烯環中填充矽酸鹽，直至距聚氯乙烯環上部平面之高度成為5.0 mm為止，並以最大加壓7 MPa進行3分鐘加壓而使聚氯乙烯環表面變得平滑，於除壓後5分鐘於聚氯乙烯環之表面產生***； 特性2：在設置於平面上之高度5.0 mm、直徑10 mm之粉體試樣用聚氯乙烯環中填充矽酸鹽，直至距聚氯乙烯環上部平面之高度成為3.0 mm為止，並以最大加壓5 MPa進行3分鐘加壓而使聚氯乙烯環表面變得平滑，於除壓後5分鐘未於聚氯乙烯環之表面產生***。Such as the hardening composition of claim 1 or 2, wherein the silicate has both the following characteristics 1 and 2: Feature 1: Fill the polyvinyl chloride ring for powder samples with a height of 5.0 mm and a diameter of 10 mm on a flat surface until the height from the upper surface of the polyvinyl chloride ring becomes 5.0 mm, and the maximum Press 7 MPa for 3 minutes to smooth the surface of the polyvinyl chloride ring, and bulge on the surface of the polyvinyl chloride ring 5 minutes after depressurization; Feature 2: Fill the polyvinyl chloride ring for a powder sample with a height of 5.0 mm and a diameter of 10 mm on a flat surface until the height from the upper surface of the polyvinyl chloride ring becomes 3.0 mm, and the maximum Press 5 MPa for 3 minutes to smooth the surface of the polyvinyl chloride ring, and no bulge on the surface of the polyvinyl chloride ring 5 minutes after depressurization. 如請求項1至3中任一項之硬化性組成物，其中，矽酸鹽之最大直徑L₁ 、與上述最大直徑L₁ 正交之直徑L₂ 、及厚度W滿足下述式（a）、（b）： 0.2L₁ ≦L₂ ≦L₁ （a） 0.001L₁ ≦W≦0.08L₁ （b）。The requested item 1-1 The curable composition according to any 3, wherein the maximum diameter of silicate ₁ L, and L _2, and _a thickness orthogonal to the diameter of the maximum diameter W L satisfies the following formula (a) _{, (b): 0.2L 1 ≦} L 2 ≦ L 1 (a) 0.001L 1 ≦ W ≦ 0.08L 1 (b). 如請求項1之硬化性組成物，其中，矽酸鹽為親油性矽酸鹽。Such as the hardening composition of claim 1, wherein the silicate is a lipophilic silicate. 如請求項1至5中任一項之硬化性組成物，其中，矽酸鹽包含鹼金屬。The curable composition according to any one of claims 1 to 5, wherein the silicate contains an alkali metal. 如請求項1至6中任一項之硬化性組成物，其中，矽酸鹽之鎂含量為10重量%以上。The curable composition according to any one of claims 1 to 6, wherein the magnesium content of the silicate is 10% by weight or more. 如請求項1至7中任一項之硬化性組成物，其中，矽酸鹽為薄片狀矽酸鹽，鈉含量未達3.0重量%。The curable composition according to any one of claims 1 to 7, wherein the silicate is a flaky silicate, and the sodium content is less than 3.0% by weight. 如請求項1至4、6至8中任一項之硬化性組成物，其中，矽酸鹽為薄片狀矽酸鹽，鉀含量為1.0重量%以上。The curable composition according to any one of claims 1 to 4 and 6 to 8, wherein the silicate is a flaky silicate, and the potassium content is 1.0% by weight or more. 如請求項1至4、6至9中任一項之硬化性組成物，其中，矽酸鹽為薄片狀矽酸鹽，鋁含量為0.5重量%以上。The curable composition according to any one of claims 1 to 4 and 6 to 9, wherein the silicate is a flaky silicate, and the aluminum content is 0.5% by weight or more. 如請求項1至10中任一項之硬化性組成物，其中，矽酸鹽包含氟原子。The curable composition according to any one of claims 1 to 10, wherein the silicate contains fluorine atoms. 如請求項1至11中任一項之硬化性組成物，其中，矽酸鹽為雲母。The curable composition according to any one of claims 1 to 11, wherein the silicate is mica. 如請求項1至12中任一項之硬化性組成物，其中， 硬化性化合物係下述式（1）所表示之化合物：

[式中，R¹ 、R² 相同或不同，表示硬化性官能基，D¹ 、D² 相同或不同，表示單鍵或連結基，L表示具有包含下述式（I）所表示之結構、及下述式（II）所表示之結構之重複單位的2價基；

（式中，Ar¹ ～Ar³ 相同或不同，表示伸芳基、或2個以上之伸芳基經由單鍵或者連結基鍵結而成之基，X表示-CO-、-S-、或-SO₂ -，Y相同或不同，表示-S-、-SO₂ -、-O-、-CO-、-COO-、或-CONH-，n表示0以上之整數）]。The curable composition according to any one of claims 1 to 12, wherein the curable compound is a compound represented by the following formula (1):

[In the formula, R ¹ and R ^{2 are the} same or different, representing a curable functional group, D ¹ and D ^{2 are the} same or different, representing a single bond or a linking group, and L represents having a structure represented by the following formula (I), And the divalent group of the repeating unit of the structure represented by the following formula (II);

(In the formula, Ar ¹ to Ar ^{3 are the} same or different, and represent an aryl extension group, or a group formed by two or more aryl extension groups bonded via a single bond or a linking group, and X represents -CO-, -S-, or -SO ₂ -, Y is the same or different, represents -S-, -SO ₂ -, -O-, -CO-, -COO-, or -CONH-, n represents an integer of 0 or more)]. 如請求項13之硬化性組成物，其中，式（1）中之R¹ 、R² 相同或不同，為具有環狀醯亞胺結構之硬化性官能基。The curable composition of claim 13, wherein R ¹ and R ² in formula (1) are the same or different, and are curable functional groups having a cyclic imine structure. 如請求項13之硬化性組成物，其中，式（1）中之R¹ 、R² 相同或不同，為選自下述式（r-1）～（r-6）所表示之基中之基：

（式中，自氮原子延伸之鍵結鍵與D¹ 或D² 鍵結）。The curable composition of claim 13, wherein R ¹ and R ² in formula (1) are the same or different, and are selected from the groups represented by the following formulas (r-1) to (r-6) base:

(In the formula, the bonding bond extending from the nitrogen atom is bonded to D ¹ or D ² ). 一種硬化物，其係請求項1至15中任一項之硬化性組成物之硬化物。A hardened product, which is a hardened product of the hardenable composition of any one of claims 1 to 15. 一種半硬化物，其係請求項1至15中任一項之硬化性組成物之半硬化物。A semi-hardened product, which is a semi-hardened product of the hardenable composition of any one of claims 1 to 15. 一種積層體，其具有請求項16之硬化物積層於基板之構成。A laminate having a structure in which the hardened substance of claim 16 is laminated on a substrate. 如請求項18之積層體，其中，基板為銅基板。Such as the laminate of claim 18, wherein the substrate is a copper substrate. 一種電子裝置，其具有印刷基板，該印刷基板係於由請求項1至15中任一項之硬化性組成物之硬化物所構成之基板上實施導體配線而成者。An electronic device having a printed circuit board formed by implementing conductor wiring on a substrate formed of a hardened product of the hardenable composition of any one of claims 1 to 15.

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