TW202022006A - Adhesive composition using imide bond-containing resin and phosphorous compound - Google Patents

Abstract

無。

Description

Adhesive composition using resin with imine bond and phosphorus compound

The present invention relates to an adhesive composition using a resin having an imine bond and a phosphorus compound, and to adhesive films, covering films, and copper-clad laminates using the aforementioned adhesive composition. laminate), and flexible printed wiring boards.

Flexible printed wiring boards are widely used in electronic equipment parts that require flexibility and space saving, such as: liquid crystal displays, plasma displays and other display device substrates, mobile phones, digital cameras, handheld game consoles, etc. Relay cables, operation switch boards, etc., and further expansion of applications is expected.

Adhesives used in flexible printed wiring boards are used in adhesive films, cover films, copper-clad laminates and other parts that constitute flexible wiring boards. Adhesion, heat resistance, and flame retardancy are required , Insulation reliability.

With the lighter, thinner, shorter and smaller electronic devices in recent years, flexible printed wiring boards have developed higher wiring density. In order to achieve further high-density wiring, it is necessary to reduce the space between the circuit and the circuit. The adhesive used in the flexible printed wiring board requires a further improvement in insulation reliability.

As the adhesive used in flexible printed wiring boards, epoxy resins, acrylic resins, urethane resins, etc. have been used in the past, but they are heat-resistant in terms of high-density and lead-free solders that correspond to wiring in recent years. Insufficient performance, as a heat-resistant adhesive to replace them, some people have explored polyimide resins.

Furthermore, in order to impart flame retardancy to the adhesive used in the flexible printed wiring board, a method of blending a phosphorus compound that does not contain a halogen element such as bromine is widely used. From the viewpoints of heat resistance, flame retardancy, and compatibility, among them, phosphinic acid derivatives having a chemical structure represented by the general formula (4) (commonly referred to as DOP) are widely used.

As a specific example of the aforementioned phosphinic acid derivative, for example, use of 9,10-dihydro-9-oxa-10-phosphinphenanthrene-10-oxide represented by chemical formula (5) and chemical formula (6) Shown as 9,10-dihydro-10-benzyl-9-oxa-10-phosphinphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H represented by chemical formula (7) -9-oxa-10-phosphinphenanthrene-10-oxide and other methods (for example, refer to Patent Documents 1 and 2).

[Prior technical literature] [Patent Literature] [Patent Document 1] Japanese Patent No. 5278785 [Patent Document 2] JP 2011-148862 A

[Problems to be solved by the invention]

However, the 9,10-dihydro-9-oxa-10-phosphinphenanthrene-10-oxide represented by the chemical formula (5) has a low thermal weight loss temperature due to its small molecular weight. If a part of it is not hardened and remains, there will be The problem of reduced heat resistance. In addition, the 9,10-dihydro-10-benzyl-9-oxa-10-phosphinphenanthrene-10-oxide represented by the chemical formula (6) has a relatively small molecular weight and a large plasticizing effect. It is easy to seep under high temperature and high humidity environment and reduce the reliability of insulation. Furthermore, the 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphinphenanthrene-10-oxide represented by the chemical formula (7) has low solubility in the solvent, so it has The problem of reduced handling.

The present invention was completed in order to solve the above-mentioned problems of the prior art, and its purpose is to provide an adhesive composition which has excellent adhesiveness, heat resistance, flame resistance, handling properties, and high insulation reliability. [Means to solve the problem]

In order to achieve the above-mentioned object, the present inventors have intensively studied, and as a result, they have achieved the present invention by combining a resin having an imine bond and a specific phosphorus compound.

That is, the present invention is composed of the following configurations.

通式(1)中的n為2～6之整數，多個X分別獨立為CH₂ 或O。An adhesive composition characterized by containing a resin with an imine bond and a phosphorus compound represented by the general formula (1),

In the general formula (1), n is an integer of 2 to 6, and a plurality of Xs are independently CH ₂ or O.

通式(2)中的X為CH₂ 或O，

通式(3)中的X為CH₂ 或O。The phosphorus compound represented by the general formula (1) is preferably the phosphorus compound represented by the general formula (2) and/or the phosphorus compound represented by the general formula (3),

X in the general formula (2) is CH ₂ or O,

X in the general formula (3) is CH ₂ or O.

The aforementioned resin having an imine bond is based on polyimide resin, polyimide imide resin, polyether imide resin, polyether ether ketone resin, polyester imine resin or polycarbonate imine Resin is preferred. In addition, as the copolymerization component of the resin having an amide bond, a modified acrylonitrile butadiene rubber containing trimellitic anhydride or both terminal carboxyl groups is preferred.

It is preferable to further contain an epoxy resin, and the properties of the aforementioned epoxy resin are liquid at 25°C, and it is preferable to have two or more epoxy groups in one molecule.

The adhesive composition described in any of the foregoing is characterized by being used for printed wiring boards. An adhesive film characterized by using the aforementioned adhesive composition. A cover film or copper-clad laminated board, which is characterized by using the aforementioned adhesive film. A flexible printed wiring board characterized by using the aforementioned cover film or copper-clad laminate. [Effects of Invention]

According to the present invention, by combining a resin having an imine bond and a specific phosphorus compound, an adhesive composition with excellent adhesiveness, heat resistance, flame resistance, handling properties, and further high insulation reliability can be obtained. And the adhesive film, cover film, copper-clad laminate, and flexible printed wiring board using it.

>Resin with imine bond> The resin having an amide bond used in the adhesive composition of the present invention is one having more than one amide bond in the repeating unit of the resin, for example: polyimide resin, polyamide bond Imine resin, polyether imine resin, polyether ether ketone resin, polyester imine resin, polycarbonate imine resin, etc. It is preferable that the amide bond has two or more in the repeating unit of the resin. The resin system having an imine bond preferably has an acid component and a diisocyanate component or a diamine component as a copolymer component. Hereinafter, the diisocyanate component or the diamine component is also collectively referred to as an amine component. The acid component may be any one of an acid component (aromatic acid component) having an aromatic ring, an aliphatic acid component, or an alicyclic acid component, but is preferably a polycarboxylic acid component having an aromatic ring. In addition, the amine component (diisocyanate component or diamine component) may be any of an amine component having an aromatic ring, an aliphatic amine component, or an alicyclic amine component, but it is preferably an amine component having an aromatic ring . That is, it is preferable to consist of the structural unit derived from the polycarboxylic acid component which has an aromatic ring, and the structural unit derived from the diisocyanate component which has an aromatic ring, or the diamine component which has an aromatic ring.

The resin having an imine bond used in the adhesive composition of the present invention preferably has a carboxyl group or an acid anhydride group as a reactive functional group. The acid value of the resin having an imine bond is preferably at least 5 mgKOH/g, more preferably at least 10 mgKOH/g, and still more preferably at least 20 mgKOH/g. It is more preferably 150 mgKOH/g or less, more preferably 120 mgKOH/g or less, and still more preferably 100 mgKOH/g or less. By setting it within the above range, the number of cross-linking points with epoxy resin and hardener will increase, and the cross-linking density of the thermally cured coating film will increase, and the heat resistance can be improved.

As the acid component of the resin having an imine bond of the present invention, it is preferable to use a polycarboxylic acid component having an aromatic ring. As the aromatic polycarboxylic acid component, an aromatic polycarboxylic acid anhydride is preferable, and specifically, it is more preferable to use trimellitic anhydride (TMA). By using trimellitic anhydride, in addition to the imine bond, amide bond can also be formed, which can improve the solvent solubility of the resin. The trimellitic anhydride is preferably 30 mol% or more when the total acid component is 100 mol%, more preferably 40 mol% or more, and still more preferably 50 mol% or more. Moreover, the upper limit is not limited, and 100 mol% does not matter, but it is preferably 90 mol% or less, more preferably 80 mol% or less, and still more preferably 70 mol% or less.

Examples of polycarboxylic acid components having aromatic rings other than trimellitic anhydride include: pyromellitic dianhydride (PMDA), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 3 ,3',4,4'-Biphenyltetracarboxylic dianhydride (BPDA), ethylene glycol ditrimellitic anhydride (TMEG), propylene glycol ditrimellitic anhydride, 1,4-butanediol ditrimellitic anhydride , Hexanediol bistrimellitic anhydride, polyethylene glycol bistrimellitic anhydride, polypropylene glycol bistrimellitic anhydride and other olefin-based glycols bistrimellitic anhydride, 1,2,5,6-naphthalenetetracarboxylic acid Anhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 3,3',4 ,4'-Diphenylsulfonic acid tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis( 2,3- or 3,4-dicarboxyphenyl)malonic anhydride, 2,2-bis(2,3- or 3,4-dicarboxyphenyl)malonic anhydride, 2,2-bis(4- (2,3- or 3,4-dicarboxyphenoxy)phenyl]malonic anhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis[4-(2,3 -Or 3,4-dicarboxyphenoxy)phenyl]malonic anhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane Dianhydride and so on. These can be used singly, or they can be used in combination.

As other acid components, aliphatic or alicyclic anhydrides, aromatic, aliphatic or alicyclic dicarboxylic acids can be used. For example, it is possible to use: hydrogenation of any of the ingredients listed in the preceding paragraph. Specific examples include: 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, meso-butane-1,2,3,4-tetra Formic acid dianhydride, pentane-1,2,4,5-tetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohex-1-ene-2,3,5,6 -Tetracarboxylic dianhydride, 3-ethylcyclohex-1-ene-3-(1,2), 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexane-3-( 1,2),5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohex-1-ene-3-(1,2),5,6-tetracarboxylic dianhydride, 1-ethyl Cyclohexane-1-(1,2),3,4-tetracarboxylic dianhydride, 1-propylcyclohexane-1-(2,3),3,4-tetracarboxylic dianhydride, 1,3 -Dipropylcyclohexane-1-(2,3),3-(2,3)-tetracarboxylic dianhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride, bicyclo[ 2.2.1]Heptane-2,3,5,6-tetracarboxylic dianhydride, 1-propylcyclohexane-1-(2,3),3,4-tetracarboxylic dianhydride, 1,3-di Propylcyclohexane-1-(2,3),3-(2,3)-tetracarboxylic dianhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride, bicyclo[2.2. 1]Heptane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7- Ene-2,3,5,6-tetracarboxylic dianhydride, cyclohexane dicarboxylic acid, etc. As aromatic dicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, oxydibenzoic acid, stilbene dicarboxylic acid, etc. are mentioned, for example. As aliphatic dicarboxylic acids, for example, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, eicosanedioic acid, 2-methyl Alkyl succinic acid, 2-methyl adipic acid, 3-methyl adipic acid, 3-methyl pentane dicarboxylic acid, 2-methyl octane dicarboxylic acid, 3,8-dimethyl decane dicarboxylic acid , 3,7-dimethyldecanedicarboxylic acid, 9,12-dimethyleicosandioic acid, fumaric acid, maleic acid, etc. These can be used singly, or they can be used in combination. In consideration of heat resistance, adhesion, solubility, cost-effectiveness, etc., sebacic acid, 1,4-cyclohexanedicarboxylic acid, or isophthalic acid is preferable, and sebacic acid is more preferable. When these ingredients are used, from the viewpoint of the heat resistance and flame retardancy of the resulting resin with an imine bond, when the total acid component is set to 100 mol%, it is more than 5 mol%. Preferably, it is more preferably 10 mol% or more, and still more preferably 20 mol% or more. Moreover, 60 mol% or less is preferable, 50 mol% or less is more preferable, and 45 mol% or less is still more preferable.

As the amine component (diisocyanate component or diamine component) used in the present invention, an amine component (aromatic diisocyanate or aromatic diamine) having an aromatic ring is preferred. As the diisocyanate having an aromatic ring, for example, diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,2'- or 3,3'- or 4,2'-or 4,3'-or 5,2'-or 5,3'-or 6,2'-or 6,3'-dimethyldiphenylmethane-2,4'-diisocyanate , 3,2'-or 3,3'-or 4,2'-or 4,3'-or 5,2'-or 5,3'-or 6,2'-or 6,3'-diethyl Diphenylmethane-2,4'-diisocyanate, 3,2'-or 3,3'-or 4,2'-or 4,3'-or 5,2'-or 5,3'-or 6,2'-or 6,3'-dimethoxydiphenylmethane-2,4'-diisocyanate, diphenylmethane-3,3'-diisocyanate, diphenylmethane-3,4' -Diisocyanate, diphenyl ether-4,4'-diisocyanate, benzophenone-4,4'-diisocyanate, diphenylene-4,4'-diisocyanate, 2,4-diisocyanate Toluene, 2,6-toluene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, naphthalene-2,6-diisocyanate, 4,4'-[2,2bis( 4-phenoxyphenyl)propane)diisocyanate, 3,3'-or 2,2'-dimethylbiphenyl-4,4'-diisocyanate, 3,3'-or 2,2'-diisocyanate Ethyl biphenyl-4,4'-diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, 3,3'-diethoxybiphenyl-4,4'- Diisocyanate, etc. Examples of the diamine component having an aromatic ring include diamines corresponding to these diisocyanates. These can be used singly, or they can be used in combination. Among them, diphenylmethane-4,4'-diisocyanate is preferred.

For the amine component having an aromatic ring, when the total amine component is set to 100 mol%, 80 mol% or more is preferable, more preferably 90 mol% or more, and more preferably 95 mol% or more, 100 mol% The ear% does not matter. By setting it in the above range, a resin having an amide bond excellent in adhesiveness and heat resistance can be obtained. As the amine component, the diisocyanate component having an aromatic ring may be used alone, the diamine component having an aromatic ring may be used alone, or they may be used in combination. Among them, it is preferable to use the diisocyanate component having an aromatic ring alone.

In the range that does not impair the effect of the present invention, aliphatic amine components (aliphatic diisocyanate or aliphatic diamine) or alicyclic amine components (alicyclic diisocyanate or alicyclic diamine) can be used as other amines ingredient. For example, a diisocyanate or a diamine obtained by hydrogenating any of the components listed in the preceding paragraph can be used. Specific examples can also be: isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, ethyl diisocyanate Ester, propyl diisocyanate, hexamethyl diisocyanate and corresponding diamines. These can be used singly, or they can be used in combination. From the viewpoint of the heat resistance and flame retardancy of the obtained resin with imidine bond, when the total amine component is set to 100 mol%, 20 mol% or less is preferable for these components, and more preferably It is 10 mol% or less, more preferably 5 mol% or less, and it does not matter if it is 0 mol%.

The resin with the imine bond of the present invention can increase the reaction point with epoxy resin and improve the heat resistance of the resulting adhesive composition within the range that does not impair the effect of the present invention. The copolymerization has 3 Compounds with more than one functional group. Examples include: polyfunctional carboxylic acids such as trimesic acid, dicarboxylic acids having hydroxyl groups such as 5-hydroxyisophthalic acid, dicarboxylic acids having amino groups such as 5-aminoisophthalic acid, glycerin, polyglycerin Those having 3 or more hydroxyl groups, and those having 3 or more amino groups such as ginseng (2-aminoethyl)amine. From the standpoint of heat resistance, among these, polyfunctional carboxylic acids such as trimesic acid are preferred. When the total acid content is set to 100 mol%, 10 mol% or less is more Preferably, 5 mol% or less is more preferable. If it is more than 10 mol%, there is a possibility of gelation during polymerization or formation of insoluble matter.

The resin with imine bond of the present invention can copolymerize two terminal carboxyl groups modified acrylonitrile butadiene rubber, polyester diol, polyether diol, polycarbonate diol, dimer acid, hydrogenated dimer Acid, dimer acid diol, two terminal carboxyl modified polysiloxane, two terminal anhydride modified polysiloxane, two terminal carboxyl modified polybutadiene, two terminal carboxyl modified hydrogenated polybutadiene , Polybutadienediol, hydrogenated polybutadienediol and other soft components are used as flexibility and adhesiveness imparting components. From the viewpoint of flexibility and adhesion, among these, acrylonitrile butadiene rubber modified with carboxyl groups at both ends is preferred. When using these soft components, when the total resin solid content is 100% by mass, 10% by mass or more is preferable, and 20% by mass or more is more preferable. In addition, 60% by mass or less is preferable, and 50% by mass or less is more preferable. By setting it within the above range, the effects of adhesion, heat resistance, and flame retardancy can be imparted to the resin without compromising flexibility.

The resin having an imine bond of the present invention can be produced by the following well-known methods: a method of producing an acid component and a diisocyanate component (isocyanate method); or reacting an acid component and a diamine component to form an amide After acid, the method of closing the ring (direct method); or the method of reacting a compound with acid anhydride and chlorine with diamine (the chlorine method), etc. Industrially, the isocyanate method is advantageous.

The following is a description of the production method of resins with imidine bonds based on the representative isocyanate method, but by using the corresponding amine, acid, and chlorine, the above-mentioned direct method and chlorine method can also be produced in the same way. Resin with imine bond.

The polymerization reaction of the resin having an imine bond of the present invention can be carried out by stirring the acid component and the diisocyanate component in a solvent while heating to 60°C to 200°C, as known conventionally. At this time, the molar ratio of the acid component/diisocyanate component is preferably in the range of 85/100 to 100/100. In addition, generally, the content of the acid component and the diisocyanate component in the resin having an imine bond is the same as the ratio of the respective components during polymerization. In addition, in order to promote the reaction, use: alkali metals such as sodium fluoride, potassium fluoride, sodium methoxide, triethylenediamine, triethylamine, 1,8-diazebicyclo[5,4,0]- Amines such as 7-undecene, 1,5-diazebicyclo[4,3,0]-5-nonene, and catalysts such as dibutyltin dilaurate. If these catalysts are too small, the effect of the catalyst cannot be obtained. If they are too large, side reactions may occur. Therefore, the number of moles of the acid component or the isocyanate component is more than 100% for use. 0.01-5 mol% is preferably, and more preferably 0.1-3 mol%.

The resin having an imidine bond preferably has a molecular weight equivalent to a logarithmic viscosity of 0.1 to 0.8 (dl/g) at 30°C, more preferably a logarithm equivalent to 0.2 to 0.7 (dl/g) The molecular weight of the viscosity is more preferably a molecular weight corresponding to the logarithmic viscosity of 0.25 to 0.65 (dl/g). By setting in the above range, excellent adhesiveness and heat resistance can be expressed.

The glass transition temperature of the resin having an imine bond is preferably 80°C or higher, more preferably 100°C or higher, and still more preferably 120°C or higher. Furthermore, the upper limit is not particularly limited, but 300°C or lower is preferable, 290°C or lower is more preferable, and 285°C or lower is still more preferable. By setting in the above range, excellent adhesiveness and heat resistance can be expressed.

As a solvent that can be used for the polymerization of the resin having an imine bond of the present invention, for example, N-methyl-2-pyrrolidone, γ-butyrolactone, dimethylimidazolidone, dimethylene Dimethyl acetamide, dimethyl acetamide, cyclohexanone, cyclopentanone, etc., in terms of low boiling point and good polymerization efficiency, among them, dimethyl acetamide is the more good. In addition, after polymerization, the solvent used in the polymerization or other low boiling point solvents can be used to dilute to adjust the concentration of non-volatile components and the viscosity of the solution.

Examples of low boiling point solvents include aromatic solvents such as toluene and xylene, aliphatic solvents such as hexane, heptane, and octane, alcoholic solvents such as methanol, ethanol, propanol, butanol, and isopropanol, Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone and other ketone solvents, diethyl ether, tetrahydrofuran and other ether solvents, ethyl acetate, butyl acetate, isobutyl acetate And other ester solvents.

The content of the resin having an imine bond in the non-volatile component of the adhesive composition of the present invention is preferably 40% by mass or more, more preferably 45% by mass or more, and still more preferably 50% by mass or more. In addition, 90% by mass or less is preferable, 80% by mass or less is more preferable, and 70% by mass or less is still more preferable. By setting in the above range, the excellent adhesiveness and heat resistance of the adhesive composition can be exhibited.

>Phosphorus compound represented by general formula (1)> The adhesive composition of the present invention contains a phosphorus compound represented by general formula (1) (hereinafter also referred to as a phosphorus compound of general formula (1)). By containing the phosphorus compound of the general formula (1), an adhesive composition with excellent adhesiveness, heat resistance, flame resistance and insulation reliability can be obtained. In the general formula (1), n is an integer of 2-6, preferably an integer of 2-5, more preferably an integer of 2-4, still more preferably 2 or 3, particularly preferably 2. The position of the substituent when n is 2 is not particularly limited, and it may be any of the 1, 2 (ortho), 1, 3 (met), or 1, 4 (para) positions, preferably 1,3 digits (between position) or 1,4 digits (pair position). The position of the substituent when n is 3 is not particularly limited, and it can be any of positions 1, 2, 3, 1, 2, 4 or 1, 3, and 5, and the position of the substituent when n is 4 It is not particularly limited, and may be any of 1, 2, 3, 4, 1, 2, 3, 5, or 1, 2, 4, and 5. Among them, n is 2 and the position of the substituent is 1,3 (meta) or 1,4 (para). Multiple Xs are independently "*-CH ₂ -*" or "*-O-*" (* is directly bonded to the position of the aromatic ring and the phosphorus atom of the general formula (1), and is only represented as CH ₂ or O). It is preferable that at least one of the plurality of X is O, more preferably two or more are O, still more preferably three or more are O, and particularly preferably all X are O. The phosphorus compound of the general formula (1) may be a single compound or a mixture of multiple compounds with different substituents. The phosphorus compound of the general formula (1) has a relatively large molecular weight and a small plasticizing effect, so it will not bleed out in a high temperature and high humidity environment and can exhibit excellent insulation reliability.

The content of the phosphorus compound of the general formula (1) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 15 parts by mass relative to 100 parts by mass of the resin having an imine bond Above, it is particularly preferably 20 parts by mass or more. Furthermore, 100 parts by mass or less is preferable, 90 parts by mass or less is more preferable, 80 parts by mass or less is still more preferable, and 70 parts by mass or less is particularly preferable. By setting in the above range, excellent adhesion, heat resistance, flame retardancy and insulation reliability can be exhibited.

As the phosphorus compound of the general formula (1), a phosphorus compound having the structure shown in the chemical formula (8) and/or chemical formula (9) (hereinafter also referred to as the phosphorus compound of the chemical formula (8) and the chemical formula (9) respectively) Phosphorus compounds) are preferred. Among the phosphorus compounds of the general formula (1), the ratio of the total amount of the phosphorus compounds of the chemical formula (8) and/or the chemical formula (9) is preferably 30% by mass or more, more preferably 50% by mass or more, and still more preferably It is 80% by mass or more, particularly preferably 90% by mass or more, and 100% by mass is fine. By containing in the above ratio, excellent insulation reliability can be expressed.

Since the phosphorus compound of the general formula (1) has high solubility in a solvent, it has good handling properties even after the adhesive composition is produced. Examples of solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, dimethylimidazolidone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, Cyclohexanone, cyclopentanone, etc. In addition, examples of low boiling point solvents include aromatic solvents such as toluene and xylene, aliphatic solvents such as hexane, heptane, and octane, alcohols such as methanol, ethanol, propanol, butanol, and isopropanol. Solvents, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone and other ketone solvents, diethyl ether, tetrahydrofuran and other ether solvents, ethyl acetate, butyl acetate, isoacetate Ester solvents such as butyl ester. The phosphorus compound of the general formula (1) is preferably dissolved in the aforementioned solvent at room temperature (25° C.) by 10% by mass or more, more preferably 20% by mass or more.

A phosphorus compound other than the phosphorus compound of the general formula (1) can be added in a range that does not impair the effect of the present invention. Examples include: Sanko (stock) product names BCA, HCA (registered trademark), BzHCA, M-Acid, M-Ester, HCA-HQ, HCA-NQ and other phosphinic acid derivatives, Dahachi Chemical (stock) The product names CR-733S, CR-741, PX-200, PX-202, ADK STAB (registered trademark) FP-600, PFR and other condensed phosphate compounds, Otsuka Chemical (Stock) ) Product names SPB-100, SPE-100, SPB-100L, SPH-100, Fushimi Pharmaceutical Co., Ltd. product names FP-100, FP-110, FP-300, FP-400, FP-430 , FP-500, FP-800E, FP-800H, FP-900H, FP-1000 and other cyclic phosphazene compounds, Clariant Japan's trade name Exolit (registered trademark) OP series and other phosphorous aluminum salt compounds, Nissan Chemical (stock) product name PHOSMEL (registered trademark) 200 and other melamine compounds, ADEKA (stock) product name ADK STAB FP-2100JC, FP-2200S, FP-2500S and other intumescent flame retardants, etc. It can be used alone or in combination with multiple.

The preferable phosphorus content in the non-volatile component of the adhesive composition of the present invention is 1.0 to 5.0 mass%, more preferably 1.0 to 3.0 mass%. If the phosphorus content is low, good flame retardancy cannot be obtained. On the contrary, if it is high, adhesiveness, heat resistance, and insulation reliability tend to decrease.

A flame retardant containing no phosphorus can be added in a range that does not impair the effect of the present invention. For example, the trade name HYGILITE (registered trademark) H-42, H-42M, H-43, H-43M and other aluminum hydroxide manufactured by Showa Denko Corporation, and the trade name KISUMA manufactured by Kyowa Chemical Industry Co., Ltd. Registered trademarks) Magnesium hydroxide such as 5, 8, 5Q-S, 200-06H, trade names MC-4000, MC-4500, MC-6000, etc. manufactured by Nissan Chemical Co., Ltd., etc. It can be used alone or in combination of multiple.

In the adhesive composition of the present invention, epoxy resin can be blended. The content of the epoxy resin is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and still more preferably 25 parts by mass or more with respect to 100 parts by mass of the resin having an imine bond. Moreover, 100 parts by mass or less is preferable, 80 parts by mass or less is more preferable, and 70 parts by mass or less is still more preferable. By setting it as the above upper limit or less, the content ratio of the resin which has an imine bond can maintain a certain amount or more. Therefore, the epoxy resin does not remain uncured, and the heat resistance after curing of the adhesive composition becomes good. Moreover, by setting it as the above-mentioned lower limit or more, a sufficient crosslinking reaction can be formed with the resin which has an imine bond, and the heat resistance and insulation reliability of the adhesive composition after hardening become favorable.

The epoxy resin used as the adhesive composition of the present invention does not matter if it is liquid, semi-solid or solid at 25°C, but it is liquid at 25°C and has two or more in one molecule The epoxy-based epoxy resin is preferred. The aforementioned epoxy resin can be modified, and can contain sulfur atoms, nitrogen atoms, phosphorus atoms, etc. in the molecular framework. Examples include: bisphenol A type epoxy resin, bisphenol F type epoxy resin, or hydrogenated ones, phenol novolak type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, NBR (Acrylonitrile butadiene rubber modified with both terminal carboxyl groups) modified epoxy resin, dimer acid modified epoxy resin, polybutadiene modified epoxy resin, aliphatic epoxy resin, alicyclic epoxy Resin etc. Examples of these commercially available products include: trade names jER (registered trademark) 825, jER827, jER828, YL980, manufactured by Mitsubishi Chemical Corporation, and EPICLON (registered trademark) 840, 840 manufactured by DIC (Stock) -S, 850, 850-S, EXA-850CRP, 850-LC, product names YD-127, YD-128, YD-128G, YD-128S, YD-128CA, YD manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. -8125, YD-825GS, YD-825GHS and other bisphenol A liquid epoxy resins, product names of Mitsubishi Chemical Corporation jER806, jER806H, jER807, YL983U, DIC (shares) product names EPICLON 830, 830- S, 835, EXA-830CRP, EXA-830LVP, EXA-835LV, product name YDF-170, YDF-170N, YDF-8170C, YDF-870GS and other bisphenol F liquid rings manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Hydrogenated bisphenol A liquid epoxy resin, products manufactured by Mitsubishi Chemical Corporation, such as YX8000 and YX8034 manufactured by Mitsubishi Chemical Corporation, and ST-3000 manufactured by Nippon Steel & Sumitomo Chemical Corporation, manufactured by Mitsubishi Chemical Corporation Name jER152, DIC (stock) product name EPICLON N-730A and other phenol novolac type liquid epoxy resin, DIC (stock) product name EPICLON HP-4032D and other naphthalene type liquid epoxy resin, ADEKA (stock) product The trade name of ADEKA RESIN (registered trademark) EP-4088S, EP-4088L and other dicyclopentadiene liquid epoxy resins, the trade name of DIC (shares) such as EPICLON TSR-960, TSR-601 and other NBR modified epoxy resins , Mitsubishi Chemical Co., Ltd. product names jER871, jER872, Nippon Steel & Sumikin Chemical Co., Ltd. product names Epotohto (registered trademark) YD-172 and other dimer acid-modified epoxy resins, Japan Soda Co., Ltd. Butadiene-modified epoxy resins such as JP-100, JP-200, JP-400, etc., and CELLOXIDE (registered trademark) 2021P, 2081, etc. alicyclic epoxy resins manufactured by Daicel Chemical Industry Co., Ltd. , Triglycidyl isocyanurate such as TEPIC (registered trademark) manufactured by Nissan Chemical Industry Co., Ltd., and the trade name DENACOL (registered trademark) EX-1000 series, DENACOL L series, manufactured by Nagase ChemteX (shares) DENACOL DLC series, DENAREX (registered trademark) series, EX991, etc. can be used alone or in combination.

As the epoxy resin, an epoxy resin that is semi-solid or solid at 25°C can also be used. Epoxy resins that are semi-solid or solid at 25°C can be modified, and can contain sulfur atoms, nitrogen atoms, and phosphorus atoms in the molecular framework. Examples include: bisphenol A type epoxy resin, bisphenol F type epoxy resin, or hydrogenated ones, phenol novolak type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, Naphthalene epoxy resin, dicyclopentadiene epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, etc. Examples of these commercially available products include: product names jER1001, jER1004, jER1007, jER1010 manufactured by Mitsubishi Chemical Co., Ltd., and product names Epotohto YD-134, YD-011 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. YD-014, YD-017, DIC (stock) product names EPICLON 860, 1050, 1055, 2050, 3050, 4050, 7050 and other bisphenol A epoxy resins, Mitsubishi Chemical (stock) product names jER4004P, jER4005P, jER4007P, jER4010P, bisphenol F-type epoxy resins such as Epotohto YDF-2001, YDF-2004 manufactured by Nippon Steel & Sumikin Chemicals, and ST-4000D manufactured by Nippon Steel & Sumikin Chemicals And other hydrogenated bisphenol A epoxy resins, the product name jER154 manufactured by Mitsubishi Chemical Corporation, the product name EPICLON N-740, N-770, N-775 manufactured by DIC Corporation, and the product manufactured by Nippon Kayaku Co., Ltd. Trade name EPPN (registered trademark) 201, EPPN-501H, EPPN-501HY, EPPN-502H, NC-2000L, trade name DEN-438 manufactured by Dow Chemical, etc. Phenolic novolac type epoxy resin, manufactured by DIC (stock) The trade name of EPICLON N-660, N-665, N-670, N-673, N-680, N-690, N-695, the trade name of Nippon Steel & Sumikin Chemical Co., Ltd. Epotohto YDCN-700-7 , YDCN-700-10, EOCN (registered trademark)-1020, EOCN-102S, EOCN-103S, EOCN-104S and other cresol novolac epoxy resins manufactured by Nippon Kayaku Co., Ltd., Mitsubishi Chemical Co., Ltd. ) Product names YX4000, YX4000H, Nippon Kayaku Co., Ltd. product names NC-3000, NC-3000L, NC-3000H, NC-3100 and other biphenyl type epoxy resins, DIC (Stock) product names EPICLON HP-4700, HP-4710, HP-4770, HP-5000, HP-6000, Nippon Kayaku Co., Ltd.'s trade names NC-7000L, NC-7300L and other naphthalene type epoxy resins, DIC (stock) The trade name of EPICLON HP-7200L, HP-7200, HP-7200H, HP-7200HH, HP-7200HHH, the trade name XD-1000 manufactured by Nippon Kayaku Co., Ltd. and other dicyclopentadiene epoxy resins, Daicel Chemical Industry The trade name of EHPE (registered trademark) 3150 and other alicyclic epoxy resins, EXA-9726 and other phosphorus-containing epoxy resins, etc. manufactured by DIC (Stock) can be used alone or in combination It doesn't hurt to use it.

Part of epoxy resins and phosphorus compounds usually contains chlorine as an impurity during the manufacturing process. However, from the viewpoint of reducing the environmental load, it is required to reduce the amount of halogens, and it is known that if chlorine, especially hydrolyzable chlorine is large, insulation properties are reduced. Therefore, the total chlorine content in the non-volatile components of the adhesive composition is preferably 500 ppm or less, and more preferably 300 ppm or less.

The adhesive composition of the present invention can add an organic solvent with a surface tension of 33 dyn/cm or less in addition to the aforementioned solvents in order to improve coating stability within a range that does not impair the effects of the present invention. Examples include: aromatic solvents such as toluene and xylene, aliphatic solvents such as hexane, heptane, and octane, alcoholic solvents such as methanol, ethanol, propanol, butanol, and isopropanol, acetone, methyl Ketone solvents such as ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone, ether solvents such as diethyl ether and tetrahydrofuran, and ester solvents such as ethyl acetate, butyl acetate, and isobutyl acetate , Acetate-based solvents such as diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate, etc., which can be used alone or in combination with multiple. The blending amount of the solvent is not particularly limited as long as it can dissolve the resin having an imine bond. With respect to 100 parts by mass of the resin having an imine bond, 50 parts by mass or more is preferred, and more preferably 100 parts by mass or more. More preferably, it is 200 parts by mass or more. In addition, 2000 parts by mass or less is preferable, 1500 parts by mass or less is more preferable, and 1000 parts by mass or less is still more preferable.

In the adhesive composition of the present invention, a surface modifier can be added to improve coating stability within a range that does not impair the effect of the present invention. From the viewpoint of adhesiveness, the surface modifier preferably has a boiling point of 150°C or lower, and more preferably has a boiling point of 120°C or lower. Specifically, it is not particularly limited, but includes: SURFYNOL (registered trademark) 104E, 104H, 104A, 104PA, 104S, 420, 440, 465, 485, SE, SE-F, manufactured by Nissin Chemical Industry Co., Ltd. OLFINE (registered trademark) EXP.4001, 4123.4200.4300, etc. These can be used alone or in combination with multiple. The blending amount of these surface modifiers is based on the total mass of the resin having an imine bond and the epoxy resin in the adhesive composition, preferably 0.01 to 0.5% by mass, more preferably 0.05 ～0.3% by mass. If the blending amount of the surface modifier is small, it may become difficult to obtain coating stability, and if the blending amount is large, it may become difficult to develop adhesiveness.

The adhesive composition of the present invention can add a high heat-resistant resin in order to improve the insulation reliability in a higher-level high-temperature and high-humidity environment within a range that does not impair the effects of the present invention. As the high heat resistance resin, a resin having a glass transition temperature of 200°C or higher is preferable, and a resin having a glass transition temperature of 250°C or higher is more preferable. Specifically, it does not specifically limit, but a polyimide resin, a polyimide imine resin, a polyether imine resin, a polyether ether ketone resin, etc. are mentioned. In addition, the high heat-resistant resin is preferably dissolved in a solvent. As those satisfying these conditions, when the structural unit derived from the total acid component is set to 100 mol%, a resin having an aromatic ring-containing polycarboxylic acid anhydride of 90 mol% or more is preferred. Polyimide resin is the best. The specific raw material system is as described above.

In the adhesive composition of the present invention, in a range that does not impair the effects of the present invention, in order to promote curing, a glycidyl amine epoxy resin may be further added in addition to the aforementioned epoxy resin. The addition amount of the glycidyl amine epoxy resin is preferably 0.01% to 5% by mass relative to the total mass of the resin having an imine bond in the adhesive composition and the aforementioned epoxy resin. 0.05% by mass to 2% by mass is more preferable. If the blending amount of the glycidylamine epoxy resin is small, there is a possibility that the effect of accelerating hardening cannot be obtained. If the blending amount is large, the effect of promoting the hardening of epoxy groups is great, and the reaction between the reactive functional groups of the resin having an imine bond and the epoxy groups may not proceed sufficiently, and the heat resistance and adhesiveness may decrease. . Examples of the glycidyl amine epoxy resin include: trade names TETRAD (registered trademark)-X, TETRAD-C manufactured by Mitsubishi Gas Chemical Co., Ltd., trade names jER630, jER604 manufactured by Mitsubishi Chemical Co., Ltd., and new Product names YH-434, YH-434L manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., product names manufactured by ADEKA RESIN EP-3950S, EP-3950L, EP-3980S, and products manufactured by Nippon Kayaku Co., Ltd. Names such as GAN (registered trademark), GOT (registered trademark), etc., can be used alone or in combination.

The adhesive composition of the present invention can be added with a curing agent and a curing accelerator for epoxy resin within a range that does not impair the effect of the present invention. The curing agent is not particularly limited as long as it is a compound that reacts with epoxy resin, and examples thereof include amine curing agents, compounds having phenolic hydroxyl groups, compounds having carboxylic acids, and compounds having acid anhydrides. The hardening catalyst is not particularly limited as long as it promotes the reaction of the epoxy resin with the resin having an imine bond and the above-mentioned hardener. Examples include: Shikoku Kasei Industrial Co., Ltd. (trade names) 2MZ, 2E4MZ , C11Z, C17Z, 2PZ, 1B2MZ, 2MZ-CN, 2E4MZ-CN, C11Z-CN, 2PZ-CN, 2PHZ-CN, 2MZ-CNS, 2E4MZ-CNS, 2PZ-CNS, 2MZ-AZINE, 2E4MZ-AZINE, C11ZINE , 2MA-OK, 2P4MHZ, 2PHZ, 2P4BHZ and other imidazole derivatives, betaguanidine, benzoguanamine and other guanamines, diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiamine Benzene, dicyandiamine, urea, urea derivatives, melamine, polyamines such as polyhydrazine, these organic acid salts and/or epoxy adducts, amine complexes of boron trifluoride, ethyl Trimethylamine-S-tris, 2,4-diamino-S-tris, 2,4-diamino-6-xylyl-S-tris and other trimethylamine derivatives, trimethylamine , Triethanolamine, N,N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methyl 𠰌line, hexa (N-methyl) melamine, 2,4,6-ginseng (dimethyl Amine phenol), tetramethylguanidine, DBU (1,8-diazebicyclo[5,4,0]-7-undecene), DBN (1,5-diazebicyclo[4,3,0 ]-5-nonene) and other tertiary amines, these organic acid salts and/or tetraphenyl borate, polyvinylphenol, polyvinylphenol bromide, tributylphosphine, triphenylphosphine, ginseng -2-cyanoethyl phosphine and other organic phosphines, tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide, hexadecyl tributyl phosphonium chloride, tetraphenyl phosphonium tetraphenyl borate, etc. Grade phosphonium salts, benzyl trimethyl ammonium chloride, phenyl tributyl ammonium chloride and other quaternary ammonium salts, the aforementioned polycarboxylic anhydrides, diphenyl phosphonium tetrafluoroborate, triphenyl hexafluoroantimonate Aluminium, 2,4,6-triphenylthiopyrylium hexafluorophosphate, IRGACURE 261 (manufactured by Ciba Specialty Chemicals), OPTOMER SP-170 (manufactured by ADEKA) and other photocationic polymerization catalysts, benzene Ethylene maleic anhydride resin, phenyl isocyanate and dimethylamine and other molar reactants, toluene diisocyanate, isophorone diisocyanate and other organic polyisocyanates and dimethylamine etc. molar reaction Things etc. These can be used singly, or they can be used in combination.

In the adhesive composition of the present invention, a silane coupling agent can be added for the purpose of improving adhesiveness within a range that does not impair the effect of the present invention. The silane coupling agent is not particularly limited as long as it is known in the past. Specific examples thereof include: aminosilane, mercaptosilane, vinylsilane, epoxysilane, methacrylylsilane, isocyanate silane, ketimine silane, or mixtures or reactants of these, or their combination with Compounds derived from the reaction of polyisocyanates, etc. As such a silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3- Aminopropylethyl diethoxysilane, bistrimethoxysilylpropylamine, bistriethoxysilylpropylamine, bismethoxydimethoxysilylpropylamine, bisethoxy Diethoxysilylpropylamine, N-2-(aminoethyl)-3-aminopropyl trimethoxysilane, N-2-(aminoethyl)-3-aminopropyl Methyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylethyl Aminosilanes such as diethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyl Diethoxysilane, γ-mercaptopropylethyldiethoxysilane and other mercaptosilanes, vinyl trimethoxysilane, vinyl triethoxysilane, ginseng-(2-methoxyethoxy) Vinyl silane such as vinyl silane, γ-glycidoxy propyl trimethoxy silane, γ-glycidoxy propyl dimethyl ethoxy silane, γ-glycidoxy propyl methyl Diethoxysilane, β-(3,4-epoxycyclohexyl) ethyl methyl dimethoxy silane, γ-glycidoxy propyl trimethoxy silane, β-(3,4-ring Oxycyclohexyl) ethyl trimethoxysilane and other silyl oxides, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane and other methacryloxysilanes, isocyanate propyl triethoxysilane, isocyanate propyl Isocyanate silanes such as trimethoxysilane, ketimine silanes such as ketiminated propyl trimethoxy silane, and ketimated propyl triethoxy silane can be used alone or in combination of multiple. Among these silane coupling agents, epoxy silane has a reactive epoxy group and can react with a resin having an imine bond, so it is preferable from the viewpoint of improving heat resistance and humidity resistance. In addition, the addition amount of the silane coupling agent is based on the non-volatile components of the resin composition, and is preferably 0 to 3% by mass, more preferably 0 to 2% by mass. If the blending amount is large, the heat resistance may decrease.

Regarding fillers The adhesive composition of the present invention can be added with organic and inorganic fillers for the purpose of improving soldering heat resistance within a range that does not impair the effects of the present invention. As an organic filler, powders, such as polyimide and polyimide of heat-resistant resin, are mentioned. In addition, examples of inorganic fillers include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titanium dioxide (TiO ₂ ), tantalum pentoxide (Ta ₂ O ₅ ), and zirconium dioxide (ZrO ₂ ). , Silicon nitride (Si ₃ N ₄ ), barium titanate (BaO・TiO ₂ ), barium carbonate (BaCO ₃ ), lead titanate (PbO・TiO ₂ ), lead zirconate titanate (PZT), lanthanum zirconate titanate Lead (PLZT), gallium oxide (Ga ₂ O ₃ ), spinel (MgO・Al ₂ O ₃ ), mullite (3Al ₂ O ₃・2SiO ₂ ), cordierite (2MgO・2Al ₂ O ₃・5SiO ₂ ), talc (3MgO・4SiO ₂・H ₂ O), aluminum titanate (TiO ₂ -Al ₂ O ₃ ), zirconium dioxide containing yttrium (Y ₂ O ₃ -ZrO ₂ ), barium silicate (BaO・8SiO ₂ ), boron nitride (BN), calcium carbonate (CaCO ₃ ), calcium sulfate (CaSO ₄ ), zinc oxide (ZnO), magnesium titanate (MgO・TiO ₂ ), barium sulfate (BaSO ₄ ), organic Bentonite, clay, mica, aluminum hydroxide, magnesium hydroxide, etc., in terms of ease of dispersion and heat resistance improvement effects, among these, silica is preferred. These can be used singly, or they can be used in combination. In addition, the addition amount of these organic and inorganic fillers is based on the non-volatile components of the adhesive composition, and is preferably 1-30% by mass, more preferably 3-15% by mass. If the blending amount is large, the adhesive coating film will become brittle, and if the blending amount is small, there is a possibility that a sufficient heat resistance improvement effect may not be obtained.

An example of the manufacturing method of the adhesive composition of the present invention will be described. Blended with a solvent solution of resin with imine bond (hereinafter also referred to as resin varnish with imidine bond), a solvent solution of epoxy resin (hereinafter also referred to as epoxy varnish), the formula (1) Phosphorus compounds etc. are stirred in such a way that the system becomes uniform. When a filler is used, what is made into a slurry form with the above-mentioned solvent is added as a filler, and it is stirred further. Thereby, the adhesive composition of the present invention can be obtained. In addition, when obtaining the adhesive composition, it is possible to add a dilution solvent for adjusting the viscosity, a hardening accelerator, etc. as needed.

The adhesive composition of the present invention can be used as an adhesive composition suitable for flexible printed wiring boards. The adhesive composition is applied to a substrate such as a film, and the layer of the adhesive composition after drying is called an adhesive layer, which is used as a flexible printed wiring board composed of an adhesive composition The parts of the adhesive include: adhesive films for reinforcing plates, adhesive films for interlayer applications, covering films, and copper-clad laminates.

Adhesive film is a film composed of "protective film/adhesive layer" or "protective film/adhesive layer/protective film". There is also a case where an insulating film layer is provided in the adhesive layer, and its structure is "protective film/adhesive layer/insulating film/adhesive layer/protective film layer". It is mostly used in flexible printed wiring boards as adhesive films for reinforcement boards and adhesive films for interlayer applications. Insulating film is composed of polyimide, polyamidoimide, polyester, polyphenylene sulfide, polyether ether, polyether ether ketone, polyaramide, polycarbonate, polyaromatic ester and other plastics The film with a thickness of 1 to 200 μm can be laminated with multiple films selected from these. The protective film is not particularly limited as long as it can be peeled off without impairing the characteristics of the adhesive. Examples include polyethylene, polypropylene, polyolefin, polyester, polymethylpentene, polyvinyl chloride, and polyvinylidene fluoride. Plastic films such as ethylene and polyphenylene sulfide, films coated with silicone or fluoride or other release agents, laminated paper, paper impregnated or coated with peelable resin, etc.

The cover film is a film composed of "insulating film/adhesive layer" or "insulating film/adhesive layer/protective film".

Copper-clad laminate is a laminate composed of "copper foil/adhesive layer/insulating film" or "copper foil/adhesive layer/insulating film/adhesive layer/copper foil". The copper foil is not particularly limited, but can be used: rolled copper foil and electrolytic copper foil used in the past for flexible printed wiring boards.

In any of the above applications, it can also be obtained by coating the adhesive composition on a film or copper foil used as a substrate, drying the solvent, and performing thermocompression bonding and thermal curing treatment with the adherend. Adhesive film and cover film are also based on the purpose of adjusting the fluidity of the adhesive composition during thermocompression bonding. After the solvent is dried, heat treatment is performed to make the resin with the imine bond and the phosphorus with the reactive functional group Partial reaction of the compound with epoxy resin. In addition, the state before thermocompression bonding is called the B stage.

In any of the above-mentioned applications, it is better to require adhesiveness, heat resistance, and insulation reliability after thermal curing, and more flame retardancy. In addition, the adhesive film and cover film are usually wound, stored, cut, and punched in the B-stage state, and the flexibility of the B-stage state is also necessary. On the other hand, copper-clad laminates usually undergo thermocompression bonding and thermal curing immediately after the B-stage state is formed, and the degree of flexibility required for the B-stage state is not as good as that of cover film and adhesive film.

For the adhesive film and cover film of the present invention, it is preferable that the amount of residual solvent in the adhesive layer in the B-stage state is less than 1.5% by mass. More preferably, it is 1.0% by mass or less. The residual solvent is the solvent used in the adhesive composition that has not been completely removed in the B-stage formation step. When multiple solvents are used in combination, a solvent with a higher boiling point remains. If the amount of residual solvent is large, the insulation reliability is reduced. Therefore, as the amount of residual solvent, the amount of residual solvent in the adhesive layer in the B-stage state is preferably less than 1.5% by mass, and more preferably 1.0% by mass or less. .

The adhesive composition of the present invention comprising a resin having an imine bond and a phosphorus compound of the general formula (1) is excellent in adhesion, heat resistance, flame retardancy, and insulation reliability. In addition, the phosphorus compound of the general formula (1) has excellent solvent solubility and therefore excellent handling properties. Furthermore, the phosphorus compound of the general formula (1) has excellent compatibility with the resin having an amide bond, and has a relatively large molecular weight and a small plasticizing effect. Therefore, it has the property that it is not easy to bleed out under a high temperature and high humidity environment. Therefore, the adhesive composition of the present invention comprising a resin having an imine bond and a phosphorus compound of the general formula (1) exhibits high insulation reliability. [Example]

The following examples demonstrate the effects of the present invention, but the present invention is not limited to these. In addition, the evaluation of the characteristics in the examples was performed by the following method. In the examples and comparative examples, only parts are described as parts by mass.

Logarithmic viscosity: The resin having an imine bond was dissolved in N-methyl-2-pyrrolidone so that the polymer concentration became 0.5 g/dl. The solution viscosity and solvent viscosity of the obtained solution were measured by Ubbelohde viscometer at 30°C, and the logarithmic viscosity was calculated according to the following formula. Logarithmic viscosity (dl/g) = [ln(V2/V1)]/V3 In the above formula, V1 represents the viscosity of the resin solution measured by the Ubbelohde viscometer, and V2 represents the viscosity of the solvent measured by the Ubbelohde viscometer. V1 and V2 are calculated from the time for the resin solution and solvent (N-methyl-2-pyrrolidone) to pass through the capillary of the viscometer. In addition, V3 is the resin concentration (g/dl).

Acid value: Dissolve 0.1g of resin with imine bond in 20ml of N-methyl-2-pyrrolidone, use vanillolphthalein as an indicator, titrate with 0.1N KOH ethanol solution, and measure every 10 ⁶ g Resin's carboxyl equivalent (eq/ton), calculate the acid value according to the following formula. Acid value (mgKOH/g)=[carboxy equivalent (eq/ton)×56.12]/1000

Glass transition temperature: Coat the solution of the resin with the imine bond on the shiny surface of the copper foil, and dry it with a hot air dryer at 140°C for 3 minutes. After that, the resin-coated copper foil was obtained by drying in a nitrogen atmosphere at 250°C for 30 minutes. Thereafter, by etching the copper foil, a resin film with a thickness of 20 μm was produced. The glass transition point of the resin film thus produced was measured by the TMA (thermomechanical analysis device) stretching method under the conditions of a load of 50 mN and a heating rate of 10° C./min.

Adhesion: The adhesive composition solution is applied to a polyimide (PI) film (APICAL (registered trademark) 12.5NPI manufactured by Kaneka) so that the thickness of the adhesive layer becomes 20μm after drying, and the hot air circulation type dryer is used to Dry at 140°C for 3 minutes to obtain a B-stage state sample (PI film/adhesive layer). Using a vacuum laminator, make the adhesive coated surface of the sample (PI film/adhesive layer) and the rolled copper foil (JX Metal BHY-13F-T: thickness 18μm) in the B-stage state at 160°C , 20kgf, 60 seconds under reduced pressure, thermal compression bonding. Thereafter, it was heated and cured at 170°C for 3 hours. For the cured sample (PI film/adhesive layer/rolled copper foil), use a tensile tester (AUTOGRAPH AG-X plus manufactured by Shimadzu) to set the polyimide film to 90° at a temperature of 25°C. The direction is torn off at a speed of 50mm/min, and the bonding strength is measured. ◎: The bonding strength is above 0.7N/mm or the polyimide film is broken ○: The bonding strength is 0.5N/mm or more and less than 0.7N/mm ×: Bonding strength is less than 0.5N/mm

Soldering heat resistance: Prepare a heat-cured sample (PI film/adhesive layer/rolled copper foil) in the same way as the evaluation of adhesiveness, cut it into a 20mm square, and float in a solder bath at 300°C with the polyimide side facing up. 1 minute. Evaluate appearance. ○: No swelling or peeling ×: Swelling or peeling

Flame retardancy: A solution of the adhesive composition was applied to a polyimide film (APICAL 12.5NPI manufactured by Kaneka) so that the thickness of the adhesive layer after drying became 20μm, and dried in a hot air circulating dryer at 140°C for 3 minutes, Obtain the B-stage sample (PI film/adhesive layer). Using a vacuum laminator, make the adhesive coating surface of the B-stage sample (PI film/adhesive layer) and the polyimide film (APICAL 12.5NPI manufactured by Kaneka) at 160℃, 20kgf, 60 Heat compression under reduced pressure within seconds. Thereafter, it was heated and cured at 170°C for 3 hours. According to UL-94VTM standards, the cured sample (PI film/adhesive layer/PI film) was evaluated for flame retardancy. ○: equivalent to VTM-0 ×: Does not meet VTM-0

Insulation reliability: The adhesive composition solution is applied to a polyimide film (APICAL 12.5NPI manufactured by Kaneka) so that the thickness of the adhesive layer after drying becomes 20μm, and it is dried at 140°C with a hot air circulation dryer In 3 minutes, the sample in the B-stage state (PI film/adhesive layer) is obtained. Using a vacuum laminator, the adhesive coating surface of the sample (PI film/adhesive layer) in the B-stage state and the etching process of L/S=50/50μm into a comb-shaped pattern of single-sided copper The laminated board (using the trade name ESPANEX (registered trademark) MC12-25-00CEM manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) was thermocompression bonded at 160°C, 20kgf, and 60 seconds under reduced pressure. Thereafter, it was heated and cured at 170°C for 3 hours. In an environment with a temperature of 85°C and a humidity of 85%, a 200V voltage was applied to the cured sample (PI film/adhesive layer/single-sided copper-clad laminate) for 250 hours. ◎: Resistance value after 250 hours is 1×10 ¹⁰ Ω or more, and no dendrites ○: Resistance value after 250 hours is 1×10 ⁹ Ω or more and less than 1×10 ¹⁰ Ω, and no dendrites are generated× ：The resistance value after 250 hours is less than 1×10 ⁹ Ω or dendrites are generated.××: Short circuit within 250 hours

Polymerization of resins 1～2 with imine bond: The resin composition (mol%) of the raw materials shown in Table 1 was used to polymerize the resin with the imine bond. Specifically, polymerization is performed as follows.

Polymerization of resin 1 with imine bond Add 110.47g (0.575 mol) of TMA (trimellitic anhydride), 80.90g (0.40 mol) of sebacic acid, 87.5g (0.025) to a four-neck separable flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube and a thermometer. Mol) NBR (both terminal carboxyl modified acrylonitrile butadiene rubber), 250.25g (1.00 mol) MDI (diphenylmethane-4,4'-diisocyanate) and resin after decarboxylation 714.50 g of dimethylacetamide was added so that the concentration of the component became 40% by mass, and the mixture was heated to 100°C under nitrogen to react for 2 hours, and then heated to 150°C to react for 5 hours. After that, 396.94 g of dimethylacetamide was added and diluted so that the concentration of the resin component became 30% by mass, to obtain a solution of resin 1 having an imine bond.

Polymerization of resin 2 with imine bond Add 192.13g (1.00 mol) of trimellitic anhydride and 225.23g (0.90 mol) of diphenylmethane-4,4'-di to a four-neck separable flask equipped with a stirrer, cooling tube, nitrogen introduction tube and thermometer. Add 494.05 g of N-methyl-2-pyrrolidone so that the concentration of the isocyanate and the resin component after decarboxylation becomes 40% by mass, and the reaction is heated to 100°C under nitrogen for 2 hours, and then heated to The reaction was carried out at 150°C for 5 hours. After that, 117.63 g of dimethylacetamide was added and diluted so that the concentration of the resin component became 35% by mass, to obtain a solution of resin 2 having an imine bond.

【Table 1】

Production of adhesive composition solution: The dimethylacetamide solution or N-methyl of the adhesive compositions of Examples 1 to 6 and Comparative Examples 1 to 4 were prepared according to the adhesive ratio shown in Table 2 (solid content (mass%)) The -2-pyrrolidone solution was evaluated for the above characteristics.

As can be seen from Table 2, the adhesive compositions of Examples 1 to 6 satisfying the conditions of the present invention show excellent results in adhesiveness, soldering heat resistance, flame retardancy, and insulation reliability. On the other hand, they do not contain phosphorus compounds. Comparative Example 1, Comparative Example 2 and Comparative Example 3 that did not contain the phosphorus compound of the general formula (1), and Comparative Example 4 that did not contain a resin with an imine bond were the results that none of the characteristics were satisfied.

［產業上之可利用性］【Table 2】

[Industrial availability]

The adhesive composition of the present invention is excellent in adhesiveness, heat resistance, flame retardancy, handling, and insulation reliability by combining a resin having an imine bond with a specific phosphorus compound, and is suitable for bonding films and covering films , Copper-clad laminates, etc., extremely useful.

Claims (12)

An adhesive composition characterized by containing a resin with an imine bond and a phosphorus compound represented by the general formula (1),

In the general formula (1), n is an integer of 2 to 6, and a plurality of Xs are independently CH ₂ or O. Such as the adhesive composition of claim 1, wherein the phosphorus compound represented by the general formula (1) is the phosphorus compound represented by the general formula (2) and/or the phosphorus compound represented by the general formula (3),

X in the general formula (2) is CH ₂ or O,

X in the general formula (3) is CH ₂ or O. According to the adhesive composition of claim 1 or 2, wherein the resin having an imine bond is a polyimide resin, a polyimide resin, a polyetherimine resin, a polyetheretherketone resin, Polyester imide resin or polycarbonate imide resin. The adhesive composition of claim 1 or 2, which contains trimellitic anhydride as a copolymerization component of the resin having an imine bond. The adhesive composition of claim 1 or 2, which contains acrylonitrile butadiene rubber modified with two terminal carboxyl groups as a copolymerization component of the resin having an imine bond. Such as the adhesive composition of claim 1 or 2, which further contains epoxy resin. The adhesive composition of claim 6, wherein the epoxy resin is liquid at 25°C and has more than two epoxy groups in one molecule. Such as the adhesive composition of claim 1 or 2, which is used for printed wiring boards. An adhesive film characterized by using the adhesive composition according to any one of claims 1 to 8. A cover film characterized by using an adhesive film as in Claim 9. A copper-clad laminated board characterized by the use of an adhesive film as in claim 9. A flexible printed wiring board characterized by using a cover film as in claim 10 or a copper-clad laminate as in claim 11.