TW201930257A - Dimer diamine composition, method for producing the same and resin film having high transparency and low degree of coloring while using dimer diamine - Google Patents

Abstract

Provided is a resin film having high transparency and low degree of coloring while using dimer diamine. A dimer diamine composition is composed mainly of dimer diamine obtained by substituting two terminal carboxylic acid groups of a dimer acid with a primary aminomethyl group or an amino group, and quantified by 1H-NMR, an aliphatic double bond is 1.0 mol% or less with respect to 1 mol of CH2 groups (-CH2-) in a primary aminomethyl group (NH2CH2-). A resin film having a thickness of 30 ≤m obtained by using this dimer diamine composition in an amount of 40 mol% or more based on the total diamine components is characterized by: (i) a transmittance of light having a wavelength of 400 nm is 70% or more, (ii) a YI value is 5 or less, and (iii) the total light transmittance (T.T.) is 90% or more.

Description

Dimer diamine composition, manufacturing method thereof, and resin film

The present invention relates to a dimer diamine composition containing a dimer diamine as a main component, a method for producing the same, and a resin film.

In recent years, with the progress of miniaturization, weight reduction, and space saving of electronic devices, flexible printed wiring boards (FPC; Flexible Printed Circuits) that are thin and light, have flexibility, and have excellent durability even after repeated bending. ) The need increases. FPC can realize three-dimensional and high-density packaging even in a limited space. Therefore, it is used in electronic devices such as hard disk drives (HDD), digital video disks (DVD), and smart phones. The use of parts such as wiring, cables, and connectors for moving parts is expanding.

In addition, due to the further advancement of higher functionality of electronic equipment, it is also necessary to cope with high frequency of transmission signals. When the transmission loss in the transmission path is high when a high-frequency signal is transmitted, disadvantages such as a loss of an electric signal or a long delay time of the signal occur. Therefore, in the future, it is also important to reduce transmission loss in FPC. Requires high-frequency FPC or adhesives.

Furthermore, as a technology related to an adhesive layer containing polyimide as a main component, it has been proposed to apply a crosslinked polyimide resin to an adhesive layer such as a coverlay film, and the crosslinked polymer The fluorene imine resin is obtained by reacting a polyfluorene imine using a diamine component containing a dimer diamine as a raw material and an amino compound having at least two primary amino groups as functional groups (for example, Patent Document 1). In addition, it has been proposed to apply a resin composition to a copper-clad laminate, which is a combination of a thermosetting resin such as polyimide and epoxy resin using dimer diamine as a diamine component, and A combination agent (for example, patent document 2).

Dimer acid is a dimerized fatty acid. It uses natural fatty acids such as soybean oil fatty acids, tall oil fatty acids, and rapeseed oil fatty acids as raw materials and refined oleic acid and linoleic acid. Acid, linolenic acid, erucic acid, etc., and obtained by performing a Diels-Alder reaction (for example, patent document 3). It is known that a polyacid compound containing a dimer acid is obtained as a fatty acid of a raw material or a mixture of fatty acids of a trimer or higher. Therefore, the commercially available dimer diamine is actually a mixture containing a monoamine, a triamine, and the like derived from a fatty acid as a raw material thereof in addition to the diamine component. In addition, in the present invention, a composition in the state of such a mixture may be expressed as a "dimer diamine composition". [Prior Art Literature]

[Patent Literature] [Patent Literature 1] Japanese Patent Laid-Open No. 2013-1730 [Patent Literature 2] Japanese Patent Laid-Open No. 2017-119361 [Patent Literature 3] Japanese Patent Laid-Open No. 2017-137375

[Problems to be Solved by the Invention] When a commercially available dimer diamine is used as a diamine component to produce a polyimide resin film, there is a problem that the transparency of the film is reduced or coloration occurs.

Therefore, an object of the present invention is to provide a resin film that uses dimer diamine, has high transparency, and has a low degree of coloration. [Technical means to solve the problem]

The present inventors conducted diligent research, and as a result, they obtained the following insight: When a polyimide using a dimer diamine composition as a diamine component to produce a resin film, the The amount of the double bond of the fatty acid, which is a raw material, affects the coloring of the resin film, and further the storage stability and the filling property between circuit wiring. Furthermore, it was found that by controlling the amount of double bonds contained in the dimer diamine composition, a resin film with high transparency and low degree of coloring can be stably produced, and the present invention has been completed.

That is, the dimer diamine composition of the present invention is a dimer diamine in which a dimer diamine obtained by substituting two terminal carboxylic acid groups of a dimer acid with a primary aminomethyl group or an amino group as a main component. The composition is characterized in that the aliphatic double bond quantified by ¹ H-nuclear magnetic resonance (NMR) is relative to the CH ₂ group (-CH ₂ -in the primary aminomethyl group (NH ₂ CH _2- )). ) 1 mol and 1.0 mol% or less.

Regarding the dimer diamine composition of the present invention, the following component (a) to component (a) are calculated as an area percentage of a chromatogram obtained by measuring the dimer diamine composition using colloidal permeation chromatography. The component (c) in c) may be 2% or less; (a) a dimer diamine; (b) the terminal carboxylic acid group of a monobasic acid compound having a carbon number in the range of 10 to 40 is substituted into a first order A monoamine compound derived from aminomethyl or amino group; (c) An amine compound obtained by substituting a terminal carboxylic acid group of a polybasic acid compound having a hydrocarbon group in the carbon number range of 41 to 80 with a primary aminomethyl group or amino group (Wherein the dimer diamine is excluded).

The method for producing a dimer diamine composition of the present invention is characterized by dimerizing a raw material of a dimer diamine in which two terminal carboxylic acid groups containing a dimer acid are substituted with a primary aminomethyl group or an amino group. The diamine composition is processed by reducing the content of the aliphatic double bond to obtain the dimer diamine composition.

The resin film of the present invention is a resin film obtained by forming a polyimide, and the polyimide contains a tetracarboxylic anhydride component and 40 mols with respect to all diamine components. % Or more of the diamine component of the dimer diamine composition is reacted, and when the thickness is 30 μm, the following conditions i) to iii) are satisfied; i) the transmittance of light with a wavelength of 400 nm 70% or more, ii) a yellow index (YI) value of 5 or less, iii) a total light transmittance (TT) of 90% or more. [Effect of the invention]

According to the dimer diamine composition of the present invention, the amount of double bonds is controlled. Therefore, by using the dimer diamine composition, it is possible to stably produce polyimide made of polyimide with high transparency and low degree of coloration. Resin film. Therefore, it is possible to stabilize the quality and improve the yield in the production of the resin film.

Embodiments of the present invention will be described in detail. The dimer diamine composition of the present embodiment is a dimer diamine in which two terminal carboxylic acid groups of a dimer acid are substituted with a primary aminomethyl group or an amino group as a main component. Regarding the dimer diamine composition, the proportion of the aliphatic double bond quantified by ¹ H-NMR is relative to the CH ₂ group (-CH _2- ) in the primary aminomethyl group (NH ₂ CH _2- ). It is 1.0 mol% or less, preferably 0.8 mol% or less. The dimer diamine composition can stably produce a resin film using polyimide by suppressing the ratio of aliphatic double bonds to 1.0 mol% or less, and having high transparency, low coloring degree, and improved visibility. Furthermore, by suppressing the ratio of the aliphatic double bond to 1.0 mol% or less, the storage stability of the resin film and the filling property between circuit wirings can also be improved. When the ratio of the aliphatic double bond exceeds 1.0 mol%, the resin film produced using dimer diamine as a raw material is colored yellow to tan, and transparency is reduced. In addition, the storage stability of the resin film and the fillability between circuit wirings are also reduced.

The dimer diamine is a liquid aliphatic diamine at normal temperature, and a polyfluorene imide obtained as a diamine component has an aliphatic chain (or alicyclic) structure. The aliphatic chain (or alicyclic) structure reduces interactions such as π-π stacking between polymer chains, improves solubility in solvents, and is difficult to generate charge migration in terms of chemical structure. Therefore, it should originally make polyfluorene Imine is nearly colorless and transparent. However, polyimide obtained from a commercially available dimer diamine composition has low transparency and is colored. In addition, as a commercially available dimer diamine composition, even if a composition having a low YI value is selected, the YI value of the polyfluorene imine obtained may not necessarily be reduced. As described above, the commercially available dimer diamine composition is a mixture containing a monoamine, a triamine, and the like derived from a fatty acid as a raw material in addition to the diamine component, and contains a rich double bond. In this embodiment, it is based on the amount of double bonds contained in the dimer diamine composition, especially the amount of aliphatic double bonds, the reduction in transparency of the resin film, the coloration, and further the storage stability or the filling property between circuit wiring Reducing the amount of fatty double bonds related to this insight. The amount of the aliphatic double bond is based on the integrated value of the ¹ H peak derived from the aliphatic double bond as seen from 4.6 ppm to 5.7 ppm using ¹ H-NMR relative to the amino group seen from 2.6 ppm to 2.9 ppm. ¹ H ratio of an integrated value of peak CH ₂ group bonded (NH ₂ CH ₂ CH ₂ in), and the obtained calculated value based on the following equation. Aliphatic double bond ratio [mol%] = (X / Y) × 100 [ herein, X is an integral value of 4.6 ppm ~ ¹ H peak of 5.7 ppm, Y is the ¹ H peak of 2.6 ppm ~ 2.9 ppm Integral value]

The commercially available dimer diamine composition contains a double bond derived from an aromatic ring in addition to the aliphatic double bond. However, in this embodiment, the proportion of the aliphatic double bond is considered and controlled. The proportion of the aromatic ring quantified by ¹ H-NMR is preferably 20 mol% or less with respect to 1 mol of the amino group.

The dimer diamine composition of the present embodiment preferably contains the following component (a) and controls the amounts of the component (b) and the component (c). Component (a) is a dimer diamine. The component (a) dimer diamine means that two terminal carboxylic acid groups (-COOH) of a dimer acid are substituted with a primary aminomethyl group (-CH ₂ -NH ₂ ) or an amino group (-NH ₂ ) Diamine. Dimer acid is a known dibasic acid obtained through the intermolecular polymerization of unsaturated fatty acids. Its industrial manufacturing process has been roughly standardized in the industry, and it uses clay catalysts to make the unsaturated 11 to 22 carbons. Obtained by dimerizing fatty acids. The industrially obtained dimer acid is a dibasic acid having a carbon number of 36 which is obtained by dimerizing an unsaturated fatty acid having a carbon number of 18 such as oleic acid, linoleic acid, and linolenic acid, and is contained depending on the degree of purification. Any amount of monomeric acid (18 carbons), trimer acid (54 carbons), and other polymerized fatty acids with 20 to 54 carbons.

The dimer diamine composition of the present embodiment can also be purified by a method such as molecular distillation of the raw material dimer diamine composition to increase the content of the dimer diamine of the component (a) to 96% by weight or more, preferably 97% by weight or more, more preferably 98% by weight or more. By setting the diamine diamine content of the component (a) to 96% by weight or more, it is possible to suppress an increase in the molecular weight distribution of the polyfluorene. Furthermore, if it is technically feasible, all (100% by weight) of the dimer diamine composition is optimally composed of the dimer diamine as the component (a).

Component (b) is a monoamine compound obtained by substituting a terminal carboxylic acid group of a monobasic acid compound having a carbon number in the range of 10 to 40 with a primary aminomethyl group or an amino group. The monobasic acid compound having a carbon number in the range of 10 to 40 is a monounsaturated fatty acid having a carbon number in the range of 10 to 20 as a raw material derived from a dimer acid, and a carbon number which is a by-product when the dimer acid is produced A mixture of monobasic acid compounds in the range of 21 to 40. Monoamine compounds are obtained by substituting the terminal carboxylic acid group of these monoacid compounds with a primary aminomethyl group or an amino group.

The component (b) monoamine compound is a component that suppresses an increase in the molecular weight of the polyfluorene imine. During the polymerization of polyamic acid or polyimide, the monofunctional amino group of the monoamine compound reacts with the terminal acid anhydride group of polyamino acid or polyimide, whereby the terminal acid anhydride group is blocked, Thereby, an increase in the molecular weight of polyamidic acid or polyimide is suppressed.

Component (c) is an amine compound obtained by substituting a terminal carboxylic acid group of a polybasic acid compound having a hydrocarbon group in the range of 41 to 80 with a primary aminomethyl or amino group (wherein the dimer diamine except). The polybasic acid compound having a hydrocarbon group having a carbon number in the range of 41 to 80 is a polybasic acid compound having a tribasic acid compound having a carbon number in the range of 41 to 80 as a by-product when a dimer acid is produced as a main component. In addition, it may contain a polymerized fatty acid other than a dimer acid having 41 to 80 carbon atoms. An amine compound is obtained by substituting the terminal carboxylic acid group of these polybasic acid compounds with a primary aminomethyl group or an amino group.

The amine compound of the component (c) is a component that promotes an increase in the molecular weight of polyimide. The trifunctional amino group derived from a trimeric acid as a main component is reacted with a terminal amino anhydride group of polyamidic acid or polyimide, and the molecular weight of polyimide sharply increases. In addition, an amine compound derived from a polymerized fatty acid other than a dimer acid having 41 to 80 carbon atoms also increases the molecular weight of polyimide and causes gelation of polyamidic acid or polyimide.

In addition, in this embodiment, the component which reduces the unsaturation by the double bond reduction process mentioned later is also contained in a component (a)-a component (c).

The dimer diamine composition can be quantified by measuring with a gel permeation chromatography (GPC) using components (a) to (c). In order to easily confirm the peak start, peak top, and peak end of each component of the dimer diamine composition, it is preferable to use acetic anhydride and pyridine for the dimer diamine. The composition processed sample used cyclohexanone as an internal standard substance. The sample thus prepared can be used to quantify each component using the area percentage of the chromatogram of GPC. The peak start and peak end of each component can be used as the minimum value of each peak curve, and the area percentage of a chromatogram can be calculated based on these minimum values.

The dimer diamine composition is preferably an area percentage of a chromatogram obtained by GPC measurement, and the component (c) is 2% or less, and more preferably 1% or less. By setting it as such a range, the aliphatic double bond in a dimer diamine composition can be reduced effectively. The component (c) may not be contained in the dimer diamine composition.

The area percentage of the chromatogram of the component (b) is preferably 3% or less, more preferably 2% or less, and still more preferably 1% or less. By setting it as such a range, the fall of the molecular weight of a polyimide can be suppressed, and also the range of the molar ratio of the tetracarboxylic anhydride component and the diamine component can be expanded. The component (b) may not be contained in the dimer diamine composition.

In addition, the total of the component (b) and the component (c) is preferably 4% or less, and preferably less than 4%. When the total of the component (b) and the component (c) is 4% or less, the aliphatic double bond in the dimer diamine composition can be effectively reduced, and the molecular weight distribution of the polyfluorene imine can be suppressed.

[Manufacturing method of dimer diamine composition] The dimer diamine composition of the present embodiment can be produced by using a raw material dimer diamine composition containing the component (a) dimer diamine. (For example, a commercially available dimer diamine composition) is subjected to a treatment such as hydrogenation, distillation, etc. (sometimes referred to as a "double bond reduction treatment") to reduce the content of the aliphatic double bond. When distillation is performed as a double bond reduction treatment, the component (b), the component (c), and the like may be simultaneously reduced. Here, the distillation for reducing the content of the aliphatic double bond is preferably a vacuum distillation, a vacuum distillation, a steam distillation, or the like. The hydrogenation for reducing the content of the aliphatic double bond is preferably performed using a catalyst such as nickel, platinum, palladium, copper, chromium, or sodium formate.

The raw material dimer diamine composition before the double bond reduction treatment can be obtained as a commercially available product, and examples thereof include PRIAMINE 1073 (trade name) manufactured by Japan Croda Japan Co., Ltd., and Japan Heda Co., Ltd. (Croda Japan) company's PRIAMINE 1074 (trade name), Croda Japan company's PRIAMINE 1075 (trade name), and so on.

[Production of polyimide] Next, a method for producing polyimide using the dimer diamine composition of the present embodiment will be described. Polyfluorene imine can be obtained by fluorinating a polyphosphonium acid of a precursor obtained by reacting a tetracarboxylic anhydride component and a diamine component.

Examples of tetracarboxylic anhydrides that can be used in the production of polyimide include 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, and Phenylbis (trimellitic acid monoester) dianhydride, 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 2, 3 ', 3,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenone Ketone tetracarboxylic dianhydride or 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 2,3', 3,4'-diphenyl ether tetracarboxylic dianhydride, bis (2 , 3-dicarboxyphenyl) ether dianhydride, 3,3 '', 4,4 ''-p-terphenyltetracarboxylic dianhydride, 2,3,3 '', 4 ''-p-terphenyl Tetracarboxylic dianhydride or 2,2 '', 3,3 ''-p-terphenyltricarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -propane dianhydride, or 2, 2-bis (3,4-dicarboxyphenyl) -propane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride or bis (3,4-dicarboxyphenyl) methane dianhydride, bis ( 2,3-dicarboxyphenyl) fluorene dianhydride or bis (3,4-dicarboxyphenyl) fluorene dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, or 1, 1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2,7,8-phenanthrene-tetracarboxylic dianhydride, 1,2,6,7-phenanthrene-tetracarboxylic Dianhydride or 1,2,9,10-phenanthrene-tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) tetra Fluoropropane dianhydride, 2,3,5,6-cyclohexane dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2 , 3,6,7-naphthalene tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic acid di Anhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride or 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3, 6,7- (or 1,4,5,8-) tetrachloronaphthalene-1,4,5,8- (or 2,3,6,7-) tetracarboxylic dianhydride, 2,3,8, 9-fluorene-tetracarboxylic dianhydride, 3,4,9,10-fluorene-tetracarboxylic dianhydride, 4,5,10,11-fluorene-tetracarboxylic dianhydride or 5,6,11,12- Hydrazone-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3, 4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 4,4'-bis (2,3-dicarboxyphenoxy) diphenylmethane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, p-phenylene Bis (trimellitic acid monoester anhydride), ethylene glycol ditrimellitic anhydride, 2,2'-bis (4- (3,4-dicarboxyphenoxy) phenyl) Hexafluoropropane dianhydride dianhydride. Among these, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, and ethylene glycol bisisocyanate are preferable from the viewpoint of producing polyimide having high transparency and low degree of coloration. Acid dianhydrides such as trimellitic anhydride and 2,2'-bis (4- (3,4-dicarboxyphenoxy) phenyl) hexafluoropropane dianhydride. In addition, when using 2,2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride or 3,3 ', 4 In the case of 4,4'-benzophenonetetracarboxylic dianhydride, there are ketone groups present in the molecular skeleton, which react with the amino group of the component (b) or the component (c) to form a C = N bond. In this case, it is preferable to obtain a polyfluorene imine having a high molecular weight.

A part or all of the diamine component can use the dimer diamine composition of this embodiment. By using the dimer diamine composition of the present embodiment at 40 mol% or more, preferably 60 mol% to 100 mol%, with respect to all diamine components, the resin obtained from polyimide can be improved. The transparency of the film reduces the degree of coloration and improves visibility. Furthermore, storage stability and filling properties between circuit wirings can also be improved. If the amount of the dimer diamine composition relative to all the diamine components is less than 40 mol%, the effect of improving the transparency of the resin film cannot be sufficiently obtained, and further, the improvement of storage stability or the improvement in circuit wiring Filling effect.

Examples of diamine components other than the dimer diamine composition that can be used in the production of polyimide include aromatic diamine compounds and aliphatic diamine compounds. Specific examples of these include 1,4-diaminobenzene (p-PDA; p-phenylenediamine), 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB) , 2,2'-n-propyl-4,4'-diaminobiphenyl (m-NPB), 4-aminophenyl-4'-aminobenzoate (APAB), 2,2-bis [4 -(3-aminophenoxy) phenyl] propane, bis [4- (3-aminophenoxy) phenyl] fluorene, bis [4- (3-aminophenoxy)] biphenyl, bis [1 -(3-aminophenoxy)] biphenyl, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (3-aminophenoxy) phenyl] ether, bis [4 -(3-aminophenoxy)] benzophenone, 9,9-bis [4- (3-aminophenoxy) phenyl] fluorene, 2,2-bis- [4- (4-aminobenzene (Oxy) phenyl] hexafluoropropane, 2,2-bis- [4- (3-aminophenoxy) phenyl] hexafluoropropane, 3,3'-dimethyl-4,4'diaminodiamine Benzene, 4,4'-methylenebis-o-toluidine, 4,4'-methylenebis-2,6-dimethylaniline, 4,4'-methylene-2,6-diethyl Aniline, 3,3'-diaminodiphenylethane, 3,3'-diaminobiphenyl, 3,3'-dimethoxybenzidine, 3,3 ''-diamino-p-terphenyl , 4,4 '-[1,4-phenylenebis (1-methylethylene)] bisaniline, 4,4'-[1,3-phenylenebis (1-methylethylene) )] Bisaniline, bis (p-aminocyclohexyl) methane, bis (p-β-amino-third butylphenyl) ether, bis (p-β-methyl-δ-aminopentyl) benzene, p- Bis (2-methyl-4-aminopentyl) benzene, p-bis (1,1-dimethyl-5-aminopentyl) benzene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,4-bis (β-amino-third butyl) toluene, 2,4-diaminotoluene, m-xylene-2,5-diamine, p-xylene-2,5-diamine, m-xylylene Methylamine, p-xylylenediamine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5-diamino-1,3,4-oxadiazole, verazine, 2'-methoxy -4,4'-diaminobenzidine aniline, 4,4'-diaminobenzidine aniline, 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene, 6 -Amino-2- (4-aminophenoxy) benzoxazole, 1,3-bis (3-aminophenoxy) benzene, 2,2'-bis (trifluoromethyl) -4,4 ' -Diaminobiphenyl, 4,4'-bis (2- (trifluoromethyl) -4-aminophenoxy) biphenyl, 2,2-bis (4- (2- (trifluoromethyl)- 4-aminophenoxy) phenyl) hexafluoropropane, 4,4'-bis (3- (trifluoromethyl) -4-aminophenoxy) biphenyl, 4,4'-bis (3- ( Trifluoromethyl) -4-aminophenoxy) biphenyl, p-bis [(2-trifluoromethyl) -4-aminophenoxy] benzene And other diamine compounds. Among these, 2,2-bis- [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9 are preferred from the viewpoint of producing polyfluorene imine with high transparency and low degree of coloration. , 9-bis [4- (3-aminophenoxy) phenyl] fluorene, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 4,4'-bis ( 2- (trifluoromethyl) -4-aminophenoxy) biphenyl, 2,2-bis (4- (2- (trifluoromethyl) -4-aminophenoxy) phenyl) hexafluoropropane 4,4'-bis (3- (trifluoromethyl) -4-aminophenoxy) biphenyl, 4,4'-bis (3- (trifluoromethyl) -4-aminophenoxy) Diamine compounds such as biphenyl and p-bis [(2-trifluoromethyl) -4-aminophenoxy] benzene.

Polyfluorene imine can be produced by reacting the tetracarboxylic acid anhydride and a diamine component in a solvent, and heating and ring-closing the polyphosphonic acid after forming the polyphosphonic acid. For example, a tetracarboxylic dianhydride and a diamine component are dissolved in an organic solvent at approximately equal moles, and the polymerization reaction is performed by stirring at a temperature in a range of 0 ° C to 100 ° C for 30 minutes to 24 hours, thereby obtaining Polyamidic acid as a precursor of polyimide. During the reaction, the reaction component is dissolved so that the produced precursor is in a range of 5% to 50% by weight in the organic solvent, preferably in a range of 10% to 40% by weight. Examples of the organic solvent used in the polymerization include N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), and N, N-diethylacetamidine. Amine, N-methyl-2-pyrrolidone (NMP), 2-butanone, dimethylsulfinium (DMSO), hexamethylphosphoramidine, N-methylcaprolactam, dimethyl sulfate , Cyclohexanone, dioxane, tetrahydrofuran, diethylene glycol diglyme, triethylene glycol dimethyl ether (triglyme), cresol and the like. These solvents may be used in combination of two or more kinds, and an aromatic hydrocarbon such as xylene and toluene may also be used in combination. In addition, the use amount of such an organic solvent is not particularly limited, and it is preferred to adjust the use amount of the polyamine solution obtained by the polymerization reaction to a use amount of about 5 to 50% by weight.

The synthesized polyamic acid is generally used advantageously as a reaction solvent solution, and can be concentrated, diluted, or replaced with other organic solvents as needed. In addition, since polyamic acid is generally excellent in solvent solubility, it is favorably used. The viscosity of the polyamic acid solution is preferably in the range of 500 cps to 100,000 cps. If it deviates from the above range, defects such as uneven thickness and streaks are likely to occur in the film during a coating operation using a coater or the like.

The method of polyimide polyimide to form polyimide is not particularly limited. For example, it can be suitably performed in the solvent at a temperature in the range of 80 ° C to 400 ° C for 1 to 24 hours. Heat treatment. The temperature may be heated under a fixed temperature condition, or the temperature may be changed in the middle of the step.

The weight average molecular weight of polyfluorene imine is preferably in a range of, for example, 10,000 to 200,000, and if it is within the range, it is easy to control the weight average molecular weight of polyfluorene. In addition, when it is used as an adhesive for FPC, for example, the weight average molecular weight of polyfluorene imine is more preferably in the range of 40,000 to 150,000. When the weight average molecular weight of the polyimide is less than 40,000, the flow resistance tends to deteriorate. On the other hand, when the weight average molecular weight of the polyimide exceeds 150,000, the viscosity is excessively increased and it is insoluble in a solvent, and there is a tendency that defects such as uneven thickness and streaks of the adhesive layer tend to occur during the coating operation.

[Resin film] The resin film is a resin film made of polyimide, which contains a tetracarboxylic anhydride component and 40 mol% or more of all diamine components, preferably 60 mol. Ear% to 100 mole% The diamine component of the dimer diamine composition of this embodiment reacts. When the thickness of the resin film of this embodiment is 30 μm, the following conditions i) to iii) are satisfied.

i) The transmittance of light with a wavelength of 400 nm is 70% or more. The transmittance of light having a wavelength of 400 nm is 70% or more, and the transparency of the resin film can be ensured. When the transmittance of light having a wavelength of 400 nm is less than 70%, the transparency is low and the visibility of the resin film is reduced.

ii) YI value is 5 or less. When the YI value is 5 or less, preferably 4 or less, the resin film can be made nearly colorless. When the YI value exceeds 5, yellow to yellow-brown coloring is enhanced, and the visibility of the resin film is reduced.

iii) The total light transmittance (T.T.) is above 90%. When the total light transmittance (T.T.) is 90% or more, white turbidity caused by reflection and scattering of light in the resin film is suppressed, and it becomes a film having excellent transparency. When the total light transmittance (T.T.) is less than 90%, the turbidity becomes high, and the transparency of the resin film decreases.

The form of the resin film of the present embodiment is not particularly limited, and may be a film (sheet), or may be laminated on, for example, a copper foil, a glass plate, a polyimide film, a polyimide film, a polyester film, or the like. The state on the substrate.

In addition, the thickness of the resin film can be appropriately set according to the purpose of use. For example, in the case of an adhesive layer applied to FPC, in order to ensure adhesion, the thickness can be set within a range of preferably 1 μm to 100 μm. It is preferably within a range of 5 μm to 50 μm.

The method for forming the resin film of the present embodiment is not particularly limited, and examples thereof include the following methods: [1] A solution of a polyamic acid is applied to a support substrate and dried, and then imidized to produce a resin. Film method (hereinafter, cast method); [2] coating and drying a polyamic acid solution on a supporting substrate, peeling the polyamic acid gel film from the supporting substrate, and performing A method for producing a resin film by imidization. In addition, when the resin film produced in the present embodiment includes a plurality of polyimide resin layers, examples of the method for producing the resin film include the following methods. [3] The support substrate is repeatedly applied multiple times. A method of polyamic acid solution drying, followed by a method of fluorimidization (hereinafter, a sequential coating method); [4] a multilayer structure in which polyamic acid is simultaneously applied to a supporting substrate by multilayer extrusion After drying, a method of sulfonimidization (hereinafter, a multilayer extrusion method) is performed. The method for applying the polyimide solution (or polyamic acid solution) to the substrate is not particularly limited, and for example, coating can be performed using a coating machine such as a corner wheel, a die, a doctor blade, and a die lip. When forming a multi-layered polyimide layer, the following method is preferred: an operation in which a polyimide solution (or a polyamic acid solution) is applied to a substrate and dried is repeated.

The resin film of this embodiment has improved storage stability or filling properties between circuit wirings, and can therefore be used in various applications such as insulating resin layers, adhesive layers, and protective layers in electronic devices and the like. The important characteristics of the dimer diamine include polyimide, which can impart low elastic modulus, softness, adhesion, and improve the dielectric properties of polyimide (low dielectric constant, low dielectric constant). Electrical loss tangent), and it was confirmed that these properties were hardly affected even when a composition having a reduced amount of aliphatic double bonds was used as the dimer diamine composition. Therefore, the resin film of the present embodiment can be preferably used for applications such as a circuit board such as an FPC, an adhesive layer in a cover film, or a bonding sheet in a multilayer circuit board. In addition, the resin film of this embodiment is excellent in transparency, has a low elastic modulus, and can suppress residual stress. Therefore, the resin film can also be used as an image display device in, for example, organic electroluminescence (EL), liquid crystal, and the like. Touch screen materials, thin film transistor (TFT) substrate materials, transparent electrode substrate materials, and light receiving devices such as thin-film solar cells are used.

[Metal-Clad Laminate] The metal-clad laminate includes an insulating resin layer and a metal layer laminated on at least one side of the insulating resin layer. In such a metal-clad laminate, the insulating resin layer has a single or multiple polyimide layers. In addition, as long as at least one layer (preferably an adhesive layer) of the polyimide layer has the same configuration as the resin film of the present embodiment, it is preferable to improve the adhesion between the insulating resin layer and the metal layer. It is preferable that the adhesion layer which contacts the metal layer among the insulating resin layers has the same structure as the resin film of this embodiment. The material of the metal layer in the metal-clad laminate is not particularly limited, and examples include copper, stainless steel, iron, nickel, beryllium, aluminum, zinc, indium, silver, gold, tin, zirconium, tantalum, titanium, lead, and magnesium , Manganese and alloys thereof. Among these, copper or a copper alloy is particularly preferred. The material of the wiring layer in the circuit board described later is also the same as that of the metal layer. As a preferable specific example of a metal-clad laminated board, a copper-clad laminated board (CCL) etc. are mentioned, for example.

The metal-clad laminate can be prepared, for example, by preparing an insulating resin film including the resin film of the present embodiment, sputtering the metal to form a seed layer, and then forming a metal layer by, for example, plating.

In addition, the metal-clad laminate can be prepared by preparing an insulating resin film including the resin film of the present embodiment and laminating a metal foil by a method such as thermocompression bonding.

Furthermore, a metal-clad laminate can be prepared by casting a polyamic acid coating solution using a diamine component on a metal foil, drying the coating solution, forming a coating film, and then performing a heat treatment to perform imidization. A polyfluorene imine layer is formed, and the diamine component contains a predetermined amount of the dimer diamine composition of the present embodiment.

[Circuit Board] The circuit board includes an insulating resin layer and a wiring layer formed on the insulating resin layer. In the circuit board of this embodiment, the insulating resin layer may have a single layer or a plurality of polyimide layers. In this case, at least one layer (preferably an adhesive layer) of the polyimide layer may have the same configuration as the resin film of the present embodiment. In addition, in order to improve the adhesion between the insulating resin layer and the wiring layer, it is preferable that the adhesive layer in contact with the wiring layer in the insulating resin layer has the same configuration as the resin film of the present embodiment.

The method for manufacturing the circuit board is not limited. For example, it may be a method of preparing a metal-clad laminate composed of an insulating resin layer and a metal layer, and etching the metal layer to form a subtractive method of wiring. The insulating resin layer includes the The resin film has a polyimide layer having the same structure. In addition, it is also possible to use a semi-additive method in which a seed layer is formed on the insulating resin layer, a resist is patterned, and a metal is patterned to form a wiring. The insulating resin layer is a semi-additive method. It contains a polyimide layer having the same structure as the resin film of the present embodiment. [Example]

Hereinafter, the present invention will be specifically described using examples, but the present invention is not limited to these examples at all. In the following examples, unless otherwise specified, various measurements and evaluations are performed in accordance with the following.

[Calculation of aliphatic double bond ratio and aromatic ring ratio] The aliphatic double bond ratio and aromatic ring ratio of the dimer diamine composition were calculated in the following order. First, about 50 μl of the dimer diamine composition was dissolved in 550 μl of Tetrahydrofuran-d8 (THF-d8) to prepare a sample. The prepared sample was subjected to liquid ¹ H-NMR measurement at room temperature using an FT-NMR apparatus (JNM-ECA400 manufactured by Japan Electron Optics Laboratory (JEOL)). The saw in 4.6 ppm ~ 5.7 ppm originating from the aliphatic double integration value by ¹ H relative to the peak originating from a direct bond seen in 2.6 ppm ~ 2.9 ppm at the junction of CH ₂ NH ₂ group of the group The ratio of the integrated value of the ¹ H peak to the integrated value of the ¹ H peak derived from the aromatic ring seen at 6.6 ppm to 7.2 ppm is derived from the direct bonding to NH as seen at 2.6 ppm to 2.9 ppm. The ratio of the integrated value of the ¹ H peak of the ₂ -group CH ₂ group was calculated as the ratio of the aliphatic double bond and the proportion of the aromatic ring as shown in the following formula. Proportion of aliphatic double bond [mol%] = (X / Y) × 100 Proportion of aromatic ring [mol%] = (Z / Y) × 100 [Here, X is a ¹ H peak value from 4.6 ppm to 5.7 ppm integration value, Y is a ¹ H integral value of the peak 2.6 ppm ~ 2.9 ppm is, Z is a (derived from an aromatic ring) ¹ H integral value of the peak 6.6 ppm ~ 7.2 ppm in]

[Calculation of Area Percentage of GPC and Chromatogram] (a) Dimer diamine; (b) Substituting the terminal carboxylic acid group of a monobasic acid compound having a carbon number in the range of 10 to 40 with a primary aminomethyl or amino group The obtained monoamine compound; (c) an amine compound obtained by substituting a terminal carboxylic acid group of a polybasic acid compound having a hydrocarbon group in a carbon number range of 41 to 80 with a primary aminomethyl group or an amino group (wherein the Except dimer diamine).

[Calculation of Area Percentage of GPC and Chromatogram] About GPC, 20 mg of a dimer diamine composition was added to 200 mg of a pretreated diamine using 200 μL of acetic anhydride, 200 μL of pyridine, and 2 mL of THF. The solution was diluted with 10 mL of THF (containing 1000 ppm of cyclohexanone) to prepare a sample. For the prepared samples, the trade name manufactured by Tosoh Co., Ltd. was used: HLC-8220 GPC with a column of TSK-gel G2000HXL, G1000HXL, G1000HXL, a flow rate of 1 mL / min, and the column (oven) temperature. The measurement was performed under the conditions of 40 ° C and an injection volume of 50 μL. In addition, cyclohexanone is processed as a standard substance in order to correct the elution time.

At this time, the peak top of the cyclohexanone main peak was adjusted from a retention time of 27 minutes to 31 minutes, and the peak peak to peak end of the cyclohexanone main peak was adjusted for 2 minutes. In addition, the peak top of the main peak except the peak of cyclohexanone is changed from 18 minutes to 19 minutes, and the peak of the main peak except the peak of cyclohexanone is changed from 2 minutes to the end of the peak. Each component (a) to component (c) was detected under the conditions of 4 minutes and 30 seconds; (a) the component represented by the main peak; (b) the minimum value of the time side with the late retention time in the main peak was used as a reference, The component indicated by the GPC peak detected at a later time; (c) The component indicated by the GPC peak detected at an earlier time based on the minimum value of the time side with the earlier retention time in the main peak.

[Calculation of light transmittance (400 nm transmittance), b *, YI] The light transmittance (400 nm transmittance), b *, and YI of the dimer diamine composition are UV-3600 Plus manufactured by Shimadzu Corporation Ultraviolet-visible-near infrared spectrophotometer (UV-VIS-NIR SPECTROPHOTOMETER) and quartz standard groove with 1 cm optical path length, using xylene as a control (blank) and according to Japanese Industrial Standards (JIS) Z 8722 Determination. The light transmittance (400 nm transmittance), b *, and YI of the film were measured using a UV-3600 Plus UV-visible-near infrared spectrophotometer (UV-VIS-NIR SPECTROPHOTOMETER) manufactured by Shimadzu Corporation and measured according to JIS Z 8722 .

[Calculation of total light transmittance (TT), HAZE (turbidity)] The total light transmittance (TT), HAZE (turbidity) of the film is a haze meter (HAZE METER) NDH5000 manufactured by Nippon Denshoku and is based on JIS K 7136 was determined.

[Measurement of weight average molecular weight (Mw) of polyimide] The weight average molecular weight was measured using a colloidal permeation chromatography (using HLC-8220GPC manufactured by Tosoh Corporation). Polystyrene was used as the standard material, and tetrahydrofuran was used as the developing solvent.

The abbreviations used in this example represent the following compounds. In addition, "%" of a component (b) and a component (c) shows the area percentage of the chromatogram in GPC measurement. BTDA: 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride

[DDA1 ～ DDA5] DDA1: Distilled and refined by trade name: PRIAMINE 1075 manufactured by Croda Japan Co., Ltd. (component (a): 96.1% by weight, component (b) : 2.4%, ingredient (c): 1.5%) DDA2: Distilled and refined by trade name: PRIAMINE 1075 manufactured by Croda Japan Co., Ltd. (ingredient (a): 97.8 % By weight, ingredient (b): 0.3%, ingredient (c): 1.9%) DDA3: Distilled and refined by trade name: PRIAMINE 1075 manufactured by Croda Japan Co., Ltd. (Ingredients (a): 98.5% by weight, ingredients (b): 0.2%, ingredients (c): 1.3%) DDA4: Trade name manufactured by Croda Japan Co., Ltd .: PRIAMINE 1075 Distilled and refined (component (a): 98.8% by weight, component (b): 0.2%, component (c): 1.0%) DDA5: Trade name manufactured by Croda Japan Co., Ltd. : Purified by PRIAMINE 1075 Fraction (a): 98.9% by weight, component (b): 0.2%, component (c): 0.9%) NMP: N-methyl-2-pyrrolidone Further, distillation purification is performed by vacuum distillation.

The calculation of the aliphatic double bond ratio and aromatic ring ratio, light transmittance (400 nm transmittance), and b * and YI of DDA1 to DDA5 are as shown in Table 1 below.

[Table 1]

[Example 1] A 1000 ml separable flask was charged with 56.22 g of BTDA (0.174 mol), 93.78 g of DDA1 (0.176 mol), 210 g of NMP, and 140 g of xylene at 40 ° C. Mix thoroughly for 1 hour to prepare a polyamine solution. The polyfluorenic acid solution was heated to 190 ° C, heated and stirred for 4 hours, and 140 g of xylene was added to prepare polyimide solution 1 (solid content: 30% by weight, weight-average molecular weight) at which the imidization was completed. : 63,300). The obtained polyethyleneimine solution 1 was coated on one side of a polyethylene terephthalate (PET) film subjected to release treatment, and dried at 80 ° C for 15 minutes to prepare a resin film. 1 (thickness: 22 μm). Table 2 shows the thickness, light transmittance (400 nm transmittance), b *, YI, total light transmittance (T.T.), and HAZE (turbidity) of the resin film 1.

[Example 2 to Example 5] A polyfluorene imine solution 2 to a polyfluorene imine solution 5 was prepared in the same manner as in Example 1 except that DDA shown in Table 1 was used. Thickness, light transmittance (400 nm transmittance), b *, YI, total light transmittance (TT) of the resin films 2 to 5 obtained by using the polyfluorene imine solution 2 to the polyfluorene imine solution 5 And HAZE (turbidity) are shown in Table 2.

[Table 2]

[DDA6 ～ DDA8] DDA6: manufactured by Croda Japan Co., Ltd., trade name: PRIAMINE 1075 (ingredient (a): 97.0% by weight, ingredient (b): 0.7%, ingredient (c ): 2.3%) DDA7: manufactured by Croda Japan Co., Ltd., trade name: PRIAMINE 1075 (ingredient (a): 95.8% by weight, ingredient (b): 0.2%, ingredient (c ): 4.0%) DDA8: manufactured by Croda Japan Co., Ltd., trade name: PRIAMINE 1075 (ingredient (a): 97.3% by weight, ingredient (b): 0.2%, ingredient (c ): 2.5%)

If the ratio of the aliphatic double bond and the aromatic ring, the light transmittance (400 nm transmittance), and b * and YI of DDA6 to DDA8 are calculated, they are as shown in Table 3 below.

[table 3]

[Comparative Example 1 to Comparative Example 3] Except that DDA6 to DDA8 shown in Table 3 were used, polyimide solution 6 to polyimide solution 8 were prepared in the same manner as in Example 1. Thickness, light transmittance (400 nm transmittance), b *, YI, total light transmittance (TT) of the resin films 6 to 8 obtained using the polyfluorene imine solution 6 to the polyfluorene imine solution 8 And HAZE (turbidity) are shown in Table 4.

[Table 4]

From Tables 1 and 2, and comparisons with Tables 3 and 4, it was confirmed that in Examples 1 to 5, it was possible to obtain transparency by using a dimer diamine composition having a reduced proportion of aliphatic double bonds. Polyimide resin film with high properties, low coloring, and good visibility. On the other hand, in Comparative Examples 1 to 3 using a diamine component that does not control the proportion of aliphatic double bonds, although the YI value of the raw material itself is low, it is a resin compared to Examples 1 to 5. The result was that the film had low transparency, strong coloring, and poor visibility.

As mentioned above, although embodiment of this invention was described in detail for the purpose of illustration, this invention is not limited to the said embodiment.

no

no

Claims (4)

A dimer diamine composition, characterized in that it is a dimer having a dimer diamine obtained by substituting two terminal carboxylic acid groups of a dimer acid with a primary aminomethyl group or an amino group as a main component. A diamine composition and an aliphatic double bond quantified by ¹ H-NMR with respect to 1 mole of the CH ₂ group in the primary aminomethyl NH ₂ CH ₂ -is 1.0 mole% or less. The dimer diamine composition according to item 1 of the scope of the patent application, wherein: the area percentage of a chromatogram obtained by measuring the dimer diamine composition using colloidal permeation chromatography is as follows: The component (c) of the components (a) to (c) is 2% or less; (a) a dimer diamine; (b) a monobasic acid compound having a carbon number in the range of 10 to 40 Monoamine compound obtained by substituting a terminal carboxylic acid group for a primary aminomethyl group or an amino group; (c) Substituting a terminal carboxylic acid group for a polycarboxylic acid compound having a hydrocarbon group having a carbon number in the range of 41 to 80 to a primary aminomethyl group Or an amine compound derived from an amino group, wherein the dimer diamine is excluded. A method for producing a dimer diamine composition, characterized in that it is the method for producing a dimer diamine composition as described in item 1 or 2 of the scope of patent application, and The dimer diamine composition, which is a raw material of a dimer diamine in which two terminal carboxylic acid groups are substituted with a primary aminomethyl group or an amino group, is treated to reduce the content of an aliphatic double bond, thereby obtaining the dimer. Polymer diamine composition. A resin film characterized in that it is a resin film obtained by forming a polyimide, and the polyimide contains a tetracarboxylic anhydride component and 40 moles with respect to all diamine components. The diamine component of the dimer diamine composition described in item 1 or 2 of the patent application range is reacted, and the following conditions i) to iii) are satisfied when the thickness is 30 μm I) the transmittance of light with a wavelength of 400 nm is 70% or more, ii) the yellow index value is 5 or less, and iii) the total light transmittance TT is 90% or more.