TW202233416A - Polyimide resin composition, adhesive composition, film adhesive material, adhesive sheet, copper foil with resin, copper clad laminate, printed wiring board and polyimide film a polyimide resin layer with low dielectric constant, low dielectric loss tangent and excellent solder heat resistance - Google Patents
Polyimide resin composition, adhesive composition, film adhesive material, adhesive sheet, copper foil with resin, copper clad laminate, printed wiring board and polyimide film a polyimide resin layer with low dielectric constant, low dielectric loss tangent and excellent solder heat resistance Download PDFInfo
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- 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
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- B32B15/00—Layered products comprising a layer of metal
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- B32B27/00—Layered products comprising a layer of synthetic resin
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- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
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- 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
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- C08G73/1075—Partially aromatic polyimides
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- 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
- C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
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- 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
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C09J179/00—Adhesives 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 C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C09J179/00—Adhesives 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 C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C09J179/085—Unsaturated polyimide precursors
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/12—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- C08J2379/00—Characterised by the use of 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 C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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Abstract
Description
本發明係關於聚醯亞胺樹脂組成物、接著劑組成物、膜狀接著材料、接著片材、附樹脂之銅箔、覆銅積層板、印刷配線板及聚醯亞胺膜。The present invention relates to a polyimide resin composition, an adhesive composition, a film-like adhesive material, an adhesive sheet, a copper foil with resin, a copper-clad laminate, a printed wiring board, and a polyimide film.
撓性印刷配線板（FPWB：Flexible Printed Wiring Board）及印刷電路板（PCB：Printed Circuit Board）以及使用其等之多層配線板廣泛用於：行動電話、智慧型手機等移動型通訊設備及其基地台裝置；伺服器、路由器等網路相關電子設備；大型電腦等產品中。Flexible Printed Wiring Board (FPWB: Flexible Printed Wiring Board) and Printed Circuit Board (PCB: Printed Circuit Board) and multilayer wiring boards using them are widely used in: mobile phones, smart phones and other mobile communication equipment and their bases devices; network-related electronic equipment such as servers and routers; large computers and other products.
此外，近年來，在此等產品中，為了高速傳輸及處理大容量的資訊，使用高頻電訊號，但是高頻訊號非常容易衰減，因而尋求在前述多層配線板上亦儘量抑制傳輸損耗之方法。In addition, in recent years, in these products, high-frequency electrical signals are used for high-speed transmission and processing of large-capacity information, but high-frequency signals are easily attenuated. Therefore, a method to minimize transmission loss is sought on the aforementioned multilayer wiring board. .
抑制多層配線板中的傳輸損耗之手段，例如，在積層印刷配線板或印刷電路板時，可考慮使用聚醯亞胺樹脂作為具有介電常數及介電損耗角正切均小的特性（以下亦稱為低介電特性）之接著劑組成物。As a means of suppressing transmission loss in multilayer wiring boards, for example, in the case of laminating printed wiring boards or printed circuit boards, polyimide resins can be considered as having low dielectric constant and dielectric loss tangent (hereinafter also referred to as the called low dielectric properties) of the adhesive composition.
如此的聚醯亞胺，已知一種用於使具有絕緣樹脂層、接著層及金屬層之覆金屬積層板中之接著層形成之樹脂，且該樹脂具有四羧酸殘基及源自二聚酸之二胺殘基（專利文獻1）。該聚醯亞胺具有芳香環，因此會表現出優異的焊接耐熱性。Such a polyimide is known as a resin for forming an adhesive layer in a metal-clad laminate having an insulating resin layer, an adhesive layer, and a metal layer, and the resin has a tetracarboxylic acid residue and is derived from dimerization. Acid diamine residue (Patent Document 1). The polyimide has an aromatic ring and thus exhibits excellent soldering heat resistance.
不過，在FPWB等製造中，在剝離聚對苯二甲酸乙二酯（剝離PET）及剝離紙等支撐體上，雖然經歷塗布接著劑組成物並在加熱下使其乾燥之步驟，但如此的支撐體缺乏耐熱性，因此其乾燥通常在150℃以下的溫度下進行。在此前提下，在製造專利文獻1的聚醯亞胺時，將N-甲基吡咯烷酮（NMP）及二甲苯用作有機溶劑。然而，如NMP之含有氮原子之有機溶劑，因為沸點高，在前述溫度下使樹脂組成物乾燥時容易殘留，容易對聚醯亞胺樹脂層的低介電特性及焊接耐熱性產生不良影響。此外，如二甲苯之芳香族烴會對人體及環境造成危害，因此，在使用上並不適合。 ［先前技術文獻］ ［專利文獻］ However, in the production of FPWB, etc., on a support such as release polyethylene terephthalate (release PET) and release paper, the adhesive composition is applied and dried under heating, but such The support lacks heat resistance, so its drying is usually performed at a temperature of 150°C or lower. Under this premise, N-methylpyrrolidone (NMP) and xylene were used as organic solvents when the polyimide of Patent Document 1 was produced. However, organic solvents containing nitrogen atoms, such as NMP, tend to remain when the resin composition is dried at the aforementioned temperature due to their high boiling point, which tends to adversely affect the low dielectric properties and soldering heat resistance of the polyimide resin layer. In addition, aromatic hydrocarbons such as xylene are harmful to human body and the environment, so they are not suitable for use. [Prior Art Literature] [Patent Literature]
［專利文獻1］日本特開2018-140544號公報[Patent Document 1] Japanese Patent Application Laid-Open No. 2018-140544
［發明所欲解決之技術問題］[Technical problem to be solved by the invention]
本發明提供一種聚醯亞胺樹脂組成物，即使不使用含有氮原子之有機溶劑以及芳香族烴，該聚醯亞胺樹脂組成物在加熱下的乾燥中，有機溶劑容易揮發，並且，提供具有低介電常數及低介電損耗角正切以及優異的焊接耐熱性之聚醯亞胺樹脂層。 ［技術手段］ The present invention provides a polyimide resin composition, which is easy to volatilize the organic solvent during drying under heating even without using an organic solvent containing nitrogen atoms and aromatic hydrocarbons, and provides a polyimide resin composition having Polyimide resin layer with low dielectric constant, low dielectric loss tangent and excellent soldering heat resistance. [Technical means]
本發明人為了解決前述課題而進行深入研究後，發現在特定的有機溶劑之組合中，能解決前述課題，從而完成本發明。即，在本發明中，提供以下內容。The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, found that the above-mentioned problems can be solved in a combination of a specific organic solvent, and completed the present invention. That is, in the present invention, the following contents are provided.
1. 一種聚醯亞胺樹脂組成物，其含有聚醯亞胺（A）以及兩種以上的不同的有機溶劑（B），該聚醯亞胺（A）為含有芳香族四羧酸酐（a1）及含二聚物二胺之二胺（a2）之單體群的反應物；其特徵係， （B）成分含有酯（B1）以及選自由酮、醚、脂肪族烴及脂環族烴所成群中之至少一種有機溶劑（B2）。 1. A polyimide resin composition, which contains polyimide (A) and two or more different organic solvents (B), and the polyimide (A) is a polyimide containing aromatic tetracarboxylic anhydride (a1 ) and a reactant of a monomer group containing a diamine (a2) of a dimer diamine; characterized by, (B) Component contains ester (B1) and at least one organic solvent (B2) selected from the group consisting of ketones, ethers, aliphatic hydrocarbons, and alicyclic hydrocarbons.
2. 如前項1所述之聚醯亞胺樹脂組成物，其中，（a2）成分進一步含有脂環族二胺及／或芳香族二胺。2. The polyimide resin composition according to the above item 1, wherein the component (a2) further contains an alicyclic diamine and/or an aromatic diamine.
3. 如前項1或2所述之聚醯亞胺樹脂組成物，其中，以質量比計，（B1）成分及（B2）成分的含有比率為（B1）／（B2）=10／90～90／10。3. The polyimide resin composition according to the above item 1 or 2, wherein the content ratio of the component (B1) and the component (B2) in terms of mass ratio is (B1)/(B2)=10/90～ 90/10.
4. 如前項1至3中任一項所述之聚醯亞胺樹脂組成物，其中，（B）成分不含芳香族烴。4. The polyimide resin composition according to any one of 1 to 3 above, wherein the component (B) does not contain aromatic hydrocarbons.
5. 如前項1至4中任一項所述之聚醯亞胺樹脂組成物，其中，（B1）成分為脂肪族酯。5. The polyimide resin composition according to any one of 1 to 4 above, wherein the component (B1) is an aliphatic ester.
6. 一種接著劑組成物，其特徵係含有如前項1至5中任一項所述之聚醯亞胺樹脂組成物及交聯劑。6. An adhesive composition characterized by containing the polyimide resin composition and the crosslinking agent as described in any one of the preceding items 1 to 5.
7. 一種膜狀接著材料，其特徵係含有如前項6所述之接著劑組成物之硬化物。7. A film-like adhesive material characterized by containing a cured product of the adhesive composition described in the preceding item 6.
8. 一種接著片材，其特徵係在支撐膜之至少單面上具有如前項7所述之膜狀接著材料。8. An adhesive sheet, characterized by having the film-like adhesive material as described in the preceding item 7 on at least one side of a support film.
9. 一種附樹脂之銅箔，其特徵係包含如前項7所述之膜狀接著材料及銅箔。9. A resin-attached copper foil characterized by comprising the film-like adhesive material and copper foil as described in the preceding item 7.
10. 一種覆銅積層板，其特徵係包含如前項9所述之附樹脂之銅箔以及銅箔或絕緣性片材。10. A copper-clad laminate, characterized by comprising the resin-attached copper foil and copper foil or insulating sheet as described in the preceding item 9.
11. 一種印刷配線板，其特徵係在如前項10所述之覆銅積層板之銅箔面上具有電路圖案。11. A printed wiring board characterized by having a circuit pattern on the copper foil surface of the copper-clad laminate as described in the preceding item 10.
12. 一種聚醯亞胺膜，其特徵係其為如前項1至5中任一項所述之聚醯亞胺樹脂組成物之硬化物。 ［發明之效果］ 12. A polyimide film, characterized in that it is a cured product of the polyimide resin composition described in any one of the preceding items 1 to 5. [Effect of invention]
根據本發明之聚醯亞胺樹脂組成物，即使不使用含有氮原子之有機溶劑以及芳香族烴，該聚醯亞胺樹脂組成物在加熱下的乾燥中，有機溶劑容易揮發，並且，提供具有低介電常數及低介電損耗角正切以及優異的焊接耐熱性之聚醯亞胺樹脂層。According to the polyimide resin composition of the present invention, even if the organic solvent containing nitrogen atoms and aromatic hydrocarbons are not used, the polyimide resin composition is easily volatilized during drying under heating, and the polyimide resin composition has Polyimide resin layer with low dielectric constant, low dielectric loss tangent and excellent soldering heat resistance.
本發明之聚醯亞胺樹脂組成物含有聚醯亞胺（A）（以下稱為（A）成分），該聚醯亞胺（A）為含有芳香族四羧酸酐（a1）（以下稱為（a1）成分）及含二聚物二胺之二胺（a2）（以下稱為（a2）成分）之單體群的反應物。The polyimide resin composition of the present invention contains polyimide (A) (hereinafter referred to as component (A)) containing aromatic tetracarboxylic anhydride (a1) (hereinafter referred to as component (A)). (a1) component) and the reactant of the monomer group containing the diamine (a2) (henceforth (a2) component) containing dimer diamine.
（a1）成分沒有特別限定，可列舉例如：2,2’,3,3’-聯苯四甲酸二酐、2,3’,3,4’-聯苯四甲酸二酐、3,3’,4,4’-聯苯四甲酸二酐、均苯四甲酸二酐、1,2,3,4-苯四甲酸酐、3,3’,4,4’-二苯基碸四甲酸二酐、4,4’-氧基二鄰苯二甲酸酐、4,4’-[丙-2,2-二基雙(1,4-伸苯基氧基)]二鄰苯二甲酸二酐、2,2’,3,3’-二苯甲酮四甲酸二酐、2,3,3’,4’-二苯甲酮四甲酸二酐、3,3’,4,4’-二苯甲酮四甲酸二酐、2,3’,3,4’-二苯基醚四甲酸二酐、雙(2,3-二羧基苯基)醚二酐、雙(2,3-二羧基苯基)甲烷二酐、雙(3,4-二羧基苯基)甲烷二酐、1,1-雙(2,3-二羧基苯基)乙烷二酐、1,1-雙(3,4-二羧基苯基)乙烷二酐、2,2-雙(2,3-二羧基苯基)丙烷二酐、2,2-雙(3,4-二羧基苯基)丙烷二酐、雙(2,3-二羧基苯氧基苯基)碸二酐、雙(3,4-二羧基苯氧基苯基)碸二酐、1,4,5,8-萘四甲酸酐、2,3,6,7-萘四甲酸酐、2,3,6,7-蒽四甲酸二酐、1,2,5,6-萘四甲酸二酐、1,4,5,8-萘四甲酸二酐、2,3,6,7-萘四甲酸二酐、4,8-二甲基-1,2,3,5,6,7-六氫萘-1,2,5,6-四甲酸二酐、2,2-雙(3,4-二羧基苯基)六氟丙烷二酐、2,2-雙(3,3’,4,4’-四羧基苯基)四氟丙烷二酐等。此等可單獨使用，亦可並用兩種以上。The component (a1) is not particularly limited, and examples thereof include 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3',3,4'-biphenyltetracarboxylic dianhydride, 3,3' ,4,4'-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 1,2,3,4-mellitic anhydride, 3,3',4,4'-diphenyltetracarboxylic acid Anhydride, 4,4'-oxydiphthalic anhydride, 4,4'-[propan-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride , 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-bis Benzophenone tetracarboxylic dianhydride, 2,3',3,4'-diphenyl ether tetracarboxylic dianhydride, bis(2,3-dicarboxyphenyl) ether dianhydride, bis(2,3-dicarboxylate) Phenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3, 4-Dicarboxyphenyl)ethanedianhydride, 2,2-bis(2,3-dicarboxyphenyl)propanedianhydride, 2,2-bis(3,4-dicarboxyphenyl)propanedianhydride, Bis(2,3-dicarboxyphenoxyphenyl) bis(3,4-dicarboxyphenoxyphenyl) bis(3,4-dicarboxyphenoxyphenyl) bis(3,4-dicarboxyphenoxyphenyl) dianhydride, 1,4,5,8-naphthalenetetracarboxylic anhydride, 2 ,3,6,7-naphthalene tetracarboxylic anhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetra Formic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6- Tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(3,3',4,4'-tetracarboxyphenyl)tetrafluoropropane Dianhydride, etc. These may be used alone or in combination of two or more.
其中，（a1）成分，從聚醯亞胺樹脂層的可撓性、焊接耐熱性之觀點而言，理想為由下述通式（1）所示之化合物。
[化1]
由通式（1）所示之化合物，可列舉例如：2,2’,3,3’-聯苯四甲酸二酐、3,3’,4,4’-聯苯四甲酸二酐、3,3’,4,4’-二苯基碸四甲酸二酐、3,3’,4,4’-二苯甲酮四甲酸二酐、3,3’,4,4’-二苯基醚四甲酸二酐、2,2-雙(3,4-二羧基苯基)六氟丙烷二酐、2,2-雙(3,3’,4,4’-四羧基苯基)四氟丙烷二酐、4,4’-[丙-2,2-二基雙(1,4-伸苯基氧基)]二鄰苯二甲酸二酐、2,2-雙(2,3-二羧基苯基)丙烷二酐、2,2-雙(3,4-二羧基苯基)丙烷二酐、2,2’-雙(3,4-二羧基苯氧基苯基)碸二酐等。此等可單獨使用，亦可並用兩種以上。其中，從（A）成分相對於有機溶劑可良好地溶解之觀點而言，理想為2,2-雙(3,4-二羧基苯基)六氟丙烷二酐、4,4’-[丙-2,2-二基雙(1,4-伸苯基氧基)]二鄰苯二甲酸二酐。The compound represented by the general formula (1) includes, for example: 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3 ,3',4,4'-diphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl Ether tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(3,3',4,4'-tetracarboxyphenyl)tetrafluoro Propane dianhydride, 4,4'-[Propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride, 2,2-bis(2,3-di Carboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)stilbene dianhydride, etc. . These may be used alone or in combination of two or more. Among them, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 4,4′-[propane dianhydride, 4,4′-[propane dianhydride, 4,4′- -2,2-Diylbis(1,4-phenyleneoxy)]diphthalic dianhydride.
在構成（A）成分之單體群100莫耳%中，（a1）成分的使用量沒有特別限定，通常為10莫耳%～90莫耳%，理想為25莫耳%～75莫耳%。The amount of the component (a1) used is not particularly limited in 100 mol % of the monomer group constituting the component (A), but is usually 10 mol % to 90 mol %, preferably 25 mol % to 75 mol % .
此外，在構成（A）成分之單體群100莫耳%中，由通式（1）所示之四羧酸酐的使用量沒有特別限定，通常為10莫耳%～90莫耳%，理想為25莫耳%～75莫耳%。In addition, the usage-amount of the tetracarboxylic anhydride represented by the general formula (1) is not particularly limited in 100 mol % of the monomer group constituting the component (A), but is usually 10 mol % to 90 mol %, preferably It is 25 mol% to 75 mol%.
在（a1）成分100莫耳%中，由通式（1）所示之四羧酸酐的使用量沒有特別限定，通常為10莫耳%～100莫耳%，理想為50莫耳%～100莫耳%。The usage-amount of the tetracarboxylic anhydride represented by the general formula (1) is not particularly limited in 100 mol % of the component (a1), but is usually 10 mol % to 100 mol %, preferably 50 mol % to 100 mol %. Mol%.
（a2）成分為含有二聚物二胺之二胺。The component (a2) is a diamine containing dimer diamine.
二聚物二胺係指將二聚酸之全部羧基取代為一級胺基或一級胺基甲基而成的物質（例如，參照日本特開平9-12712號公報）。在此，二聚酸係指主要含有將油酸、亞油酸及亞麻酸等不飽和脂肪酸二聚化而得到的碳數36的二元酸的物質，並根據其純化程度，含有碳數18的單體酸、碳數54的三聚酸、碳數20～90的聚合脂肪酸。又，雖然前述二聚酸中含有雙鍵，但亦可以例如藉由氫化反應來降低不飽和度。The dimer diamine refers to a substance obtained by substituting all the carboxyl groups of the dimer acid with primary amino groups or primary amino methyl groups (for example, refer to Japanese Patent Application Laid-Open No. 9-12712). Here, dimer acid refers to a substance mainly containing a dibasic acid having 36 carbon atoms obtained by dimerizing unsaturated fatty acids such as oleic acid, linoleic acid, and linolenic acid, and, depending on the degree of purification, contains 18 carbon atoms. monomeric acid, trimer acid with carbon number 54, polymerized fatty acid with carbon number 20-90. Moreover, although the said dimer acid contains a double bond, it is also possible to reduce the degree of unsaturation by, for example, a hydrogenation reaction.
前述二聚物二胺沒有特別限定，可列舉例如由下述通式（2）所示的物質。又，在通式（2）中，理想係m＋n＝6～17，理想係p＋q＝8～19，虛線部意指碳-碳單鍵或碳-碳雙鍵。The said dimer diamine is not specifically limited, For example, what is represented by the following general formula (2) is mentioned. Moreover, in general formula (2), ideal system m+n=6-17, ideal system p+q=8-19, and a dotted line part means a carbon-carbon single bond or a carbon-carbon double bond.
[化2]
此外，二聚物二胺的市售品，可列舉：「Versamine551」、「Versamine552」（以上為Cognis Japan股份有限公司製）；「PRIAMINE1073」、「PRIAMINE1074」、「PRIAMINE1075」（以上為Croda Japan股份有限公司製）等。In addition, commercial products of dimer diamines include "Versamine 551", "Versamine 552" (the above are Cognis Japan Co., Ltd.); limited company), etc.
此外，二聚物二胺可直接使用，亦可使用經過蒸餾等純化處理的二聚物二胺。In addition, the dimer diamine may be used as it is, or the dimer diamine which has been purified by distillation or the like may be used.
在構成（A）成分之單體群100莫耳%中，二聚物二胺的使用量沒有特別限定，通常為5莫耳%以上，理想為25莫耳%～75莫耳%。The use amount of the dimer diamine is not particularly limited in 100 mol % of the monomer group constituting the component (A), but is usually 5 mol % or more, preferably 25 mol % to 75 mol %.
此外，在（a2）成分100莫耳%中，二聚物二胺的使用量沒有特別限定，通常為10莫耳%以上，理想為30莫耳%～100莫耳%。Moreover, the usage-amount of dimer diamine is not specifically limited in 100 mol% of (a2) component, Usually, it is 10 mol% or more, Preferably it is 30 mol% - 100 mol%.
此外，（a2）成分亦可含有除二聚物二胺以外之二胺（a2-1）（以下稱為（a2-1）成分）。（a2-1）成分，例如亦可含有脂肪族二胺、脂環族二胺、芳香族二胺、二胺基醚、二胺基聚矽氧烷。又，對於此等胺，係將二聚物二胺排除在外。Moreover, (a2) component may contain diamine (a2-1) (henceforth (a2-1) component) other than dimer diamine. The component (a2-1) may contain, for example, aliphatic diamine, alicyclic diamine, aromatic diamine, diamine ether, and diamine polysiloxane. In addition, dimer diamine is excluded from these amines.
脂肪族二胺，可列舉例如：乙二胺、1,3-二胺基丙烷、1,4-二胺基丁烷、1,5-二胺基戊烷、1,6-二胺基己烷、1,7-二胺基庚烷、1,8-二胺基辛烷、1,9-二胺基壬烷、1,10-二胺基癸烷、1,11-二胺基十一烷、1,12-二胺基十二烷等。Aliphatic diamine, for example: ethylene diamine, 1, 3- diamino propane, 1, 4- diamino butane, 1, 5- diamino pentane, 1, 6- diamino hexane Alkane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminodecane Monoalkane, 1,12-diaminododecane, etc.
脂環族二胺，可列舉例如：二胺基環己烷、二胺基二環己基甲烷、二甲基二胺基二環己基甲烷、二胺基二環己基丙烷、四甲基二胺基二環己基甲烷、1,3-雙(胺基甲基)環己烷、1,4-雙(胺基甲基)環己烷、二胺基雙環[2.2.1]庚烷、雙(胺基甲基)-雙環[2.2.1]庚烷、3(4),8(9)-雙(胺基甲基)三環[5.2.1.0(2,6)]癸烷、異佛爾酮二胺等。Alicyclic diamines include, for example, diaminocyclohexane, diaminodicyclohexylmethane, dimethyldiaminodicyclohexylmethane, diaminodicyclohexylpropane, and tetramethyldiamine Dicyclohexylmethane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, diaminobicyclo[2.2.1]heptane, bis(amine) methyl)-bicyclo[2.2.1]heptane, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0(2,6)]decane, isophorone Diamine etc.
芳香族二胺，可列舉例如： 2,2’-二胺基聯苯、3,3’-二胺基聯苯、4,4’-二胺基聯苯、2,2’-二甲基-4,4’-二胺基聯苯、2,2’-二乙基-4,4’-二胺基聯苯、2,2’-二正丙基-4,4’-二胺基聯苯等二胺基聯苯； 2,2-雙[4-(3-胺基苯氧基)苯基]丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷等雙胺基苯氧基苯基丙烷； 3,3’-二胺基二苯基醚、3,4’-二胺基二苯基醚、4,4’-二胺基二苯基醚等二胺基二苯基醚； 對苯二胺、間苯二胺等苯二胺； 3,3’-二胺基二苯基硫醚、3,4’-二胺基二苯基硫醚、4,4’-二胺基二苯基硫醚等二胺基二苯基硫醚； 3,3’-二胺基二苯基碸、3,4’-二胺基二苯基碸、4,4’-二胺基二苯基碸等二胺基二苯基碸； 3,3’-二胺基二苯甲酮、3,4’-二胺基二苯甲酮、4,4’-二胺基二苯甲酮等二胺基二苯甲酮； 3,3’-二胺基二苯基甲烷、3,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基甲烷、雙[4-(3-胺基苯氧基)苯基]甲烷等二胺基二苯基甲烷； 2,2-二(3-胺基苯基)丙烷、2,2-二(4-胺基苯基)丙烷、2-(3-胺基苯基)-2-(4-胺基苯基)丙烷等二胺基苯基丙烷； 2,2-二(3-胺基苯基)-1,1,1,3,3,3-六氟丙烷、2,2-二(4-胺基苯基)-1,1,1,3,3,3-六氟丙烷、2-(3-胺基苯基)-2-(4-胺基苯基)-1,1,1,3,3,3-六氟丙烷等二胺基苯基六氟丙烷； 1,1-二(3-胺基苯基)-1-苯基乙烷、1,1-二(4-胺基苯基)-1-苯基乙烷、1-(3-胺基苯基)-1-(4-胺基苯基)-1-苯基乙烷等二胺基苯基苯基乙烷； 1,3-雙(3-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,4-雙(3-胺基苯氧基)苯、1,4-雙(4-胺基苯氧基)苯等雙胺基苯氧基苯； 1,3-雙(3-胺基苯甲醯基)苯、1,3-雙(4-胺基苯甲醯基)苯、1,4-雙(3-胺基苯甲醯基)苯、1,4-雙(4-胺基苯甲醯基)苯等雙胺基苯甲醯基苯； 1,3-雙(3-胺基-α,α-二甲基苄基)苯、1,3-雙(4-胺基-α,α-二甲基苄基)苯、1,4-雙(3-胺基-α,α-二甲基苄基)苯、1,4-雙(4-胺基-α,α-二甲基苄基)苯等雙胺基二甲基苄基苯； 1,3-雙(3-胺基-α,α-二三氟甲基苄基)苯、1,3-雙(4-胺基-α,α-二三氟甲基苄基)苯、1,4-雙(3-胺基-α,α-二三氟甲基苄基)苯、1,4-雙(4-胺基-α,α-二三氟甲基苄基)苯等雙胺基二三氟甲基苄基苯； 4,4’-雙(3-胺基苯氧基)聯苯、4,4’-雙(4-胺基苯氧基)聯苯、雙[1-(3-胺基苯氧基)]聯苯等胺基苯氧基聯苯； 雙[4-(3-胺基苯氧基)苯基]酮、雙[4-(4-胺基苯氧基)苯基]酮等胺基苯氧基苯基酮； 雙[4-(3-胺基苯氧基)苯基]硫醚、雙[4-(4-胺基苯氧基)苯基]硫醚等胺基苯氧基苯基硫醚； 雙[4-(3-胺基苯氧基)苯基]碸、雙[4-(4-胺基苯氧基)苯基]碸等胺基苯氧基苯基碸； 雙[4-(3-胺基苯氧基)苯基]醚、雙[4-(4-胺基苯氧基)苯基]醚等胺基苯氧基苯基醚； 2,2-雙[4-(3-胺基苯氧基)苯基]丙烷、2,2-雙[3-(3-胺基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷等胺基苯氧基苯基丙烷； 1,3-雙[4-(3-胺基苯氧基)苯甲醯基]苯、1,3-雙[4-(4-胺基苯氧基)苯甲醯基]苯、1,4-雙[4-(3-胺基苯氧基)苯甲醯基]苯、1,4-雙[4-(4-胺基苯氧基)苯甲醯基]苯等雙(胺基苯氧基苯甲醯基)苯； 1,3-雙[4-(3-胺基苯氧基)-α,α-二甲基苄基]苯、1,3-雙[4-(4-胺基苯氧基)-α,α-二甲基苄基]苯、1,4-雙[4-(3-胺基苯氧基)-α,α-二甲基苄基]苯、1,4-雙[4-(4-胺基苯氧基)-α,α-二甲基苄基]苯等雙(胺基苯氧基-α,α-二甲基苄基)苯； 4,4’-雙[4-(4-胺基苯氧基)苯甲醯基]二苯基醚等雙[(胺基芳氧基)苯甲醯基]二苯基醚； 4,4’-雙[4-(4-胺基-α,α-二甲基苄基)苯氧基]二苯甲酮等雙(胺基-α,α-二甲基苄基苯氧基)二苯甲酮； 4,4’-雙[4-(4-胺基-α,α-二甲基苄基)苯氧基]二苯基碸等雙[胺基-α,α-二甲基苄基苯氧基]二苯基碸； 4,4’-雙[4-(4-胺基苯氧基)苯氧基]二苯基碸等雙[胺基苯氧基苯氧基]二苯基碸； 3,3’-二胺基-4,4’-二苯氧基二苯甲酮、3,3’-二胺基-4,4’-二聯苯氧基二苯甲酮等二胺基二芳氧基二苯甲酮； 3,3’-二胺基-4-苯氧基二苯甲酮、3,3’-二胺基-4-聯苯氧基二苯甲酮等二胺基芳氧基二苯甲酮； 1-(4-胺基苯基)-2,3-二氫-1,3,3-三甲基-1H-茚-5-胺、9,9-雙(4-胺基苯基)芴等。 Aromatic diamines, such as: 2,2'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diamino Diaminobiphenyls such as biphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 2,2'-di-n-propyl-4,4'-diaminobiphenyl; Bisaminophenoxy such as 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane Phenylpropane; 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether and other diaminodiphenyl ethers; P-phenylenediamine, m-phenylenediamine and other phenylenediamines; Diaminodiphenyl sulfide such as 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide ; 3,3'-diaminodiphenyl bismuth, 3,4'-diaminodiphenyl bismuth, 4,4'-diaminodiphenyl bismuth and other diaminodiphenyl bismuths; 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone and other diaminobenzophenones; 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis[4-(3-aminophenoxy base) phenyl] methane and other diaminodiphenylmethanes; 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2-(3-aminophenyl)-2-(4-aminophenyl) ) propane and other diaminophenyl propanes; 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1,1, Diamines such as 3,3,3-hexafluoropropane, 2-(3-aminophenyl)-2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane phenyl hexafluoropropane; 1,1-bis(3-aminophenyl)-1-phenylethane, 1,1-bis(4-aminophenyl)-1-phenylethane, 1-(3-aminobenzene base)-1-(4-aminophenyl)-1-phenylethane and other diaminophenylphenylethanes; 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1, Bisaminophenoxybenzenes such as 4-bis(4-aminophenoxy)benzene; 1,3-bis(3-aminobenzyl)benzene, 1,3-bis(4-aminobenzyl)benzene, 1,4-bis(3-aminobenzyl)benzene , 1,4-bis(4-aminobenzyl)benzene and other bisaminobenzylbenzenes; 1,3-bis(3-amino-α,α-dimethylbenzyl)benzene, 1,3-bis(4-amino-α,α-dimethylbenzyl)benzene, 1,4- Bis(3-amino-α,α-dimethylbenzyl)benzene, 1,4-bis(4-amino-α,α-dimethylbenzyl)benzene and other bisaminodimethylbenzyl groups benzene; 1,3-bis(3-amino-α,α-ditrifluoromethylbenzyl)benzene, 1,3-bis(4-amino-α,α-ditrifluoromethylbenzyl)benzene, 1,4-bis(3-amino-α,α-ditrifluoromethylbenzyl)benzene, 1,4-bis(4-amino-α,α-ditrifluoromethylbenzyl)benzene, etc. bisaminoditrifluoromethylbenzylbenzene; 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[1-(3-aminophenoxy)] Aminophenoxybiphenyl such as biphenyl; Aminophenoxyphenyl ketones such as bis[4-(3-aminophenoxy)phenyl]ketone, bis[4-(4-aminophenoxy)phenyl]ketone; Aminophenoxyphenyl sulfide such as bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl]sulfide; Double [4- (3-amino phenoxyl) benzenelbenzyl] 碸, double [4- (4-amino benzenoxyl) benzylbenzyl] Aminophenoxyphenyl ethers such as bis[4-(3-aminophenoxy)phenyl]ether and bis[4-(4-aminophenoxy)phenyl]ether; 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3 ,3,3-hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane and other aminophenoxy phenylpropane; 1,3-bis[4-(3-aminophenoxy)benzyl]benzene, 1,3-bis[4-(4-aminophenoxy)benzyl]benzene, 1, Bis(amino) such as 4-bis[4-(3-aminophenoxy)benzyl]benzene, 1,4-bis[4-(4-aminophenoxy)benzyl]benzene phenoxybenzyl)benzene; 1,3-bis[4-(3-aminophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-aminophenoxy)-α, α-Dimethylbenzyl]benzene, 1,4-bis[4-(3-aminophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(4 - Bis(aminophenoxy-α,α-dimethylbenzyl)benzene such as aminophenoxy)-α,α-dimethylbenzyl]benzene; 4,4'-bis[4-(4-aminophenoxy)benzyl]diphenyl ether and other bis[(aminoaryloxy)benzyl]diphenyl ethers; 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzophenone and other bis(amino-α,α-dimethylbenzylphenoxy base) benzophenone; 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]diphenyl bis[amino-α,α-dimethylbenzylphenoxy base] diphenyl sulfone; 4,4'-bis[4-(4-aminophenoxy)phenoxy]diphenyl bis[aminophenoxyphenoxy]diphenyl bismuth; 3,3'-Diamino-4,4'-diphenoxybenzophenone, 3,3'-diamino-4,4'-diphenyloxybenzophenone and other diamine groups diaryloxybenzophenones; 3,3'-diamino-4-phenoxybenzophenone, 3,3'-diamino-4-biphenoxybenzophenone and other diaminoaryloxybenzophenones; 1-(4-Aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine, 9,9-bis(4-aminophenyl)fluorene Wait.
二胺基醚，可列舉例如：雙(胺基甲基)醚、雙(2-胺基乙基)醚、雙(3-胺基丙基)醚、雙[(2-胺基甲氧基)乙基]醚、雙[2-(2-胺基乙氧基)乙基]醚、雙[2-(3-胺基丙氧基)乙基]醚、1,2-雙(胺基甲氧基)乙烷、1,2-雙(2-胺基乙氧基)乙烷、1,2-雙[2-(胺基甲氧基)乙氧基]乙烷、1,2-雙[2-(2-胺基乙氧基)乙氧基]乙烷、乙二醇雙(3-胺基丙基)醚、二乙二醇雙(3-胺基丙基)醚、三乙二醇雙(3-胺基丙基)醚等。Diamino ethers, for example, bis(aminomethyl) ether, bis(2-aminoethyl) ether, bis(3-aminopropyl) ether, bis[(2-aminomethoxy) ) ethyl] ether, bis[2-(2-aminoethoxy)ethyl]ether, bis[2-(3-aminopropoxy)ethyl]ether, 1,2-bis(amino) Methoxy)ethane, 1,2-bis(2-aminoethoxy)ethane, 1,2-bis[2-(aminomethoxy)ethoxy]ethane, 1,2- Bis[2-(2-aminoethoxy)ethoxy]ethane, ethylene glycol bis(3-aminopropyl) ether, diethylene glycol bis(3-aminopropyl) ether, triethylene glycol Ethylene glycol bis(3-aminopropyl) ether, etc.
二胺基聚矽氧烷，可列舉例如：α,ω-雙(2-胺基乙基)聚二甲基矽氧烷、α,ω-雙(3-胺基丙基)聚二甲基矽氧烷、α,ω-雙(4-胺基丁基)聚二甲基矽氧烷、α,ω-雙(5-胺基戊基)聚二甲基矽氧烷、α,ω-雙[3-(2-胺基苯基)丙基]聚二甲基矽氧烷、α,ω-雙[3-(4-胺基苯基)丙基]聚二甲基矽氧烷等。Diaminopolysiloxane, for example: α,ω-bis(2-aminoethyl)polydimethylsiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane Siloxane, α,ω-Bis(4-aminobutyl)dimethylsiloxane, α,ω-Bis(5-aminopentyl)dimethylsiloxane, α,ω- Bis[3-(2-aminophenyl)propyl]dimethylsiloxane, α,ω-bis[3-(4-aminophenyl)propyl]dimethylsiloxane, etc. .
此等（a2-1）成分可單獨使用，亦可並用兩種以上。其中，從聚醯亞胺樹脂層表現出優異的焊接耐熱性之觀點而言，理想為脂環族二胺、芳香族二胺，更理想為芳香族二胺。These (a2-1) components may be used alone or in combination of two or more. Among them, an alicyclic diamine and an aromatic diamine are preferable from the viewpoint that the polyimide resin layer exhibits excellent soldering heat resistance, and an aromatic diamine is more preferable.
在構成（A）成分之單體群100莫耳%中，（a2-1）成分的使用量沒有特別限定，通常為90莫耳%以下，理想為50莫耳%以下。The usage-amount of (a2-1) component is not specifically limited in 100 mol% of the monomer group which comprises (A) component, Usually, it is 90 mol% or less, Preferably it is 50 mol% or less.
此外，在（a2）成分100莫耳%中，（a2-1）成分的使用量沒有特別限定，通常為90莫耳%以下，理想為70莫耳%以下Moreover, the usage-amount of the component (a2-1) is not particularly limited in 100 mol % of the component (a2), but is usually 90 mol % or less, preferably 70 mol % or less.
本發明之（A）成分可以藉由各種習知的製造方法而得到。其製造方法，可列舉例如包含以下步驟之方法等：使含有（a1）成分及（a2）成分之單體群在溫度理想為30℃～120℃左右、更理想為40℃～100℃左右並且時間理想為0.1小時～2小時左右、更理想為0.1小時～0.5小時左右的情況下進行複加成反應而得到複加成物之步驟；使得到的複加成物理想在80℃～250℃左右、更理想在80℃～170℃左右的溫度下理想進行0.5小時～50小時左右、更理想進行1小時～20小時左右的醯亞胺化反應，即脫水閉環反應之步驟。又，（a1）成分及（a2）成分的混合方法、順序等沒有特別限定。(A) component of this invention can be obtained by various conventional manufacturing methods. The production method thereof includes, for example, a method including a step of heating the monomer group containing the component (a1) and the component (a2) at a temperature of preferably about 30°C to 120°C, more preferably about 40°C to 100°C, and the like. The time is ideally about 0.1 hour to 2 hours, more preferably about 0.1 hour to 0.5 hours, and the step of carrying out the complex addition reaction to obtain the complex adduct; The imidization reaction, that is, the dehydration ring-closure reaction, is preferably carried out at a temperature of about 80°C to 170°C, preferably about 0.5 hours to 50 hours, more preferably about 1 hour to 20 hours. In addition, the mixing method, order, etc. of (a1) component and (a2) component are not specifically limited.
又，在進行醯亞胺化反應之步驟中，可以使用各種習知的反應觸媒、脫水劑及後述之有機溶劑（B），此等可單獨使用，亦可並用兩種以上。In addition, in the step of carrying out the imidization reaction, various conventional reaction catalysts, dehydrating agents, and organic solvents (B) described later may be used, and these may be used alone or in combination of two or more.
反應觸媒可列舉：三乙胺等脂肪族三級胺；二甲基苯胺等芳香族三級胺；吡啶、甲基吡啶、異喹啉等雜環式三級胺等。此外，脫水劑可列舉乙酸酐等脂肪族羧酸酐以及苯甲酸酐等芳香族羧酸酐等。Examples of the reaction catalyst include aliphatic tertiary amines such as triethylamine; aromatic tertiary amines such as dimethylaniline; and heterocyclic tertiary amines such as pyridine, picoline, and isoquinoline. Moreover, as a dehydrating agent, aliphatic carboxylic acid anhydrides, such as acetic anhydride, and aromatic carboxylic acid anhydrides, such as benzoic anhydride, etc. are mentioned.
當在製造（A）成分時使用後述之有機溶劑（B）時，將其使用量調節為使反應濃度為5質量%～60質量%，理想為20質量%～50質量%。When using the below-mentioned organic solvent (B) at the time of manufacture of (A) component, the usage-amount is adjusted so that the reaction concentration may be 5 mass % - 60 mass %, Preferably it is 20 mass % - 50 mass %.
（A）成分的醯亞胺閉環率沒有特別限定，從得到軟化點及柔軟性均高的（A）成分之觀點而言，理想為90%～100%，更理想為95%～100%左右。 藉由使（A）成分的醯亞胺閉環率在前述範圍內，推定（A）成分容易形成硬鏈段及軟鏈段之結構，軟化點及柔軟性均會變高。在此，「醯亞胺閉環率」係指（A）成分的聚醯亞胺樹脂中的環狀醯亞胺鍵的含量，例如可以藉由NMR或IR分析等各種光譜手段來確定。 The imide ring closure ratio of the component (A) is not particularly limited, but from the viewpoint of obtaining the component (A) having high softening point and flexibility, it is preferably 90% to 100%, and more preferably about 95% to 100%. . When the imide ring closure ratio of the (A) component is within the above-mentioned range, it is presumed that the (A) component is likely to form a structure of a hard segment and a soft segment, and that both the softening point and the flexibility become high. Here, the "imide ring closure rate" refers to the content of cyclic imide bonds in the polyimide resin of the component (A), and can be determined by various spectroscopic means such as NMR or IR analysis, for example.
（A）成分的物性沒有特別限定。（A）成分的重量平均分子量理想為20,000～100,000。（A）成分的數平均分子量理想為5,000～50,000。重量平均分子量及數平均分子量能以例如藉由凝膠滲透層析法（GPC）所測定之聚苯乙烯換算值而求出。The physical properties of the component (A) are not particularly limited. The weight average molecular weight of the component (A) is desirably 20,000 to 100,000. The number average molecular weight of the component (A) is desirably 5,000 to 50,000. The weight-average molecular weight and the number-average molecular weight can be determined, for example, as polystyrene-equivalent values measured by gel permeation chromatography (GPC).
從製造覆銅積層板等積層體時藉由加壓硬化更容易進行加工之觀點而言，本發明之（A）成分的軟化點理想為50℃～250℃左右，更理想為80℃～200℃左右。又，軟化點係指在使用市售的測定器（產品名「ARES-2KSTD-FCO-STD」、Rheometric Scientific公司製）等所測定之儲存模數的曲線中，儲存模數開始降低之溫度。The softening point of the component (A) in the present invention is desirably about 50°C to 250°C, and more desirably 80°C to 200°C, from the viewpoint of making it easier to process by press hardening when manufacturing a laminate such as a copper-clad laminate. ℃ or so. The softening point refers to the temperature at which the storage modulus begins to decrease in the storage modulus curve measured using a commercially available measuring device (product name "ARES-2KSTD-FCO-STD", manufactured by Rheometric Scientific Corporation).
本發明之聚醯亞胺樹脂組成物係含有兩種以上不同的有機溶劑（B）（以下稱為（B）成分）。The polyimide resin composition of the present invention contains two or more different organic solvents (B) (hereinafter referred to as (B) component).
本發明之聚醯亞胺樹脂組成物中（B）成分的含量沒有特別限定，相對於聚醯亞胺樹脂組成物100質量份，理想為50質量份～1000質量份（不揮發成分換算），更理想為100質量份～400質量份（不揮發成分換算）。The content of component (B) in the polyimide resin composition of the present invention is not particularly limited, but is preferably 50 parts by mass to 1,000 parts by mass (in terms of non-volatile components) relative to 100 parts by mass of the polyimide resin composition, More preferably, it is 100 mass parts - 400 mass parts (nonvolatile content conversion).
（B）成分係含有酯（B1）（以下稱為（B1）成分）以及選自由酮、醚、脂肪族烴及脂環族烴所成群中之至少一種有機溶劑（B2）（以下稱為（B2）成分）。(B) Component contains ester (B1) (hereinafter referred to as (B1) component) and at least one organic solvent (B2) selected from the group consisting of ketones, ethers, aliphatic hydrocarbons and alicyclic hydrocarbons (hereinafter referred to as "component"). (B2) Ingredient).
（B1）成分若為酯，可以使用各種習知的成分。具體而言，可列舉脂肪族酯、脂環族酯、芳香族酯。又，此處的脂肪族酯係意指不具有環狀結構之酯，亦包含碳酸二甲酯、碳酸二乙酯等碳酸烷基酯。其中，（B1）成分的沸點理想在60℃以上150℃以下。若（B1）成分具有前述沸點，則在支撐膜或銅箔上塗布聚醯亞胺樹脂組成物或含有該組成物之接著劑組成物時，（B1）成分不會揮發，因此能夠防止塗布不均勻或孔洞的產生等。此外，在將前述此等組成物的塗布層乾燥時，（B1）成分變得容易揮發，因此在得到的硬化物的層中沒有（B1）成分殘留，其結果則顯示出低介電特性。又，前述沸點的上限值及下限值可列舉：145、140、135、130、125、120、115、110、105、100、95、90、85、80、75、70、65等。此外，基於與前述相同的理由，（B1）成分的沸點更理想在70℃以上140℃以下。前述沸點係常壓下的值，採用化學製造商的目錄與Chemical Book中記載的值（以下相同）。As long as the component (B1) is an ester, various known components can be used. Specifically, aliphatic ester, alicyclic ester, and aromatic ester are mentioned. In addition, the aliphatic ester here means an ester which does not have a cyclic structure, and also includes alkyl carbonates, such as dimethyl carbonate and diethyl carbonate. Among them, the boiling point of the component (B1) is preferably 60°C or higher and 150°C or lower. When the component (B1) has the above-mentioned boiling point, when the polyimide resin composition or the adhesive composition containing the composition is coated on the support film or copper foil, the component (B1) does not volatilize, so that it is possible to prevent the coating from being damaged. generation of uniformity or voids, etc. In addition, when the coating layer of these compositions is dried, the component (B1) is easily volatilized, so the component (B1) does not remain in the layer of the obtained cured product, and as a result, low dielectric properties are exhibited. Moreover, 145, 140, 135, 130, 125, 120, 115, 110, 105, 100, 95, 90, 85, 80, 75, 70, 65 etc. are mentioned as the upper limit and lower limit of the said boiling point. Moreover, for the same reason as described above, the boiling point of the component (B1) is more preferably 70° C. or higher and 140° C. or lower. The above-mentioned boiling point is a value under normal pressure, and the value described in the chemical manufacturer's catalog and Chemical Book (the same below) is used.
在理想的（B1）成分中，脂肪族酯可列舉例如：甲酸正丙酯（80℃）、甲酸異丙酯（68℃）、甲酸正丁酯（106℃）、甲酸異丁酯（98℃）、甲酸二級丁酯（99℃）、甲酸三級丁酯（82℃）、甲酸正戊酯（130℃）、甲酸異戊酯（124℃）、乙酸乙酯（77℃）、乙酸正丙酯（102℃）、乙酸異丙酯（89℃）、乙酸正丁酯（126℃）、乙酸異丁酯（118℃）、乙酸二級丁酯（112℃）、乙酸三級丁酯（97℃）、乙酸正戊酯（149℃）、乙酸異戊酯（142℃）、乙酸二級戊酯（121℃）、乙酸三級戊酯（123℃）、丙酸甲酯（80℃）、丙酸乙酯（99℃）、丙酸正丙酯（123℃）、丙酸異丙酯（108℃）、丙酸正丁酯（145℃）、丙酸異丁酯（138℃）、丙酸二級丁酯（133℃）、丙酸三級丁酯（118℃）、丁酸甲酯（102℃）、丁酸乙酯（121℃）、丁酸正丙酯（143℃）、丁酸異丙酯（129℃）、異丁酸甲酯（92℃）、異丁酸乙酯（112℃）、異丁酸正丙酯（134℃）、異丁酸異丙酯（120℃）、異丁酸異丁酯（147℃）、異丁酸二級丁酯（112℃）、戊酸甲酯（126℃）、戊酸乙酯（145℃）、己酸甲酯（150℃）、碳酸二甲酯（90℃）、碳酸甲乙酯（107℃）、碳酸二乙酯（126℃）等。又，括弧內的溫度表示各化合物在常壓下的沸點（以下相同）。Among the desirable components (B1), aliphatic esters include, for example, n-propyl formate (80°C), isopropyl formate (68°C), n-butyl formate (106°C), and isobutyl formate (98°C) ), tertiary butyl formate (99°C), tertiary butyl formate (82°C), n-amyl formate (130°C), isoamyl formate (124°C), ethyl acetate (77°C), n-acetic acid Propyl acetate (102°C), isopropyl acetate (89°C), n-butyl acetate (126°C), isobutyl acetate (118°C), tertiary butyl acetate (112°C), tertiary butyl acetate ( 97°C), n-amyl acetate (149°C), isoamyl acetate (142°C), di-amyl acetate (121°C), tri-amyl acetate (123°C), methyl propionate (80°C) , ethyl propionate (99℃), n-propyl propionate (123℃), isopropyl propionate (108℃), n-butyl propionate (145℃), isobutyl propionate (138℃), Secondary butyl propionate (133°C), tertiary butyl propionate (118°C), methyl butyrate (102°C), ethyl butyrate (121°C), n-propyl butyrate (143°C), Isopropyl butyrate (129℃), methyl isobutyrate (92℃), ethyl isobutyrate (112℃), n-propyl isobutyrate (134℃), isopropyl isobutyrate (120℃) ), isobutyl isobutyrate (147℃), secondary butyl isobutyrate (112℃), methyl valerate (126℃), ethyl valerate (145℃), methyl hexanoate (150℃) ), dimethyl carbonate (90°C), ethyl methyl carbonate (107°C), diethyl carbonate (126°C), etc. In addition, the temperature in parenthesis shows the boiling point of each compound under normal pressure (it is the same below).
在理想的（B1）成分中，脂環族酯可列舉：環丙烷甲酸甲酯（119℃）、環丙烷甲酸乙酯（131℃）、環丁烷甲酸甲酯（135℃）等。Among desirable (B1) components, alicyclic esters include methyl cyclopropanecarboxylate (119°C), ethyl cyclopropanecarboxylate (131°C), methyl cyclobutanecarboxylate (135°C), and the like.
此等（B1）成分可單獨使用，亦可將兩種以上組合使用。其中，從（A）成分與（B1）成分良好的相溶性之觀點而言，理想為脂肪族酯，更理想為乙酸正丁酯、碳酸二乙酯。These (B1) components may be used alone or in combination of two or more. Among them, from the viewpoint of good compatibility between the (A) component and the (B1) component, an aliphatic ester is preferable, and n-butyl acetate and diethyl carbonate are more preferable.
（B2）成分若為酮、醚、脂肪族烴、脂環族烴，可以使用各種習知的成分。此等（B2）成分可單獨使用，亦可將兩種以上組合使用。其中，（B2）成分的沸點理想在60℃以上150℃以下。若（B2）成分具有前述沸點，則在支撐膜或銅箔上塗布聚醯亞胺樹脂組成物或含有該組成物之接著劑組成物時，（B2）成分不會揮發，因此能夠防止塗布不均勻或孔洞的產生等。此外，在將前述此等組成物的塗布層乾燥時，（B2）成分變得容易揮發，因此在得到的硬化物的層中沒有（B2）成分殘留，其結果則顯示出低介電特性。此外，前述沸點的上限值及下限值可列舉：145、140、135、130、125、120、115、110、105、100、95、90、85、80、75、70、65等。此外，基於與前述相同的理由，（B2）成分的沸點更理想在70℃以上140℃以下。As the component (B2), as long as it is a ketone, an ether, an aliphatic hydrocarbon, or an alicyclic hydrocarbon, various known components can be used. These (B2) components may be used alone or in combination of two or more. Among them, the boiling point of the component (B2) is preferably 60°C or higher and 150°C or lower. When the component (B2) has the above-mentioned boiling point, when the polyimide resin composition or the adhesive composition containing the composition is coated on the support film or copper foil, the component (B2) does not volatilize, so that it is possible to prevent the coating from being damaged. generation of uniformity or voids, etc. In addition, when the coating layer of these compositions is dried, the component (B2) is easily volatilized, so the component (B2) does not remain in the layer of the obtained cured product, and as a result, low dielectric properties are exhibited. Moreover, 145, 140, 135, 130, 125, 120, 115, 110, 105, 100, 95, 90, 85, 80, 75, 70, 65, etc. are mentioned as the upper limit and lower limit of the said boiling point. Moreover, it is more preferable that the boiling point of (B2) component is 70 degreeC or more and 140 degrees C or less for the same reason as mentioned above.
在理想的（B2）成分中，酮可列舉例如：甲基乙基酮（80℃）、甲基正丙基酮（102℃）、甲基異丙基酮（93℃）、正丁基甲基酮（127℃）、異丁基甲基酮（116℃）、二級丁基甲基酮（116℃）、三級丁基甲基酮（106℃）、二乙基酮（101℃）、乙基正丙基酮（123℃）、乙基異丙基酮（115℃）、正丁基乙基酮（147℃）、乙基異丁基酮（136℃）、三級丁基乙基酮（125℃）、二正丙基酮（145℃）等脂肪族酮；環丙基甲基酮（114℃）、環丁酮（99℃）、環丁基甲基酮（138℃）、環戊酮（131℃）等脂環族酮等。此等可單獨使用，亦可將兩種以上組合使用。In the ideal (B2) component, examples of ketones include methyl ethyl ketone (80° C.), methyl n-propyl ketone (102° C.), methyl isopropyl ketone (93° C.), and n-butyl methyl ketone. (127℃), isobutyl methyl ketone (116℃), tertiary butyl methyl ketone (116℃), tertiary butyl methyl ketone (106℃), diethyl ketone (101℃), ethyl n-propyl ketone ( 123°C), ethyl isopropyl ketone (115°C), n-butyl ethyl ketone (147°C), ethyl isobutyl ketone (136°C), tertiary butyl ethyl ketone (125°C), two Aliphatic ketones such as n-propyl ketone (145°C); cyclopropyl methyl ketone (114°C), cyclobutanone (99°C), cyclobutyl methyl ketone (138°C), cyclopentanone (131°C) and other lipids Cyclic ketones, etc. These may be used alone or in combination of two or more.
在理想的（B2）成分中，醚可列舉例如：乙基正丙基醚（62℃）、二正丙基醚（90℃）、異丙基正丙基醚（83℃）、二異丙醚（69℃）等脂肪族單醚；1,2-二甲氧基乙烷（85℃）、1,1-二乙氧基乙烷（103℃）、1,2-二乙氧基乙烷（121℃）、1,2-二甲氧基丙烷（96℃）、2,2-二甲氧基丙烷（80℃）、1,1-二乙氧基丙烷（123℃）、2,2-二乙氧基丙烷（113℃）等脂肪族二醚；三乙氧基甲烷（143℃）、1,1,1-三甲氧基乙烷（107℃）等脂肪族三醚；甲氧基環戊烷（106℃）、甲氧基環己烷（135℃）等脂環族單醚等。此等可單獨使用，亦可將兩種以上組合使用。Among the desirable (B2) components, ethers include, for example, ethyl n-propyl ether (62° C.), di-n-propyl ether (90° C.), isopropyl n-propyl ether (83° C.), diisopropyl ether. Aliphatic monoethers such as ether (69°C); 1,2-dimethoxyethane (85°C), 1,1-diethoxyethane (103°C), 1,2-diethoxyethane alkane (121°C), 1,2-dimethoxypropane (96°C), 2,2-dimethoxypropane (80°C), 1,1-diethoxypropane (123°C), 2,2-dimethoxypropane (123°C) Aliphatic diethers such as 2-diethoxypropane (113°C); aliphatic triethers such as triethoxymethane (143°C), 1,1,1-trimethoxyethane (107°C); methoxy Alicyclic monoethers such as cyclopentane (106°C), methoxycyclohexane (135°C), etc. These may be used alone or in combination of two or more.
在理想的（B2）成分中，脂肪族烴可列舉例如：正己烷（69℃）、正庚烷（94℃）、正辛烷（126℃）等正構烷烴；2-甲基戊烷（60℃）、3-乙基戊烷（93℃）、2-甲基己烷（90℃）、3-甲基己烷（92℃）、3-乙基己烷（118℃）、2-甲基庚烷（116℃）、3-甲基庚烷（120℃）、4-甲基庚烷（117℃）、3-乙基庚烷（143℃）、2-甲基辛烷（143℃）、3-甲基辛烷（144℃）、4-甲基辛烷（142℃）等單烷基烷烴；2,2-二甲基戊烷（79℃）、2,4-二甲基戊烷（80℃）、2,2-二甲基己烷（106℃）、2,3-二甲基己烷（115℃）、2,4-二甲基己烷（108℃）、2,5-二甲基己烷（108℃）、4-乙基-2-甲基己烷（134℃）、2,2-二甲基庚烷（133℃）、2,3-二甲基庚烷（140℃）、2,4-二甲基庚烷（133℃）、2,5-二甲基庚烷（136℃）、3,3-二甲基庚烷（137℃）、3,4-二甲基庚烷（140℃）等二烷基烷烴等。此等可單獨使用，亦可將兩種以上組合使用。Among desirable components (B2), examples of aliphatic hydrocarbons include n-paraffins such as n-hexane (69°C), n-heptane (94°C), and n-octane (126°C); 2-methylpentane ( 60°C), 3-ethylpentane (93°C), 2-methylhexane (90°C), 3-methylhexane (92°C), 3-ethylhexane (118°C), 2- Methylheptane (116°C), 3-methylheptane (120°C), 4-methylheptane (117°C), 3-ethylheptane (143°C), 2-methyloctane (143°C) ℃), 3-methyloctane (144℃), 4-methyloctane (142℃) and other monoalkyl alkanes; 2,2-dimethylpentane (79℃), 2,4-dimethyl pentane (80°C), 2,2-dimethylhexane (106°C), 2,3-dimethylhexane (115°C), 2,4-dimethylhexane (108°C), 2,5-Dimethylhexane (108°C), 4-ethyl-2-methylhexane (134°C), 2,2-dimethylheptane (133°C), 2,3-dimethylhexane base heptane (140℃), 2,4-dimethylheptane (133℃), 2,5-dimethylheptane (136℃), 3,3-dimethylheptane (137℃), 3,4-Dimethylheptane (140℃) and other dialkyl alkanes, etc. These may be used alone or in combination of two or more.
在理想的（B2）成分中，脂環族烴可列舉例如：環己烷（81℃）、環庚烷（118℃）等環烷烴；乙基環丁烷（70℃）、甲基環戊烷（72℃）、乙基環戊烷（103℃）、正丙基環戊烷（131℃）、異丙基環戊烷（126℃）、異丁基環戊烷（148℃）、甲基環己烷（101℃）、乙基環己烷（132℃）、甲基環庚烷（145℃）等單烷基環烷烴；1,1-二甲基環己烷（118℃）、1-乙基-3-甲基環己烷（150℃）等二烷基環烷烴等。此等可單獨使用，亦可將兩種以上組合使用。Among desirable components (B2), examples of alicyclic hydrocarbons include cycloalkanes such as cyclohexane (81°C) and cycloheptane (118°C); ethylcyclobutane (70°C), methylcyclopentane alkane (72℃), ethylcyclopentane (103℃), n-propylcyclopentane (131℃), isopropylcyclopentane (126℃), isobutylcyclopentane (148℃), methyl Monoalkylcycloalkanes such as cyclohexane (101℃), ethylcyclohexane (132℃), methylcycloheptane (145℃); 1,1-dimethylcyclohexane (118℃), 1-ethyl-3-methylcyclohexane (150°C) and other dialkylcycloalkanes, etc. These may be used alone or in combination of two or more.
此等（B2）成分中，從（A）成分與（B2）成分良好的相溶性之觀點而言，理想含有醚、脂環族烴。Among these (B2) components, it is desirable to contain ether and alicyclic hydrocarbon from the viewpoint of good compatibility between (A) component and (B2) component.
（B1）成分及（B2）成分的含有比率，在（A）成分的製造中，從能夠充分溶解所生成的聚醯胺酸及聚醯亞胺樹脂並除去作為副產物而生成的水之觀點而言，以質量比計，理想係（B1）/（B2）=10/90～90/10，更理想係15/85～85/15，進一步理想係20/80～80/20。The content ratio of the component (B1) and the component (B2) is, in the production of the component (A), from the viewpoint of sufficiently dissolving the produced polyamic acid and polyimide resin and removing the water produced as a by-product. In terms of mass ratio, the ideal system (B1)/(B2)=10/90 to 90/10, the more ideal system is 15/85 to 85/15, and the further ideal system is 20/80 to 80/20.
[接著劑組成物] 本發明之接著劑組成物係含有本發明之聚醯亞胺樹脂組成物及交聯劑。 [Adhesive composition] The adhesive composition of the present invention contains the polyimide resin composition of the present invention and a crosslinking agent.
本發明之接著劑組成物中之聚醯亞胺樹脂組成物的含量沒有特別限定，將接著劑組成物作為100質量%，理想為10質量%～99.5質量%左右。The content of the polyimide resin composition in the adhesive composition of the present invention is not particularly limited, but is preferably about 10 to 99.5 mass %, taking the adhesive composition as 100 mass %.
本發明之接著劑組成物中（A）成分的含量沒有特別限定，將接著劑組成物的不揮發成分作為100%質量%，理想為2質量%～98質量%左右。The content of the component (A) in the adhesive composition of the present invention is not particularly limited, but is preferably about 2 to 98 mass %, taking the nonvolatile content of the adhesive composition as 100% by mass.
交聯劑，只要是作為聚醯亞胺的交聯劑而發揮作用，可以不特別限定地使用各種習知的交聯劑。交聯劑可單獨使用，亦可並用兩種以上。交聯劑理想為選自由環氧化物、苯并噁嗪、雙馬來醯亞胺及氰酸酯所成群中之至少一種。As long as the crosslinking agent functions as a crosslinking agent for polyimide, various known crosslinking agents can be used without particular limitation. The crosslinking agent may be used alone or in combination of two or more. The crosslinking agent is desirably at least one selected from the group consisting of epoxides, benzoxazines, bismaleimides, and cyanates.
環氧化物，可列舉：苯酚酚醛清漆型環氧化物、甲酚酚醛清漆型環氧化物、雙酚A型環氧化物、雙酚F型環氧化物、雙酚S型環氧化物、氫化雙酚A型環氧化物、氫化雙酚F型環氧化物、二苯乙烯型環氧化物、含三嗪骨架之環氧化物、含芴骨架之環氧化物、線狀脂肪族環氧化物、脂環式環氧化物、縮水甘油胺型環氧化物、三酚甲烷型環氧化物、烷基改性三酚甲烷型環氧化物、聯苯型環氧化物、含雙環戊二烯骨架之環氧化物、含萘骨架之環氧化物、芳基伸烷基型環氧化物、四縮水甘油基苯二甲基二胺、作為前述環氧化物之二聚酸改性物之二聚酸改性環氧化物、二聚酸二縮水甘油酯等。此外，環氧化物的市售品，可列舉：三菱化學股份有限公司製的「jER828」、「jER834」、「jER807」、「jER604」、「jER630」；日鐵化學材料股份有限公司製的「ST-3000」；大賽璐（Daicel）股份有限公司製的「CELLOXIDE 2021P」；日鐵化學材料股份有限公司製的「YD-172-X75」；三菱瓦斯化學股份有限公司製的「TETRAD-X」等。此等之中，從焊接耐熱性與低介電特性的平衡之觀點而言，理想選自由雙酚A型環氧化物、雙酚F型環氧化物、氫化雙酚A型環氧化物及脂環式環氧化物所成群中之至少一種。Examples of epoxides include: phenol novolac type epoxide, cresol novolak type epoxide, bisphenol A type epoxide, bisphenol F type epoxide, bisphenol S type epoxide, hydrogenated bisphenol A Phenol A type epoxide, hydrogenated bisphenol F type epoxide, stilbene type epoxide, epoxide containing triazine skeleton, epoxide containing fluorene skeleton, linear aliphatic epoxide, lipid Cyclic epoxide, glycidylamine type epoxide, trisphenolmethane type epoxide, alkyl modified trisphenolmethane type epoxide, biphenyl type epoxide, epoxy containing dicyclopentadiene skeleton Compounds, epoxides containing a naphthalene skeleton, arylalkylene-type epoxides, tetraglycidyl xylylenediamine, dimer acid-modified epoxy compounds that are dimer acid-modified products of the aforementioned epoxides compound, dimer acid diglycidyl ester, etc. In addition, commercial products of epoxides include "jER828", "jER834", "jER807", "jER604", and "jER630" manufactured by Mitsubishi Chemical Co., Ltd.; "jER630" manufactured by Nippon Steel Chemical Materials Co., Ltd. ST-3000"; "CELLOXIDE 2021P" manufactured by Daicel Co., Ltd.; "YD-172-X75" manufactured by Nippon Steel Chemical Co., Ltd.; "TETRAD-X" manufactured by Mitsubishi Gas Chemical Co., Ltd. Wait. Among them, from the viewpoint of the balance between soldering heat resistance and low dielectric properties, it is preferably selected from bisphenol A type epoxy, bisphenol F type epoxy, hydrogenated bisphenol A type epoxy and lipid At least one of the group of cyclic epoxides.
尤其，通式（3）的四縮水甘油基二胺與前述聚醯亞胺的相溶性良好。此外，若使用該物質，接著劑層的低損耗模量化變得容易，其焊接耐熱性及低介電特性亦變得良好。
[化3]
使用環氧化物作為交聯劑時，可以並用各種習知的環氧化物用硬化劑、活性酯系硬化劑。此等硬化劑可單獨使用，亦可並用兩種以上。When an epoxide is used as a crosslinking agent, various conventional hardeners for epoxides and active ester-based hardeners can be used in combination. These curing agents may be used alone or in combination of two or more.
環氧化物用硬化劑，可列舉例如：琥珀酸酐、鄰苯二甲酸酐、馬來酸酐、偏苯三甲酸酐、均苯四甲酸酐、六氫鄰苯二甲酸酐、3-甲基六氫鄰苯二甲酸酐、4-甲基-六氫鄰苯二甲酸酐、或者4-甲基六氫鄰苯二甲酸酐與六氫鄰苯二甲酸酐之混合物、四氫鄰苯二甲酸酐、甲基-四氫鄰苯二甲酸酐、納迪克酸酐（nadic anhydride）、甲基納迪克酸酐、降莰烷-2,3-二甲酸酐、甲基降莰烷-2,3-二甲酸酐、甲基環己烯二甲酸酐、3-十二烯基琥珀酸酐、辛烯基琥珀酸酐等酸酐系硬化劑； 二氰二胺（DICY）、芳香族二胺（商品名「Lonzacure M-DEA」、「Lonzacure M-DETDA」等，均為Lonza Japan股份有限公司製）、脂肪族胺等胺系硬化劑； 苯酚酚醛清漆樹脂、甲酚酚醛清漆樹脂、雙酚A型酚醛清漆樹脂、三嗪改性苯酚酚醛清漆樹脂、含酚性羥基之磷腈（大塚化學股份有限公司製的商品名「SPH-100」等）等酚系硬化劑； 馬來酸改性松香及其氫化物等松香系硬化劑； 環狀磷腈系化合物等。 Examples of curing agents for epoxides include succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, and 3-methylhexahydrophthalic anhydride. Phthalic anhydride, 4-methyl-hexahydrophthalic anhydride, or a mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl phthalate base-tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, Acid anhydride-based hardeners such as methylcyclohexenedicarboxylic anhydride, 3-dodecenylsuccinic anhydride, and octenylsuccinic anhydride; Dicyandiamide (DICY), aromatic diamine (trade names "Lonzacure M-DEA", "Lonzacure M-DETDA", etc., all manufactured by Lonza Japan Co., Ltd.), aliphatic amines and other amine-based hardeners; Phenol novolac resin, cresol novolak resin, bisphenol A novolak resin, triazine-modified phenol novolak resin, phosphazene containing phenolic hydroxyl group (trade name "SPH-100" manufactured by Otsuka Chemical Co., Ltd. etc.) and other phenolic hardeners; Rosin-based hardeners such as maleic acid-modified rosin and its hydrides; Cyclic phosphazene compounds, etc.
活性酯系硬化劑，可列舉例如：日本特開2019-183071中記載之含有雙環戊二烯基二酚結構之物質、含有萘結構之物質、苯酚酚醛清漆之乙醯化物、苯酚酚醛清漆之苯甲醯化物等。 活性酯系硬化劑的市售品，可列舉例如： 含有雙環戊二烯基二酚結構之物質為「EXB9451」、「EXB9460」、「EXB9460S」、「HPC-8000」、「HPC-8000H」、「HPC-8000-65T」、「HPC-8150-62T」、「HPC-8000H-65MT」、「HPC-8000L-65MT」、「EXB-8000L」、「EXB-8000L-65MT」、「EXB-8150-65T」（以上為DIC股份有限公司製）； 含有萘結構之物質為「EXB9416-70BK」（DIC股份有限公司製）； 苯酚酚醛清漆之乙醯化物為「DC808」（三菱化學股份有限公司製）； 苯酚酚醛清漆之苯甲醯化物為「YLH1026」、「YLH1030」、「YLH1048」（三菱化學股份有限公司製）等。 Active ester-based hardeners include, for example, substances containing a dicyclopentadienyl diphenol structure, substances containing a naphthalene structure, acetylated compounds of phenol novolacs, and benzene of phenol novolacs described in Japanese Patent Laid-Open No. 2019-183071 Formazan, etc. Commercially available products of active ester-based curing agents include, for example: Substances containing dicyclopentadienyl diphenol structure are "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", "HPC-8000-65T", "HPC-8150-62T" ", "HPC-8000H-65MT", "HPC-8000L-65MT", "EXB-8000L", "EXB-8000L-65MT", "EXB-8150-65T" (the above are manufactured by DIC Corporation); The substance containing naphthalene structure is "EXB9416-70BK" (manufactured by DIC Corporation); The acetyl compound of phenol novolac is "DC808" (manufactured by Mitsubishi Chemical Corporation); The benzyl compounds of phenol novolac are "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation) and the like.
活性酯系硬化劑亦可以使用藉由各種習知的方法而製造之物質，作為其例子，可列舉日本專利第5152445號公報中記載之使多官能酚化合物與芳香族羧酸類發生反應而得到之物質等。As the active ester-based curing agent, those produced by various conventional methods can be used, and examples thereof include those obtained by reacting a polyfunctional phenol compound with an aromatic carboxylic acid as described in Japanese Patent No. 5152445. material, etc.
在前述硬化劑中，理想為活性酯系硬化劑、酚系硬化劑，尤其理想為活性酯系硬化劑。硬化劑的使用量沒有特別限定，將前述接著劑組成物的不揮發成分作為100質量%，理想為0.1質量%～40質量%左右，更理想為1質量%～10質量%左右。Among the above-mentioned curing agents, an active ester-based curing agent and a phenol-based curing agent are desirable, and an active ester-based curing agent is particularly desirable. The usage-amount of a hardening|curing agent is not specifically limited, It is about 0.1 mass % - 40 mass % preferably, and about 1 mass % - 10 mass % is more preferable, taking the nonvolatile matter of the said adhesive composition as 100 mass %.
此外，並用環氧化物及環氧化物用硬化劑作為交聯劑時，可以進一步並用反應觸媒。反應觸媒可單獨使用，亦可並用兩種以上。反應觸媒可列舉：1,8-二氮雜-雙環[5.4.0]十一碳烯-7、三伸乙基二胺、苄基二甲胺、三乙醇胺、二甲基胺基乙醇、參(二甲基胺基甲基)苯酚等三級胺；2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2-十七烷基咪唑等咪唑類；三丁基膦、甲基二苯基膦、三苯基膦、二苯基膦、苯基膦等有機膦；四苯基鏻・四苯基硼酸鹽、2-乙基-4-甲基咪唑・四苯基硼酸鹽、N-甲基嗎啉・四苯基硼酸鹽等四苯基硼鹽等。此外，該反應觸媒的使用量沒有特別限定，將前述接著劑組成物的不揮發成分作為100質量%，理想為0.01質量%～5質量%左右。In addition, when an epoxide and a curing agent for epoxides are used in combination as a crosslinking agent, a reaction catalyst may be used in combination. The reaction catalyst may be used alone or in combination of two or more. Examples of reaction catalysts include: 1,8-diaza-bicyclo[5.4.0]undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, Tertiary amines such as ginseng (dimethylaminomethyl)phenol; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; Tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine and other organic phosphines; tetraphenylphosphonium tetraphenyl borate, 2-ethyl-4-methylimidazole・Tetraphenyl borate such as tetraphenyl borate, N-methylmorpholine, tetraphenyl borate, etc. In addition, the usage-amount of this reaction catalyst is not specifically limited, It is about 0.01 mass % - 5 mass % ideally, considering the non-volatile matter of the said adhesive composition as 100 mass %.
苯并噁嗪，可列舉：6,6-(1-甲基亞乙基)雙(3,4-二氫-3-苯基-2H-1,3-苯并噁嗪)、6,6-(1-甲基亞乙基)雙(3,4-二氫-3-甲基-2H-1,3-苯并噁嗪)等。又，亦可以在噁嗪環的氮上鍵結苯基、甲基、環己基等。此外，苯并噁嗪的市售品，可列舉：四國化成工業股份有限公司製的「苯并噁嗪F-a型」、「苯并噁嗪P-d型」；AIR WATER公司製的「RLV-100」等。Benzoxazine, 6,6-(1-methylethylene)bis(3,4-dihydro-3-phenyl-2H-1,3-benzoxazine), 6,6 -(1-Methylethylene)bis(3,4-dihydro-3-methyl-2H-1,3-benzoxazine) and the like. Moreover, a phenyl group, a methyl group, a cyclohexyl group, etc. may be bonded to the nitrogen of the oxazine ring. In addition, commercial products of benzoxazine include "benzoxazine F-a type" and "benzoxazine P-d type" manufactured by Shikoku Chemical Industry Co., Ltd.; "RLV-100" manufactured by Air Water Co., Ltd. "Wait.
雙馬來醯亞胺，可列舉：4,4’-二苯基甲烷雙馬來醯亞胺、間伸苯基雙馬來醯亞胺、雙酚A二苯基醚雙馬來醯亞胺、3,3’-二甲基-5,5’-二乙基-4,4’-二苯基甲烷雙馬來醯亞胺、4-甲基-1,3-伸苯基雙馬來醯亞胺、1,6’-雙馬來醯亞胺-(2,2,4-三甲基)己烷、4,4’-二苯基醚雙馬來醯亞胺、4,4’-二苯基碸雙馬來醯亞胺等。此外，雙馬來醯亞胺的市售品，可列舉：JFE化學股份有限公司製的「BAF-BMI」、大和化成工業股份有限公司製的「BMI-1000H」等。Bismaleimide, for example: 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide , 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide Imide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether bismaleimide, 4,4' - Diphenyl bismaleimide, etc. Moreover, as a commercial item of bismaleimide, "BAF-BMI" by JFE Chemical Co., Ltd., "BMI-1000H" by Yamato Chemical Industry Co., Ltd., etc. are mentioned.
氰酸酯，可列舉：2-烯丙基苯酚氰酸酯、4-甲氧基苯酚氰酸酯、2,2-雙(4-異氰氧基苯基)-1,1,1,3,3,3-六氟丙烷、雙酚A氰酸酯、二烯丙基雙酚A氰酸酯、4-苯基苯酚氰酸酯、1,1,1-參(4-氰氧基苯基)乙烷、4-枯基苯酚氰酸酯、1,1-雙(4-氰氧基苯基)乙烷、4,4’-雙苯酚氰酸酯以及2,2-雙(4-氰氧基苯基)丙烷等。此外，氰酸酯的市售品，可列舉：Lonza Japan 股份有限公司製的「PRIMASET BTP-6020S」等。The cyanate esters include: 2-allylphenol cyanate, 4-methoxyphenol cyanate, 2,2-bis(4-isocyanoxyphenyl)-1,1,1,3 ,3,3-Hexafluoropropane, Bisphenol A Cyanate, Diallyl Bisphenol A Cyanate, 4-Phenyl Phenol Cyanate, 1,1,1-Sample(4-cyanooxybenzene) yl)ethane, 4-cumylphenolcyanate, 1,1-bis(4-cyanophenyl)ethane, 4,4'-bisphenolcyanate and 2,2-bis(4- cyanophenyl) propane, etc. Moreover, as a commercial item of a cyanate ester, "PRIMASET BTP-6020S" by Lonza Japan Co., Ltd. etc. are mentioned.
本發明之接著劑組成物中之交聯劑的含量沒有特別限定。相對於前述接著劑組成物中之本發明的（A）成分100質量份（不揮發成分換算），該交聯劑的含量理想為1質量份～900質量份左右。The content of the crosslinking agent in the adhesive composition of the present invention is not particularly limited. The content of the crosslinking agent is desirably about 1 to 900 parts by mass relative to 100 parts by mass (in terms of non-volatile content) of the component (A) of the present invention in the adhesive composition.
將接著劑組成物的不揮發成分作為100質量%，本發明之接著劑組成物中交聯劑的含量理想為1質量%～80質量%左右。The content of the crosslinking agent in the adhesive composition of the present invention is desirably about 1 to 80 mass %, taking the nonvolatile content of the adhesive composition as 100 mass %.
本發明之接著劑組成物中亦可以含有阻燃劑。阻燃劑可單獨使用，亦可並用兩種以上。阻燃劑，可列舉例如磷系阻燃劑、無機填料等。The adhesive composition of the present invention may also contain a flame retardant. The flame retardant may be used alone or in combination of two or more. Examples of the flame retardant include phosphorus-based flame retardants, inorganic fillers, and the like.
磷系阻燃劑，可列舉：聚磷酸或磷酸酯、不具有酚性羥基之磷腈衍生物等。在該磷腈衍生物中，從阻燃性、耐熱性、耐滲出性等觀點而言，理想為環狀磷腈衍生物。環狀磷腈衍生物的市售品，可列舉：大塚化學股份有限公司製的「SPB-100」、伏見製藥所股份有限公司製的「Rabitle FP-300B」等。Phosphorus-based flame retardants include polyphosphoric acid, phosphoric acid ester, phosphazene derivatives having no phenolic hydroxyl group, and the like. Among the phosphazene derivatives, cyclic phosphazene derivatives are preferable from the viewpoints of flame retardancy, heat resistance, bleeding resistance, and the like. Commercially available cyclic phosphazene derivatives include "SPB-100" manufactured by Otsuka Chemical Co., Ltd., "Rabitle FP-300B" manufactured by Fushimi Pharmaceutical Co., Ltd., and the like.
無機填料，可列舉例如：二氧化矽填料、磷系填料、氟系填料、無機離子交換體填料等。又，二氧化矽填料亦可以使用其表面經矽烷偶聯劑等處理劑改性的二氧化矽填料。此外，無機填料的市售品，可列舉：電氣化學工業股份有限公司製的「FB-3SDC」、「SFP-20M」；Admatechs股份有限公司製的「SC-2500-SPJ」、「SC-2500-SXJ」、「SC-2500-SVJ」；科萊恩化學（Clariant chemicals）股份有限公司製的「Exolit OP935」；喜多村股份有限公司製的「KTL-500F」；東亞合成股份有限公司製的「IXE」等。The inorganic fillers include, for example, silica fillers, phosphorus-based fillers, fluorine-based fillers, inorganic ion exchanger fillers, and the like. In addition, the silica filler whose surface is modified by a treatment agent such as a silane coupling agent can also be used. In addition, commercially available inorganic fillers include "FB-3SDC" and "SFP-20M" manufactured by Denki Chemical Industry Co., Ltd.; "SC-2500-SPJ" and "SC-2500" manufactured by Admatechs Co., Ltd. -SXJ", "SC-2500-SVJ"; "Exolit OP935" manufactured by Clariant Chemicals Co., Ltd.; "KTL-500F" manufactured by Kitamura Co., Ltd.; "IXE" manufactured by Toagosei Co., Ltd. "Wait.
本發明之接著劑組成物中之阻燃劑的含量沒有特別限定。相對於前述接著劑組成物中之本發明的（A）成分100質量份（不揮發成分換算），該阻燃劑的含量理想為1質量份～150質量份。The content of the flame retardant in the adhesive composition of the present invention is not particularly limited. The content of the flame retardant is preferably 1 part by mass to 150 parts by mass relative to 100 parts by mass (in terms of non-volatile content) of the component (A) of the present invention in the adhesive composition.
本發明之接著劑組成物中亦可以含有通式：W-Si(R 1) a(OR 2) 3-a（式中，W表示含有與酸酐基反應的官能團之基團，R 1表示氫或碳數1～8之烴基，R 2表示碳數1～8之烴基，a表示0、1或2）表示之反應性烷氧基矽基化合物。藉由反應性烷氧基矽基化合物，可維持由本發明之接著劑組成物構成之接著劑層的低介電特性並同時調節其熔融黏度。其結果，可以提高該接著劑層與支撐體的界面密著力（所謂的錨固效果），同時可以抑制從該支撐體的端部產生的該硬化層的滲出。 The adhesive composition of the present invention may also contain the general formula: W-Si(R 1 ) a (OR 2 ) 3-a (in the formula, W represents a group containing a functional group that reacts with an acid anhydride group, and R 1 represents hydrogen or a hydrocarbon group with 1 to 8 carbon atoms, R 2 represents a hydrocarbon group with 1 to 8 carbon atoms, and a represents a reactive alkoxysilyl compound represented by 0, 1 or 2). By means of the reactive alkoxysilyl compound, the low dielectric properties of the adhesive layer composed of the adhesive composition of the present invention can be maintained and the melt viscosity thereof can be adjusted at the same time. As a result, the interfacial adhesion force between the adhesive layer and the support body (so-called anchor effect) can be improved, and exudation of the hardened layer from the end of the support body can be suppressed.
前述通式的W中所含之反應性官能基，可列舉胺基、環氧基及硫醇基等。The reactive functional group contained in W in the aforementioned general formula includes an amine group, an epoxy group, and a thiol group.
W含有胺基之化合物，可列舉：N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷及3-脲基丙基三烷氧基矽烷等。W含有環氧基之化合物，可列舉例如：2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷及3-環氧丙氧基丙基三乙氧基矽烷等。W含有硫醇基之化合物，可列舉例如：3-巰基丙基三甲氧基矽烷、3-巰基丙基三乙氧基矽烷、3-巰基丙基甲基二甲氧基矽烷及3-巰基丙基甲基二乙氧基矽烷等。此等之中，從反應性及流動控制效果良好之觀點而言，理想為W含有胺基之化合物。Compounds containing an amino group include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-amino Propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and 3-ureidopropyltrialkoxysilane, etc. Compounds containing an epoxy group in W include, for example: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3- Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane, etc. Compounds containing a thiol group include, for example: 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyl Methylmethyldiethoxysilane, etc. Among these, from the viewpoint of good reactivity and flow control effect, a compound containing an amine group is desirable.
本發明之接著劑組成物中之反應性烷氧基矽基化合物的含量沒有特別限定。相對於前述接著劑組成物中之本發明的（A）成分100質量份（不揮發成分換算），該反應性烷氧基矽基化合物的含量理想為0.01質量份～5質量份。The content of the reactive alkoxysilyl compound in the adhesive composition of the present invention is not particularly limited. The content of the reactive alkoxysilyl compound is preferably 0.01 to 5 parts by mass relative to 100 parts by mass (in terms of non-volatile content) of the component (A) of the present invention in the adhesive composition.
本發明之接著劑組成物亦可以含有不屬於本發明之聚醯亞胺樹脂組成物、交聯劑、阻燃劑、反應性烷氧基矽基化合物、前述有機溶劑中之任一種之物質作為添加劑。The adhesive composition of the present invention may also contain any of the polyimide resin composition, crosslinking agent, flame retardant, reactive alkoxysilyl compound, and the aforementioned organic solvent, which do not belong to the present invention, as a substance. additive.
添加劑，可列舉：開環酯化反應觸媒、脫水劑、增塑劑、耐候劑、抗氧化劑、熱穩定劑、潤滑劑、抗靜電劑、增白劑、著色劑、導電劑、脫模劑、表面處理劑、黏度調節劑、二氧化矽填料及氟填料等。Additives include: ring-opening esterification catalysts, dehydrating agents, plasticizers, weathering agents, antioxidants, heat stabilizers, lubricants, antistatic agents, brighteners, colorants, conductive agents, mold release agents , Surface treatment agent, viscosity modifier, silica filler and fluorine filler, etc.
前述添加劑的含量沒有特別限定，相對於接著劑組成物的不揮發成分100質量份，可列舉：小於1質量份、小於0.1質量份、小於0.01質量份、0質量份等。The content of the additive is not particularly limited, but may include less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, and the like with respect to 100 parts by mass of the nonvolatile content of the adhesive composition.
前述添加劑的含量沒有特別限定，相對於本發明之（A）成分100質量份（不揮發成分換算），可列舉：小於1質量份、小於0.1質量份、小於0.01質量份、0質量份等。Content of the said additive is not specifically limited, With respect to 100 mass parts (non-volatile content conversion) of (A) component of this invention, it is less than 1 mass part, less than 0.1 mass part, less than 0.01 mass part, 0 mass part etc. are mentioned.
本發明之接著劑組成物，可以藉由將前述交聯劑、以及根據需要之前述阻燃劑、反應性烷氧基矽基化合物及添加劑溶解在本發明之聚醯亞胺樹脂組成物中而得到。又，在前述接著劑組成物的製備中，可以進一步配合前述之（B）成分。The adhesive composition of the present invention can be prepared by dissolving the above-mentioned crosslinking agent, and optionally the above-mentioned flame retardant, reactive alkoxysilyl compound and additives in the polyimide resin composition of the present invention. get. Moreover, in the preparation of the said adhesive composition, the said (B) component may be mix|blended further.
[膜狀接著材料] 本發明之膜狀接著材料係含有本發明之接著劑組成物的硬化物。膜狀接著材料的製造方法，可列舉包含以下步驟之方法等：將前述接著劑組成物塗布在適當的支撐體上之步驟、藉由加熱使有機溶劑揮發而使其硬化之步驟、剝離該支撐體之步驟等。此外，接著材料的厚度沒有特別限定，理想為3μm～40μm左右。支撐體，可列舉：剝離紙、剝離膜、後述之支撐膜等。此外，在製造前述膜狀接著材料時，亦可以並用前述接著劑組成物與前述接著劑組成物以外的各種習知之接著劑組成物。 [Film Adhesive Material] The film-like adhesive material of the present invention is a cured product containing the adhesive composition of the present invention. The production method of the film-like adhesive material includes a method including the following steps: a step of applying the above-mentioned adhesive composition on an appropriate support, a step of volatilizing an organic solvent by heating to harden it, and peeling off the support body steps, etc. In addition, the thickness of the adhesive material is not particularly limited, but is preferably about 3 μm to 40 μm. As a support, a release paper, a release film, the support film mentioned later, etc. are mentioned. Moreover, when manufacturing the said film-shaped adhesive material, you may use together the said adhesive agent composition and various conventional adhesive agent compositions other than the said adhesive agent composition.
[接著片材] 本發明之接著片材係在支撐膜之至少單面上具有本發明膜狀接著材料。 [Next sheet] The adhesive sheet of the present invention has the film-like adhesive material of the present invention on at least one side of the support film.
前述接著片材，例如可以藉由在支撐膜之上塗布本發明之接著劑組成物並經加熱使其硬化而得到，或者藉由在支撐膜之上貼合本發明之膜狀接著材料而得到。The aforementioned adhesive sheet can be obtained, for example, by coating the adhesive composition of the present invention on a support film and curing it by heating, or by laminating the film-like adhesive material of the present invention on the support film. .
前述支撐膜，可列舉：聚醯亞胺；聚酯；聚醯亞胺-二氧化矽混合物；聚乙烯；聚丙烯；聚對苯二甲酸乙二酯；聚萘二甲酸乙二酯；聚甲基丙烯酸甲酯樹脂；聚苯乙烯樹脂；聚碳酸酯樹脂；丙烯腈-丁二烯-苯乙烯樹脂；由對苯二甲酸乙二酯、苯酚、鄰苯二甲酸、羥基萘甲酸等與對羥基苯甲酸得到的芳香族系聚酯樹脂（所謂液晶聚合物，Kuraray股份有限公司製，「Vecstar」等）；環烯烴聚合物；氟系樹脂（聚四氟乙烯（PTFE）、全氟烷氧基烷烴（PFA）、聚偏二氟乙烯（PVDF）等）等。聚醯亞胺包含本發明之前述聚醯亞胺膜。The aforementioned support film may include: polyimide; polyester; polyimide-silicon dioxide mixture; polyethylene; polypropylene; polyethylene terephthalate; polyethylene naphthalate; polyethylene Methyl acrylate resin; polystyrene resin; polycarbonate resin; acrylonitrile-butadiene-styrene resin; Aromatic polyester resins obtained from benzoic acid (so-called liquid crystal polymers, manufactured by Kuraray Co., Ltd., "Vecstar", etc.); cycloolefin polymers; fluorine-based resins (polytetrafluoroethylene (PTFE), perfluoroalkoxy alkane (PFA), polyvinylidene fluoride (PVDF), etc.). The polyimide includes the aforementioned polyimide film of the present invention.
將本發明之接著劑組成物塗布在前述支撐膜上時，其塗布方法亦沒有特別限定，可列舉例如使用逗號式塗布機、模塗布機、刮刀塗布機、唇式塗布機等塗布機進行等。塗布層的厚度亦沒有特別限定，乾燥後的厚度理想為1μm～100μm左右，更理想為3μm～50μm左右。此外，該接著片材的接著劑層亦可由各種保護膜進行保護。When the adhesive composition of the present invention is coated on the support film, the coating method is not particularly limited, and for example, it can be carried out using a coating machine such as a comma coater, a die coater, a knife coater, and a lip coater. . The thickness of the coating layer is also not particularly limited, but the thickness after drying is preferably about 1 μm to 100 μm, and more preferably about 3 μm to 50 μm. Moreover, the adhesive layer of this adhesive sheet may be protected by various protective films.
[附樹脂之銅箔] 本發明之附樹脂之銅箔係包含本發明之膜狀接著材料及銅箔。具體而言，附樹脂之銅箔可為在銅箔上塗布本發明之接著劑組成物並加熱硬化而得到，或者可為在銅箔上貼合本發明之膜狀接著材料而得到。銅箔，可列舉例如壓延銅箔及電解銅箔，亦可以使用施有各種表面處理（粗化、防鏽化等）之銅箔。防鏽化處理，可列舉使用含有Ni、Zn、Sn等的鍍液之鍍處理、鉻酸鹽處理等之所謂的鏡面化處理。 [Copper foil with resin] The resin-attached copper foil of the present invention includes the film-like adhesive material and copper foil of the present invention. Specifically, the resin-attached copper foil can be obtained by coating the adhesive composition of the present invention on the copper foil and heat-hardening, or can be obtained by laminating the film-like adhesive material of the present invention on the copper foil. The copper foil includes, for example, a rolled copper foil and an electrolytic copper foil, and a copper foil to which various surface treatments (roughening, rust prevention, etc.) are applied can also be used. The anti-rust treatment includes plating treatment using a plating solution containing Ni, Zn, Sn, etc., and so-called mirror treatment such as chromate treatment.
銅箔的厚度亦沒有特別限定，理想為1μm～100μm左右，更理想為2μm～38μm左右。此外，塗布手段可列舉前述之方法。The thickness of the copper foil is also not particularly limited, but is preferably about 1 μm to 100 μm, and more preferably about 2 μm to 38 μm. In addition, as a coating means, the method mentioned above can be mentioned.
此外，附樹脂之銅箔的接著劑層或膜狀接著材料可以是未硬化的，或者亦可以是在加熱下部分硬化或完全硬化的。部分硬化之接著劑層或膜狀接著材料處於被稱為所謂B階段的狀態。此外，接著劑層或膜狀接著材料的厚度亦沒有特別限定，理想為0.5μm～30μm左右。此外，亦可以在該附樹脂之銅箔的銅箔上進一步貼合樹脂，從而製成雙面附樹脂之銅箔。In addition, the adhesive layer or film-like adhesive material of the resin-attached copper foil may be uncured, or may be partially or completely cured by heating. The partially cured adhesive layer or film-like adhesive is in a state called a so-called B-stage. In addition, the thickness of the adhesive layer or the film-like adhesive material is not particularly limited, but is preferably about 0.5 μm to 30 μm. In addition, the resin-attached copper foil can be further bonded with resin to form a double-sided resin-attached copper foil.
[覆銅積層板] 本發明之覆銅積層板係包含本發明之附樹脂之銅箔以及銅箔或絕緣性片材。覆銅積層板亦被稱為CCL（Copper Clad Laminate）。具體而言，覆銅積層板係在各種習知的銅箔或絕緣性片材之至少單面或兩面上，在加熱下壓接前述附樹脂之銅箔而成。在貼合於單面之情況下，亦可以在另一面壓接與前述附樹脂之銅箔不同的材料。此外，該覆銅積層板中之附樹脂之銅箔、銅箔及絕緣性片材的張數沒有特別限定。 [Copper clad laminate] The copper-clad laminate of the present invention includes the resin-attached copper foil and the copper foil or insulating sheet of the present invention. Copper Clad Laminate is also known as CCL (Copper Clad Laminate). Specifically, the copper-clad laminate is formed by pressing the resin-attached copper foil on at least one side or both sides of various conventional copper foils or insulating sheets under heating. In the case of lamination on one side, a material different from the aforementioned copper foil with resin can also be crimped on the other side. In addition, the number of sheets of resin-attached copper foil, copper foil, and insulating sheet in the copper-clad laminate is not particularly limited.
在一個實施型態中，絕緣性片材理想為預浸料或前述之支撐膜。預浸料係指在玻璃布等增強材料中含浸樹脂並使其硬化至B階段而成之片材狀材料（JIS C 5603）。該樹脂使用本發明之（A）成分、酚樹脂、環氧樹脂、聚酯樹脂、液晶聚合物、芳香族聚醯胺樹脂等絕緣性樹脂。絕緣性片材的厚度沒有特別限定，理想為20μm～500μm左右。加熱條件沒有特別限定，理想為150℃～280℃左右（更理想為170℃～240℃左右）；以及壓接條件沒有特別限定，理想為0.5MPa～20MPa左右（更理想為1MPa～8MPa左右）。In one embodiment, the insulating sheet is desirably a prepreg or the aforementioned support film. Prepreg refers to a sheet-like material obtained by impregnating a reinforcing material such as glass cloth with resin and hardening it to the B stage (JIS C 5603). As the resin, insulating resins such as the component (A) of the present invention, phenol resins, epoxy resins, polyester resins, liquid crystal polymers, and aromatic polyamide resins are used. The thickness of the insulating sheet is not particularly limited, but is preferably about 20 μm to 500 μm. The heating conditions are not particularly limited, but are preferably about 150°C to 280°C (more preferably about 170°C to 240°C); and the crimping conditions are not particularly limited, but are preferably about 0.5MPa to 20MPa (more preferably about 1MPa to 8MPa) .
[印刷配線板] 本發明之印刷配線板係在本發明之覆銅積層板的銅箔面上具有電路圖案。在覆銅積層板的銅箔面上形成電路圖案之圖案化手段，可列舉減成法、半加成法。半加成法，可列舉如下方法：在覆銅積層板的銅箔面上利用抗蝕劑膜進行圖案化後，進行電解鍍銅，除去抗蝕劑，並利用鹼液進行蝕刻。此外，該印刷配線板中的電路圖案層的厚度沒有特別限定。此外，亦可以將該印刷配線板作為芯，在該芯上積層相同的印刷配線板或其他習知的印刷配線板或印刷電路板，從而得到多層基板。在積層時，可以並用前述接著劑組成物與前述接著劑組成物以外的其他習知的接著劑組成物。此外，多層基板中的積層數沒有特別限定。此外，亦可以在每次積層時***設置通孔，對內部進行鍍處理。前述電路圖案的線寬／間距比沒有特別限定，理想為1μm／1μm～100μm／100μm左右。此外，前述電路圖案的高度亦沒有特別限定，理想為1μm～50μm左右。 [Printed Wiring Board] The printed wiring board of the present invention has a circuit pattern on the copper foil surface of the copper-clad laminate of the present invention. The patterning means for forming the circuit pattern on the copper foil surface of the copper clad laminate include the subtractive method and the semi-additive method. As the semi-additive method, after patterning with a resist film on the copper foil surface of the copper-clad laminate, electrolytic copper plating is performed, the resist is removed, and the etching is performed with an alkaline solution. In addition, the thickness of the circuit pattern layer in this printed wiring board is not specifically limited. In addition, this printed wiring board may be used as a core, and the same printed wiring board or other conventional printed wiring boards or printed wiring boards may be laminated on the core to obtain a multilayer substrate. At the time of lamination, the adhesive composition described above and other conventional adhesive compositions other than the adhesive composition described above may be used in combination. In addition, the number of build-up layers in the multilayer substrate is not particularly limited. In addition, it is also possible to insert through holes every time the layers are stacked, and to perform plating processing on the inside. The line width/pitch ratio of the circuit pattern is not particularly limited, but is preferably about 1 μm/1 μm to 100 μm/100 μm. Moreover, the height of the said circuit pattern is not specifically limited, either, Preferably it is about 1 micrometer - about 50 micrometers.
[聚醯亞胺膜] 本發明之聚醯亞胺膜係本發明之聚醯亞胺樹脂組成物的硬化物。 [Polyimide film] The polyimide film of the present invention is a cured product of the polyimide resin composition of the present invention.
本發明之聚醯亞胺膜的製造方法，可列舉將前述聚醯亞胺樹脂組成物塗布在前述支撐體上後，經加熱使其硬化而形成聚醯亞胺樹脂層後，從該聚醯亞胺樹脂層剝離支撐體之方法等。The method for producing a polyimide film of the present invention includes applying the polyimide resin composition on the support, and then curing it by heating to form a polyimide resin layer. A method of peeling off the support from the imine resin layer, and the like.
將聚醯亞胺樹脂組成物塗布在支撐體上的方法沒有特別限定，可列舉前述之塗布方法。此外，熱處理條件亦沒有特別限定，可列舉例如在溫度100℃～180℃左右加熱0.5小時～3小時左右之方法等。The method of coating the polyimide resin composition on the support is not particularly limited, and the above-mentioned coating methods are exemplified. In addition, the heat treatment conditions are not particularly limited either, and for example, a method of heating at a temperature of about 100° C. to 180° C. for about 0.5 hours to 3 hours, etc. can be mentioned.
熱處理後之聚醯亞胺樹脂層的厚度沒有特別限定，乾燥後的厚度理想為1μm～50μm左右。The thickness of the polyimide resin layer after the heat treatment is not particularly limited, but the thickness after drying is preferably about 1 μm to 50 μm.
只要不損害本發明之效果，用於本發明之聚醯亞胺膜之聚醯亞胺樹脂組成物亦可以含有各種添加劑。該添加劑，可列舉：脫水劑、增塑劑、耐候劑、抗氧化劑、熱穩定劑、潤滑劑、抗靜電劑、增白劑、著色劑、導電劑、脫模劑、表面處理劑、黏度調節劑、無機填料、無機顏料、有機顏料等。The polyimide resin composition used in the polyimide film of the present invention may contain various additives as long as the effects of the present invention are not impaired. The additives include dehydrating agents, plasticizers, weathering agents, antioxidants, heat stabilizers, lubricants, antistatic agents, whitening agents, colorants, conductive agents, mold release agents, surface treatment agents, and viscosity modifiers. agents, inorganic fillers, inorganic pigments, organic pigments, etc.
無機填料，可列舉例如：二氧化矽填料、磷系填料、氟系填料、無機離子交換體填料等。又，二氧化矽填料亦可以使用其表面經矽烷偶聯劑等處理劑改性的二氧化矽填料。此外，無機填料的市售品，可列舉：電氣化學工業股份有限公司製的「FB-3SDC」、「SFP-20M」；Admatechs股份有限公司製的「SC-2500-SPJ」、「SC-2500-SXJ」、「SC-2500-SVJ」；科萊恩化學股份有限公司製的「Exolit OP935」；喜多村股份有限公司製的「KTL-500F」；東亞合成股份有限公司製的「IXE」等。The inorganic fillers include, for example, silica fillers, phosphorus-based fillers, fluorine-based fillers, inorganic ion exchanger fillers, and the like. In addition, the silica filler whose surface is modified by a treatment agent such as a silane coupling agent can also be used. In addition, commercially available inorganic fillers include "FB-3SDC" and "SFP-20M" manufactured by Denki Chemical Industry Co., Ltd.; "SC-2500-SPJ" and "SC-2500" manufactured by Admatechs Co., Ltd. -SXJ", "SC-2500-SVJ"; "Exolit OP935" manufactured by Clariant Chemical Co., Ltd.; "KTL-500F" manufactured by Kitamura Co., Ltd.; "IXE" manufactured by Toagosei Co., Ltd., etc.
無機顏料，可列舉：鎘紅、鎘檸檬黃、鎘黃橙、二氧化鈦、炭黑、黑色氧化鐵、黑色錯合物無機顏料等。Examples of inorganic pigments include cadmium red, cadmium tartrazine, cadmium yellow orange, titanium dioxide, carbon black, black iron oxide, black complex inorganic pigments, and the like.
有機顏料，可列舉：苯胺黑、苝黑（perylene black）、蒽醌黑、聯苯胺系黃色顏料、酞菁藍、酞菁綠等。The organic pigments include aniline black, perylene black, anthraquinone black, benzidine-based yellow pigments, phthalocyanine blue, phthalocyanine green, and the like.
本發明之聚醯亞胺樹脂組成物中之添加劑的含量沒有特別限定，相對於（A）成分100質量份（不揮發成分換算），理想為1質量份～150質量份。 ［實施例］ The content of the additive in the polyimide resin composition of the present invention is not particularly limited, but is preferably 1 to 150 parts by mass relative to 100 parts by mass of (A) component (in terms of non-volatile content). [Example]
以下，列舉實施例對本發明進行具體說明，但本發明並不限定於此等實施例。此外，只要沒有特別說明，「%」均為質量基準。Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these Examples. In addition, unless otherwise specified, "%" is the quality standard.
實施例1 在具備攪拌器、分水器、溫度計及氮氣導入管的反應容器中，加入4,4’-[丙-2,2-二基雙(1,4-伸苯基氧基)]二鄰苯二甲酸二酐（商品名「BisDA-1000」，SABIC創新塑膠日本（SABIC Innovative Plastics Japan）有限責任公司製，以下簡稱為BisDA）200.0g、碳酸二乙酯619.0g、1,2-二甲氧基乙烷132.6g及甲基環己烷132.6g，加熱至75℃。接著，緩慢添加二聚物二胺（商品名「PRIAMINE 1075」，Croda Japan股份有限公司製，以下記為PRIAMINE 1075）197.8g後，加熱至115℃，歷時10小時實施醯亞胺化反應，由此得到聚醯亞胺的溶液（不揮發成分30%）。將得到的溶液作為聚醯亞胺樹脂組成物使用（以下相同）。 Example 1 4,4'-[Propane-2,2-diylbis(1,4-phenyleneoxy)]di-o-phenylene was placed in a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen introduction tube. Diformic dianhydride (trade name "BisDA-1000", manufactured by SABIC Innovative Plastics Japan Co., Ltd., hereinafter referred to as BisDA) 200.0 g, diethyl carbonate 619.0 g, 1,2-dimethoxy 132.6 g of methyl ethane and 132.6 g of methylcyclohexane were heated to 75°C. Next, 197.8 g of dimer diamine (trade name "PRIAMINE 1075", manufactured by Croda Japan Co., Ltd., hereinafter referred to as PRIAMINE 1075) 197.8 g was slowly added, and then heated to 115° C. to carry out imidization reaction for 10 hours. This gave a solution of polyimide (non-volatile content 30%). The obtained solution was used as a polyimide resin composition (the same applies hereinafter).
實施例2～實施例18、比較例1 變更為表1所示之組成及使用量，用與實施例1相同的方法進行，分別得到不揮發成分30%的聚醯亞胺樹脂。 Example 2 to Example 18, Comparative Example 1 The composition and usage amount shown in Table 1 were changed, and the same method as in Example 1 was carried out to obtain a polyimide resin with a non-volatile content of 30%, respectively.
比較例2、比較例3 將溶劑的種類變更為表1所示之溶劑，用與實施例1相同的方法進行，但生成的聚醯胺酸不溶解，未得到聚醯亞胺。 Comparative Example 2, Comparative Example 3 The kind of solvent was changed to the solvent shown in Table 1, and the same method as in Example 1 was carried out, but the produced polyamic acid was not dissolved, and no polyimide was obtained.
＜評價樣品的製作＞ 將實施例1～實施例18及比較例1的聚醯亞胺樹脂組成物塗布在剝離紙（三榮化研（Sun A. Kaken）股份有限公司製）上，在150℃使其乾燥5分鐘，進一步繼續在170℃使其乾燥30分鐘後，剝下剝離紙，由此得到膜厚25μm的聚醯亞胺膜。將該膜進行2層積層，藉由120℃的熱壓使其熔融，製作評價用樣品。 <Preparation of evaluation samples> The polyimide resin compositions of Examples 1 to 18 and Comparative Example 1 were coated on release paper (manufactured by Sun A. Kaken Co., Ltd.), and dried at 150° C. for 5 minutes. , after further drying at 170° C. for 30 minutes, the release paper was peeled off to obtain a polyimide film with a film thickness of 25 μm. This film was laminated in two layers and melted by hot pressing at 120° C. to prepare a sample for evaluation.
＜相對介電常數及介電損耗角正切＞ 使用網路分析儀（是德科技（Keysight Technologies）公司製，裝置名：「P5003A」）及測定頻率10.124GHz的分離柱介電質共振器（QWED公司製）來測定未***任何物質的共振器本體的共振頻率及其峰的Q值。 接著，將前述評價用樣品裁斷成4cm×5cm製作試驗片後，以總厚度為100μm以上的方式重疊複數張試驗片並***共振器內後，測定***試驗片時的共振頻率及Q值。 相對介電常數（Dk）由共振器本體與***試驗片時的共振頻率之差算出，介電損耗角正切（Df）由共振器本體與***試驗片時的Q值之差及共振頻率之差算出。結果示於表1。 <Relative permittivity and dielectric loss tangent> A network analyzer (manufactured by Keysight Technologies, device name: "P5003A") and a separation-column dielectric resonator (manufactured by QWED) with a measurement frequency of 10.124 GHz were used to measure the resonator without inserting any substance. The resonant frequency of the body and the Q value of its peak. Next, the sample for evaluation was cut into 4 cm×5 cm to prepare test pieces, and after stacking a plurality of test pieces so as to have a total thickness of 100 μm or more and inserting them into the resonator, the resonance frequency and Q value when the test pieces were inserted were measured. The relative permittivity (Dk) is calculated from the difference between the resonator body and the resonance frequency when the test piece is inserted, and the dielectric loss tangent (Df) is calculated from the difference between the resonator body and the Q value when the test piece is inserted and the difference between the resonance frequencies Calculate. The results are shown in Table 1.
[表1]
表1中的縮寫如下。 ＜芳香族四羧酸酐＞ （a1）成分 ・BisDA：4,4’-[丙-2,2-二基雙(1,4-伸苯基氧基)]二鄰苯二甲酸二酐，商品名：「BisDA-1000」，SABIC創新塑膠日本有限責任公司製 ・6FDA：2,2-雙(3,4-二羧基苯基)六氟丙烷二酐，大金股份有限公司製 ＜二胺＞ （a2）成分 ・DDA：二聚物二胺，商品名：「PRIAMINE 1075」，Croda Japan股份有限公司製 ・ODA：4,4’-二胺基苯基醚，和歌山精化工業股份有限公司製 ＜有機溶劑＞ （B1）成分 ・DEC：碳酸二乙酯（沸點：126℃） ・AcOBu：乙酸正丁酯（沸點：126℃） （B2）成分 ・DMG：1,2-二甲氧基乙烷（沸點：82℃） ・MEK：甲基乙基酮（沸點：80℃） ・MIBK：甲基異丁基酮（沸點：116℃） ・MCH：甲基環己烷（沸點：101℃） ・OCT：正辛烷（沸點：126℃） ・C-800：2-甲基庚烷（沸點：116℃，商品名：「KYOWASOL C-800」，KH Neochem股份有限公司製） （其他溶劑） ・DMAc：N,N-二甲基乙醯胺（沸點：165℃） Abbreviations in Table 1 are as follows. <Aromatic tetracarboxylic anhydride> (a1) Ingredients ・BisDA: 4,4'-[Propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride, trade name: "BisDA-1000", SABIC Innovative Plastics Japanese limited liability company ・6FDA: 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, manufactured by Daikin Co., Ltd. ＜Diamine＞ (a2) Ingredients ・DDA: dimer diamine, trade name: "PRIAMINE 1075", manufactured by Croda Japan Co., Ltd. ・ODA: 4,4'-diaminophenyl ether, manufactured by Wakayama Seika Industry Co., Ltd. ＜Organic solvent＞ (B1) Ingredients ・DEC: Diethyl carbonate (boiling point: 126°C) ・AcOBu: n-butyl acetate (boiling point: 126°C) (B2) Ingredients ・DMG: 1,2-dimethoxyethane (boiling point: 82°C) ・MEK: methyl ethyl ketone (boiling point: 80°C) ・MIBK: methyl isobutyl ketone (boiling point: 116°C) ・MCH: Methylcyclohexane (boiling point: 101°C) ・OCT: n-octane (boiling point: 126°C) ・C-800: 2-methylheptane (boiling point: 116°C, trade name: "KYOWASOL C-800", manufactured by KH Neochem Co., Ltd.) (other solvents) ・DMAc: N,N-Dimethylacetamide (boiling point: 165°C)
＜接著劑組成物的製作＞ 評價例1 將實施例1的聚醯亞胺樹脂組成物100.0g（不揮發成分30.0g）、作為交聯劑之多官能環氧樹脂（商品名：「TETRAD-X」，三菱瓦斯化學股份有限公司製）0.78g（不揮發成分0.78g）、作為硬化劑之活性酯樹脂（商品名：「EPICLON HPC-8000-65T」，DIC股份有限公司製）2.67g（不揮發成分1.75g）及咪唑系環氧樹脂（商品名：「Curesol 2E4MZ-A」，四國化成工業股份有限公司製）0.008g（不揮發成分0.008g）、作為無機填料之二氧化矽（商品名：「SC-2500-SPJ」，Admatechs 股份有限公司製）32.5g（不揮發成分32.5g）以及作為有機溶劑之環戊酮62.1g混合，並充分攪拌，由此得到不揮發成分33%的接著劑組成物。 <Preparation of adhesive composition> Evaluation Example 1 100.0 g of the polyimide resin composition of Example 1 (30.0 g of non-volatile content) and a polyfunctional epoxy resin as a crosslinking agent (trade name: "TETRAD-X", manufactured by Mitsubishi Gas Chemical Co., Ltd.) 0.78 g (0.78 g of non-volatile content), 2.67 g of active ester resin (trade name: "EPICLON HPC-8000-65T", manufactured by DIC Corporation) as a hardener (1.75 g of non-volatile content), and imidazole-based epoxy resin Resin (trade name: "Curesol 2E4MZ-A", manufactured by Shikoku Chemical Industry Co., Ltd.) 0.008 g (non-volatile content 0.008 g), silica as an inorganic filler (trade name: "SC-2500-SPJ", Admatechs Co., Ltd.) 32.5 g (non-volatile content 32.5 g) and 62.1 g of cyclopentanone as an organic solvent were mixed and stirred sufficiently to obtain an adhesive composition with a non-volatile content of 33%.
評價例2～評價例4、比較評價例1 分別使用表2所示之聚醯亞胺樹脂組成物，用與評價例1相同的方法進行，分別得到不揮發成分33%的接著劑組成物。 Evaluation Example 2 to Evaluation Example 4, Comparative Evaluation Example 1 Using the polyimide resin compositions shown in Table 2, the same method as in Evaluation Example 1 was carried out to obtain adhesive compositions having a non-volatile content of 33%, respectively.
＜接著片材的製作＞ 將得到的接著劑組成物使用間隙塗布機塗布在剝離紙（三榮化研股份有限公司製）上而使乾燥後的厚度為25μm後，在150℃下使其乾燥5分鐘，得到接著片材（剝離紙／接著劑層）。 <Production of adhesive sheet> The obtained adhesive composition was coated on release paper (manufactured by Sanei Kaken Co., Ltd.) using a gap coater so that the thickness after drying was 25 μm, and then dried at 150° C. for 5 minutes to obtain an adhesive sheet. (Release paper/adhesive layer).
＜相對介電常數及介電損耗角正切的測定＞ 從前述的接著片材（剝離紙／接著劑層）上將剝離紙剝離，將接著劑層置於加壓用支撐體上，進而在接著劑層之側經由相同的加壓用支撐體藉由在壓力5MPa、180℃下加熱加壓90分鐘而使其硬化，由此製作熱硬化後的接著片材（支撐體／接著劑層／支撐體）。從該接著片材上取下加壓用的支撐體，對於接著劑層，用與前述段落相同的方法計算出相對介電常數（Dk）及介電損耗角正切（Df）。結果示於表2。 <Measurement of relative permittivity and dielectric loss tangent> The release paper is peeled off from the aforementioned adhesive sheet (release paper/adhesive layer), the adhesive layer is placed on the support for pressing, and then the adhesive layer is placed on the side of the adhesive layer through the same support for pressing by The adhesive sheet (support body/adhesive layer/support body) after thermosetting was produced by heating and pressing at a pressure of 5 MPa and 180° C. for 90 minutes to be cured. The support for pressing was removed from the adhesive sheet, and the relative permittivity (Dk) and the dielectric loss tangent (Df) were calculated for the adhesive layer in the same manner as in the previous paragraph. The results are shown in Table 2.
＜覆銅積層板的製作＞ 從前述的接著片材（剝離紙／接著劑層）上將剝離紙剝離，將其重疊在市售的電解銅箔（產品名「F2-WS」，古河電氣工業股份有限公司製）（膜厚18μm）的鏡面側上，將另一面重疊在市售的聚醯亞胺膜（商品名「Kapton 100EN」，東麗杜邦（DU PONT-TORAY）股份有限公司製，膜厚25μm，熱膨脹係數：15ppm/℃）上，製作聚醯亞胺膜-接著劑層-電解銅箔的積層體。接著，將其置於加壓用支撐體上，從上方向隔著由相同材料得到的支撐體藉由在壓力5MPa、溫度180℃下加熱加壓90分鐘而使其硬化，由此製作覆銅積層板。 <Production of copper clad laminate> The release paper was peeled off from the above-mentioned adhesive sheet (release paper/adhesive layer), and it was superimposed on a commercially available electrolytic copper foil (product name "F2-WS", manufactured by Furukawa Electric Co., Ltd.) (film thickness 18 μm) on the mirror surface side, and the other side was superimposed on a commercially available polyimide film (trade name “Kapton 100EN”, manufactured by DU PONT-TORAY Co., Ltd., film thickness 25 μm, thermal expansion coefficient: 15 ppm /°C), a laminate of polyimide film-adhesive layer-electrolytic copper foil was produced. Next, it was placed on a support body for pressing, and the support body obtained from the same material was hardened by heating and pressing at a pressure of 5 MPa and a temperature of 180° C. for 90 minutes from above, thereby producing a copper cladding. laminate.
＜接著性試驗＞ 對於前述的覆銅積層板，根據JIS C 6481（撓性印刷配線板用覆銅積層板的試驗方法），測定剝離強度（N/mm）。結果示於表2。 <Adhesion test> The peel strength (N/mm) of the above-mentioned copper-clad laminate was measured according to JIS C 6481 (Test method for copper-clad laminates for flexible printed wiring boards). The results are shown in Table 2.
＜焊接耐熱性試驗＞ 將前述的覆銅積層板在溫度23℃、濕度50%的恆溫室中放置24小時後，使銅箔側朝下，漂浮在288℃的焊浴中，確認有無發泡，並按照以下標準進行評價。結果示於表2。 （評價標準） ○：外觀沒有變化 ×：有發泡、膨脹 <Soldering heat resistance test> After placing the aforementioned copper clad laminate in a constant temperature chamber with a temperature of 23°C and a humidity of 50% for 24 hours, float the copper foil side down in a solder bath at 288°C to confirm whether there is foaming, and proceed according to the following standards Evaluation. The results are shown in Table 2. (evaluation standard) ○: No change in appearance ×: There is foaming and swelling
[表2]
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