TW202328310A - Coating composition, preparation methods of the coating composition and polyimide resin wherein the coating composition includes polyamic acid and a solvent - Google Patents

Coating composition, preparation methods of the coating composition and polyimide resin wherein the coating composition includes polyamic acid and a solvent Download PDF

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TW202328310A
TW202328310A TW111140421A TW111140421A TW202328310A TW 202328310 A TW202328310 A TW 202328310A TW 111140421 A TW111140421 A TW 111140421A TW 111140421 A TW111140421 A TW 111140421A TW 202328310 A TW202328310 A TW 202328310A
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tetracarboxylic dianhydride
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coating composition
aromatic
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田所恵典
西條秀樹
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日商東京應化工業股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The object of the present invention is to provide a coating composition capable of forming a polyimide resin having less coloration and excellent mechanical properties, a method for producing the coating composition, and a method for producing a polyimide resin using the coating composition. The solution of the present invention includes a coating composition of polyamic acid (A) and a solvent (S), wherein the polyamic acid (A) includes polymers of alicyclic tetracarboxylic dianhydride (A1-1), a small amount of aromatic tetracarboxylic acid dianhydride (A1-2) and aromatic diamine compound (A2).

Description

塗料組成物、塗料組成物之製造方法，及聚醯亞胺樹脂之製造方法Coating composition, manufacturing method of coating composition, and manufacturing method of polyimide resin

本發明係關於塗料組成物、與該塗料組成物之製造方法、與使用該塗料組成物之聚醯亞胺樹脂之製造方法。The present invention relates to a coating composition, a method for producing the coating composition, and a method for producing a polyimide resin using the coating composition.

聚醯亞胺樹脂由於具有優異之耐熱性、機械性強度及絕緣性，或低介電常數等之特性，故在如各種元件或多層配線基板等之電子基板般的電氣･電子零件，被廣泛作為絕緣材料或保護材料使用。 Polyimide resin is widely used in electrical and electronic components such as electronic substrates such as various components or multilayer wiring boards due to its excellent heat resistance, mechanical strength, insulation, and low dielectric constant. Used as insulating or protective material.

一般而言，聚醯亞胺樹脂係藉由將四羧酸二酐成分與二胺成分於極性有機溶劑中聚合所得之聚醯胺酸進行熱處理而形成。亦有這般的背景，電子材料用之聚醯亞胺製品多數作為如聚醯胺酸般之聚醯亞胺前驅體的溶液供給。具體而言，製造電氣･電子零件時，聚醯亞胺前驅體的溶液於形成絕緣材料或保護材料的點，藉由塗佈或注入等之方法供給後，熱處理聚醯亞胺前驅體的溶液，而形成絕緣材料或保護材料。Generally, the polyimide resin is formed by heat-treating polyamic acid obtained by polymerizing tetracarboxylic dianhydride components and diamine components in a polar organic solvent. There is also such a background. Most polyimide products used in electronic materials are supplied as solutions of polyimide precursors such as polyamic acid. Specifically, in the manufacture of electrical and electronic parts, the solution of the polyimide precursor is supplied by coating or injection at the point where the insulating material or protective material is formed, and then the solution of the polyimide precursor is heat-treated , and form an insulating material or a protective material.

關於這般的聚醯亞胺樹脂之技術開拓已被認真研究，揭示有包含聚醯胺酸等之各種樹脂組成物(例如參照專利文獻1等)。 [先前技術文獻] [專利文獻] Technological development of such polyimide resins has been earnestly studied, and various resin compositions including polyamic acid and the like have been disclosed (for example, refer to Patent Document 1 and the like). [Prior Art Literature] [Patent Document]

[專利文獻1]日本特開2018-58918號公報[Patent Document 1] Japanese Patent Laid-Open No. 2018-58918

[發明欲解決之課題][Problem to be solved by the invention]

於聚醯亞胺樹脂、尤其是聚醯亞胺薄膜，有因用途，而期望著色少或拉伸彈性率等之機械特性優異的情況。惟，將專利文獻1等所記載之樹脂組成物作為塗料組成物使用，製造聚醯亞胺樹脂時，有難以形成兼備著色少與優異之機械特性的聚醯亞胺樹脂的問題。In polyimide resins, especially polyimide films, depending on the application, less coloring or excellent mechanical properties such as tensile modulus may be desired. However, when a polyimide resin is produced using the resin composition described in Patent Document 1 and the like as a paint composition, it is difficult to form a polyimide resin having both less coloring and excellent mechanical properties.

本發明係鑑於上述之課題而完成者，以提供一種可形成兼備著色少與優異之機械特性之聚醯亞胺樹脂的塗料組成物、與該塗料組成物之製造方法、與使用該塗料組成物之聚醯亞胺樹脂之製造方法作為目的。 [用以解決課題之手段] The present invention was made in view of the above-mentioned problems to provide a coating composition capable of forming a polyimide resin having less coloration and excellent mechanical properties, a method for producing the coating composition, and a coating composition using the coating composition The production method of the polyimide resin is the purpose. [Means to solve the problem]

本發明者們發現在包含聚醯胺酸(A)、與溶媒(S)之塗料組成物，藉由將脂環式四羧酸二酐(A1-1)、與少量之芳香族四羧酸二酐(A1-2)、與芳香族二胺化合物(A2)的聚合物作為聚醯胺酸(A)使用，可解決上述之課題，而終至完成本發明。更具體而言，本發明係提供以下者。The present inventors found that in the coating composition comprising polyamic acid (A) and solvent (S), by adding alicyclic tetracarboxylic dianhydride (A1-1) and a small amount of aromatic tetracarboxylic acid The use of a polymer of dianhydride (A1-2) and aromatic diamine compound (A2) as polyamic acid (A) solves the above-mentioned problems, and finally completes the present invention. More specifically, the present invention provides the following.

本發明之第1態樣為一種塗料組成物，其特徵為 包含聚醯胺酸(A)、與溶媒(S)， 聚醯胺酸(A)為四羧酸二酐(A1)及芳香族二胺化合物(A2)之聚合物， 四羧酸二酐(A1)係僅由脂環式四羧酸二酐(A1-1)及芳香族四羧酸二酐(A1-2)所構成， 芳香族四羧酸二酐(A1-2)的質量相對於四羧酸二酐(A1)之莫耳數的比率，為0.1莫耳%以上6莫耳%以下。 A first aspect of the present invention is a paint composition characterized by Contains polyamide (A), and vehicle (S), Polyamic acid (A) is a polymer of tetracarboxylic dianhydride (A1) and aromatic diamine compound (A2), Tetracarboxylic dianhydride (A1) is composed only of alicyclic tetracarboxylic dianhydride (A1-1) and aromatic tetracarboxylic dianhydride (A1-2), The ratio of the mass of the aromatic tetracarboxylic dianhydride (A1-2) to the number of moles of the tetracarboxylic dianhydride (A1) is 0.1 mol % or more and 6 mol % or less.

本發明之第2態樣為一種塗料組成物之製造方法，其係包含： 將四羧酸二酐(A1)及芳香族二胺化合物(A2)於溶媒(S)中聚合，使聚醯胺酸(A)生成，或 使四羧酸二酐(A1)及芳香族二胺化合物(A2)聚合，生成聚醯胺酸(A)後，將經單離之聚醯胺酸(A)與溶媒(S)混合之塗料組成物之製造方法，其特徵為 四羧酸二酐(A1)係僅由脂環式四羧酸二酐(A1-1)及芳香族四羧酸二酐(A1-2)構成， 芳香族四羧酸二酐(A1-2)的質量相對於四羧酸二酐(A1)之莫耳數的比率，為0.1莫耳%以上6莫耳%以下。 The second aspect of the present invention is a method for producing a paint composition, which includes: Polymerize tetracarboxylic dianhydride (A1) and aromatic diamine compound (A2) in solvent (S) to generate polyamic acid (A), or Polymerization of tetracarboxylic dianhydride (A1) and aromatic diamine compound (A2) to produce polyamic acid (A) and then mixing the isolated polyamic acid (A) with solvent (S) A method for producing a composition characterized by Tetracarboxylic dianhydride (A1) is composed only of alicyclic tetracarboxylic dianhydride (A1-1) and aromatic tetracarboxylic dianhydride (A1-2), The ratio of the mass of the aromatic tetracarboxylic dianhydride (A1-2) to the number of moles of the tetracarboxylic dianhydride (A1) is 0.1 mol % or more and 6 mol % or less.

本發明之第3態樣為一種聚醯亞胺樹脂之製造方法，其係包含： 成形該第1態樣之塗料組成物之成形步驟、與 加熱經成形之塗料組成物，使其醯亞胺化之醯亞胺化步驟。 [發明效果] The 3rd aspect of the present invention is a kind of manufacturing method of polyimide resin, and it is to comprise: The forming step of forming the coating composition of the first aspect, and The imidization step of heating the formed coating composition to imidize it. [Invention effect]

根據本發明，可提供一種可形成兼備著色少與優異之機械特性之聚醯亞胺樹脂的塗料組成物、與該塗料組成物之製造方法、與使用該塗料組成物之聚醯亞胺樹脂之製造方法。According to the present invention, it is possible to provide a coating composition capable of forming a polyimide resin having less coloration and excellent mechanical properties, a method for producing the coating composition, and a polyimide resin using the coating composition. Manufacturing method.

≪塗料組成物≫≪Paint composition≫

塗料組成物包含聚醯胺酸(A)、與溶媒(S)。該塗料組成物係使用在聚醯亞胺樹脂的形成。The coating composition includes polyamic acid (A), and a solvent (S). The coating composition is used in the formation of polyimide resin.

以下，關於塗料組成物之必須或任意的成分進行說明。Hereinafter, the essential or optional components of the paint composition will be described.

＜聚醯胺酸(A)＞ 塗料組成物包含聚醯胺酸(A)。聚醯胺酸(A)係硬化塗料組成物時所生成之聚醯亞胺樹脂的前驅體聚合物。 ＜Polyamide (A)＞ The coating composition contains polyamic acid (A). Polyamic acid (A) is a precursor polymer of polyimide resin produced when the coating composition is cured.

聚醯胺酸(A)係四羧酸二酐(A1)及芳香族二胺化合物(A2)之聚合物。四羧酸二酐(A1)係僅由脂環式四羧酸二酐(A1-1)及芳香族四羧酸二酐(A1-2)構成。芳香族四羧酸二酐(A1-2)的質量相對於四羧酸二酐(A1)之莫耳數的比率，為0.1莫耳%以上6莫耳%以下。 藉由使用該聚醯胺酸(A)，並使用塗料組成物，可形成兼備著色少與優異之機械特性之聚醯亞胺樹脂。 作為機械特性，通常而言，為拉伸彈性率、拉伸強度、斷裂伸長率、熱膨脹率(CTE)等。 Polyamic acid (A) is a polymer of tetracarboxylic dianhydride (A1) and aromatic diamine compound (A2). Tetracarboxylic dianhydride (A1) consists only of alicyclic tetracarboxylic dianhydride (A1-1) and aromatic tetracarboxylic dianhydride (A1-2). The ratio of the mass of the aromatic tetracarboxylic dianhydride (A1-2) to the number of moles of the tetracarboxylic dianhydride (A1) is 0.1 mol % or more and 6 mol % or less. By using this polyamic acid (A) and using a coating composition, the polyimide resin which has little coloring and excellent mechanical characteristics can be formed. Generally, the mechanical properties include tensile modulus, tensile strength, elongation at break, coefficient of thermal expansion (CTE), and the like.

以下，針對使用在聚醯胺酸(A)的製造之四羧酸二酐(A1)、與芳香族二胺化合物(A2)、與聚醯胺酸(A)之製造方法，於以下進行說明。Hereinafter, the production method of tetracarboxylic dianhydride (A1), aromatic diamine compound (A2), and polyamic acid (A) used in the production of polyamic acid (A) will be described below. .

[四羧酸二酐(A1)] 四羧酸二酐(A1)係僅由脂環式四羧酸二酐(A1-1)及芳香族四羧酸二酐(A1-2)構成。芳香族四羧酸二酐(A1-2)的質量相對於四羧酸二酐(A1)之莫耳數的比率，為0.1莫耳%以上6莫耳%以下。 芳香族四羧酸二酐(A1-2)的質量相對於四羧酸二酐(A1)之莫耳數的比率，較佳為0.2莫耳%以上5.5莫耳%以下，更佳為0.5莫耳%以上5莫耳%以下。 [Tetracarboxylic dianhydride (A1)] Tetracarboxylic dianhydride (A1) consists only of alicyclic tetracarboxylic dianhydride (A1-1) and aromatic tetracarboxylic dianhydride (A1-2). The ratio of the mass of the aromatic tetracarboxylic dianhydride (A1-2) to the number of moles of the tetracarboxylic dianhydride (A1) is 0.1 mol % or more and 6 mol % or less. The ratio of the mass of aromatic tetracarboxylic dianhydride (A1-2) to the number of moles of tetracarboxylic dianhydride (A1) is preferably 0.2 mol% or more and 5.5 mol% or less, more preferably 0.5 mol% More than ear% and less than 5 mole%.

(脂環式四羧酸二酐(A1-1)) 作為脂環式四羧酸二酐(A1-1)的合適之例，可列舉下述式(a1-1)表示之化合物。四羧酸二酐(A1-1)可1種單獨使用，亦可組合2種以上使用。 (式(a1-1)中，A 1為包含未包含芳香族基之脂環的碳原子數4以上50以下之4價的有機基。在式(a1-1)，2個羧酸酐基係鍵結在脂環上)。 (Alicyclic tetracarboxylic dianhydride (A1-1)) As a suitable example of alicyclic tetracarboxylic dianhydride (A1-1), the compound represented by following formula (a1-1) is mentioned. Tetracarboxylic dianhydride (A1-1) may be used individually by 1 type, and may use it in combination of 2 or more types. (In formula (a1-1), A1 is a tetravalent organic group with 4 to 50 carbon atoms including an alicyclic ring that does not contain an aromatic group. In formula (a1-1), two carboxylic acid anhydride groups are bonded to the aliphatic ring).

式(a1-1)中，A 1為包含未包含芳香族基之脂環的碳原子數4以上50以下之4價的有機基。在式(a1-1)之A 1除了2個羧酸酐基之外，可具有1個或複數個取代基。 作為取代基的合適之例，較佳為氟原子、碳原子數1以上6以下之烷基、碳原子數1以上6以下之烷氧基、碳原子數1以上6以下之氟化烷基、碳原子數1以上6以下之氟化烷氧基。又，式(a1-1)表示之化合物除了酸酐基之外，可包含羧基、羧酸酯基。 取代基為氟化烷基或氟化烷氧基時，較佳為全氟烷基或全氟烷氧基。 In the formula (a1-1), A 1 is a tetravalent organic group having 4 to 50 carbon atoms including an alicyclic ring not containing an aromatic group. A 1 in formula (a1-1) may have one or plural substituents in addition to two carboxylic acid anhydride groups. Suitable examples of substituents are preferably fluorine atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, fluorinated alkyl groups having 1 to 6 carbon atoms, A fluorinated alkoxy group having 1 to 6 carbon atoms. Moreover, the compound represented by formula (a1-1) may contain a carboxyl group and a carboxylate group other than an acid anhydride group. When the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, it is preferably a perfluoroalkyl group or a perfluoroalkoxy group.

脂環式四羧酸二酐(A1-1)係具有2個鍵結在脂環上之羧酸酐基，未包含芳香族基之化合物。脂環式四羧酸二酐可具有直鏈狀或分枝鏈狀之鏈狀脂肪族基。 脂環式四羧酸二酐(A1-1)所具有之脂環及鏈狀脂肪族基除了碳原子及氫原子之外，可包含鹵素原子、氧原子、氮原子及硫原子。例如氧原子、氮原子或硫原子作為選自含氮雜環基、-CONH-、-NH-、-N=N-、-CH=N-、-COO-、-O-、-CO-、-SO-、-SO 2-、-S-及-S-S-中之基，可包含在脂環及鏈狀脂肪族基。 Alicyclic tetracarboxylic dianhydride (A1-1) is a compound which has two carboxylic acid anhydride groups bonded to an alicyclic ring and does not contain an aromatic group. The alicyclic tetracarboxylic dianhydride may have a linear or branched chain aliphatic group. The alicyclic and chain aliphatic groups which the alicyclic tetracarboxylic dianhydride (A1-1) has may contain a halogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom other than a carbon atom and a hydrogen atom. For example, an oxygen atom, a nitrogen atom or a sulfur atom is selected from a nitrogen-containing heterocyclic group, -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, The groups in -SO-, -SO 2 -, -S- and -SS- may be included in alicyclic and chain aliphatic groups.

脂環式四羧酸二酐(A1-1)所包含之脂環可為單環，亦可為多環。作為多環式之脂環式構造，例如可列舉聯環[2.2.1]庚烷等之橋接脂環式構造等。例如橋接脂環式構造可與其他橋接脂環式構造及/或非橋接脂環式構造縮合，亦可橋接脂環式構造藉由與其他橋接脂環式構造及/或非橋接脂環式構造螺鍵結來連結。藉由使用脂環式四羧酸二酐(A1-1)，使用塗料組成物，而得到透明性優異之聚醯亞胺樹脂。The alicyclic ring contained in the alicyclic tetracarboxylic dianhydride (A1-1) may be monocyclic or polycyclic. Examples of the polycyclic alicyclic structure include bridged alicyclic structures such as bicyclo[2.2.1]heptane, and the like. For example, bridged alicyclic structures can be condensed with other bridged alicyclic structures and/or non-bridged alicyclic structures, and bridged alicyclic structures can also be condensed with other bridged alicyclic structures and/or non-bridged alicyclic structures. Screw key to connect. By using the alicyclic tetracarboxylic dianhydride (A1-1) and using the coating composition, a polyimide resin excellent in transparency was obtained.

作為脂環式四羧酸二酐(A1-1)之合適的具體例，可列舉1,2,4,5-環己烷四羧酸二酐、聯環[2.2.2]辛烷-2,3,5,6-四羧酸二酐、聯環[2.2.2]辛-7-烯-2,3,5,6-四羧酸二酐、5-(2,5-二側氧基四氫呋喃-3-基)-3-甲基-3-環已烯-1,2-二羧酸酐、4-(2,5-二側氧基四氫呋喃-3-基)-四氫化萘-1,2-二羧酸酐、四氫呋喃-2,3,4,5-四羧酸二酐、1,2,3,4-環戊烷四羧酸二酐、1,2,3,4-環丁烷四羧酸二酐、1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐及1,4-二甲基-1,2,3,4-環丁烷四羧酸二酐等。Specific examples of alicyclic tetracarboxylic dianhydride (A1-1) include 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo[2.2.2]octane-2 ,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 5-(2,5-two side oxygen yltetrahydrofuran-3-yl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 4-(2,5-dipentoxytetrahydrofuran-3-yl)-tetrahydronaphthalene-1 ,2-dicarboxylic anhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane Alkane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride and 1,4-dimethyl-1,2,3,4-cyclobutane Alkane tetracarboxylic dianhydride, etc.

又，作為脂環式四羧酸二酐(A1-1)，較佳為下述式(a2)表示之化合物。使用下述式(a2)表示之化合物時，有容易得到透明性優異之聚醯亞胺樹脂的傾向。 尚，從原料化合物之純化容易的點來看，式(a2)中之a較佳為5以下，更佳為3以下。又，由於原料化合物之化學的安定性優異，a較佳為1以上，更佳為2以上。 式(a2)中之a特佳為2或3。 Moreover, as alicyclic tetracarboxylic dianhydride (A1-1), the compound represented by following formula (a2) is preferable. When a compound represented by the following formula (a2) is used, it tends to be easy to obtain a polyimide resin excellent in transparency. Furthermore, a in the formula (a2) is preferably 5 or less, more preferably 3 or less, from the viewpoint of ease of purification of the raw material compound. Moreover, since the chemical stability of the raw material compound is excellent, a is preferably 1 or more, more preferably 2 or more. a in the formula (a2) is particularly preferably 2 or 3.

(式(a2)中，R a11、R a12及R a13分別獨立為選自由氫原子、碳原子數1以上5以下之烷基及氟原子所構成之群組中之1種，a為0以上12以下之整數)。 (In formula (a2), R a11 , R a12 and R a13 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and a fluorine atom, and a is 0 or more an integer below 12).

可作為式(a2)中之R a11選擇之烷基，係碳原子數為1以上5以下之烷基。烷基之碳原子數再更佳為1以上4以下，特佳為1以上3以下。 R a11為烷基時，該烷基可為直鏈狀，亦可為分枝鏈狀。 The alkyl group that can be selected as R a11 in formula (a2) is an alkyl group having 1 to 5 carbon atoms. The number of carbon atoms in the alkyl group is still more preferably from 1 to 4, particularly preferably from 1 to 3. When R a11 is an alkyl group, the alkyl group may be linear or branched.

作為式(a2)中之R a11，從式(a2)表示之四羧酸二酐的取得或純化容易的點來看，更佳為氫原子、甲基、乙基、n-丙基或異丙基，特佳為氫原子或甲基。 式(a2)中之複數個R a11由於式(a2)表示之四羧酸二酐的純化容易，故較佳為相同之基。 As R a11 in the formula (a2), it is more preferable to be a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an iso The propyl group is particularly preferably a hydrogen atom or a methyl group. The plurality of R a11 in the formula (a2) are preferably the same group because the purification of the tetracarboxylic dianhydride represented by the formula (a2) is easy.

式(a2)中之a表示0以上12以下之整數。a之值超過12時，給予式(a2)表示之4價的有機基之四羧酸二酐的純化困難。 從式(a2)表示之四羧酸二酐的純化容易的點來看，a的上限較佳為5，更佳為3。 從式(a2)表示之四羧酸二酐之化學的安定性的點來看，a的下限較佳為1，更佳為2。 式(a2)中之a特佳為2或3。 a in the formula (a2) represents an integer of 0 to 12. When the value of a exceeds 12, purification of tetracarboxylic dianhydride which gives a tetravalent organic group represented by formula (a2) becomes difficult. The upper limit of a is preferably 5, more preferably 3, from the viewpoint of easy purification of tetracarboxylic dianhydride represented by formula (a2). The lower limit of a is preferably 1, more preferably 2 from the viewpoint of the chemical stability of tetracarboxylic dianhydride represented by formula (a2). a in the formula (a2) is particularly preferably 2 or 3.

可作為式(a2)中之R a12及R a13選擇之碳原子數1以上5以下之烷基，係與可作為R a11選擇之碳原子數1以上5以下之烷基相同。 R a12及R a13從式(a2)表示之四羧酸二酐之純化容易的點來看，較佳為氫原子或碳原子數1以上5以下之烷基，特佳為氫原子或甲基。 The alkyl group having 1 to 5 carbon atoms that can be selected as R a12 and R a13 in formula (a2) is the same as the alkyl group having 1 to 5 carbon atoms that can be selected as R a11 . R a12 and R a13 are preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, particularly preferably a hydrogen atom or a methyl group, from the viewpoint of ease of purification of the tetracarboxylic dianhydride represented by the formula (a2). .

作為式(a2)表示之四羧酸二酐，例如可列舉降冰片烷-2-螺環-α-環戊酮-α’-螺環-2’’-降冰片烷-5,5’’,6,6’’-四羧酸二酐(別名「降冰片烷-2-螺環-2’-環戊酮-5’-螺環-2’’-降冰片烷-5,5’’,6,6’’-四羧酸二酐」)、甲基降冰片烷-2-螺環-α-環戊酮-α’-螺環-2’’-(甲基降冰片烷)-5,5’’,6,6’’-四羧酸二酐、降冰片烷-2-螺環-α-環己酮-α’-螺環-2’’-降冰片烷-5,5’’,6,6’’-四羧酸二酐(別名「降冰片烷-2-螺環-2’-環己酮-6’-螺環-2’’-降冰片烷-5,5’’,6,6’’-四羧酸二酐」)、甲基降冰片烷-2-螺環-α-環己酮-α’-螺環-2’’-(甲基降冰片烷)-5,5’’,6,6’’-四羧酸二酐、降冰片烷-2-螺環-α-環丙酮-α’-螺環-2’’-降冰片烷-5,5’’,6,6’’-四羧酸二酐、降冰片烷-2-螺環-α-環丁酮-α’-螺環-2’’-降冰片烷-5,5’’,6,6’’-四羧酸二酐、降冰片烷-2-螺環-α-環庚酮-α’-螺環-2’’-降冰片烷-5,5’’,6,6’’-四羧酸二酐、降冰片烷-2-螺環-α-環辛酮-α’-螺環-2’’-降冰片烷-5,5’’,6,6’’-四羧酸二酐、降冰片烷-2-螺環-α-環壬酮-α’-螺環-2’’-降冰片烷-5,5’’,6,6’’-四羧酸二酐、降冰片烷-2-螺環-α-環癸酮-α’-螺環-2’’-降冰片烷-5,5’’,6,6’’-四羧酸二酐、降冰片烷-2-螺環-α-環十一烷酮-α’-螺環-2’’-降冰片烷-5,5’’,6,6’’-四羧酸二酐、降冰片烷-2-螺環-α-環十二烷酮-α’-螺環-2’’-降冰片烷-5,5’’,6,6’’-四羧酸二酐、降冰片烷-2-螺環-α-環十三烷酮-α’-螺環-2’’-降冰片烷-5,5’’,6,6’’-四羧酸二酐、降冰片烷-2-螺環-α-環十四烷酮-α’-螺環-2’’-降冰片烷-5,5’’,6,6’’-四羧酸二酐、降冰片烷-2-螺環-α-環十五烷酮-α’-螺環-2’’-降冰片烷-5,5’’,6,6’’-四羧酸二酐、降冰片烷-2-螺環-α-(甲基環戊酮)-α’-螺環-2’’-降冰片烷-5,5’’,6,6’’-四羧酸二酐、降冰片烷-2-螺環-α-(甲基環己酮)-α’-螺環-2’’-降冰片烷-5,5’’,6,6’’-四羧酸二酐等。Examples of the tetracarboxylic dianhydride represented by the formula (a2) include norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'' ,6,6''-tetracarboxylic dianhydride (alias "norbornane-2-spiro-2'-cyclopentanone-5'-spiro-2''-norbornane-5,5'' ,6,6''-tetracarboxylic dianhydride"), methylnorbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-(methylnorbornane)- 5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclohexanone-α'-spiro-2''-norbornane-5,5 '',6,6''-tetracarboxylic dianhydride (alias "norbornane-2-spiro-2'-cyclohexanone-6'-spiro-2''-norbornane-5,5 '',6,6''-tetracarboxylic dianhydride"), methylnorbornane-2-spiro-α-cyclohexanone-α'-spiro-2''-(methylnorbornane )-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopropanone-α'-spiro-2''-norbornane-5, 5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclobutanone-α'-spiro-2''-norbornane-5,5'' ,6,6''-Tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloheptanone-α'-spiro-2''-norbornane-5,5'',6, 6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclooctanone-α'-spiro-2''-norbornane-5,5'',6,6'' -Tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclononone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic Acid dianhydride, norbornane-2-spiro-α-cyclodecanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride , Norbornane-2-spirocycle-α-cycloundecone-α'-spirocycle-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, Norbornane-2-spiro-α-cyclododecanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane Bornane-2-spiro-α-cyclotridecanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane Alkane-2-spiro-α-cyclotetradecanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane -2-Spiro-α-Cyclopentadecanone-α'-Spiro-2''-Norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane- 2-Spiro-α-(methylcyclopentanone)-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane -2-spiro-α-(methylcyclohexanone)-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, etc.

又，作為式(a2)表示之四羧酸二酐，從使用塗料組成物所製造之聚醯亞胺樹脂的熱物性、機械物性、光學特性、電氣特性良好的點來看，較佳為含有下述式(a2-1)表示之化合物(A2-1)及下述式(a2-2)表示之化合物(A2-2)當中之至少1種，且為化合物(A2-1)及化合物(A2-2)之總量為30莫耳%以上之四羧酸二酐， (式(a2-1)中，R a11、R a12、R a13、a係與式(a2)中之R a11、R a12、R a13、a同義)。 (式(a2-2)中，R a11、R a12、R a13、a係與式(a2)中之R a11、R a12、R a13、a同義)。 Also, as the tetracarboxylic dianhydride represented by the formula (a2), it is preferable to contain At least one of compound (A2-1) represented by the following formula (a2-1) and compound (A2-2) represented by the following formula (a2-2), and compound (A2-1) and compound ( A2-2) The total amount of tetracarboxylic dianhydride is more than 30 mole%, (In formula (a2-1), R a11 , R a12 , R a13 , and a are synonymous with R a11 , R a12 , R a13 , and a in formula (a2). (In formula (a2-2), R a11 , R a12 , R a13 , and a are synonymous with R a11 , R a12 , R a13 , and a in formula (a2).

式(a2-1)表示之化合物(A2-1)係2個降冰片烷基反式配置，且相對於該2個降冰片烷基的個別，係環烷酮之羰基成為端之立體配置的式(a2)表示之四羧酸二酐的異構體。 式(a2-2)表示之化合物(A2-2)係2個降冰片烷基順式配置，且相對於該2個降冰片烷基的個別，係環烷酮之羰基成為端之立體配置的式(a2)表示之四羧酸二酐的異構體。 尚，將這般的異構體以上述比率含有之四羧酸二酐之製造方法亦並未特別限制，可適當採用公知之方法，例如可適當採用國際公開第2014/034760號所記載之方法等。 The compound (A2-1) represented by the formula (a2-1) has two norbornyl groups trans-configured, and relative to each of the two norbornyl groups, the carbonyl group of the cycloalkanone is end-stereo-configured An isomer of tetracarboxylic dianhydride represented by formula (a2). The compound (A2-2) represented by the formula (a2-2) has two norbornyl groups arranged in cis, and relative to each of the two norbornyl groups, the carbonyl group of the cycloalkanone is end-stereo-configured An isomer of tetracarboxylic dianhydride represented by formula (a2). Also, the method for producing tetracarboxylic dianhydride containing such isomers at the above ratio is not particularly limited, and known methods can be appropriately used, for example, the method described in International Publication No. 2014/034760 can be appropriately used wait.

(芳香族四羧酸二酐(A1-2)) 芳香族四羧酸二酐(A1-2)係於其構造中包含芳香環之四羧酸二酐。作為芳香族四羧酸二酐(A1-2)，自以往，即可無特別限制使用被使用在聚醯亞胺樹脂的製造之芳香族四羧酸二酐。 (Aromatic tetracarboxylic dianhydride (A1-2)) Aromatic tetracarboxylic dianhydride (A1-2) is a tetracarboxylic dianhydride containing an aromatic ring in its structure. As the aromatic tetracarboxylic dianhydride (A1-2), conventionally, the aromatic tetracarboxylic dianhydride used for manufacture of a polyimide resin can be used without limitation.

作為芳香族四羧酸二酐(A1-2)之合適的具體例，例如可列舉均苯四甲酸二酐、1,4-雙(3,4-二羧基苯氧基)苯二酐、3,3’,4,4’-氧基雙鄰苯二甲酸二酐、3,3’,4,4’-聯苯基四羧酸二酐、2,3,3’,4’-聯苯基四羧酸二酐、3,3’,4,4’-二苯基甲酮四羧酸二酐、3,3’,4,4’-二苯基碸四羧酸二酐及萘-1,4,5,8-四羧酸二酐等。Specific examples of suitable aromatic tetracarboxylic dianhydrides (A1-2) include pyromellitic dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 3 ,3',4,4'-Oxydiphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyl base tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, 3,3',4,4'-diphenylphenone tetracarboxylic dianhydride and naphthalene- 1,4,5,8-tetracarboxylic dianhydride, etc.

作為芳香族四羧酸二酐，又，例如亦可為下述式(a1-2)~(a1-4)表示之化合物。 Moreover, as an aromatic tetracarboxylic dianhydride, the compound represented by following formula (a1-2)-(a1-4) can also be used, for example.

在上述式(a1-2)及式(a1-3)，R a1、R a2及R a3分別表示可被鹵素取代之脂肪族基、氧原子、硫原子、透過1個以上之2價元素的芳香族基之任一者，或藉由該等之組合構成之2價的基。R a2及R a3可為相同，亦可為相異。 亦即，R a1、R a2及R a3可包含碳-碳之單鍵、碳-氧-碳之醚鍵或鹵素元素(氟、氯、溴、碘)。作為式(a1-2)表示之化合物，可列舉2,2-雙(3,4-二羧基苯氧基)丙烷二酐及1,4-雙(3,4-二羧基苯氧基)苯二酐等。 In the above formula (a1-2) and formula (a1-3), R a1 , R a2 and R a3 respectively represent an aliphatic group which may be substituted by a halogen, an oxygen atom, a sulfur atom, or a divalent element through which one or more Any of the aromatic groups, or a divalent group constituted by a combination thereof. R a2 and R a3 may be the same or different. That is, R a1 , R a2 and R a3 may contain a carbon-carbon single bond, a carbon-oxygen-carbon ether bond, or a halogen element (fluorine, chlorine, bromine, iodine). Examples of compounds represented by formula (a1-2) include 2,2-bis(3,4-dicarboxyphenoxy)propane dianhydride and 1,4-bis(3,4-dicarboxyphenoxy)benzene Dianhydride, etc.

又，在上述式(a1-4)，R a4、R a5表示可被鹵素取代之脂肪族基、透過1個以上之2價元素的芳香族基、鹵素任一者，或藉由該等之組合構成之1價的取代基。R a4及R a5亦可分別為相同，亦可為相異。作為式(a1-4)表示之化合物，亦可使用二氟均苯四甲酸二酐及二氯均苯四甲酸二酐等。 Also, in the above formula (a1-4), R a4 and R a5 represent either an aliphatic group that may be substituted by halogen, an aromatic group through one or more divalent elements, halogen, or any of these A monovalent substituent in combination. R a4 and R a5 may be respectively the same or different. As a compound represented by formula (a1-4), difluoropyromellitic dianhydride, dichloropyromellitic dianhydride, and the like can also be used.

作為用以得到於分子構造內含有氟之含氟聚醯亞胺的四羧酸二酐，例如可列舉(三氟甲基)均苯四甲酸二酐、二(三氟甲基)均苯四甲酸二酐、二(七氟丙基)均苯四甲酸二酐、五氟乙基均苯四甲酸二酐、雙{3,5-二(三氟甲基)苯氧基}均苯四甲酸二酐、2,2-雙(3,4-二羧基苯基)六氟丙烷二酐、5,5’-雙(三氟甲基)-3,3’,4,4’-四羧基聯苯基二酐、2,2’,5,5’-肆(三氟甲基)-3,3’,4,4’-四羧基聯苯基二酐、5,5’-雙(三氟甲基)-3,3’,4,4’-四羧基二苯基醚二酐、5,5’-雙(三氟甲基)-3,3’,4,4’-四羧基二苯基甲酮二酐、雙{(三氟甲基)二羧基苯氧基}苯二酐、雙{(三氟甲基)二羧基苯氧基}(三氟甲基)苯二酐、雙(二羧基苯氧基)(三氟甲基)苯二酐、雙(二羧基苯氧基)雙(三氟甲基)苯二酐、雙(二羧基苯氧基)肆(三氟甲基)苯二酐、2,2-雙{4-(3,4-二羧基苯氧基)苯基}六氟丙烷二酐、雙{(三氟甲基)二羧基苯氧基}聯苯基二酐、雙{(三氟甲基)二羧基苯氧基}雙(三氟甲基)聯苯基二酐、雙{(三氟甲基)二羧基苯氧基}二苯基醚二酐、雙(二羧基苯氧基)雙(三氟甲基)聯苯基二酐、二氟均苯四甲酸二酐、1,4-雙(3,4-二羧基三氟苯氧基)四氟苯二酐、1,4-雙(3,4-二羧基三氟苯氧基)八氟聯苯基二酐等。Examples of tetracarboxylic dianhydrides used to obtain fluorine-containing polyimides containing fluorine in their molecular structure include (trifluoromethyl)pyromellitic dianhydride, bis(trifluoromethyl)pyromellitic Formic dianhydride, bis(heptafluoropropyl)pyromellitic dianhydride, pentafluoroethylpyromellitic dianhydride, bis{3,5-bis(trifluoromethyl)phenoxy}pyromellitic acid Dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 5,5'-bis(trifluoromethyl)-3,3',4,4'-tetracarboxybis Phenyl dianhydride, 2,2',5,5'-tetra(trifluoromethyl)-3,3',4,4'-tetracarboxybiphenyl dianhydride, 5,5'-bis(trifluoromethyl) Methyl)-3,3',4,4'-tetracarboxydiphenyl ether dianhydride, 5,5'-bis(trifluoromethyl)-3,3',4,4'-tetracarboxydiphenyl Methyl ketone dianhydride, bis{(trifluoromethyl)dicarboxyphenoxy}phthalic anhydride, bis{(trifluoromethyl)dicarboxyphenoxy}(trifluoromethyl)phthalic anhydride, bis( Dicarboxyphenoxy)(trifluoromethyl)phthalic anhydride, bis(dicarboxyphenoxy)bis(trifluoromethyl)phthalic anhydride, bis(dicarboxyphenoxy)tetra(trifluoromethyl) Phthalic anhydride, 2,2-bis{4-(3,4-dicarboxyphenoxy)phenyl}hexafluoropropane dianhydride, bis{(trifluoromethyl)dicarboxyphenoxy}biphenyl anhydride, bis{(trifluoromethyl)dicarboxyphenoxy}bis(trifluoromethyl)biphenyl dianhydride, bis{(trifluoromethyl)dicarboxyphenoxy}diphenylether dianhydride, Bis(dicarboxyphenoxy)bis(trifluoromethyl)biphenyl dianhydride, difluoropyromellitic dianhydride, 1,4-bis(3,4-dicarboxytrifluorophenoxy)tetrafluoro Phthalic anhydride, 1,4-bis(3,4-dicarboxytrifluorophenoxy)octafluorobiphenyldianhydride, etc.

[芳香族二胺化合物(A2)] 作為芳香族二胺化合物(A2)，自以往，即可無特別限定使用被使用在聚醯亞胺樹脂的製造之具有芳香族基的二胺化合物。於此，將2個胺基皆與芳香族基鍵結之二胺化合物作為芳香族二胺化合物(A2)。 [Aromatic diamine compound (A2)] As an aromatic diamine compound (A2), the diamine compound which has an aromatic group used conventionally in manufacture of a polyimide resin can be used without limitation. Here, the diamine compound whose two amine groups are all bonded to an aromatic group is made into an aromatic diamine compound (A2).

作為芳香族二胺化合物(A2)，通常可使用下述式(a3-1)表示之化合物。芳香族二胺化合物(A2)可1種單獨使用，亦可組合2種以上使用。 (式(a3-1)中，A 2表示包含芳香族基之2價的有機基。式(a3-1)中之二個胺基皆與芳香族基鍵結)。 As an aromatic diamine compound (A2), the compound represented by following formula (a3-1) can be used normally. The aromatic diamine compound (A2) may be used individually by 1 type, and may use it in combination of 2 or more types. (In the formula (a3-1), A 2 represents a divalent organic group including an aromatic group. Both of the two amine groups in the formula (a3-1) are bonded to the aromatic group).

式(a3-1)中，A 2為包含芳香族基之2價的有機基。作為A 2之有機基，除了在式(a3-1)之2個胺基之外，可具有1個或複數個取代基。 作為取代基的合適之例，較佳為氟原子、碳原子數1以上6以下之烷基、碳原子數1以上6以下之烷氧基、碳原子數1以上6以下之氟化烷基、碳原子數1以上6以下之氟化烷氧基或羥基。 取代基為氟化烷基或氟化烷氧基時，較佳為全氟烷基或全氟烷氧基。 In the formula (a3-1), A 2 is a divalent organic group including an aromatic group. The organic group of A2 may have one or more substituents in addition to the two amino groups in the formula (a3-1). Suitable examples of substituents are preferably fluorine atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, fluorinated alkyl groups having 1 to 6 carbon atoms, A fluorinated alkoxy group or hydroxyl group having 1 to 6 carbon atoms. When the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, it is preferably a perfluoroalkyl group or a perfluoroalkoxy group.

式(a3-1)中，作為A 2之有機基的碳原子數的下限值較佳為6。作為上限值，較佳為50，更佳為30。 In formula (a3-1), the lower limit of the number of carbon atoms in the organic group of A2 is preferably 6. The upper limit is preferably 50, more preferably 30.

作為A 2之有機基，可為芳香族基本身，亦可為2個以上之芳香族基透過脂肪族烴基及鹵素化脂肪族烴基，或包含氧原子、硫原子及氮原子等之雜原子的鍵結而鍵結之基。作為A 2所包含之包含氧原子、硫原子及氮原子等之雜原子的鍵結，可列舉-CONH-、-NH-、-N=N-、-CH=N-、-COO-、-O-、-CO-、-SO-、-SO 2-、-S-及-S-S-等，較佳為-O-、-CO-、-SO-、-SO 2-、-S-及-S-S-。 The organic group of A2 can be an aromatic group itself, or two or more aromatic groups through aliphatic hydrocarbon groups and halogenated aliphatic hydrocarbon groups, or heteroatoms including oxygen atoms, sulfur atoms, nitrogen atoms, etc. Bonded and bonded base. Examples of bonds of heteroatoms including oxygen atoms, sulfur atoms, and nitrogen atoms included in A2 include -CONH-, -NH-, -N=N-, -CH=N-, -COO-, - O-, -CO-, -SO-, -SO 2 -, -S- and -SS-, etc., preferably -O-, -CO-, -SO-, -SO 2 -, -S- and - SS-.

與A 2中之胺基鍵結之芳香環較佳為苯環。與A 2中之胺基鍵結之環為包含2以上之環的縮合環時，較佳為與該縮合環中之胺基鍵結之環為苯環。 又，A 2所包含之芳香環亦可為芳香族雜環。 The aromatic ring bonded to the amine group in A2 is preferably a benzene ring. When the ring bonded to the amino group in A2 is a condensed ring containing two or more rings, it is preferable that the ring bonded to the amino group in the condensed ring is a benzene ring. In addition, the aromatic ring included in A2 may be an aromatic heterocyclic ring.

A 2為包含芳香族環之有機基時，從使用塗料組成物所形成之硬化物之耐熱性的點來看，芳香族二胺化合物(A2)較佳為下述式(21)~(24)表示之化合物當中之至少1種。 (式(21)~(24)中，R 111表示選自由氫原子、氟原子、羥基、碳原子數1以上4以下之烷基，及碳原子數1以上4以下之鹵素化烷基所構成之群組中之1種。式(24)中，Q表示9,9’-亞茀基，或選自由式：-C 6H 4-、-CONH-C 6H 4-NHCO-、-NHCO-C 6H 4-CONH-、-O-C 6H 4-CO-C 6H 4-O-、-OCO-C 6H 4-COO-、-OCO-C 6H 4-C 6H 4-COO-、-OCO-、-O-、-S-、-CO-、-CONH-、-SO 2-、-C(CF 3) 2-、-C(CH 3) 2-、-CH 2-、-O-C 6H 4-C(CH 3) 2-C 6H 4-O-、-O-C 6H 4-C(CF 3) 2-C 6H 4-O-、-O-C 6H 4-SO 2-C 6H 4-O-、 -C(CH 3) 2-C 6H 4-C(CH 3) 2-、-O-C 10H 6-O-、-O-C 6H 4-C 6H 4-O-及-O-C 6H 4-O-表示之基所構成之群組中之1種。 在Q之例示中，-C 6H 4-為伸苯基，較佳為m-伸苯基及p-伸苯基，更佳為p-伸苯基。又，-C 10H 6-為萘二基，較佳為萘-1,2-二基、萘-1,4-二基、萘-2,3-二基、萘-2,6-二基及萘-2,7-二基，更佳為萘-1,4-二基及萘-2,6-二基)。 When A2 is an organic group containing an aromatic ring, the aromatic diamine compound (A2) is preferably represented by the following formulas (21) to (24) from the viewpoint of the heat resistance of the cured product formed using the coating composition. ) at least one of the compounds represented. (In the formulas (21) to (24), R111 represents a group consisting of a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group with 1 to 4 carbon atoms, and a halogenated alkyl group with 1 to 4 carbon atoms. One of the groups. In formula (24), Q represents 9,9'- fenylene, or is selected from the formula: -C 6 H 4 -, -CONH-C 6 H 4 -NHCO-, -NHCO -C 6 H 4 -CONH-, -OC 6 H 4 -CO-C 6 H 4 -O-, -OCO-C 6 H 4 -COO-, -OCO-C 6 H 4 -C 6 H 4 -COO -, -OCO-, -O-, -S-, -CO-, -CONH-, -SO 2 -, -C(CF 3 ) 2 -, -C(CH 3 ) 2 -, -CH 2 -, -OC 6 H 4 -C(CH 3 ) 2 -C 6 H 4 -O-, -OC 6 H 4 -C(CF 3 ) 2 -C 6 H 4 -O-, -OC 6 H 4 -SO 2 -C 6 H 4 -O-, -C(CH 3 ) 2 -C 6 H 4 -C(CH 3 ) 2 -, -OC 10 H 6 -O-, -OC 6 H 4 -C 6 H 4 - One of the groups represented by O- and -OC 6 H 4 -O-. In the example of Q, -C 6 H 4 - is phenylene, preferably m-phenylene and p-phenylene, more preferably p-phenylene. Also, -C 10 H 6 - is naphthalene diyl, preferably naphthalene-1,2-diyl, naphthalene-1,4-diyl, naphthalene -2,3-diyl, naphthalene-2,6-diyl and naphthalene-2,7-diyl, more preferably naphthalene-1,4-diyl and naphthalene-2,6-diyl).

作為式(21)~(24)中之R 111，從所形成之聚醯亞胺樹脂的耐熱性的觀點來看，更佳為氫原子、羥基、氟原子、甲基、乙基或三氟甲基，特佳為氫原子、羥基或三氟甲基。 R 111 in the formulas (21) to (24) is more preferably a hydrogen atom, a hydroxyl group, a fluorine atom, a methyl group, an ethyl group or a trifluoro A methyl group is particularly preferably a hydrogen atom, a hydroxyl group or a trifluoromethyl group.

作為式(24)中之Q，從所形成之聚醯亞胺樹脂之耐熱性的點來看，較佳為9,9’-亞茀基、-O-C 6H 4-O-、-C(CF 3) 2-、-O-、-C(CH 3) 2-、-CH 2-或-O-C 6H 4-C(CH 3) 2-C 6H 4-O-、-CONH-，更佳為-CONH-、-O-C 6H 4-O-、-C(CF 3) 2-或-O-，特佳為-CONH-。 As Q in the formula (24), from the viewpoint of the heat resistance of the polyimide resin to be formed, 9,9'-berylene, -OC 6 H 4 -O-, -C( CF 3 ) 2 -, -O-, -C(CH 3 ) 2 -, -CH 2 - or -OC 6 H 4 -C(CH 3 ) 2 -C 6 H 4 -O-, -CONH-, more Preferably it is -CONH-, -OC 6 H 4 -O-, -C(CF 3 ) 2 - or -O-, particularly preferably -CONH-.

作為式(a3-1)表示之芳香族二胺化合物，可適合使用以下所示之化合物。 亦即，作為芳香族二胺化合物(A2)，可列舉p-苯二胺、m-苯二胺、2,4-二胺基甲苯、4,4’-二胺基聯苯基、4,4’-二胺基-2,2’-雙(三氟甲基)聯苯基、3,3’-二胺基二苯基碸、4,4’-二胺基二苯基碸、4,4’-二胺基二苯基硫化物、4,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基醚、3,4’-二胺基二苯基醚、3,3’-二胺基二苯基醚、4,4’-二胺基苯甲醯苯胺、3,3’-二胺基苯甲醯苯胺、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,3-雙(3-胺基苯氧基)苯、4,4’-雙(4-胺基苯氧基)聯苯基、雙[4-(4-胺基苯氧基)苯基]碸、雙[4-(3-胺基苯氧基)苯基]碸、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷、9,9-雙(4-胺基苯基)茀、9,9-雙(4-胺基-3-甲基苯基)茀，及4,4’-[1,4-伸苯基雙(1-甲基乙烷-1,1-二基)]二苯胺等。此等當中，從價格、取得容易性等來看，較佳為p-苯二胺、m-苯二胺、2,4-二胺基甲苯、4,4’-二胺基二苯基醚及4,4’-二胺基苯甲醯苯胺。 As the aromatic diamine compound represented by formula (a3-1), the compounds shown below can be suitably used. That is, examples of the aromatic diamine compound (A2) include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminobiphenyl, 4, 4'-Diamino-2,2'-bis(trifluoromethyl)biphenyl, 3,3'-diaminodiphenyl, 4,4'-diaminodiphenyl, 4 ,4'-Diaminodiphenyl sulfide, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminobenzanilide, 3,3'-diaminobenzaniline, 1,4-bis(4-amine phenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)benzene Phenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]pyridine, bis[4-(3-aminophenoxy)phenyl]pyridine, 2,2-bis[ 4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-amino Phenyl) fluorene, 9,9-bis(4-amino-3-methylphenyl) fluorine, and 4,4'-[1,4-phenylene bis(1-methylethane-1, 1-diyl)] diphenylamine and the like. Among these, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, and 4,4'-diaminodiphenyl ether are preferable in terms of price and availability. and 4,4'-diaminobenzamide aniline.

芳香族二胺化合物(A2)為下述式(25)表示之化合物亦佳。 (式(25)中，Ar 1及Ar 2分別獨立為碳原子數6以上18以下之芳香族烴基，R 112為氫原子或1價的有機基)。 The aromatic diamine compound (A2) is also preferably a compound represented by the following formula (25). (In formula (25), Ar 1 and Ar 2 are each independently an aromatic hydrocarbon group having 6 to 18 carbon atoms, and R 112 is a hydrogen atom or a monovalent organic group).

作為式(25)表示之芳香族二胺化合物(A2)之具體例，可列舉2,4-雙(4-胺基苯胺基)-1,3,5-三𠯤、2,4-雙(4-胺基苯胺基)-6-甲基-1,3,5-三𠯤、2,4-雙(4-胺基苯胺基)-6-乙基-1,3,5-三𠯤、2,4-雙(4-胺基苯胺基)-6-苯基-1,3,5-三𠯤、2,4-雙(4-胺基苯胺基)-6-胺基-1,3,5-三𠯤、2,4-雙(4-胺基苯胺基)-6-甲基胺基-1,3,5-三𠯤、2,4-雙(4-胺基苯胺基)-6-二甲基胺基-1,3,5-三𠯤、2,4-雙(4-胺基苯胺基)-6-乙基胺基-1,3,5-三𠯤、2,4-雙(4-胺基苯胺基)-6-二乙基胺基-1,3,5-三𠯤、2,4-雙(4-胺基苯胺基)-6-苯胺基-1,3,5-三𠯤，及2,4-雙(4-胺基苯胺基)-6-二苯基胺基-1,3,5-三𠯤等。 此等當中，較佳為2,4-雙(4-胺基苯胺基)-6-胺基-1,3,5-三𠯤、2,4-雙(4-胺基苯胺基)-6-甲基胺基-1,3,5-三𠯤、2,4-雙(4-胺基苯胺基)-6-乙基胺基-1,3,5-三𠯤，及2,4-雙(4-胺基苯胺基)-6-苯胺基-1,3,5-三𠯤，更佳為2,4-雙(4-胺基苯胺基)-6-苯胺基-1,3,5-三𠯤。 Specific examples of the aromatic diamine compound (A2) represented by the formula (25) include 2,4-bis(4-aminoanilino)-1,3,5-trisalpine, 2,4-bis( 4-aminoanilino)-6-methyl-1,3,5-trimethanone, 2,4-bis(4-aminoanilino)-6-ethyl-1,3,5-trimethanone, 2,4-bis(4-aminoanilino)-6-phenyl-1,3,5-trimethanone, 2,4-bis(4-aminoanilino)-6-amino-1,3 ,5-Trisalpine, 2,4-bis(4-aminoanilino)-6-methylamino-1,3,5-trithiol, 2,4-bis(4-aminoanilino)- 6-Dimethylamino-1,3,5-trimethanol, 2,4-bis(4-aminoanilino)-6-ethylamino-1,3,5-trimethanol, 2,4 -Bis(4-aminoanilino)-6-diethylamino-1,3,5-trimethanone, 2,4-bis(4-aminoanilino)-6-anilino-1,3 , 5-three 𠯤, and 2,4-bis(4-aminoanilino)-6-diphenylamino-1,3,5-three 𠯤, etc. Among these, 2,4-bis(4-aminoanilino)-6-amino-1,3,5-trimethanone, 2,4-bis(4-aminoanilino)-6 -Methylamino-1,3,5-tri-methanol, 2,4-bis(4-aminoanilino)-6-ethylamino-1,3,5-tri-methanol, and 2,4- Bis(4-aminoanilino)-6-anilino-1,3,5-trisulfone, more preferably 2,4-bis(4-aminoanilino)-6-anilino-1,3, 5- Three 𠯤.

[聚醯胺酸(A)之製造方法] 聚醯胺酸(A)係藉由例如將四羧酸二酐(A1)及芳香族二胺化合物(A2)於有機溶媒中聚合獲得。 合成聚醯胺酸(A)時之四羧酸二酐(A1)及芳香族二胺化合物(A2)的使用量並未特別限定。相對於四羧酸二酐(A1)1莫耳，較佳為使用芳香族二胺化合物(A2)0.50莫耳以上1.50莫耳以下，更佳為使用0.60莫耳以上1.30莫耳以下，特佳為使用0.70莫耳以上1.20莫耳以下。 所得之聚醯胺酸(A)的重量平均分子量配合其用途適當設定即可。重量平均分子量例如為5000以上，較佳為7500以上，更佳為10000以上。另一方面，所得之聚醯胺酸(A)的重量平均分子量例如為100000以下，較佳為80000以下，更佳為75000以下。 此重量平均分子量若調整四羧酸二酐(A1)與芳香族二胺化合物(A2)的摻合量，或溶媒或反應溫度等之反應條件，定為上述之值即可。 [Manufacturing method of polyamide acid (A)] Polyamic acid (A) is obtained by, for example, polymerizing tetracarboxylic dianhydride (A1) and aromatic diamine compound (A2) in an organic solvent. The usage-amount of tetracarboxylic dianhydride (A1) and aromatic diamine compound (A2) at the time of synthesizing polyamic acid (A) is not specifically limited. Relative to 1 mole of tetracarboxylic dianhydride (A1), it is preferable to use 0.50 mole to 1.50 mole of aromatic diamine compound (A2), more preferably to use 0.60 mole to 1.30 mole, especially preferred In order to use 0.70 mol or more and 1.20 mol or less. The weight average molecular weight of the obtained polyamic acid (A) should just be set suitably according to the use. The weight average molecular weight is, for example, 5,000 or more, preferably 7,500 or more, more preferably 10,000 or more. On the other hand, the weight average molecular weight of the obtained polyamic acid (A) is, for example, 100,000 or less, preferably 80,000 or less, more preferably 75,000 or less. This weight average molecular weight may be set to the above-mentioned value by adjusting the blending amount of tetracarboxylic dianhydride (A1) and aromatic diamine compound (A2), or reaction conditions such as solvent or reaction temperature.

四羧酸二酐(A1)與芳香族二胺化合物(A2)的反應，通常於有機溶媒中進行。四羧酸二酐(A1)與二胺化合物(A2)的反應所使用之有機溶媒，若為可溶解四羧酸二酸酐(A1)及芳香族二胺化合物(A2)，不會與四羧酸二酐(A1)及芳香族二胺化合物(A2)反應之有機溶媒，則並未特別限定。有機溶媒可單獨或混合2種以上使用。The reaction of tetracarboxylic dianhydride (A1) and aromatic diamine compound (A2) is usually carried out in an organic solvent. If the organic solvent used for the reaction of tetracarboxylic dianhydride (A1) and diamine compound (A2) is soluble in tetracarboxylic dianhydride (A1) and aromatic diamine compound (A2), it will not react with tetracarboxylic dianhydride (A1) The organic solvent for the reaction between the acid dianhydride (A1) and the aromatic diamine compound (A2) is not particularly limited. An organic solvent can be used individually or in mixture of 2 or more types.

作為四羧酸二酐(A1)與芳香族二胺化合物(A2)的反應所使用之有機溶媒之例，可列舉N-甲基-2-吡咯烷酮、N,N-二甲基乙醯胺、N,N-二乙基乙醯胺、N,N-二甲基甲醯胺、N,N-二乙基甲醯胺、N-甲基己內醯胺及N,N,N’,N’-四甲基脲等之含氮極性溶媒；二甲基亞碸；乙腈；二乙二醇二甲基醚、二乙二醇二乙基醚、二噁烷及四氫呋喃等之醚類。Examples of the organic solvent used for the reaction between the tetracarboxylic dianhydride (A1) and the aromatic diamine compound (A2) include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N-methylcaprolactam and N,N,N',N Nitrogen-containing polar solvents such as '-tetramethylurea; dimethylsulfoxide; acetonitrile; ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane, and tetrahydrofuran.

此等之有機溶劑當中，從生成之聚醯胺酸(A)之溶解性來看，較佳為N-甲基-2-吡咯烷酮、N,N-二甲基乙醯胺、N,N-二乙基乙醯胺、N,N-二甲基甲醯胺、N,N-二乙基甲醯胺、N-甲基己內醯胺及N,N,N’,N’-四甲基脲等之含氮極性溶劑。Among these organic solvents, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N- Diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N-methylcaprolactam and N,N,N',N'-tetramethyl Nitrogen-containing polar solvents such as urea.

使四羧酸二酐(A1)、與芳香族二胺化合物(A2)反應時之溫度，只要反應能良好進行，並未特別限定。通常而言，四羧酸二酐(A1)、與芳香族二胺化合物(A2)的反應溫度較佳為-5℃以上150℃以下，更佳為0℃以上120℃以下，特佳為0℃以上70℃以下。使四羧酸二酐(A1)、與芳香族二胺化合物(A2)反應之時間，雖因反應溫度而成為相異，但通常而言，較佳為1小時以上50小時以下，更佳為2小時以上40小時以下，特佳為5小時以上30小時以下。The temperature at the time of making tetracarboxylic dianhydride (A1) and an aromatic diamine compound (A2) react is not specifically limited as long as reaction progresses favorably. Generally speaking, the reaction temperature between tetracarboxylic dianhydride (A1) and aromatic diamine compound (A2) is preferably from -5°C to 150°C, more preferably from 0°C to 120°C, especially preferably at 0°C. Above 70°C. The time for reacting the tetracarboxylic dianhydride (A1) and the aromatic diamine compound (A2) varies depending on the reaction temperature, but generally, it is preferably from 1 hour to 50 hours, and more preferably from 1 hour to 50 hours. More than 2 hours and less than 40 hours, especially preferably more than 5 hours and less than 30 hours.

藉由以上說明之方法，而得到包含聚醯胺酸(A)之溶液。 可直接將如上述進行所得之包含聚醯胺酸(A)之溶液作為塗料組成物使用，或亦可使用在塗料組成物的調製。將如上述進行所得之包含聚醯胺酸(A)之溶液於減壓下，於不會產生對聚醯胺酸(A)之聚醯亞胺樹脂的變換程度的低溫，亦可將從聚醯胺酸(A)之溶液去除溶劑的至少一部分所得之聚醯胺酸(A)之糊料或固體使用在塗料組成物的調製。 By the method explained above, the solution containing polyamide acid (A) was obtained. The solution containing polyamic acid (A) obtained as described above can be directly used as a coating composition, or can also be used in the preparation of a coating composition. The solution containing polyamic acid (A) obtained as described above is under reduced pressure, and at a low temperature that does not produce the degree of transformation of the polyimide resin of polyamic acid (A), it is also possible to obtain the solution from polyamic acid (A). The paste or solid of the polyamic acid (A) obtained by removing at least a part of the solvent from the solution of the amide acid (A) is used in the preparation of a paint composition.

在塗料組成物之聚醯胺酸(A)的含量可考量塗料組成物的塗佈性或對聚醯胺酸(A)之溶媒(S)的溶解性等適當決定。通常而言，在塗料組成物之聚醯胺酸(A)的含量相對於塗料組成物的質量，較佳為5質量%以上45質量%以下，更佳為7質量%以上40質量%以下，再更佳為10質量%以上30質量%以下。The content of the polyamic acid (A) in the paint composition can be appropriately determined in consideration of the coatability of the paint composition or the solubility to the solvent (S) of the polyamic acid (A). Generally speaking, the content of the polyamic acid (A) in the coating composition is preferably not less than 5 mass % and not more than 45 mass %, more preferably not less than 7 mass % and not more than 40 mass %, relative to the mass of the coating composition, More preferably, it is 10 mass % or more and 30 mass % or less.

＜溶媒(S)＞ 塗料組成物含有溶媒(S)。塗料組成物雖可為包含固體之糊料，亦可為溶液，但較佳為溶液。溶媒(S)可單獨或混合2種以上使用。 溶媒(S)的種類於未阻礙本發明之目的的範圍，並未特別限定，可列舉水、乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丙基醚、乙二醇單丁基醚、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單丙基醚、丙二醇單丁基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丙基醚及二乙二醇單苯基醚等之甘醇單醚；乙二醇二甲基醚、乙二醇二乙基醚、乙二醇二丙基醚、丙二醇二甲基醚、丙二醇二乙基醚、丙二醇二丙基醚、二乙二醇二甲基醚、二乙二醇二乙基醚及二乙二醇二丙基醚等之甘醇二醚；乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、乙二醇單丙基醚乙酸酯、乙二醇單丁基醚乙酸酯、乙二醇單苯基醚乙酸酯、二乙二醇單甲基醚乙酸酯，及二乙二醇單乙基醚乙酸酯等之甘醇單乙酸酯；二乙二醇單丙基醚乙酸酯、二乙二醇單丁基醚乙酸酯、二乙二醇單苯基醚乙酸酯、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、丙二醇單丙基醚乙酸酯、2-甲氧基丁基乙酸酯、3-甲氧基丁基乙酸酯、4-甲氧基丁基乙酸酯、2-甲基-3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、3-乙基-3-甲氧基丁基乙酸酯、2-乙氧基丁基乙酸酯、4-乙氧基丁基乙酸酯、4-丙氧基丁基乙酸酯、2-甲氧基戊基乙酸酯、3-甲氧基戊基乙酸酯、4-甲氧基戊基乙酸酯、2-甲基-3-甲氧基戊基乙酸酯、3-甲基-3-甲氧基戊基乙酸酯、3-甲基-4-甲氧基戊基乙酸酯，及4-甲基-4-甲氧基戊基乙酸酯等之二醇類之單醚單乙酸酯；丙酮、甲基乙基酮、二乙基酮、甲基異丁基酮、乙基異丁基酮，及環己酮等之酮類；丙酸甲酯、丙酸乙酯、丙酸丙酯、丙酸異丙酯、2-羥基丙酸甲酯、2-羥基丙酸乙酯、2-羥基-2-甲基、甲基-3-甲氧基丙酸酯、乙基-3-甲氧基丙酸酯、乙基-3-乙氧基丙酸酯、乙基-3-丙氧基丙酸酯、丙基-3-甲氧基丙酸酯、異丙基-3-甲氧基丙酸酯、乙氧基乙酸乙酯、氧基乙酸乙酯、2-羥基-3-甲基丁酸甲酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸異丙酯、乙酸丁酯、乙酸異戊酯、碳酸甲酯、碳酸乙酯、碳酸丙酯、碳酸丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、丙酮酸丁酯、乙醯乙酸甲酯、乙醯乙酸乙酯、乙酸苄酯、苯甲酸乙酯、草酸二乙酯、馬來酸二乙酯及γ-丁內酯等之酯類；二乙基醚、二丙基醚、二丁基醚、二己基醚、苄基甲基醚、苄基乙基醚及四氫呋喃等之醚類；苯、甲苯、二甲苯、乙基苯、甲酚及氯苯等之芳香族類；甲醇、乙醇、n-丙醇、異丙醇、n-丁醇、n-己醇及環己醇等之脂肪族醇類；聚乙二醇、乙二醇、二乙二醇、丙二醇及二丙二醇等之甘醇類；甘油；等。 又，上述之四羧酸二酐(A1)與芳香族二胺化合物(A2)的反應所使用之溶媒亦可適合作為溶媒(S)使用。 ＜Solvent (S)＞ The paint composition contains a solvent (S). The paint composition may be a paste containing solids or a solution, but is preferably a solution. A solvent (S) can be used individually or in mixture of 2 or more types. The type of solvent (S) is not particularly limited within the range that does not hinder the purpose of the present invention, and examples thereof include water, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monopropyl ether, Glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Glycol monoethers such as ethylene glycol monopropyl ether and diethylene glycol monophenyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol dimethyl ether Diethylene glycol diethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dipropyl ether; Alcohol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether ethyl Ester, diethylene glycol monomethyl ether acetate, and glycol monoacetate such as diethylene glycol monoethyl ether acetate; diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, etc. Glycol monobutyl ether acetate, diethylene glycol monophenyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2 -Methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3- Methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetic acid ester, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl -3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, and 4-methyl- Monoether monoacetate of diols such as 4-methoxypentyl acetate; acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, And ketones such as cyclohexanone; methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, 2-hydroxypropionate methyl ester, 2-hydroxypropionate ethyl ester, 2-hydroxy- 2-methyl, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, ethyl-3-propoxypropionate ester, propyl-3-methoxypropionate, isopropyl-3-methoxypropionate, ethyl ethoxyacetate, ethyl oxyacetate, 2-hydroxy-3-methylbutyl Methyl acetate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isopentyl acetate, methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate , ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate and gamma - Esters such as butyrolactone; ethers such as diethyl ether, dipropyl ether, dibutyl ether, dihexyl ether, benzyl methyl ether, benzyl ethyl ether and tetrahydrofuran; benzene, toluene, Aromatics such as xylene, ethylbenzene, cresol, and chlorobenzene; aliphatic alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, n-hexanol, and cyclohexanol ; Glycols such as polyethylene glycol, ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; glycerin; etc. Moreover, the solvent used for the reaction of the said tetracarboxylic dianhydride (A1) and an aromatic diamine compound (A2) can also be used suitably as a solvent (S).

溶媒(S)可包含下式(S1)表示之含氮化合物。 (式(S1)中，R S1及R S2分別獨立為碳原子數1以上3以下之烷基，R S3為氫原子或下述式(S1-1)或是下述式(S1-2)表示之基， R S4為氫原子或羥基，R S5及R S6分別獨立為氫原子、碳原子數1以上3以下之烷基，R S7及R S8分別獨立為氫原子或碳原子數1以上3以下之烷基，R S3為式(S1-1)表示之基時，R S2及R S3可彼此鍵結形成環)。 The solvent (S) may contain a nitrogen-containing compound represented by the following formula (S1). (In formula (S1), R S1 and R S2 are independently an alkyl group with 1 to 3 carbon atoms, and R S3 is a hydrogen atom or the following formula (S1-1) or the following formula (S1-2) base of representation, R S4 is a hydrogen atom or a hydroxyl group, R S5 and R S6 are each independently a hydrogen atom or an alkyl group with 1 to 3 carbon atoms, and R S7 and R S8 are each independently a hydrogen atom or an alkane with 1 to 3 carbon atoms group, when R S3 is a group represented by formula (S1-1), R S2 and R S3 may be bonded to each other to form a ring).

作為式(S1)表示之含氮化合物當中，R S3為氫原子或式(S1-1)表示之基時之具體例，可列舉N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N,N,2-三甲基丙醯胺、N-乙基,N,2-二甲基丙醯胺、N,N-二乙基-2-甲基丙醯胺、N,N,2-三甲基-2-羥基丙醯胺、N-乙基-N,2-二甲基-2-羥基丙醯胺及N,N-二乙基-2-羥基-2-甲基丙醯胺等。 Among the nitrogen-containing compounds represented by formula (S1), specific examples of when R S3 is a hydrogen atom or a group represented by formula (S1-1) include N, N-dimethylformamide, N, N-di Methylacetamide, N,N,2-trimethylpropionamide, N-ethyl,N,2-dimethylpropionamide, N,N-diethyl-2-methylpropionamide , N,N,2-trimethyl-2-hydroxypropionamide, N-ethyl-N,2-dimethyl-2-hydroxypropionamide and N,N-diethyl-2-hydroxy- 2-methylacrylamide, etc.

作為式(S1)表示之含氮化合物當中，R S3為式(S1-1)表示之基，R S2及R S3彼此鍵結而形成環時的具體例，可列舉N-甲基-2-吡咯烷酮及N-乙基-2-吡咯烷酮等。 Among the nitrogen-containing compounds represented by formula (S1), R S3 is a group represented by formula (S1-1), and specific examples of when R S2 and R S3 are bonded to each other to form a ring include N-methyl-2- Pyrrolidone and N-ethyl-2-pyrrolidone, etc.

作為式(S1)表示之含氮化合物當中，R S3為式(S1-2)表示之基時的具體例，可列舉N,N,N’,N’-四甲基脲、N,N,N’,N’-四乙基脲等。 Among the nitrogen-containing compounds represented by formula (S1), specific examples of when R S3 is a group represented by formula (S1-2) include N,N,N',N'-tetramethylurea, N,N, N', N'-tetraethylurea, etc.

作為式(S1)表示之含氮化合物的上述之例當中特佳的化合物，可列舉N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N,N,2-三甲基丙醯胺及N,N,N’,N’-四甲基脲。此等當中，較佳為N,N,2-三甲基丙醯胺及N,N,N’,N’-四甲基脲。N,N,2-三甲基丙醯胺於大氣壓下的沸點為175℃，N,N,N’,N’-四甲基脲於大氣壓下的沸點為177℃。如此，N,N,2-三甲基丙醯胺及N,N,N’,N’-四甲基脲係比較性沸點較低。 因此，使用含有包含選自N,N,2-三甲基丙醯胺及N,N,N’,N’-四甲基脲中之至少1種之溶媒(S)的塗料組成物時，形成聚醯亞胺樹脂時，於藉由加熱生成之聚醯亞胺樹脂中難以殘存溶媒(S)，難以招致所得之聚醯亞胺樹脂之機械特性的低下等。 Particularly preferred compounds among the above examples of nitrogen-containing compounds represented by formula (S1) include N,N-dimethylformamide, N,N-dimethylacetamide, N,N,2- Trimethylacrylamide and N,N,N',N'-tetramethylurea. Among these, N,N,2-trimethylacrylamide and N,N,N',N'-tetramethylurea are preferable. The boiling point of N,N,2-trimethylacrylamide at atmospheric pressure is 175°C, and the boiling point of N,N,N',N'-tetramethylurea at atmospheric pressure is 177°C. Thus, N,N,2-trimethylacrylamide and N,N,N',N'-tetramethylurea have comparatively lower boiling points. Therefore, when using a coating composition containing at least one solvent (S) selected from N,N,2-trimethylacrylamide and N,N,N',N'-tetramethylurea, When the polyimide resin is formed, the solvent (S) is unlikely to remain in the polyimide resin produced by heating, and it is difficult to cause a decrease in the mechanical properties of the obtained polyimide resin.

進而，N,N,2-三甲基丙醯胺及N,N,N’,N’-四甲基脲在EU(歐洲聯盟)之REACH規則中，不會像SVHC(Substance of Very High Concern、高憂慮物質)被指定為有有害性憂慮的物質般，而於有害性低的物質的點亦為有用。Furthermore, N,N,2-trimethylacrylamide and N,N,N',N'-tetramethylurea will not be as SVHC (Substance of Very High Concern) in the EU (European Union) REACH regulations , Highly worrying substances) are designated as substances with concern about harmfulness, and are also useful for substances with low harmfulness.

塗料組成物中之溶媒(S)的含量於未阻礙本發明之目的的範圍，並未特別限定。塗料組成物中之溶媒(S)的含量可因應塗料組成物中之固體成分含量適當調整。塗料組成物中之固體成分含量，例如為5質量%以上99.9質量%以下之範圍，較佳為5質量%以上70質量%以下，更佳為10質量%以上60質量%以下。The content of the solvent (S) in the paint composition is not particularly limited within the range that does not hinder the object of the present invention. The content of the solvent (S) in the paint composition can be appropriately adjusted according to the solid content in the paint composition. The solid content in the paint composition is, for example, in the range of 5% by mass to 99.9% by mass, preferably 5% by mass to 70% by mass, more preferably 10% by mass to 60% by mass.

＜熱鹼產生劑(B)＞ 塗料組成物以良好地進行來自藉由燒成之聚醯胺酸(A)之聚醯胺樹脂的生成為目的，可包含藉由加熱產生鹼性含氮雜環化合物的熱鹼產生劑(B)。 ＜Heat base generator (B)＞ The coating composition may contain a thermal base generator (B) that generates a basic nitrogen-containing heterocyclic compound by heating for the purpose of producing polyamide resin from polyamide acid (A) that is fired well. ).

產生熱鹼產生劑(B)之鹼性含氮雜環化合物可為脂肪族環式化合物，亦可為芳香族化合物。鹼性含氮雜環化合物為縮合2以上之單環的化合物時，2以上之單環可為僅由脂肪族環構成，亦可為僅由芳香族環構成，亦可為由脂肪族環與芳香族環的組合構成。The basic nitrogen-containing heterocyclic compound that generates the thermal base generator (B) can be an aliphatic ring compound or an aromatic compound. When the basic nitrogen-containing heterocyclic compound is a compound having two or more monocyclic rings condensed, the two or more monocyclic rings may consist of only aliphatic rings, may consist of only aromatic rings, or may consist of aliphatic rings and Combination of aromatic rings.

作為產生熱鹼產生劑(B)之鹼性含氮雜環化合物之例，可列舉吡咯烷、吡唑烷、咪唑啉啶、***啶、四唑啶、吡咯啉、吡唑啉、咪唑啉、***啉、四唑啉、吡咯、吡唑、咪唑、***及四唑等之含氮5員環化合物；哌啶、哌𠯤、三嗪烷、吡啶、嗒𠯤、嘧啶、吡𠯤等之含氮6員環；此等之化合物藉由1個以上之取代基取代之化合物；此等之化合物與環戊烷、環己烷、苯等縮合之化合物。 鹼性含氮雜環化合物為於含氮雜環上具有取代基時，作為該取代基，可列舉與後述之式(B1)中之R 1、R 2及R 3為相同之基。 Examples of basic nitrogen-containing heterocyclic compounds that generate the thermal base generator (B) include pyrrolidine, pyrazolidine, imidazoline, triazolidine, tetrazoline, pyrroline, pyrazoline, and imidazoline. , triazoline, tetrazoline, pyrrole, pyrazole, imidazole, triazole and tetrazole and other nitrogen-containing 5-membered ring compounds; Nitrogen-containing 6-membered rings; these compounds are substituted by one or more substituents; these compounds are condensed with cyclopentane, cyclohexane, benzene, etc. When the basic nitrogen-containing heterocyclic compound has a substituent on the nitrogen-containing heterocyclic ring, examples of the substituent include the same groups as R 1 , R 2 , and R 3 in the formula (B1) described later.

由於促進來自聚醯胺酸(A)之聚醯亞胺樹脂的生成的效果良好等，作為產生熱鹼產生劑(B)成分之鹼性含氮雜環化合物，較佳為下述式(B1)表示之咪唑化合物， (式(B1)中，R 1、R 2及R 3分別獨立為氫原子、鹵素原子、羥基、矽烷基、矽烷醇基、硝基、亞硝基、磺酸根基、膦基、氧膦基、膦酸根基或有機基)。 Since the effect of promoting the generation of polyimide resin from polyamic acid (A) is good, etc., the basic nitrogen-containing heterocyclic compound as a component of the thermal base generator (B) is preferably the following formula (B1 ) represents an imidazole compound, (In formula (B1), R 1 , R 2 and R 3 are independently hydrogen atom, halogen atom, hydroxyl group, silyl group, silanol group, nitro group, nitroso group, sulfonate group, phosphine group, phosphine group , phosphonate group or organic group).

作為在R 1、R 2及R 3之有機基，可列舉烷基、烯基、環烷基、環烯基、芳基、芳烷基等。此有機基可於該有機基中包含雜原子等之烴基以外之鍵結或取代基。又，此有機基可為直鏈狀、分枝鏈狀、環狀之任一者。此有機基通常雖為1價，但於形成環狀構造的情況等，亦可成為2價以上之有機基。 Examples of organic groups in R 1 , R 2 and R 3 include alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, and aralkyl. This organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. Moreover, this organic group may be linear, branched, or cyclic. This organic group is usually monovalent, but it may be a divalent or higher organic group when forming a ring structure.

R 1及R 2可鍵結該等，形成環狀構造，亦可進一步包含雜原子的鍵結。作為環狀構造，可列舉雜環烷基、雜芳基等，亦可為縮合環。 R 1 and R 2 may be bonded to these to form a ring structure, and a bond of a heteroatom may be further included. As a ring structure, a heterocycloalkyl group, a heteroaryl group, etc. are mentioned, and a condensed ring may be sufficient.

R 1、R 2及R 3之有機基所包含之鍵結只要不損害本發明之效果，並未特別限定。有機基可包含氧原子、氮原子、矽原子等之包含雜原子的鍵結。作為包含雜原子之鍵結的具體例，可列舉醚鍵、羰基鍵、硫羰基鍵、酯鍵、醯胺鍵、胺基甲酸酯鍵、醯亞胺鍵(-N=C(-R)-、-C(=NR)-：R表示氫原子或有機基)、碳酸酯鍵、磺醯基鍵、偶氮鍵等。 The bonds included in the organic groups of R 1 , R 2 and R 3 are not particularly limited as long as they do not impair the effects of the present invention. The organic group may contain heteroatom-containing linkages of oxygen atoms, nitrogen atoms, silicon atoms, and the like. Specific examples of bonds including heteroatoms include ether bonds, carbonyl bonds, thiocarbonyl bonds, ester bonds, amide bonds, urethane bonds, and imide bonds (-N=C(-R) -, -C(=NR)-: R represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, an azo bond, etc.

作為R 1、R 2及R 3之有機基可具有之包含雜原子之鍵結，從咪唑化合物之耐熱性的觀點來看，較佳為醚鍵、羰基鍵、硫羰基鍵、酯鍵、醯胺鍵、胺基甲酸酯鍵、醯亞胺鍵(-N=C(-R)-、-C(=NR)-：R表示氫原子或1價的有機基)、碳酸酯鍵、磺醯基鍵。 From the viewpoint of heat resistance of the imidazole compound, the bond including a heteroatom that the organic groups of R 1 , R 2 and R 3 may have is preferably an ether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, or an acyl bond. Amine bond, urethane bond, imide bond (-N=C(-R)-, -C(=NR)-: R represents a hydrogen atom or a monovalent organic group), carbonate bond, sulfonate Acyl group bond.

R 1、R 2及R 3之有機基為烴基以外之取代基時，R 1、R 2及R 3只要不損害本發明之效果，並未特別限定。R 1、R 2及R 3之具體例係如前述，為鹵素原子、羥基、矽烷基、矽烷醇基、硝基、亞硝基、磺酸根基、膦基、氧膦基及膦酸根基。上述取代基所包含之氫原子可藉由烴基取代。又，上述取代基所包含之烴基可為直鏈狀、分枝鏈狀及環狀之任一者。 When the organic groups of R 1 , R 2 and R 3 are substituents other than hydrocarbon groups, R 1 , R 2 and R 3 are not particularly limited as long as they do not impair the effect of the present invention. The specific examples of R 1 , R 2 and R 3 are as mentioned above, and they are halogen atom, hydroxyl group, silyl group, silanol group, nitro group, nitroso group, sulfonate group, phosphine group, phosphinyl group and phosphonate group. Hydrogen atoms contained in the above-mentioned substituents may be substituted with hydrocarbon groups. Moreover, the hydrocarbon group contained in the said substituent may be any of linear, branched and cyclic.

作為R 1、R 2及R 3，較佳為氫原子、碳原子數1以上12以下之烷基、碳原子數1以上12以下之芳基、碳原子數1以上12以下之烷氧基及鹵素原子，更佳為氫原子。 R 1 , R 2 and R 3 are preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and Halogen atom, more preferably hydrogen atom.

熱鹼產生劑(B)若為可藉由加熱，產生鹼性含氮雜環化合物的化合物，則並未特別限定。對於自以往即被摻合在各種組成物之藉由熱的作用而產生胺之化合物(熱鹼產生劑)，藉由將源自於加熱時產生之胺的骨架取代為源自所期望之鹼性含氮雜環化合物的骨架，而得到作為熱鹼產生劑(B)使用之化合物。The thermal base generator (B) is not particularly limited as long as it is a compound capable of generating a basic nitrogen-containing heterocyclic compound by heating. For compounds that generate amines by the action of heat (thermal base generators) that have been blended into various compositions conventionally, by substituting the skeleton derived from amines generated during heating with desired bases The skeleton of the nitrogen-containing heterocyclic compound is obtained to obtain a compound used as a thermal base generator (B).

作為合適的熱鹼產生劑(B)，可列舉下述式(B2)表示之化合物， (式(B2)中，R 1、R 2及R 3係與在式(B1)之此等相同，R b1及R b2分別獨立表示氫原子、鹵素原子、羥基、矽烷基、矽烷醇基、硝基、亞硝基、亞磺酸基、磺基、磺酸根基、膦基、氧膦基、膦醯基、膦酸根基或有機基，R b3、R b4、R b5、R b6及R b7分別獨立表示氫原子、鹵素原子、羥基、矽烷基、矽烷醇基、硝基、亞硝基、亞磺酸基、磺基、磺酸根基、膦基、氧膦基、膦醯基、膦酸根基、胺基、銨基或有機基，R b3、R b4、R b5、R b6及R b7可鍵結該等之2個以上，而形成環狀構造，並可包含雜原子的鍵結)。 Examples of suitable thermal base generators (B) include compounds represented by the following formula (B2): (In formula (B2), R 1 , R 2 and R 3 are the same as those in formula (B1), R b1 and R b2 independently represent hydrogen atom, halogen atom, hydroxyl group, silyl group, silanol group, Nitro, nitroso, sulfinate, sulfo, sulfonate, phosphino, phosphinyl, phosphono, phosphonate or organic, R b3 , R b4 , R b5 , R b6 and R b7 independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfinic acid group, a sulfo group, a sulfonate group, a phosphino group, a phosphine group, a phosphino group, and a phosphine group. Acid group, amine group, ammonium group or organic group, R b3 , R b4 , R b5 , R b6 and R b7 can be bonded to two or more of them to form a ring structure, and may include heteroatom bonds ).

在式(B2)中，R 1、R 2及R 3係如對於式(B1)所說明。 In formula (B2), R 1 , R 2 and R 3 are as explained for formula (B1).

在式(B2)，R b1及R b2分別獨立表示氫原子、鹵素原子、羥基、矽烷基、矽烷醇基、硝基、亞硝基、亞磺酸基、磺基、磺酸根基、膦基、氧膦基、膦醯基、膦酸根基或有機基。 In formula (B2), R b1 and R b2 independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfinate group, a sulfo group, a sulfonate group, a phosphino group , phosphine group, phosphono group, phosphonate group or organic group.

作為在R b1及R b2之有機基，可列舉對於R 1、R 2及R 3所例示之基。此有機基係與R 1、R 2及R 3的情況相同，可於該有機基中包含雜原子。又，此有機基可為直鏈狀、分枝鏈狀、環狀之任一者。 Examples of the organic groups in R b1 and R b2 include those exemplified for R 1 , R 2 and R 3 . This organic group is the same as the case of R 1 , R 2 and R 3 , and heteroatoms may be included in the organic group. Moreover, this organic group may be linear, branched, or cyclic.

以上當中，作為R b1及R b2，較佳為分別獨立為氫原子、碳原子數1以上10以下之烷基、碳原子數4以上13以下之環烷基、碳原子數4以上13以下之環烯基、碳原子數7以上16以下之芳基氧基烷基、碳原子數7以上20以下之芳烷基、具有氰基之碳原子數2以上11以下之烷基、具有羥基之碳原子數1以上10以下之烷基、碳原子數1以上10以下之烷氧基、碳原子數2以上11以下之醯胺基、碳原子數1以上10以下之醯基、碳原子數2以上11以下之酯基(-COOR、-OCOR：R表示烴基)、碳原子數6以上20以下之芳基、取代推電子性基及/或拉電子性基之碳原子數6以上20以下之芳基、取代推電子性基及/或拉電子性基之苄基、氰基。更佳為R b1及R b2雙方為氫原子，或R b1為甲基，R b2為氫原子。 Among the above, R b1 and R b2 are preferably each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, or a group having 4 to 13 carbon atoms. Cycloalkenyl group, aryloxyalkyl group with 7 to 16 carbon atoms, aralkyl group with 7 to 20 carbon atoms, alkyl group with cyano group with 2 to 11 carbon atoms, carbon group with hydroxyl group Alkyl group with 1 to 10 atoms, alkoxy group with 1 to 10 carbon atoms, amido group with 2 to 11 carbon atoms, acyl group with 1 to 10 carbon atoms, 2 or more carbon atoms Ester groups of 11 or less (-COOR, -OCOR: R represents a hydrocarbon group), aryl groups with 6 to 20 carbon atoms, aryl groups with 6 to 20 carbon atoms substituting electron-pushing groups and/or electron-withdrawing groups group, benzyl group substituting electron-pushing group and/or electron-withdrawing group, cyano group. More preferably, both R b1 and R b2 are hydrogen atoms, or R b1 is a methyl group, and R b2 is a hydrogen atom.

在式(B2)，R b3、R b4、R b5、R b6及R b7分別獨立表示氫原子、鹵素原子、羥基、巰基、硫化物基、矽烷基、矽烷醇基、硝基、亞硝基、亞磺酸基、磺基、磺酸根基、膦基、氧膦基、膦醯基、膦酸根基、胺基、銨基或有機基。 In formula (B2), R b3 , R b4 , R b5 , R b6 and R b7 independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group , sulfinic acid group, sulfonic acid group, sulfonic acid group, phosphine group, phosphinyl group, phosphonyl group, phosphonate group, amine group, ammonium group or organic group.

作為在R b3、R b4、R b5、R b6及R b7之有機基，可列舉在R 1、R 2及R 3所例示之基。此有機基係與R 1、R 2及R 3的情況相同，可於該有機基中包含雜原子等之烴基以外之鍵結或取代基。又，此有機基可為直鏈狀、分枝鏈狀、環狀之任一者。 Examples of the organic groups for R b3 , R b4 , R b5 , R b6 and R b7 include those exemplified for R 1 , R 2 and R 3 . This organic group is the same as the case of R 1 , R 2 and R 3 , and the organic group may contain a bond or a substituent other than a hydrocarbon group such as a heteroatom. Moreover, this organic group may be linear, branched, or cyclic.

對於R b3、R b4、R b5、R b6及R b7，可鍵結該等之2個以上，而形成環狀構造。R b3、R b4、R b5、R b6及R b7可分別包含：包含雜原子之鍵結。作為環狀構造，可列舉雜環烷基、雜芳基等，亦可為縮合環。例如R b3、R b4、R b5、R b6及R b7可鍵結該等之2個以上，共有鍵結R b3、R b4、R b5、R b6及R b7之苯環的原子，而形成萘、蒽、菲、茚等之縮合環。形成縮合環時，以長波長化吸收波長的點來看，較佳。 For R b3 , R b4 , R b5 , R b6 and R b7 , two or more of them may be bonded to form a ring structure. R b3 , R b4 , R b5 , R b6 and R b7 may each include: a bond including a heteroatom. As a ring structure, a heterocycloalkyl group, a heteroaryl group, etc. are mentioned, and a condensed ring may be sufficient. For example, R b3 , R b4 , R b5 , R b6 , and R b7 can be bonded to two or more of them, sharing the atoms of the benzene rings bonded to R b3 , R b4 , R b5 , R b6 , and R b7 to form Condensed rings of naphthalene, anthracene, phenanthrene, indene, etc. When forming a condensed ring, it is preferable from the point of view of making the absorption wavelength longer.

以上當中，作為R b3、R b4、R b5、R b6及R b7，較佳為分別獨立為氫原子、碳原子數1以上10以下之烷基、碳原子數4以上13以下之環烷基、碳原子數4以上13以下之環烯基、碳原子數7以上16以下之芳基氧基烷基、碳原子數7以上20以下之芳烷基、具有氰基之碳原子數2以上11以下之烷基、具有羥基之碳原子數1以上10以下之烷基、碳原子數1以上10以下之烷氧基、碳原子數2以上11以下之醯胺基、碳原子數1以上10以下之醯基、碳原子數2以上11以下之酯基、碳原子數6以上20以下之芳基、取代推電子性基及/或拉電子性基之碳原子數6以上20以下之芳基、取代推電子性基及/或拉電子性基之苄基、氰基及硝基。 Among the above, R b3 , R b4 , R b5 , R b6 , and R b7 are each independently preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a cycloalkyl group having 4 to 13 carbon atoms. , cycloalkenyl group with 4 to 13 carbon atoms, aryloxyalkyl group with 7 to 16 carbon atoms, aralkyl group with 7 to 20 carbon atoms, cyano group with 2 to 11 carbon atoms The following alkyl groups, alkyl groups having a hydroxyl group with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, amido groups with 2 to 11 carbon atoms, and 1 to 10 carbon atoms An acyl group, an ester group with 2 to 11 carbon atoms, an aryl group with 6 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms substituting an electron-pushing group and/or an electron-withdrawing group, Substituting benzyl, cyano and nitro for electron-pushing and/or electron-withdrawing groups.

於上述式(B2)表示之化合物當中，較佳為下述式(B3)表示之化合物， (式(B3)中，R 1、R 2及R 3係與式(B1)及(B2)同義。R b1~R b6係與式(B2)同義。R b8表示氫原子或有機基。R b3及R b4不會成為羥基。R b3、R b4、R b5及R b6可鍵結該等之2個以上，而形成環狀構造，並可包含雜原子的鍵結)。 Among the compounds represented by the above formula (B2), compounds represented by the following formula (B3) are preferred, (In formula (B3), R 1 , R 2 and R 3 are synonymous with formula (B1) and (B2). R b1 ~ R b6 are synonymous with formula (B2). R b8 represents a hydrogen atom or an organic group. R b3 and R b4 do not become hydroxyl groups. Two or more of R b3 , R b4 , R b5 , and R b6 may be bonded to form a ring structure, and a heteroatom bond may be included).

式(B3)表示之化合物由於具有取代基-O-R b8，相對於溶媒(S)之溶解性優異。 Since the compound represented by the formula (B3) has a substituent -OR b8 , it has excellent solubility in the solvent (S).

在式(B3)，R b8為氫原子或有機基。R b8為有機基時，作為有機基，可列舉在R 1、R 2及R 3所例示之基。此有機基可於該有機基中可包含雜原子。又，此有機基可為直鏈狀、分枝鏈狀、環狀之任一者。作為R b8，較佳為氫原子或碳原子數1以上12以下之烷基，更佳為甲基。 In formula (B3), R b8 is a hydrogen atom or an organic group. When R b8 is an organic group, examples of the organic group include those exemplified for R 1 , R 2 and R 3 . The organic group may contain heteroatoms in the organic group. Moreover, this organic group may be linear, branched, or cyclic. R b8 is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a methyl group.

將於式(B1)表示之化合物當中，特別適合作為熱鹼產生劑(B)的化合物之具體例示於以下。 Among the compounds represented by the formula (B1), specific examples of compounds that are particularly suitable as the thermal base generator (B) are shown below.

又，下述式(B4)表示之咪唑化合物亦適合作為熱鹼產生劑(B)。 (式(B4)中，R 1、R 2及R 3係與在式(B1)之此等相同，R b9表示氫原子或1價的有機基，R b10表示可具有取代基之芳香族基，R b9可與另一R b9或R b10鍵結，而形成環狀構造)。 Moreover, the imidazole compound represented by following formula (B4) is also suitable as a thermal base generator (B). (In formula (B4), R 1 , R 2 and R 3 are the same as those in formula (B1), R b9 represents a hydrogen atom or a monovalent organic group, R b10 represents an aromatic group that may have a substituent , R b9 can be bonded with another R b9 or R b10 to form a ring structure).

式(B4)中，R b9為氫原子或1價的有機基。作為1價的有機基，並未特別限定，例如亦可為可具有取代基之烷基、可具有取代基之芳香族基等。R b9為烷基時，該烷基可於鏈中具有酯鍵等。 In formula (B4), R b9 is a hydrogen atom or a monovalent organic group. It does not specifically limit as a monovalent organic group, For example, the alkyl group which may have a substituent, the aromatic group which may have a substituent, etc. may be sufficient. When R b9 is an alkyl group, the alkyl group may have an ester bond or the like in the chain.

作為烷基，例如可與在後述之式(B4a)中之R b11等相同。烷基之碳原子數較佳為1以上40以下，更佳為1以上30以下，特佳為1以上20以下，最佳為1以上10以下。 作為該烷基可具有之取代基，例如可與在後述之式(B4a)中之R b11即伸烷基可具有之取代基相同。 As an alkyl group, the same as R b11 etc. in the formula (B4a) mentioned later can be mentioned, for example. The number of carbon atoms in the alkyl group is preferably from 1 to 40, more preferably from 1 to 30, particularly preferably from 1 to 20, most preferably from 1 to 10. As a substituent which this alkyl group may have, it may be the same as the substituent which R b11 in formula (B4a) mentioned later may have, that is, an alkylene group, for example.

作為可具有取代基之芳香族基，係與在後述之式(B4a)中之R b10相同，較佳為芳基，更佳為苯基。作為R b9之可具有取代基之芳香族基，可與R b10相同，亦可為相異。 式(B4)中，較佳為一側之R b9為氫原子，更佳為一側之R b9為氫原子，另一側之R b9為可具有取代基之烷基或可具有取代基之芳香族基。 式(B4)中，R b9可與另一個R b9或R b10鍵結，而形成環狀構造。例如，至少一個之R b9為可具有取代基之烷基時，R b9可與另一個R b9或R b10鍵結，而形成環狀構造。 The aromatic group which may have a substituent is the same as R b10 in formula (B4a) described later, preferably an aryl group, more preferably a phenyl group. The aromatic group which may have a substituent as R b9 may be the same as R b10 , or may be different. In formula (B4), R b9 on one side is preferably a hydrogen atom, more preferably R b9 on one side is a hydrogen atom, and R b9 on the other side is an alkyl group that may have a substituent or an alkyl group that may have a substituent. Aromatic base. In formula (B4), R b9 may be bonded to another R b9 or R b10 to form a ring structure. For example, when at least one R b9 is an optionally substituted alkyl group, R b9 may be bonded to another R b9 or R b10 to form a ring structure.

式(B4)表示之咪唑化合物可為下述式(B4a)表示之化合物。The imidazole compound represented by the formula (B4) may be a compound represented by the following formula (B4a).

(式(B4a)中，R 1、R 2及R 3係與在式(B1)之此等相同，R b11為氫原子或烷基，R b10為可具有取代基之芳香族基，R b12為可具有取代基之伸烷基，R b12可與R b10鍵結而形成環狀構造)。 (In formula (B4a), R 1 , R 2 and R 3 are the same as those in formula (B1), R b11 is a hydrogen atom or an alkyl group, R b10 is an aromatic group that may have a substituent, R b12 It is an alkylene group which may have a substituent, and R b12 may be bonded to R b10 to form a ring structure).

式(B4a)中，R b11為氫原子或烷基。R b11為烷基時，該烷基可為直鏈烷基，亦可為分枝鏈烷基。該烷基之碳原子數雖並未特別限定，但較佳為1以上20以下，更佳為1以上10以下，再更佳為1以上5以下。 In formula (B4a), R b11 is a hydrogen atom or an alkyl group. When R b11 is an alkyl group, the alkyl group may be a straight-chain alkyl group or a branched-chain alkyl group. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably from 1 to 20, more preferably from 1 to 10, and still more preferably from 1 to 5.

作為適合作為R b11的烷基之具體例，可列舉甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、sec-丁基、tert-丁基、n-戊基、異戊基、tert-戊基、n-己基、n-庚基、n-辛基、2-乙基-n-己基、n-壬基、n-癸基、n-十一烷基、n-十二烷基、n-十三烷基、n-十四烷基、n-十五烷基、n-十六烷基、n-十七烷基、n-十八烷基、n-十九烷基及n二十烷基。 Specific examples of alkyl groups suitable as R b11 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n- Pentyl, isopentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethyl-n-hexyl, n-nonyl, n-decyl, n-undecyl base, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl , n-nonadecanyl and n-eicosyl.

式(B4a)中，R b10為可具有取代基之芳香族基。可具有取代基之芳香族基可為可具有取代基之芳香族烴基，亦可為可具有取代基之芳香族雜環基。 In formula (B4a), R b10 is an aromatic group which may have a substituent. The aromatic group which may have a substituent may be an aromatic hydrocarbon group which may have a substituent, or may be an aromatic heterocyclic group which may have a substituent.

芳香族烴基的種類於未阻礙本發明之目的的範圍，並未特別限定。芳香族烴基，亦可為單環式之芳香族基，亦可為縮合2以上之芳香族烴基而形成之基，亦可為2以上之芳香族烴基藉由單鍵鍵結而形成之基。作為芳香族烴基，較佳為苯基、萘基、聯苯基、蒽基、菲基(Phenanthrenyl)。The type of aromatic hydrocarbon group is not particularly limited within the range that does not hinder the object of the present invention. The aromatic hydrocarbon group may be a monocyclic aromatic group, a group formed by condensing two or more aromatic hydrocarbon groups, or a group formed by bonding two or more aromatic hydrocarbon groups with a single bond. The aromatic hydrocarbon group is preferably phenyl, naphthyl, biphenyl, anthracenyl, or phenanthrenyl.

芳香族雜環基的種類於未阻礙本發明之目的的範圍，並未特別限定。芳香族雜環基可為單環式基，亦可為多環式基。作為芳香族雜環基，較佳為吡啶基、呋喃基、噻吩基、咪唑基、吡唑基、噁唑基、噻唑基、異噁唑基、異噻唑基、苯并噁唑基、苯并噻唑基及苯并咪唑基。The type of aromatic heterocyclic group is not particularly limited insofar as it does not hinder the object of the present invention. The aromatic heterocyclic group may be a monocyclic group or a polycyclic group. The aromatic heterocyclic group is preferably pyridyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, benzoxazolyl, benzo Thiazolyl and benzimidazolyl.

作為苯基、多環芳香族烴基或芳香族雜環基可具有之取代基，可列舉鹵素原子、羥基、矽烷基、矽烷醇基、硝基、亞硝基、亞磺酸基、磺基、磺酸根基、膦基、氧膦基、膦醯基、膦酸根基、胺基、銨基及有機基。苯基、多環芳香族烴基或芳香族雜環基具有複數個取代基時，該複數個取代基可為相同，亦可為相異。Examples of substituents that a phenyl group, a polycyclic aromatic hydrocarbon group or an aromatic heterocyclic group may have include a halogen atom, a hydroxyl group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfinic acid group, a sulfo group, Sulfonate, phosphino, phosphinoxide, phosphono, phosphonate, amine, ammonium and organic groups. When a phenyl group, a polycyclic aromatic hydrocarbon group or an aromatic heterocyclic group has a plurality of substituents, the plurality of substituents may be the same or different.

芳香族基所具有之取代基為有機基時，作為該有機基，可列舉烷基、烯基、環烷基、環烯基、芳基及芳烷基等。此有機基可於該有機基中包含雜原子等之烴基以外之鍵結或取代基。又，此有機基可為直鏈狀、分枝鏈狀、環狀及此等之構造的組合之任一種。此有機基通常雖為1價，但形成環狀構造的情況等，可成為2價以上之有機基。When the substituent which the aromatic group has is an organic group, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group etc. are mentioned as this organic group. This organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. In addition, this organic group may be any of a straight chain, a branched chain, a ring, and a combination of these structures. This organic group is usually monovalent, but it may be a divalent or higher organic group when forming a ring structure.

於與芳香族基相鄰之碳原子上具有取代基時，鍵結在相鄰之碳原子上之2個取代基可鍵結其而形成環狀構造。作為環狀構造，可列舉脂肪族烴環或包含雜原子之脂肪族環。When there is a substituent on the carbon atom adjacent to the aromatic group, two substituents bonded to the adjacent carbon atom may bond to form a ring structure. As a cyclic structure, an aliphatic hydrocarbon ring or an aliphatic ring containing a heteroatom is mentioned.

芳香族基所具有之取代基為有機基的情況下，該有機基所包含之鍵結只要不損害本發明之效果，並未特別限定，有機基可包含氧原子、氮原子、矽原子等之包含雜原子之鍵結。作為包含雜原子之鍵結之具體例，可列舉醚鍵、羰基鍵、硫羰基鍵、酯鍵、醯胺鍵、胺基甲酸酯鍵、醯亞胺鍵(-N=C(-R)-、-C(=NR)-：R表示氫原子或有機基)、碳酸酯鍵、磺醯基鍵、偶氮鍵等。When the substituent of the aromatic group is an organic group, the bond included in the organic group is not particularly limited as long as it does not impair the effect of the present invention, and the organic group may contain oxygen atoms, nitrogen atoms, silicon atoms, etc. Contains linkages of heteroatoms. Specific examples of bonds containing heteroatoms include ether bonds, carbonyl bonds, thiocarbonyl bonds, ester bonds, amide bonds, urethane bonds, and imide bonds (-N=C(-R) -, -C(=NR)-: R represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, an azo bond, etc.

作為包含有機基可具有之雜原子的鍵結，從式(B4)或式(B4a)表示之咪唑化合物之耐熱性的觀點來看，較佳為醚鍵、羰基鍵、硫羰基鍵、酯鍵、醯胺鍵、胺基鍵(-NR-：R表示氫原子或1價的有機基)胺基甲酸酯鍵、醯亞胺鍵(-N=C(-R)-、-C(=NR)-：R表示氫原子或1價的有機基)、碳酸酯鍵、磺醯基鍵。From the viewpoint of the heat resistance of the imidazole compound represented by formula (B4) or formula (B4a) as a bond including a heteroatom that the organic group may have, an ether bond, a carbonyl bond, a thiocarbonyl bond, or an ester bond is preferable. , amide bond, amine bond (-NR-: R represents a hydrogen atom or a 1-valent organic group) urethane bond, imide bond (-N=C(-R)-, -C(= NR)-: R represents a hydrogen atom or a monovalent organic group), a carbonate bond, or a sulfonyl bond.

有機基為烴基以外之取代基時，烴基以外之取代基的種類，於不阻礙本發明之目的的範圍，並未特別限定。作為烴基以外之取代基之具體例，可列舉鹵素原子、羥基、巰基、硫化物基、氰基、異氰基、氰氧基、異氰酸基、硫氰基、異硫氰基、矽烷基、矽烷醇基、烷氧基、烷氧基羰基、胺基、單烷基胺基、二烷基鋁基、單芳基胺基、二芳基胺基、胺基甲醯基、硫代胺基甲醯基、硝基、亞硝基、羧酸酯基、醯基、醯基氧基、亞磺酸基、磺酸根基、膦基、氧膦基、膦酸根基、烷基醚基、烯基醚基、芳基醚基等。上述取代基所包含之氫原子亦可藉由烴基取代。又，上述取代基所包含之烴基可為直鏈狀、分枝鏈狀及環狀之任一者。When the organic group is a substituent other than a hydrocarbon group, the type of substituent other than a hydrocarbon group is not particularly limited as long as it does not hinder the object of the present invention. Specific examples of substituents other than hydrocarbon groups include halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, cyano groups, isocyano groups, cyanoxy groups, isocyanato groups, thiocyano groups, isothiocyano groups, and silyl groups. , silanol, alkoxy, alkoxycarbonyl, amino, monoalkylamino, dialkylaluminum, monoarylamino, diarylamine, aminoformyl, thioamine Formyl group, nitro group, nitroso group, carboxylate group, acyl group, acyloxy group, sulfinate group, sulfonate group, phosphine group, phosphine oxide group, phosphonate group, alkyl ether group, Alkenyl ether group, aryl ether group, etc. Hydrogen atoms contained in the above-mentioned substituents may also be substituted by hydrocarbon groups. Moreover, the hydrocarbon group contained in the said substituent may be any of linear, branched and cyclic.

作為苯基、多環芳香族烴基或芳香族雜環基所具有之取代基，較佳為碳原子數1以上12以下之烷基、碳原子數1以上12以下之芳基、碳原子數1以上12以下之烷氧基、碳原子數1以上12以下之芳基氧基、碳原子數1以上12以下之芳基胺基及鹵素原子。As a substituent of a phenyl group, a polycyclic aromatic hydrocarbon group, or an aromatic heterocyclic group, an alkyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and an aryl group having 1 to 12 carbon atoms are preferable. An alkoxy group having 12 or less carbon atoms, an aryloxy group having 1 or more carbon atoms but not more than 12, an arylamino group having 1 or more carbon atoms and not more than 12, and a halogen atom.

作為R b10，由於可便宜且輕易合成式(B4)或式(B4a)表示之咪唑化合物，相對於咪唑化合物之水或有機溶媒的溶解性良好，故較佳為分別為可具有取代基之苯基、呋喃基、噻吩基。 As R b10 , since the imidazole compound represented by formula (B4) or formula (B4a) can be synthesized cheaply and easily, and has good solubility in water or organic solvents of the imidazole compound, benzene which may have a substituent is preferred. base, furyl, thienyl.

式(B4a)中，R b12為可具有取代基之伸烷基。伸烷基可具有之取代基於未阻礙本發明之目的的範圍，並未特別限定。作為伸烷基可具有之取代基之具體例，可列舉羥基、烷氧基、胺基、氰基及鹵素原子等。伸烷基可為直鏈伸烷基，亦可為分枝鏈伸烷基，較佳為直鏈伸烷基。伸烷基之碳原子數並未特別限定，較佳為1以上20以下，更佳為1以上10以下，特佳為1以上5以下。尚，伸烷基之碳原子數中，未包含與伸烷基鍵結之取代基之碳原子。 In formula (B4a), R b12 is an alkylene group which may have a substituent. The substitution which an alkylene group may have is not specifically limited in the range which does not hinder the object of this invention. Specific examples of the substituent that the alkylene group may have include a hydroxyl group, an alkoxy group, an amino group, a cyano group, and a halogen atom. The alkylene group may be a straight chain alkylene group or a branched chain alkylene group, preferably a straight chain alkylene group. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably from 1 to 20, more preferably from 1 to 10, particularly preferably from 1 to 5. Also, the number of carbon atoms in the alkylene group does not include the carbon atoms of the substituent bonded to the alkylene group.

作為與伸烷基鍵結之取代基的烷氧基，可為直鏈烷氧基，亦可為分枝鏈烷氧基。作為取代基之烷氧基的碳原子數並未特別限定，較佳為1以上10以下，更佳為1以上6以下，特佳為1以上3以下。The alkoxy group as the substituent bonded to the alkylene group may be a straight chain alkoxy group or a branched chain alkoxy group. The number of carbon atoms of the alkoxy group as a substituent is not particularly limited, but is preferably from 1 to 10, more preferably from 1 to 6, and particularly preferably from 1 to 3.

作為與伸烷基鍵結之取代基的胺基，亦可為單烷基胺基或二烷基胺基。單烷基胺基或二烷基胺基所包含之烷基亦可為直鏈烷基，亦可為分枝鏈烷基。單烷基胺基或二烷基胺基所包含之烷基的碳原子數並未特別限定較佳為1以上10以下，更佳為1以上6以下，特佳為1以上3以下。The amine group as a substituent bonded to an alkylene group may be a monoalkylamine group or a dialkylamine group. The alkyl group included in the monoalkylamine group or the dialkylamine group may be a straight chain alkyl group or a branched chain alkyl group. The number of carbon atoms of the alkyl group contained in the monoalkylamine group or the dialkylamine group is not particularly limited. It is preferably from 1 to 10, more preferably from 1 to 6, and particularly preferably from 1 to 3.

作為適合作為R b12之伸烷基之具體例，可列舉亞甲基、乙烷-1,2-二基、n-丙烷-1,3-二基、n-丙烷-2,2-二基、n-丁烷-1,4-二基、n-戊烷-1,5-二基、n-己烷-1,6-二基、n-庚烷-1,7-二基、n-辛烷-1,8-二基、n-壬烷-1,9-二基、n-癸烷-1,10-二基、n-十一烷-1,11-二基、n-十二烷-1,12-二基、n-十三烷-1,13-二基、n-十四烷-1,14-二基、n-十五烷-1,15-二基、n-十六烷-1,16-二基、n-十七烷-1,17-二基、n-十八烷-1,18-二基、n-十九烷-1,19-二基及n-二十烷-1,20-二基。 Specific examples of the alkylene group suitable as R b12 include methylene, ethane-1,2-diyl, n-propane-1,3-diyl, n-propane-2,2-diyl , n-butane-1,4-diyl, n-pentane-1,5-diyl, n-hexane-1,6-diyl, n-heptane-1,7-diyl, n -octane-1,8-diyl, n-nonane-1,9-diyl, n-decane-1,10-diyl, n-undecane-1,11-diyl, n- Dodecane-1,12-diyl, n-tridecane-1,13-diyl, n-tetradecane-1,14-diyl, n-pentadecane-1,15-diyl, n-hexadecane-1,16-diyl, n-heptadecane-1,17-diyl, n-octadecane-1,18-diyl, n-nonadecane-1,19-diyl and n-eicosane-1,20-diyl.

從上述式(B4)表示之咪唑化合物當中，可便宜且容易合成的點來看，較佳為下述式(B4-1a)表示之化合物。Among the imidazole compounds represented by the above formula (B4), compounds represented by the following formula (B4-1a) are preferred because they can be synthesized cheaply and easily.

(式(B4-1a)中，R 1、R 2及R 3係與在式(B1)之此等相同，R b9係與式(B4)相同，R b13、R b14、R b15、R b16及R b17分別獨立為氫原子、鹵素原子、羥基、矽烷基、矽烷醇基、硝基、亞硝基、亞磺酸基、磺基、磺酸根基、膦基、氧膦基、膦醯基、膦酸根基、胺基、銨基或有機基。R b13、R b14、R b15、R b16及R b17當中，可至少鍵結2個，而形成環狀構造。R b9可與R b15鍵結而形成環狀構造)。 尚，在式(B4-1a)，R b13、R b14、R b15、R b16及R b17亦可為全部為氫原子。又，以對式(B4-1)表示之化合物的溶媒(S)之溶解性的點來看，較佳為R b13、R b14、R b15、R b16及R b17當中之至少一個為氫原子以外之基。 (In formula (B4-1a), R 1 , R 2 and R 3 are the same as those in formula (B1), R b9 is the same as formula (B4), R b13 , R b14 , R b15 , R b16 and R b17 are independently a hydrogen atom, a halogen atom, a hydroxyl group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfinic acid group, a sulfo group, a sulfonic acid group, a phosphino group, a phosphinyl group, a phosphono group , phosphonate group, amine group, ammonium group or organic group. Among R b13 , R b14 , R b15 , R b16 and R b17 , at least two can be bonded to form a ring structure. R b9 can be bonded to R b15 knot to form a ring structure). Furthermore, in formula (B4-1a), R b13 , R b14 , R b15 , R b16 and R b17 may all be hydrogen atoms. Also, from the viewpoint of the solubility of the compound represented by the formula (B4-1) in the solvent (S), at least one of R b13 , R b14 , R b15 , R b16 and R b17 is preferably a hydrogen atom outside the base.

R b13、R b14、R b15、R b16及R b17係與在後述之式(B4-1)中之此等相同。式(B4-1a)中，R b9可與R b15鍵結而形成環狀構造。例如，R b9為可具有取代基之烷基時，R b9可與R b15鍵結而形成環狀構造。 R b13 , R b14 , R b15 , R b16 and R b17 are the same as those in formula (B4-1) described later. In the formula (B4-1a), R b9 may be bonded to R b15 to form a ring structure. For example, when R b9 is an alkyl group which may have a substituent, R b9 may be bonded to R b15 to form a ring structure.

上述式(B4a)或式(B4-1a)表示之咪唑化合物當中，從便宜且可容易合成，對於水或有機溶劑之溶解性優異的點來看，較佳為下述式(B4-1)表示之化合物，更佳為式(B4-1)表示，R b12為亞甲基之化合物。 Among the imidazole compounds represented by the above formula (B4a) or formula (B4-1a), the following formula (B4-1) is preferable in terms of being cheap and easy to synthesize, and having excellent solubility in water or organic solvents The compound represented by is more preferably represented by the formula (B4-1), wherein R b12 is a methylene group.

(式(B4-1)中，R 1、R 2及R 3係與在式(B1)之此等相同，R b11及R b12係與在式(B4a)中之此等相同，R b13、R b14、R b15、R b16及R b17分別獨立為氫原子、鹵素原子、羥基、矽烷基、矽烷醇基、硝基、亞硝基、亞磺酸基、磺基、磺酸根基、膦基、氧膦基、膦醯基、膦酸根基、胺基、銨基或有機基。R b13、R b14、R b15、R b16及R b17當中，可至少鍵結2個，而形成環狀構造。R b12可與R b15鍵結而形成環狀構造)。 尚，在式(B4-1)，R b13、R b14、R b15、R b16及R b17亦可為全部為氫原子。又，以對式(B4-1)表示之化合物的溶媒(S)之溶解性的點來看，較佳為R b13、R b14、R b15、R b16及R b17當中之至少一個為氫原子以外之基。 (In formula (B4-1), R 1 , R 2 and R 3 are the same as those in formula (B1), R b11 and R b12 are the same as those in formula (B4a), R b13 , R b14 , R b15 , R b16 and R b17 are independently hydrogen atom, halogen atom, hydroxyl group, silyl group, silanol group, nitro group, nitroso group, sulfinate group, sulfo group, sulfonate group, phosphino group , phosphinyl group, phosphonyl group, phosphonic acid group, amine group, ammonium group or organic group. Among R b13 , R b14 , R b15 , R b16 and R b17 , at least two of them can be bonded to form a ring structure .R b12 can be bonded with R b15 to form a ring structure). Furthermore, in the formula (B4-1), all of R b13 , R b14 , R b15 , R b16 and R b17 may be hydrogen atoms. Also, from the viewpoint of the solubility of the compound represented by the formula (B4-1) in the solvent (S), at least one of R b13 , R b14 , R b15 , R b16 and R b17 is preferably a hydrogen atom outside the base.

R b13、R b14、R b15、R b16及R b17為有機基時，該有機基係與在式(B4a)之R b10作為取代基具有之有機基相同。R b13、R b14、R b15及R b16從對於咪唑化合物的溶媒(S)之溶解性的點來看，較佳為氫原子。 When R b13 , R b14 , R b15 , R b16 and R b17 are organic groups, the organic group is the same as the organic group that R b10 of the formula (B4a) has as a substituent. R b13 , R b14 , R b15 and R b16 are preferably hydrogen atoms from the viewpoint of solubility in the solvent (S) of the imidazole compound.

其中，較佳為R b13、R b14、R b15、R b16及R b17當中，至少一個為下述取代基，特佳為R b17為下述取代基。R b17為下述取代基時，較佳為R b13、R b14、R b15及R b16為氫原子。 (R b18為氫原子或有機基)。 Among them, at least one of R b13 , R b14 , R b15 , R b16 and R b17 is preferably the following substituent, and it is particularly preferred that R b17 is the following substituent. When R b17 is the following substituent, R b13 , R b14 , R b15 and R b16 are preferably hydrogen atoms. (R b18 is a hydrogen atom or an organic group).

R b18為有機基時，該有機基係與在式(B4a)之R b10作為取代基具有之有機基相同。作為R b18，較佳為烷基，更佳為碳原子數1以上8以下之烷基，特佳為碳原子數1以上3以下之烷基，最佳為甲基。 When R b18 is an organic group, the organic group is the same as the organic group that R b10 of the formula (B4a) has as a substituent. R b18 is preferably an alkyl group, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 3 carbon atoms, most preferably a methyl group.

上述式(B4-1)表示之化合物當中，較佳為下述式(B4-1-1)表示之化合物。 (在式(B4-1-1)，R 1、R 2及R 3係與在式(B1)之此等相同，R b11係與式(B4a)相同，R b19、R b20、R b21、R b22及R b23分別獨立為氫原子、羥基、矽烷基、矽烷醇基、硝基、亞硝基、亞磺酸基、磺基、磺酸根基、膦基、氧膦基、膦醯基、膦酸根基、胺基、銨基或有機基。惟，R b19、R b20、R b21、R b22及R b23當中，至少一個為氫原子以外之基)。 Among the compounds represented by the above formula (B4-1), compounds represented by the following formula (B4-1-1) are preferred. (In formula (B4-1-1), R 1 , R 2 and R 3 are the same as those in formula (B1), R b11 is the same as formula (B4a), R b19 , R b20 , R b21 , R b22 and R b23 are independently a hydrogen atom, a hydroxyl group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfinic acid group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, A phosphonate group, an amine group, an ammonium group or an organic group. However, at least one of R b19 , R b20 , R b21 , R b22 and R b23 is a group other than a hydrogen atom).

式(B4-1-1)表示之化合物當中，較佳為R b19、R b20、R b21、R b22及R b23當中，至少一個為前述之-O-R b18表示之基，特佳為R b23為-O-R b18表示之基。R b23為-O-R b18表示之基時，較佳為R b19、R b20、R b21及R b22為氫原子。 Among the compounds represented by the formula (B4-1-1), preferably at least one of R b19 , R b20 , R b21 , R b22 and R b23 is the group represented by the aforementioned -OR b18 , particularly preferably R b23 is The base represented by -OR b18 . When R b23 is a group represented by -OR b18 , R b19 , R b20 , R b21 and R b22 are preferably hydrogen atoms.

作為式(B4)或式(B4a)表示之咪唑化合物之合適的具體例，可列舉以下之化合物。 Suitable specific examples of the imidazole compound represented by formula (B4) or formula (B4a) include the following compounds.

塗料組成物中之熱鹼產生劑(B)的含量相對於固體成分全體100質量份，較佳為1質量份以上20質量份以下，更佳為2質量份以上10質量份以下。藉由使用該範圍內的量之熱鹼產生劑(B)，不會伴隨熱鹼產生劑(B)之熱分解物的過度揮發或昇華，可有效果地促進來自聚醯胺酸(A)之聚醯胺樹脂的生成。The content of the thermal base generator (B) in the paint composition is preferably from 1 to 20 parts by mass, more preferably from 2 to 10 parts by mass, based on 100 parts by mass of the total solid content. By using the thermal base generator (B) in the amount within this range, it is not accompanied by excessive volatilization or sublimation of the thermal decomposition product of the thermal base generator (B), and the thermal base generator (B) from polyamic acid (A) can be effectively promoted The generation of polyamide resin.

＜其他成分＞ 塗料組成物如有必要可含有各種添加劑。作為添加劑，可列舉著色劑、分散劑、增感劑、密著促進劑、抗氧化劑、紫外線吸收劑、抗凝聚劑、消泡劑、界面活性劑等。又，塗料組成物如有必要可包含各種填充材料或強化材料。 各種添加劑的使用量於未阻礙本發明之目的的範圍，並未特別限定。相對於塗料組成物之固體成分的質量，例如於0.001質量%以上60質量%以下的範圍內適當調整即可，較佳為0.05質量%以上5質量%以下。 填充材料或強化材料的使用量於未阻礙本發明之目的的範圍，並未特別限定。填充材料或強化材料的使用量，通常而言相對於聚醯胺酸(A)的質量，較佳為1質量%以上300質量%以下，更佳為5質量%以上200質量%以下，再更佳為10質量%以上100質量%以下。 ＜Other ingredients＞ The paint composition may contain various additives as necessary. Examples of additives include coloring agents, dispersants, sensitizers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregating agents, antifoaming agents, and surfactants. Also, the paint composition may contain various fillers or reinforcing materials as necessary. The usage-amount of various additives is not specifically limited in the range which does not hinder the object of this invention. The mass of the solid content of the paint composition may be appropriately adjusted within a range of, for example, 0.001% by mass to 60% by mass, preferably 0.05% by mass to 5% by mass. The usage-amount of a filler or a reinforcing material is not specifically limited in the range which does not hinder the object of this invention. The amount of the filler or reinforcing material used is usually preferably from 1% by mass to 300% by mass, more preferably from 5% by mass to 200% by mass, and more preferably with respect to the mass of the polyamic acid (A). Preferably, it is not less than 10% by mass and not more than 100% by mass.

如以上，根據上述之塗料組成物，可形成著色少，且拉伸彈性率、拉伸強度、斷裂伸長率及低熱膨脹性等之機械特性優異之聚醯亞胺樹脂。As above, according to the above-mentioned coating composition, it is possible to form a polyimide resin with less coloring and excellent mechanical properties such as tensile modulus of elasticity, tensile strength, elongation at break, and low thermal expansion.

≪塗料組成物之製造方法≫ 作為塗料組成物之合適的製造方法，可列舉：包含 將四羧酸二酐(A1)及芳香族二胺化合物(A2)於溶媒(S)中聚合，生成聚醯胺酸(A)或 使四羧酸二酐(A1)及芳香族二胺化合物(A2)聚合，生成聚醯胺酸(A)後，將經單離之聚醯胺酸(A)與溶媒(S)混合之方法。 係如前述，四羧酸二酐(A1)係僅由脂環式四羧酸二酐(A1-1)及芳香族四羧酸二酐(A1-2)構成。 芳香族四羧酸二酐(A1-2)的質量相對於四羧酸二酐(A1)之莫耳數的比率，為0.1莫耳%以上6莫耳%以下。 ≪Manufacturing method of paint composition≫ As suitable manufacturing method of coating composition, can enumerate: comprise Polymerize tetracarboxylic dianhydride (A1) and aromatic diamine compound (A2) in solvent (S) to generate polyamic acid (A) or A method of mixing tetracarboxylic dianhydride (A1) and aromatic diamine compound (A2) to produce polyamic acid (A) and then mixing the isolated polyamic acid (A) with solvent (S) . As mentioned above, tetracarboxylic dianhydride (A1) consists only of alicyclic tetracarboxylic dianhydride (A1-1) and aromatic tetracarboxylic dianhydride (A1-2). The ratio of the mass of the aromatic tetracarboxylic dianhydride (A1-2) to the number of moles of the tetracarboxylic dianhydride (A1) is 0.1 mol % or more and 6 mol % or less.

對於使四羧酸二酐(A1)及芳香族二胺化合物(A2)聚合之方法，係如前述。 尚，製造塗料組成物時，從包含聚醯胺酸(A)之聚合反應液，單離聚醯胺酸時，可於經單離之聚醯胺酸(A)，同伴使用在聚合之有機溶媒或未反應之單體。 The method for polymerizing tetracarboxylic dianhydride (A1) and aromatic diamine compound (A2) is as described above. Also, when producing a coating composition, when isolating polyamic acid from a polymerization reaction solution containing polyamic acid (A), it can be used in conjunction with the isolated polyamic acid (A) in the polymerization. solvent or unreacted monomer.

≪聚醯亞胺樹脂之製造方法≫ 可藉由包含成形以上說明之塗料組成物之成形步驟、與 加熱經成形之塗料組成物，使其醯亞胺化之醯亞胺化步驟的方法，製造聚醯亞胺樹脂。 ≪Manufacturing method of polyimide resin≫ It can be formed by the forming step including forming the above-described coating composition, and A method of imidizing the formed coating composition by heating and imidizing it to produce a polyimide resin.

成形塗料組成物時所成形之塗料組成物的形狀並未特別限定。成形塗料組成物之方法並未特別限定。例如可列舉於所期望之形狀的型當中注入塗料組成物之方法，或使用刮板等，於鑄型內填充塗料組成物之方法，或於基材上塗佈塗料組成物之方法等。 此等之方法當中，由於聚醯亞胺樹脂薄膜的需求大，或於聚醯亞胺樹脂製造時容易從塗料組成物良好地去除溶媒(S)等，故較佳為於基材上塗佈塗料組成物之方法。 塗料組成物的塗佈後，放置在加熱及/或真空或是減壓環境，乾燥塗佈膜，並形成乾燥膜。 The shape of the paint composition to be molded when molding the paint composition is not particularly limited. The method for forming the coating composition is not particularly limited. For example, a method of injecting a coating composition into a mold having a desired shape, a method of filling a mold with a coating composition using a squeegee, or a method of coating a coating composition on a substrate may be mentioned. Among these methods, since the polyimide resin film is in great demand, or the solvent (S) is easily removed from the coating composition when the polyimide resin is produced, it is preferable to coat the polyimide resin on the substrate. Method for coating composition. After the coating composition is applied, it is placed in a heating and/or vacuum or reduced pressure environment to dry the coating film and form a dry film.

加熱塗料組成物或乾燥步驟後之塗料組成物的溫度，若為得到所期望之性能的聚醯亞胺樹脂的溫度，則並未特別限定。加熱聚醯胺酸的溫度較佳為120℃以上450℃以下，更佳為150℃以上435℃以下。藉由以這般的範圍的溫度加熱塗料組成物，可抑制生成之聚醯亞胺樹脂的熱劣化或熱分解，可去除溶媒(S)，並且可生成聚醯亞胺樹脂。 又，由於容易形成玻璃轉移溫度及拉伸彈性率高，熱膨脹率低，著色少之聚醯亞胺樹脂，故將聚醯胺酸於70℃以上120℃以下之溫度10分鐘至2小時左右，進而於150℃以上435℃以下5分鐘至2小時左右，一邊階段性提昇溫度一邊加熱，來生成聚醯亞胺樹脂亦佳。 The temperature for heating the paint composition or the paint composition after the drying step is not particularly limited as long as it is a temperature at which the polyimide resin with desired properties can be obtained. The temperature for heating polyamic acid is preferably from 120°C to 450°C, more preferably from 150°C to 435°C. By heating the paint composition at a temperature in such a range, thermal deterioration or thermal decomposition of the produced polyimide resin can be suppressed, the solvent (S) can be removed, and the polyimide resin can be produced. In addition, since it is easy to form a polyimide resin with a high glass transition temperature, a high modulus of tensile elasticity, a low thermal expansion rate, and less coloring, the polyimide resin is kept at a temperature above 70°C and below 120°C for 10 minutes to 2 hours. Furthermore, it is also preferable to heat at 150° C. to 435° C. for about 5 minutes to 2 hours while raising the temperature step by step to produce a polyimide resin.

根據以上說明之聚醯亞胺樹脂之製造方法，可製造著色少，且拉伸彈性率、拉伸強度、斷裂伸長率及低熱膨脹性等之機械特性優異之聚醯亞胺樹脂。 [實施例] According to the production method of the polyimide resin described above, it is possible to produce a polyimide resin with less coloration and excellent mechanical properties such as tensile modulus of elasticity, tensile strength, elongation at break, and low thermal expansion. [Example]

以下，雖將本發明藉由實施例進行詳細說明，但本發明的範圍並非被限定於此等之實施例。Hereinafter, although the present invention will be described in detail through examples, the scope of the present invention is not limited to these examples.

在實施例及比較例，作為脂環式四羧酸二酐(A1-1)，係使用下述式之化合物1-1。 In Examples and Comparative Examples, Compound 1-1 of the following formula was used as alicyclic tetracarboxylic dianhydride (A1-1).

作為芳香族四羧酸二酐(A1-2)，係使用下述之化合物1-2a、1-2b及1-2c。 化合物1-2a：3,3’,4,4’-聯苯基四羧酸二酐 化合物1-2b：均苯四甲酸二酐 化合物1-2c：萘-1,4,5,8-四羧酸二酐 As the aromatic tetracarboxylic dianhydride (A1-2), the following compounds 1-2a, 1-2b, and 1-2c were used. Compound 1-2a: 3,3’,4,4’-Biphenyltetracarboxylic dianhydride Compound 1-2b: pyromellitic dianhydride Compound 1-2c: Naphthalene-1,4,5,8-tetracarboxylic dianhydride

在實施例及比較例，作為熱鹼產生劑(B)，係使用下述式之化合物。 In Examples and Comparative Examples, a compound of the following formula was used as the thermal base generator (B).

[實施例1~9及比較例1~4] 將容量30mL之三口燒瓶以熱風槍加熱，充分使其乾燥。接著，將三口燒瓶內的環境以氮取代，並將三口燒瓶內定為氮環境。於三口燒瓶內，添加作為芳香族二胺化合物(A2)之4,4’-二胺基苯甲醯苯胺0.2045g(0.90mmol：日本純良藥品股份有限公司製：DABAN)後，再添加N,N,N’,N’-四甲基脲(TMU)。攪拌三口燒瓶之內容物，而得到於TMU中分散芳香族二胺(DABAN)之漿料液。 TMU的量係與四羧酸二酐(A1)的質量、與芳香族二胺化合物(A2)的質量的合計為同質量。 接著，於三口燒瓶內添加表1所記載的種類及量之四羧酸二酐(A1)0.90mmol。然後，於氮環境下，於室溫(25℃)攪拌12小時燒瓶之內容物，而得到反應液。對於包含如此進行所得之聚醯胺酸的反應液，相對於四羧酸二酐(A1)的質量、與芳香族二胺化合物(A2)的質量的合計，加入10質量%的量之熱鹼產生劑(B)。 接著，將包含聚醯胺酸(A)之反應液以聚醯胺酸(A)的濃度成為18質量%的方式，以TMU稀釋，而得到各實施例及各比較例之塗料組成物。 [Examples 1-9 and Comparative Examples 1-4] Heat a three-neck flask with a capacity of 30mL with a heat gun to fully dry it. Next, the environment in the three-necked flask was replaced with nitrogen, and the inside of the three-necked flask was set as a nitrogen environment. In the three-necked flask, add 0.2045 g (0.90 mmol: Nippon Junyo Pharmaceutical Co., Ltd.: DABAN) of 4,4'-diaminobenzylaniline as the aromatic diamine compound (A2), and then add N, N,N',N'-Tetramethylurea (TMU). The contents of the three-necked flask were stirred to obtain a slurry liquid in which aromatic diamine (DABAN) was dispersed in TMU. The amount of TMU is the same mass as the total of the mass of the tetracarboxylic dianhydride (A1) and the mass of the aromatic diamine compound (A2). Next, 0.90 mmol of tetracarboxylic dianhydride (A1) of the kind and quantity listed in Table 1 was added in the three-necked flask. Then, the contents of the flask were stirred at room temperature (25° C.) for 12 hours under a nitrogen atmosphere to obtain a reaction liquid. To the reaction solution containing the polyamic acid obtained in this way, 10% by mass of hot alkali was added to the total mass of the tetracarboxylic dianhydride (A1) and the mass of the aromatic diamine compound (A2) Generator (B). Next, the reaction liquid containing polyamic acid (A) was diluted with TMU so that the concentration of polyamic acid (A) might become 18 mass %, and the coating composition of each Example and each comparative example was obtained.

使用如以上進行所得之各實施例及比較例之塗料組成物，依據以下之方法，進行聚醯亞胺樹脂薄膜的成膜，對於所形成之聚醯亞胺樹脂薄膜，進行黃色度(YI)、光線透過率、熱膨脹率(CTE)、斷裂伸長率、拉伸強度及拉伸彈性率的評估。將此等之評估結果記於表1。Using the coating compositions of the various examples and comparative examples obtained as above, according to the following method, film formation of polyimide resin films was carried out, and the yellowness (YI) of the formed polyimide resin films was measured. , Light transmittance, coefficient of thermal expansion (CTE), elongation at break, tensile strength and tensile modulus of elasticity. Record these evaluation results in Table 1.

＜聚醯亞胺樹脂薄膜的成膜方法＞ 於玻璃基板(縱：100mm、橫100mm、厚度1.3mm)上，將如上述進行所得之塗料組成物，以加熱硬化後之塗膜的厚度成為13μm的方式進行旋塗，形成塗膜。接著，將具備塗膜之玻璃基板以溫度50℃、壓力13Pa的條件下，進行真空乾燥，去除塗膜中之溶媒。 溶媒的去除後，將具備塗膜之玻璃基板投入以3L/分鐘的流量流動氮之惰性烘箱。於惰性烘箱內，以氮環境下、80℃的溫度條件，靜置0.5小時後，以300℃的溫度條件靜置0.5小時，進而以430℃的溫度條件(最終加熱溫度)加熱5分鐘，使塗膜硬化，而得到以由聚醯亞胺所構成之薄膜(聚醯亞胺薄膜)塗佈之聚醯亞胺塗佈玻璃。 將所得之聚醯亞胺塗佈玻璃浸漬在90℃之熱水當中，從玻璃基板使聚醯亞胺薄膜剝離，而得到聚醯亞胺薄膜(縱100mm、橫100mm、厚度13μm大小的薄膜)。 ＜Film Formation Method of Polyimide Resin Film＞ On a glass substrate (100 mm in length, 100 mm in width, and 1.3 mm in thickness), the coating composition obtained as described above was spin-coated so that the thickness of the coating film after heating and hardening became 13 μm to form a coating film. Next, the glass substrate provided with the coating film was vacuum-dried under the conditions of a temperature of 50° C. and a pressure of 13 Pa to remove the solvent in the coating film. After removal of the solvent, the glass substrate provided with the coating film was put into an inert oven flowing nitrogen at a flow rate of 3 L/min. In an inert oven, under a nitrogen atmosphere, at a temperature of 80°C, let stand for 0.5 hours, then stand at a temperature of 300°C for 0.5 hours, and then heat at a temperature of 430°C (final heating temperature) for 5 minutes, so that The coating film was cured to obtain a polyimide-coated glass coated with a thin film (polyimide film) made of polyimide. The obtained polyimide-coated glass was immersed in hot water at 90°C, and the polyimide film was peeled off from the glass substrate to obtain a polyimide film (100 mm in length, 100 mm in width, and 13 μm in thickness) .

＜黃色度(YI)、光線透過率＞ 各實施例及比較例之聚醯亞胺薄膜的光線透過率之值(單位：%)及黃色度(YI)，係藉由使用日本電色工業股份有限公司製之商品名「霧度計NDH-5000」作為測定裝置，並進行依照JIS K7361-1(1997年發行)之測定求出。光線透過率為在光線波長380nm~780nm之值。 對於黃色度，依照以下之基準，來判定評估結果。 ◎：YI值未滿4.0。 〇：YI值為4.0以上5.0以下。 ×：YI值超過5.0。 ＜Yellowness (YI), light transmittance＞ The values (unit: %) and yellowness (YI) of the light transmittance (unit: %) and the yellowness (YI) of the polyimide film of each embodiment and the comparative example are obtained by using the trade name "haze meter NDH" manufactured by Nippon Denshoku Industries Co., Ltd. -5000" was used as a measuring device, and it was determined in accordance with JIS K7361-1 (issued in 1997). The light transmittance is the value at the light wavelength of 380nm~780nm. Regarding the degree of yellowness, the evaluation results are judged according to the following criteria. ⊚: YI value is less than 4.0. 〇: YI value is not less than 4.0 and not more than 5.0. ×: YI value exceeds 5.0.

＜熱膨脹率(CTE)＞ 從各實施例及比較例之聚醯亞胺薄膜，形成縱：20mm、橫：5mm大小的測定用之薄膜。 接著，藉由利用熱機械性分析裝置(島津製作所股份有限公司製之商品名「TMA-60」)作為測定裝置，並將所得之測定用之薄膜於氮環境下，測定以昇溫速度10℃/分鐘的條件，從30℃昇溫至200℃後，一度冷卻至30℃，再度以昇溫速度10℃/分鐘的條件，從30℃昇溫至500℃時之在100℃~400℃之試料長度的變化，求出在100℃~400℃之每1℃之長度變化的平均值來測定。尚，拉伸模式定為49mN。 ＜Coefficient of Thermal Expansion (CTE)＞ From the polyimide films of the respective examples and comparative examples, a film for measurement having a size of 20 mm in length and 5 mm in width was formed. Next, by using a thermomechanical analyzer (trade name "TMA-60" manufactured by Shimadzu Corporation) as a measurement device, the obtained thin film for measurement was measured under a nitrogen atmosphere at a temperature increase rate of 10°C/ The change in the length of the sample between 100°C and 400°C when the temperature is raised from 30°C to 200°C in one minute, cooled to 30°C once, and then raised from 30°C to 500°C at a heating rate of 10°C/min , Determine the average value of the length change per 1 °C at 100 °C~400 °C. Still, the tensile mode was set at 49mN.

＜斷裂伸長率、拉伸強度及拉伸彈性率＞ 對於各實施例及比較例之聚醯亞胺薄膜，於SD型槓桿式試料裁斷器(DUMBBEL股份有限公司製之裁斷器(型式SDL-200))，安裝DUMBBEL股份有限公司製之商品名「SUPER DUMBBELL CUTTER(型：SDMK-1000-D、依照JIS K7139(2009年發行)之A22規格)」，以聚醯亞胺薄膜的大小成為全長：75mm、標籤部間距離：57mm、平行部的長度：30mm、肩部的半徑：30mm、端部的寬度：10mm、中央之平行部的寬度：5mm、厚度：13μm的方式裁斷，將DUMBBEL形狀之試驗片(除了將厚度定為13μm之外，照著JIS K7139 型A22(縮尺試驗片)之規格的試驗片)作為測定試料調製。 接著，使用張力型萬能試驗機(A&D股份有限公司製之型號「UCT-10T」)，將測定試料以夾具間的寬度成為57mm、挾住部分的寬度成為10mm(端部的全寬)的方式進行來配置後，以荷重全刻度：0.05kN、試驗速度：1~300mm/分鐘的條件，進行拉伸測定試料之拉伸試驗，求出拉伸強度、斷裂伸長率及拉伸彈性率之值。 上述之試驗係依照JIS K7162(1994年發行)之試驗。 又，斷裂伸長率之值(%)係將試驗片之平行部的長度(=平行部的長度：30mm)定為L0，將至斷裂為止之試驗片之平行部的長度(斷裂時之試驗片之平行部的長度：30mm+α)定為L，計算下述式： [斷裂伸長率(%)]={(L-L0)/L0}×100 求出。 對於拉伸彈性率，依據以下之基準，來判定評估結果。 ◎：拉伸彈性率超過7.0GPa。 〇：拉伸彈性率為5.0GPa以上7.0GPa以下。 ×：拉伸彈性率未滿5.0GPa。 ＜Elongation at break, tensile strength and tensile modulus＞ For the polyimide films of the respective examples and comparative examples, a product named "SUPER" manufactured by DUMBBEL Co., Ltd. was installed on an SD-type lever type sample cutter (a cutter made by DUMBBEL Co., Ltd. (model SDL-200)). DUMBBELL CUTTER (type: SDMK-1000-D, in accordance with A22 standard of JIS K7139 (issued in 2009))", the size of the polyimide film becomes the overall length: 75mm, the distance between the label parts: 57mm, the length of the parallel part: 30mm, radius of the shoulder: 30mm, width of the end: 10mm, width of the parallel part of the center: 5mm, thickness: 13μm, and the test piece of the DUMBBEL shape (except that the thickness is set to 13μm, according to the A test piece according to JIS K7139 type A22 (reduced scale test piece)) was prepared as a measurement sample. Next, using a tension-type universal testing machine (model "UCT-10T" manufactured by A&D Co., Ltd.), measure the sample so that the width between the grips becomes 57 mm, and the width of the pinched part becomes 10 mm (full width of the end) After the configuration is carried out, under the conditions of full load scale: 0.05kN and test speed: 1~300mm/min, carry out the tensile test of the tensile measurement sample, and obtain the values of tensile strength, elongation at break and tensile elastic modulus . The above test is based on the test of JIS K7162 (published in 1994). In addition, the value (%) of the elongation at break is defined as the length of the parallel portion of the test piece (=length of the parallel portion: 30mm) as L0, and the length of the parallel portion of the test piece until it breaks (the test piece at the time of fracture) The length of the parallel part: 30mm+α) is defined as L, and the following formula is calculated: [Elongation at break (%)]={(L-L0)/L0}×100 Find out. Regarding the tensile modulus, the evaluation results were judged on the basis of the following criteria. ⊚: The tensile modulus exceeds 7.0 GPa. ○: Tensile modulus of elasticity is not less than 5.0 GPa and not more than 7.0 GPa. ×: Tensile modulus of elasticity is less than 5.0 GPa.

根據表1，瞭解到使用由脂環式四羧酸二酐(A1-1)及芳香族四羧酸二酐(A1-2)所構成之四羧酸二酐(A)、與芳香族二胺化合物(A2)的聚合物，且芳香族四羧酸二酐(A1-2)的質量相對於四羧酸二酐(A1)之莫耳數的比率為0.1莫耳%以上6莫耳%以下的包含聚醯胺酸(A)之實施例之塗料組成物時，可形成兼備著色少與優異之機械特性之聚醯亞胺樹脂。 另一方面，根據比較例，瞭解到使用：僅使用脂環式四羧酸二酐(A1-1)作為聚醯胺酸(A)來調製，或是芳香族四羧酸二酐(A1-2)的質量相對於四羧酸二酐(A1)之莫耳數的比率超過6莫耳%的包含聚醯胺酸(A)之塗料組成物時，著色少與優異之機械特性兼備困難。 According to Table 1, it is understood that tetracarboxylic dianhydride (A) composed of alicyclic tetracarboxylic dianhydride (A1-1) and aromatic tetracarboxylic dianhydride (A1-2), and aromatic dicarboxylic acid dianhydride (A1-2) A polymer of an amine compound (A2), wherein the mass ratio of the aromatic tetracarboxylic dianhydride (A1-2) to the number of moles of the tetracarboxylic dianhydride (A1) is 0.1 mol% or more and 6 mol% When the coating composition of the following example containing polyamic acid (A) is used, the polyimide resin which has both little coloring and excellent mechanical properties can be formed. On the other hand, according to the comparative example, it is understood that use: only use alicyclic tetracarboxylic dianhydride (A1-1) as polyamic acid (A) to prepare, or aromatic tetracarboxylic dianhydride (A1-1) 2) When the ratio of the mass of the polyamic acid (A) to the molar number of the tetracarboxylic dianhydride (A1) exceeds 6 mol %, it is difficult to achieve both less coloring and excellent mechanical properties.

Claims (7)

一種塗料組成物，其特徵為包含聚醯胺酸(A)、與溶媒(S)， 前述聚醯胺酸(A)為四羧酸二酐(A1)及芳香族二胺化合物(A2)之聚合物， 前述四羧酸二酐(A1)係僅由脂環式四羧酸二酐(A1-1)及芳香族四羧酸二酐(A1-2)所構成， 前述芳香族四羧酸二酐(A1-2)的質量相對於前述四羧酸二酐(A1)之莫耳數的比率，為0.1莫耳%以上6莫耳%以下。 A kind of coating composition, it is characterized in that comprising polyamic acid (A), and solvent (S), The aforementioned polyamic acid (A) is a polymer of tetracarboxylic dianhydride (A1) and aromatic diamine compound (A2), The aforementioned tetracarboxylic dianhydride (A1) is only composed of alicyclic tetracarboxylic dianhydride (A1-1) and aromatic tetracarboxylic dianhydride (A1-2), The ratio of the mass of the aromatic tetracarboxylic dianhydride (A1-2) to the number of moles of the tetracarboxylic dianhydride (A1) is 0.1 mol % or more and 6 mol % or less. 如請求項1之塗料組成物，其中，前述脂環式四羧酸二酐(A1-1)為下述式(a2)表示之化合物， (式(a2)中，R a11、R a12及R a13分別獨立為選自由氫原子、碳原子數1以上5以下之烷基及氟原子所構成之群組中之1種，a為0以上12以下之整數)。 The coating composition according to claim 1, wherein the aforementioned alicyclic tetracarboxylic dianhydride (A1-1) is a compound represented by the following formula (a2), (In formula (a2), R a11 , R a12 and R a13 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and a fluorine atom, and a is 0 or more an integer below 12). 如請求項1或2之塗料組成物，其中，前述芳香族二胺化合物(A2)為選自下述式(21)～式(24)表示之化合物中之1種以上， (式(21)~(25)中，R 111表示選自由氫原子、氟原子、羥基、碳原子數1以上4以下之烷基及碳原子數1以上4以下之鹵素化烷基所構成之群組中之1種， 式(24)中，Q表示9,9’-亞茀基，或選自由式：-C 6H 4-、-CONH-C 6H 4-NHCO-、-NHCO-C 6H 4-CONH-、-O-C 6H 4-CO-C 6H 4-O-、-OCO-C 6H 4-COO-、-OCO-C 6H 4-C 6H 4-COO-、-OCO-、-O-、-S-、-CO-、-CONH-、-SO 2-、-C(CF 3) 2-、-C(CH 3) 2-、-CH 2-、-O-C 6H 4-C(CH 3) 2-C 6H 4-O-、-O-C 6H 4-C(CF 3) 2-C 6H 4-O-、-O-C 6H 4-SO 2-C 6H 4-O-、-C(CH 3) 2-C 6H 4-C(CH 3) 2-、-O-C 10H 6-O-、-O-C 6H 4-C 6H 4-O-及-O-C 6H 4-O-表示之基所構成之群組中之1種，-C 6H 4-為伸苯基，-C 10H 6-為萘二基)。 The coating composition according to claim 1 or 2, wherein the aromatic diamine compound (A2) is one or more compounds selected from the following formulas (21) to (24), (In the formulas (21)~(25), R111 represents a group consisting of a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group with 1 to 4 carbon atoms, and a halogenated alkyl group with 1 to 4 carbon atoms. One of the group, in formula (24), Q represents 9,9'-fenylene, or is selected from the formula: -C 6 H 4 -, -CONH-C 6 H 4 -NHCO-, -NHCO- C 6 H 4 -CONH-, -OC 6 H 4 -CO-C 6 H 4 -O-, -OCO-C 6 H 4 -COO-, -OCO-C 6 H 4 -C 6 H 4 -COO- , -OCO-, -O-, -S-, -CO-, -CONH-, -SO 2 -, -C(CF 3 ) 2 -, -C(CH 3 ) 2 -, -CH 2 -, - OC 6 H 4 -C(CH 3 ) 2 -C 6 H 4 -O-, -OC 6 H 4 -C(CF 3 ) 2 -C 6 H 4 -O-, -OC 6 H 4 -SO 2 - C 6 H 4 -O-, -C(CH 3 ) 2 -C 6 H 4 -C(CH 3 ) 2 -, -OC 10 H 6 -O-, -OC 6 H 4 -C 6 H 4 -O - and -OC 6 H 4 -O- is one of the group consisting of groups represented by -C 6 H 4 - is phenylene, -C 10 H 6 - is naphthalenediyl). 如請求項3之塗料組成物，其中，前述芳香族二胺化合物(A2)係包含前述式(24)表示之化合物。The coating composition according to claim 3, wherein the aforementioned aromatic diamine compound (A2) includes a compound represented by the aforementioned formula (24). 如請求項4之塗料組成物，其中，前述芳香族二胺化合物(A2)係以前述式(24)表示，前述Q為-CONH-之化合物。The coating composition according to claim 4, wherein the aforementioned aromatic diamine compound (A2) is represented by the aforementioned formula (24), and the aforementioned Q is a compound of -CONH-. 一種塗料組成物之製造方法，其係包含將四羧酸二酐(A1)及芳香族二胺化合物(A2)於溶媒(S)中聚合，使聚醯胺酸(A)生成，或 使前述四羧酸二酐(A1)及前述芳香族二胺化合物(A2)聚合，生成前述聚醯胺酸(A)後，將經單離之前述聚醯胺酸(A)與溶媒(S)混合之塗料組成物之製造方法，其特徵為 前述四羧酸二酐(A1)僅由脂環式四羧酸二酐(A1-1)及芳香族四羧酸二酐(A1-2)所構成， 前述芳香族四羧酸二酐(A1-2)的質量相對於前述四羧酸二酐(A1)之莫耳數的比率，為0.1質量%以上6質量%以下。 A method for producing a paint composition, which comprises polymerizing tetracarboxylic dianhydride (A1) and aromatic diamine compound (A2) in a solvent (S) to generate polyamic acid (A), or After polymerizing the above-mentioned tetracarboxylic dianhydride (A1) and the above-mentioned aromatic diamine compound (A2) to generate the above-mentioned polyamic acid (A), the isolated above-mentioned polyamic acid (A) and the solvent (S ) method for producing a mixed paint composition, characterized in that The aforementioned tetracarboxylic dianhydride (A1) is only composed of alicyclic tetracarboxylic dianhydride (A1-1) and aromatic tetracarboxylic dianhydride (A1-2), The ratio of the mass of the said aromatic tetracarboxylic dianhydride (A1-2) with respect to the number of moles of the said tetracarboxylic dianhydride (A1) is 0.1 mass % or more and 6 mass % or less. 一種聚醯亞胺樹脂之製造方法，其係包含成形如請求項1~5中任一項之前述塗料組成物之成形步驟、與 加熱經成形之前述塗料組成物，使其醯亞胺化之醯亞胺化步驟。 A method for producing a polyimide resin, which comprises a forming step of forming the aforementioned coating composition according to any one of Claims 1 to 5, and An imidization step of heating the shaped coating composition to imidize it.
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