KR101588492B1 - Polyimide resin, manufacturing method therefor, adhesive resin composition, coverlay film, and circuit board - Google Patents

Abstract

[식 중, Ar 은 방향족 테트라카르복실산 무수물로부터 유도되는 4 가의 방향족기, R₁ 은 디아미노실록산으로부터 유도되는 2 가의 디아미노실록산 잔기, R₂ 는 방향족 디아민으로부터 유도되는 2 가의 방향족 디아민 잔기를 각각 나타내고, Ar 및/또는 R₂ 중에 케톤기를 포함하고, m, n 은 각 구성 단위의 존재 몰비를 나타내고, m 은 0.75 ∼ 1.0 의 범위 내, n 은 0 ∼ 0.25 의 범위 내이다] 를 갖는 폴리이미드실록산에 있어서의 케톤기에, 적어도 2 개의 제 1 급 아미노기를 관능기로서 갖는 아미노 화합물을 반응시켜 얻어지는 폴리이미드 수지.The structural unit represented by the following general formulas (1) and (2)
[Chemical Formula 1]

Wherein Ar is a tetravalent aromatic group derived from an aromatic tetracarboxylic acid anhydride, R ₁ is a divalent diaminosiloxane residue derived from a diaminosiloxane, R ₂ is a divalent aromatic diamine residue derived from an aromatic diamine And m and n are in the range of 0.75 to 1.0 and n is in the range of 0 to 0.25, respectively, and the ketone group is contained in Ar and / or R ₂ , A polyimide resin obtained by reacting a ketone group in a mid siloxane with an amino compound having at least two primary amino groups as a functional group.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyimide resin, a method for producing the same, an adhesive resin composition, a coverlay film, and a circuit board,

The present invention relates to a polyimide resin useful as an adhesive in a circuit board such as a flexible printed wiring board, a method for producing the same, and a use thereof.

2. Description of the Related Art In recent years, demand for flexible printed circuit boards (FPCs), which are thin, lightweight, flexible, and excellent in durability even when bending is repeated, has increased along with progress in miniaturization, weight saving, and space saving of electronic devices . Since the FPC has three-dimensional and high-density mounting even in a limited space, applications of FPCs are expanding, for example, to components such as wirings, cables, and connectors for moving parts of electronic devices such as HDDs, DVDs, and cellular phones .

In the FPC, a coverlay film is used for the purpose of protecting the wiring portion. The coverlay film is formed by laminating a cover material made of a synthetic resin such as polyimide resin and an adhesive layer. In the manufacture of an FPC, a film material for a cover liner is attached to a circuit board through an adhesive layer using a method such as hot pressing. The adhesive layer is required to have high adhesion to both the circuit wiring pattern such as copper wiring and the film material for covering. As such an adhesive for a coverlay film, it is preferable to use a polyester resin having a siloxane unit and an epoxy resin mixed with a phosphate ester, a phthalic ester Based adhesive resin composition comprising at least one plasticizer selected from the group consisting of a polyester resin, a polyester resin, and a fatty acid ester (see, for example, Patent Document 1).

On the other hand, bis (3,4-dicarboxyphenyl) ether dianhydrides and bisphenols having a specific structure (hereinafter, referred to as " polyisocyanates ") have been used for the purpose of improving the low temperature sticking property, the low moisture absorption property, (Hereinafter referred to as " polyimide resin ") is reacted with another acid anhydride and / or other diamine. For the purpose of safely and stably producing a high molecular weight polyimide resin having a silicon structure in its main chain, a silicone-based diamine and a silicone-based acid dianhydride are mixed in a specific molar ratio range and subjected to heat dehydration condensation, A method of producing a polyimide resin in which aromatic diamine is added to a reaction solution at a predetermined molar ratio and reacted to control the molecular weight has been proposed (for example, Patent Document 3).

Japanese Patent Application Laid-Open No. 10-212468 Japanese Laid-Open Patent Publication No. 2006-117945 Japanese Laid-Open Patent Publication No. 2004-359874

Since a soldering process is almost indispensably included in the processing of the FPC, the adhesive used for the coverlay film is required to have high solder heat resistance. From this point of view, the polyimide resin having a relatively high heat resistance is a suitable material for an adhesive for a coverlay film, but if the solder heat resistance can be further improved, the function as an adhesive for a coverlay film can be further enhanced.

In addition, since the electronic devices for automobiles using FPCs are placed in a high-temperature environment of about 150 ° C repeatedly, the adhesive force between the coverlay film and the wiring of the FPC is deteriorated due to long-term use, Lt; / RTI > As the use of the FPC increases, it is expected that the situation in which the FPC is used not only in the automotive electronic devices but also in a severe temperature environment will increase in the future. Therefore, it is strongly desired to take countermeasures against the deterioration of the adhesive force of the coverlay film in an FPC used in a high-temperature environment.

Accordingly, an object of the present invention is to provide a polyimide resin capable of forming an adhesive layer which does not deteriorate the adhesion between the wiring layer and the coverlay film even in a use environment having excellent solder heat resistance and exposed to repeated high temperatures.

The inventors of the present invention have conducted intensive studies to solve the above problems. As a result, it has been found that when the imidized polyimide resin is reacted with an amino compound having a primary amino group, the solder heat resistance of the polyimide resin is remarkably improved, The inventors of the present invention have completed the present invention.

That is, the polyimide resin of the present invention is a polyimide resin obtained by copolymerizing an amino compound having at least two primary amino groups as functional groups in a ketone group in a polyimide siloxane having constituent units represented by the following general formulas (1) and (2) And the polyimide siloxane is crosslinked by the amino compound because the amino group reacts to form a C = N bond.

[Chemical Formula 1]

Wherein Ar is a tetravalent aromatic group derived from an aromatic tetracarboxylic acid anhydride, R ₁ is a divalent diaminosiloxane residue derived from a diaminosiloxane, R ₂ is a divalent aromatic diamine residue derived from an aromatic diamine each represents, while Ar and / or R ₂ contains a ketone group, m, and n denotes the molar ratio of the structural units present, m is in the range of 0.75 ~ 1.0 I, n is in the range of 0 to 0.25;

The adhesive resin composition of the present invention comprises the following components (A) and (B),

(A) a polyimide siloxane having a structural unit represented by the following general formula (1) and (2) and having a weight average molecular weight of 10,000 to 200,000, and

(B) an amino compound having at least two primary amino groups as a functional group, wherein the total amount of the primary amino groups is in the range of 0.004 mol to 1.5 mol based on 1 mol of the ketone group in the component (A) And contains the component (B).

(2)

Wherein Ar is a tetravalent aromatic group derived from an aromatic tetracarboxylic acid anhydride, R ₁ is a divalent diaminosiloxane residue derived from a diaminosiloxane, R ₂ is a divalent aromatic diamine residue derived from an aromatic diamine each represents, while Ar and / or R ₂ contains a ketone group, m, and n denotes the molar ratio of the structural units present, m is in the range of 0.75 ~ 1.0 I, n is in the range of 0 to 0.25;

The cured product of the present invention is obtained by curing the adhesive resin composition.

The coverlay film of the present invention is a coverlay film obtained by laminating an adhesive layer and a film material for use as a coverlay,

And the adhesive layer is formed using the adhesive resin composition.

The circuit board of the present invention comprises a substrate, a wiring layer formed on the substrate, and the coverlay film covering the wiring layer. In this case, it is preferable that the peel strength of the wiring layer and the coverlay film after the long-term heat resistance test at 150 占 폚 for 1000 hours in the atmosphere is 0.2 kN / m or more.

The method for producing a polyimide resin of the present invention comprises the steps of preparing a polyimide solution containing a polyimide siloxane having a ketone group,

Adding an amino compound having at least two primary amino groups as a functional group to the polyimide solution;

And a condensation reaction of the ketone group of the polyimide siloxane with the primary amino group of the amino compound. In this case, it is preferable that the amino compound is added so that the total amount of the primary amino groups is in the range of 0.004 mol to 1.5 mol based on 1 mol of the ketone group. Further, there is further provided a step of reacting an acid anhydride component containing an aromatic tetracarboxylic acid dianhydride with a diamine component containing a diaminosiloxane and an aromatic diamine to form the polyimide siloxane. Thus, the aromatic tetra The carboxylic acid dianhydride and the diamine component preferably contain a ketone group.

A manufacturing method of a circuit board of the present invention is a manufacturing method of a circuit board having a substrate, a wiring layer formed on the substrate, and a coverlay film covering the wiring layer,

Preparing a coverlay film having an adhesive layer by applying and drying the adhesive resin composition on a film material for use in a cover in a solution state,

Disposing the coverlay film so that the adhesive layer is in contact with the wiring layer, and thermally compressing the coverlay film,

The ketone group of the component (A) and the primary amino group of the component (B) are condensed to form a C = N bond simultaneously with the thermocompression bonding.

In each aspect of the present invention, the amino compound is preferably a dihydrazide compound.

The polyimide resin of the present invention is a polyimide resin which has at least two primary amino groups as a functional group in a ketone group contained in Ar and / or R ₂ of a polyimide siloxane having constituent units represented by the general formulas (1) and (2) It is possible to form an adhesive layer which is excellent in soldering heat resistance and does not deteriorate the adhesive force with the metal wiring layer even if it is placed in a repeated high temperature environment. Therefore, by using the polyimide resin of the present invention, the peel strength of the coverlay film formed with the adhesive layer can be increased, and the reliability of the circuit board using the coverlay film can be improved.

[Polyimide resin]

The polyimide resin of the present invention contains at least two primary amino groups in the ketone group in the group Ar and / or the group R ₂ in the polyimide siloxane having the structural units represented by the above general formulas (1) and (2) The polyimide siloxane is crosslinked with an amino compound by reacting an amino compound having a functional group to form a C = N bond.

The group Ar in the general formulas (1) and (2) is a tetravalent aromatic group derived from an aromatic tetracarboxylic acid anhydride, the group R ₁ is a divalent diaminosiloxane residue derived from a diaminosiloxane, and the group R ₂ Is a bivalent aromatic diamine residue derived from an aromatic diamine. The amount of the structural unit represented by the formula (1) in the resin is in the range of 75 mol% to 100 mol%, preferably in the range of 80 mol% to 100 mol%.

[Polyimide siloxane]

In the polyimide siloxane having the structural units represented by the general formulas (1) and (2), the group Ar and / or the group R ₂ includes a ketone group, and the ketone group participates in the reaction with the amino compound.

Examples of the aromatic tetracarboxylic acid for forming the group Ar containing a ketone group in the structural units represented by the general formulas (1) and (2) include 3,3 ', 4 (4) , 4'-benzophenone tetracarboxylic acid dianhydride (BTDA).

(3)

Examples of the aromatic tetracarboxylic acid serving as a raw material for forming the group Ar in the structural units represented by the general formulas (1) and (2) include, for example, 3,3 ' (BPDA), 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride (DSDA), pyromellitic dianhydride (PMDA), etc., Can be used. These may be used alone or in combination of two or more.

As the group R ₁ in the constituent unit represented by the general formula (1), for example, a diaminosiloxane residue derived from a diaminosiloxane represented by the following formula (4) can be mentioned.

[Chemical Formula 4]

Wherein R ₃ and R ₄ each represent a divalent organic group which may contain an oxygen atom, R ₅ to R ₈ each represent a hydrocarbon group having 1 to 6 carbon atoms, and m ₁ , the average number of repeating units, is 1 to 20 to be]

Particularly, as the group R ₁ , R ₃ and R ₄ in the formula (4) are each a divalent hydrocarbon group, R ₅ to R ₈ each are a hydrocarbon group having 1 to 6 carbon atoms, M _{1, which} is the average number of repeats, is preferably 5 to 15.

The diaminosiloxane residue is a group having a siloxane bond (Si-O-Si) in which an amino group is removed from a diaminosiloxane. However, by increasing the proportion of the siloxane bond, sufficient flexibility is obtained in the adhesive layer So that warping of the coverlay film can be suppressed. The plasticizer contains a large amount of polar groups. Therefore, as an advantage of not blending the plasticizer, the amount of the polar group contained in the adhesive resin composition using the polyimide siloxane having the constituent units represented by the general formulas (1) and (2) Can be suppressed. Therefore, in the present invention, the value of m in the formula (1) is set to 0.75 or more, preferably 0.80 or more. When the value of m is less than 0.75, the effect of suppressing warpage is not sufficiently obtained. It is also believed that by increasing the siloxane bond, there is also an effect of reducing the hardening shrinkage due to the decrease of the imide bond sites of the polyimide siloxane. From the above, the value of n in the formula (2) is set within the range of 0 to 0.25, preferably 0 to 0.2.

Thus, by introducing the siloxane skeleton into the polyimide by using the diaminosiloxane represented by the general formula (4), the resulting polyimide siloxane is provided with fluidity at the time of hot pressing to improve the filling property on the printed circuit wiring . Specific examples of the diaminosiloxane represented by the general formula (4) are diaminosiloxanes represented by the following formulas (5) to (9), and among them, aliphatic diamino siloxanes represented by the formula (5) Is more preferable. These diaminosiloxanes may be used in combination of two or more. When two or more diaminosiloxanes are combined and combined, it is preferable that 90 parts by weight or more of the aliphatic diaminosiloxane represented by the formula (5) or (6) is blended with 100 parts by weight of the total diaminosiloxane. In the formulas (4) to (9), m ₁ , the average number of repeats, is in the range of 1 to 20, preferably in the range of 5 to 15. When m ₁ is less than 1, the filling property in the case of using an adhesive is lowered, and when it exceeds 20, the adhesiveness is lowered.

[Chemical Formula 5]

Examples of the group R ₂ (bivalent aromatic diamine residue derived from an aromatic diamine) having a ketone group in the structural unit represented by the general formula (2) include those represented by the following formulas (10) and (11) . These may be used alone or in combination of two or more.

[Chemical Formula 6]

Wherein R ₉ independently represents a monovalent hydrocarbon group or alkoxy group having 1 to 6 carbon atoms, X represents CO, and n ₁ independently represents an integer of 0 to 4,

Examples of the aromatic diamine for forming the group R ₂ represented by the above formulas (10) and (11) include aromatic diamines such as 4,4'-bis (3-aminophenoxy) benzophenone (BABP) [4- (3-aminophenoxy) benzoyl] benzene (BABB).

Examples of the other aromatic diamine that is a raw material for forming the group R ₂ in the structural unit represented by the general formula (2) include 2,2-bis (4-aminophenoxyphenyl) propane (BAPP ), 2,2'-divinyl-4,4'-diaminobiphenyl (VAB), 2,2'-dimethyl-4,4'- diaminobiphenyl (m- Diethyl 4,4'-diaminobiphenyl, 2,2 ', 6,6'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-diphenyl-4,4'-dia Minibiphenyl, 9,9-bis (4-aminophenyl) fluorene, and the like. These aromatic diamines may be used alone or in combination of two or more.

The acid anhydrides and diamines serving as raw materials of the polyimide siloxane may be used alone or in combination of two or more. In addition, other acid anhydrides and diamines may be used in combination.

In order to enhance long-term heat resistance when a polyimide resin is used as an adhesive, it is preferable to use, as the aromatic tetracarboxylic acid anhydride and aromatic diamine to be used as raw materials, those having a small number of polar groups. Therefore, as the aromatic tetracarboxylic acid anhydride and the aromatic diamine, the p value, which is an index indicating the amount of the polar group contained in the molecule, calculated based on the following formulas (i) and (ii) . In particular, the p value of the aromatic diamine is more preferably 0.7 or less, and still more preferably 0.6 or less.

P value of aromatic tetracarboxylic acid anhydride = (A1 / B1) x 100 ... (I)

P value of aromatic diamine = (A2 / B2) x 100 ... (Ii)

Here, A1 = (the number of polar groups in the Ar group) x (the number of moles of the Ar group)

A2 = (number of polar groups in the group R ₂₎ × (the number of moles of group R ₂₎

           B1 = (molecular weight of group Ar) x (number of moles of group Ar)

B2 = (the molecular weight of the group R ₂ ) x (the number of moles of the group R ₂ )

The polar group as a reference for calculating the p value is divided into three levels based on the magnitude of the electric dipole moment. The first group is -X (where X is a halogen atom), -OH, -SH, -O-, -S-, -SO-, -NH-, -CO-, -CN, -PO < - >, and these are calculated as a polar group having a number of 1, respectively. The second group is -SO ₂ -, -CONH-, and these are calculated as polar groups each having 2 numbers. The third segment is -SO ₃ H, which is calculated as a polar group having _three units.

[Synthesis of polyimide siloxane]

The polyimide siloxane having the structural units represented by the general formulas (1) and (2) is obtained by reacting the aromatic tetracarboxylic acid anhydride, the diaminosiloxane and the aromatic diamine (if necessary) in a solvent to obtain a polyamic acid Followed by heating and ring closing. For example, polyamic acid which is a precursor of polyimide is obtained by dissolving an acid anhydride component and a diamine component in an almost equimolar amount in an organic solvent, and conducting polymerization reaction at a temperature in the range of 0 to 100 ° C for 30 minutes to 24 hours. In the reaction, the reaction components are dissolved so that the resulting precursor is in the range of 5 to 30% by weight, preferably 10 to 20% by weight, in the organic solvent. Examples of the organic solvent used in the polymerization reaction include N, N-dimethylformamide, N, N-dimethylacetamide (DMAC), N-methyl-2-pyrrolidone, , Dimethyl sulfate, cyclohexanone, dioxane, tetrahydrofuran, diglyme, triglyme and the like. Two or more of these solvents may be used in combination, and further, aromatic hydrocarbons such as xylene and toluene may be used in combination.

The synthesized precursor is usually advantageously used as a reaction solvent solution, but it may be condensed, diluted or replaced with another organic solvent if necessary. In addition, the precursor is advantageously used because it is generally excellent in solvent solubility. The method for imidizing the precursor is not particularly limited, and for example, a heat treatment in which the film is heated for 1 to 24 hours at a temperature within the range of 80 to 300 占 폚 is preferably employed in the above solvent.

When the polyimide siloxane having the structural units represented by the general formulas (1) and (2) is prepared, the compounding ratio of the acid anhydride component and the diamine component to be used as the raw material is not particularly limited. For example, polyimide siloxane Is preferably 1.000: 1.001 to 1.0: 1.2 in terms of the molar ratio of the acid anhydride component to the diamine component, from the viewpoint that the terminal substituent of the polyimide resin is an amino group, that is, the acid anhydride group is sealed with diamine to suppress the polarity of the polyimide resin.

The polyimide siloxane having the structural units represented by the above formulas (1) and (2) has an imide structure obtained by reaction with an aromatic tetracarboxylic acid anhydride, a diaminosiloxane and an aromatic diamine, When used as an adhesive for a coverlay film, a structure that is completely imidized to suppress the diffusion of copper is most preferable. However, a part of the polyimide may be amidic acid. In this case, the unreacted amide acid moiety (-CONH- and -COOH) is regarded as a polar group causing diffusion of copper. That is, one amide acid is calculated as a substituent having four polar groups (two of -CONH- and two of -COOH). From such a viewpoint, it is preferable to complete the imidization so that the P value described later is preferably 0.7 or less (more preferably 0.6 or less). The imidization ratio is, the Fourier transform infrared spectrophotometer (commercially available product: manufactured by Nippon spectroscopy FT / IR620) using, by measuring the infrared absorption spectrum of the polyimide film by one reflection ATR method of Korea, 1015 ㎝ ^-1 vicinity Based on the benzene ring absorber of 1780 cm & lt ^{; -1 &} gt ;.

[Amino compound]

In the polyimide resin of the present invention, examples of the amino compound having at least two primary amino groups as functional groups in the other side reacting with the ketone group of the polyimide siloxane having the structural units represented by the above-mentioned formulas (1) and (2) (I) aromatic diamines, (II) diaminosiloxanes, (III) aliphatic amines, and (IV) dihydrazide compounds.

(I) Aromatic diamine:

Examples of the aromatic diamine include those represented by the following formulas (12) and (13).

(7)

Z represents a single bond or a divalent hydrocarbon group of 1 to 15 carbon atoms, O, S, CO, SO, SO ₂ , NH ₂ or a monovalent hydrocarbon group having 1 to 6 carbon atoms; R ₁₀ represents independently a monovalent hydrocarbon group or alkoxy group having 1 to 6 carbon atoms; Or CONH, and n ₂ independently represents an integer of 0 to 4,

Examples of such aromatic diamines include 4,4'-diaminodiphenyl ether, 2'-methoxy-4,4'-diaminobenzanilide, 1,4-bis (4-aminophenoxy) benzene (4-aminophenoxy) phenyl] propane, 2,2'-dimethyl-4,4'-diaminobis Phenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, and bisaniline fluorene.

Examples of other aromatic diamines include bis [4- (3-aminophenoxy) phenyl] propane, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy)] biphenyl, bis [4- ] Biphenyl, bis [1- (3-aminophenoxy)] biphenyl, bis [4- (4-aminophenoxy) (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy)] benzophenone, bis [4- Benzophenone, bis [4,4 '- (4-aminophenoxy)] benzanilide, bis [4,4' - (3-aminophenoxy)] benzanilide, Phenyl] fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] fluorene, 9,9-bis [4- ) Phenyl] hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] 4,4'-methylene di-o-toluidine, 4,4'-methylene di-2,6-xylidine, 4,4'-methylene-2,6-diethylaniline, Diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4,4'-diaminodiphenylethane, 3,3'-diaminodiphenylethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'- - diaminodiphenylsulfone, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, benzidine, 3,3'-diaminobiphenyl , 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxybenzidine, 4,4'-diamino-p-terphenyl, p-phenylenediamine, 2,6-diaminopyridine, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis ) Benzene, 4,4 '- [1,4-phenylenebis (1-methylethylidene)] bisaniline, 4,4' - [1,3 Bis (p-aminocyclohexyl) methane, bis (p-β-amino-t-butylphenyl) ether, bis Bis (1,1-dimethyl-5-aminopentyl) benzene, 1,5-diaminonaphthalene, 2,6- Diamine, 2,4-bis (? -Amino-t-butyl) toluene, 2,4-diaminotoluene, m-xylene-2,5- diamine, p- m-xylylenediamine, p-xylylenediamine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5-diamino-1,3,4-oxadiazole, .

The above aromatic diamines may be used singly or in combination of two or more.

(II) diaminosiloxane:

The diaminosiloxane is preferably a diaminosiloxane represented by the following general formula (14) or an oligomer thereof.

[Chemical Formula 8]

(Wherein R ₁₁ and R ₁₂ represent a divalent hydrocarbon group, R ₁₃ to R _{16 each} represent a hydrocarbon group of 1 to 6 carbon atoms, and m ₁ represents a number of 1 to 20, preferably 1 to 10 )

Examples of such a diaminosiloxane include diaminopropyltetramethyldisiloxane and diaminosiloxanes represented by the above general formulas (5) to (9).

These diamino siloxanes may be used alone or in combination of two or more.

(III) Aliphatic amines:

Examples of the aliphatic amine include 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 2-methyl-1,5-diaminopentane, 1,7-diamino Heptane, 1,8-diaminooctane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,9- , Diaminoalkanes such as 1,11-diamino undecane, 1,12-diaminododecane and 4,4'-methylenebiscyclohexylamine, tris (2-aminoethyl) amine, N, N'- (2-aminoethyl) -1,3-propanediamine, bis (3-aminopropyl) ethylenediamine, 1,4-bis (3-aminopropyl) piperazine, diethylenetriamine, Amines containing a nitrogen atom such as 2'-diaminodiethylamine, 3,3'-diaminodipropylamine and N, N-bis (3-aminopropyl) methylamine, amines containing nitrogen atom such as bis (2-aminoethoxy) ethane, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [ There may be mentioned amines containing oxygen atoms, such as decane, amines or the like having a sulfur atom such as 2,2'-thio-bis (ethylamine).

These aliphatic amines may be used singly or in combination of two or more.

(IV) dihydrazide compound:

Examples of the dihydrazide compound include those represented by the following general formula (15).

[Chemical Formula 9]

In the general formula (15), R ₁₇ includes, for example, a single bond, an aliphatic group, and an aromatic group. As preferable examples of R < _{17 &} gt ;, the following compounds can be mentioned by way of example of dihydrazide compounds. For example, there may be mentioned oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, suberic acid dihydrazide, But are not limited to, dihydrazide, dihydrazide, sebastianidhydrazide, dodecane dianhydride, maleic dihydrazide, fumaric acid dihydrazide, diglycolic acid dihydrazide, , Phthalic acid dihydrazide, isophthalic acid hydrazide, terephthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 4,4-bisbenzene dihydrazide, 1,4- Diradide, 2,6-pyridine dihydrazide, itaconic acid dihydrazide, and the like.

The above-mentioned dihydrazide compounds may be used singly or in combination of two or more.

Among the amino compounds having at least two primary amino groups as functional groups as described above, a dihydrazide compound is most preferable. When the dihydrazide compound is used, the curing time of the adhesive resin composition can be shortened as compared with the case where other amino compounds are used. This is because the product obtained by the reaction of the primary amino group of the dihydrazide compound with the ketone group becomes a semicarbazone-type molecular structure and forms a dimer structure by hydrogen bonding between the NH groups between the molecules, It is believed that the reaction equilibrium is shifted toward the product side and the reverse reaction in the direction of generating the ketone group of the raw material polyimide siloxane and the amino group of the dihydrazide compound hardly occurs.

The amino compounds such as the above (I) aromatic diamines, (II) diaminosiloxanes, (III) aliphatic amines and (IV) dihydrazide compounds can be used, for example, in combination of (I) and A combination of (I) and (III), a combination of (I), (II) and (III), and combinations of (I) to (IV). Particularly, the combination of the amino compound of (I), (II) or (III) and the dihydrazide compound of (IV) It is expected that the effect of shortening the curing time is obtained according to the compounding ratio of the dihydrazide compound of (IV).

[Production of polyimide resin]

In the polyimide resin of the present invention, an amino compound having at least two primary amino groups as functional groups is added to a resin solution containing a polyimide siloxane having the structural units represented by the above general formulas (1) and (2) And then condensing the ketone group of the polyimide siloxane with the primary amino group of the amino compound. By this condensation reaction, the adhesive resin composition is cured to be a cured product. In this case, the amount of the amino compound to be added is 0.004 mol to 1.5 mol, preferably 0.005 mol to 1.2 mol, more preferably 0.03 mol to 0.9 mol, and particularly preferably 0.02 mol to 0.1 mol, in terms of the total number of the primary amino groups per mol of the ketone group It is preferable to add the amino compound so as to be 0.04 mol to 0.5 mol. The amount of the amino compound in which the total amount of the primary amino groups is less than 0.004 mol per 1 mol of the ketone group is insufficient for the crosslinking of the polyimide siloxane with the amino compound. Therefore, the adhesive resin composition containing the polyimide resin is hardened And when the addition amount of the amino compound exceeds 1.5 mol, the unreacted amino compound functions as a thermal plasticizer to lower the solder heat resistance in the copper cured product, The long-term heat resistance at a high temperature tends to be lowered.

The conditions for the condensation reaction are not particularly limited as long as the ketone group in the polyimide siloxane reacts with the primary amino group of the amino compound to form an imine bond (C = N bond). Although it depends on the kind of the amino compound, for example, when an aliphatic amine is used, it is possible to condense with a ketone group in the polyimide siloxane even at room temperature, but it is preferable to accelerate the condensation reaction by heating. In the case of using an aliphatic amine, it is preferable to carry out heat condensation in the range of, for example, 60 to 200 ° C. In the case of using an aromatic amine, heat condensation is carried out, for example, . The temperature for the heat condensation may be adjusted to, for example, to simplify the condensation process in order to release the water produced by the condensation to the outside of the system or to carry out the heat condensation reaction continuously after the synthesis of the polyimide siloxane, More preferably in the range of 120 to 220 占 폚, and more preferably in the range of 140 to 200 占 폚. The reaction time is preferably about 1 hour to 24 hours, and the end point of the reaction can be measured by measuring the infrared absorption spectrum using, for example, a Fourier transform infrared spectrophotometer (commercial product: FT / IR620 manufactured by Nihon Spectroscopy) The decrease or disappearance of the absorption peak originating from the ketone group in the polyimide siloxane near 1670 cm ^-1 and the appearance of the absorption peak originating from the imigrant near 1635 cm ^-1 .

The heating and condensation of the ketone group of the polyimide siloxane and the primary amino group of the amino compound can be carried out, for example,

(a) synthesizing (imidation) of a polyimide siloxane, followed by heating by addition of an amino compound,

(b) an excess amount of an amino compound is preliminarily injected as a diamine component, and after the synthesis (imidization) of the polyimide siloxane, a polyimide siloxane is added together with the remaining amino compounds not involved in imidization (or amidation) Heating, or

(c) heating the composition of the polyimide siloxane to which the amino compound has been added in a predetermined shape (for example, after coating it on an arbitrary substrate or after film formation).

In the case of (b) above, the excess amino compound is consumed in the reaction of sealing the acid anhydride group as a terminal substituent in the production of the polyimide siloxane, and the molecular weight of the resulting polyimide siloxane may be extremely lowered , It tends to be difficult to obtain sufficient heat resistance in the cured product. Therefore, it is preferable that the above-mentioned (b) is appropriately used within a range that does not impair the effect of the present invention when an excessive amount of amino compound is injected in advance. In order to effectively react at least two primary amino groups in an amino compound with a ketone group to form a C = N bond, the amino compound is preferably synthesized (imidized ) Is completed, it is preferable to add it. In the case of (c) above, the heat condensation can be carried out by, for example, heat of heat treatment performed when the adhesive layer of the coverlay film is formed by the composition in which the amino compound and the polyimide siloxane are mixed, And then heat or the like when thermocompression bonding is performed on a circuit board having a wiring layer.

The polyimide resin of the present invention obtained as described above is used as an adhesive agent such as a coverlay film or the like in order to maintain the adhesive force even when it is placed in a repeated high temperature environment, Is preferably 0.7 or less, more preferably 0.6 or less. The P value can be determined from the number of moles and the molecular weight of the aromatic tetracarboxylic acid anhydride residue and the aromatic diamine residue in the polyimide resin and the number of the polar groups contained in the residues as shown in the formula (iii).

 P value = {(A1 + A2) / (B1 + B2)} 100 ... (Iii)

Here, A1, A2, B1, and B2 have the same meanings as above, and the number of polar groups is calculated in the same manner as in the case of the above P value)

The P value is an index indicating the amount of the polar group contained in the polyimide resin, and the larger the P value, the larger the amount of the polar group in the polyimide resin. When used as an adhesive agent such as a coverlay film, the polar group contained in the adhesive layer causes diffusion of copper from the copper wiring. That is, when a polar group is contained in a large amount in the adhesive layer, copper from the copper wiring is diffused widely into the adhesive layer while heating is repeated. As a result, the adhesive force of the adhesive layer is weakened, and it is considered that the coverlay film is easily peeled off. In the present invention, by setting the P value of the polyimide resin to be preferably 0.7 or less (more preferably, 0.6 or less), the amount of the polar group contained in the polyimide resin can be reduced and the decrease of the adhesive force can be suppressed .

In the present invention, the calculation of the P value is carried out by using the group Ar (aromatic tetracarboxylic acid anhydride residue) and the group R ₂ (aromatic diamine residue) of the polyimide siloxane having the constitutional units represented by the general formulas (1) and (2) Is that the polarity of the entire polyimide resin is generally determined by the amount of the polar groups contained in the group Ar and the group R ₂ . Therefore, the polar group contained in the diaminosiloxane residue or the residue of the amino compound and the polar group related to the imide bond are not taken into consideration in calculating the P value.

[Action]

The reaction of the ketone group of the polyimide siloxane having the structural units represented by the general formulas (1) and (2) with the primary amino group of the amino compound is a dehydration condensation reaction, and the carbon atom of the ketone group in the polyimide siloxane and the primary As a result of the nitrogen atom of the amino group forming a C = N bond, it is thought that the polyimide siloxane is crosslinked by the amino compound to form a net-like polymer. Although it is difficult to control the orientation of the polyimide siloxane because it is difficult for the polyimide siloxane to generate intermolecular interaction, when such a cross-linked structure is formed, not only the appearance of the polyimide siloxane in its appearance is increased in molecular weight, It is considered that the heat resistance of the polyimide resin is improved and excellent solder heat resistance is obtained because the molecules can be bound to each other to some extent. In addition, since the neighborhood of the nitrogen atom in the C = N bond becomes bulky in three dimensions, the nucleophilicity of the copper atom of the polar group contained in the polyimide resin is lowered, whereby the diffusion of copper from the copper wiring into the adhesive layer And it is considered that the effect of suppressing the lowering of the adhesive strength in use in a high temperature environment can be obtained. For this reason, the amino compound used in the present invention needs to have at least two amino groups, and the number of amino groups is preferably 2 to 5, more preferably 2 to 3. Further, in the amino compound having three or more amino groups, since the cross-linked structure after the two amino groups form a C = N bond becomes bulky in three dimensions, the remaining unreacted amino group becomes difficult to react with the ketone group. Is preferably 2. Further, from the viewpoint of shortening the curing time of the adhesive resin composition as described above, it is most preferable to use a dihydrazide compound as the amino compound. The amino compound used in the present invention preferably has a molecular weight (weight average molecular weight in the case where the amino compound is an oligomer) of 5,000 or less from the viewpoint of making the network structure by crosslinking the amino compound more dense, Preferably 90 to 2,000, and more preferably 100 to 1,500. Among these, an amino compound having a molecular weight of 100 to 1,000 is particularly preferable. When the molecular weight of the amino compound is less than 90, one amino group of the amino compound forms a C = N bond to the ketone group of the polyimide siloxane, and the remaining amino group becomes bulky in three dimensions. It tends to be difficult to combine.

[Adhesive resin composition]

The adhesive resin composition of the present invention comprises a polyimide siloxane [component (A)] having a structural unit represented by the above general formulas (1) and (2) and an amino compound having at least two primary amino groups as a functional group [ B)] as an essential component. This adhesive resin composition is obtained by mixing or kneading the component (A) and the component (B), and / or by heating the component (A) and the component (B) in the presence of the ketone group of the polyimide siloxane and the amino compound Has a property of condensation reaction to form a C = N bond. That is, the polyimide resin is changed to a polyimide resin of the present invention by the condensation reaction of the polyimide siloxane and the amino compound. In the adhesive resin composition of the present invention, the weight average molecular weight of the component (A) is preferably from 10,000 to 200,000, more preferably from 20,000 to 150,000. When the weight average molecular weight of the component (A) is less than 10,000, it becomes difficult to control the flowability when the adhesive resin composition is used as a solution, and the heat resistance of the cured product tends to decrease. On the other hand, when the weight-average molecular weight exceeds 200,000, the solubility of the solvent tends to be impaired.

The adhesive resin composition preferably contains 0.004 to 1.5 mol, preferably 0.005 to 1.2 mol, more preferably 0.03 to 0.9 mol, and particularly preferably 0.04 to 0.1 mol, of primary amino groups per mol of the ketone group, 0.5 mole.

The adhesive resin composition of the present invention may contain a plasticizer together with the polyimide siloxane and the amino compound. However, the plasticizer contains a large amount of polar groups, and it is preferable that the plasticizer is not used as much as possible because it may cause diffusion of copper from the copper wiring. Further, in the adhesive resin composition of the present invention, by setting the molar ratio of diaminosiloxane of the general formula (4) in the total diamine component of the raw material to 75 mol% or more, sufficient flexibility can be obtained without adding a plasticizer, Warpage of the coverlay film can be prevented. Therefore, in the case of using a plasticizer, it is preferable that the plasticizer is blended to the extent that the effect of the present invention is not impaired.

In addition to the polyimide siloxane, the amino compound and the optional plasticizer, the adhesive resin composition of the present invention may further contain other resin components such as an epoxy resin, a curing accelerator, a coupling agent, a filler, a pigment, a solvent Can be appropriately blended. In the case of blending these optional components, the P value of the entire adhesive resin composition containing all optional components can be obtained by the following formula (iv) in which the formula (iii) is modified. Also in this case, the P value of the whole adhesive resin composition is preferably 0.7 or less (more preferably 0.6 or less), whereby the amount of the polar group contained in the adhesive resin composition can be reduced and the deterioration of the adhesive strength can be suppressed.

P value = {(A1 + A2 + An) / (B1 + B2 + Bn)} 100 ... (Iv)

[Wherein A1, A2, B1, and B2 have the same meanings as defined above,

An = (the number of polar groups in one arbitrary component) x (the number of moles of arbitrary components)

Bn = (molecular weight of one optional component) x (number of moles of optional component)

And An and Bn are added for each arbitrary component. Incidentally, the number of polar groups in any component is calculated in the same manner as in the case of the above P value)

In the case of blending optional components in the adhesive resin composition of the present invention, it is preferable that the blending amount of the optional components is 1 to 10 parts by weight, preferably 2 to 7 parts by weight, relative to 100 parts by weight of the polyimide resin, It is more preferable that the amount is in the blending amount.

The adhesive resin composition of the present invention obtained as described above has excellent flexibility and thermoplasticity when an adhesive layer is formed using the adhesive resin composition. The adhesive resin composition of the present invention can be used as a cover layer for protecting wiring portions such as FPC, Rigid- And has preferable characteristics as an adhesive for a film. When the adhesive resin composition of the present invention is used as an adhesive layer of a coverlay film, the adhesive resin composition of the present invention is applied in a solution state (for example, a varnish containing a solvent) Lt; 0 > C, the coverlay film of the present invention having the film material for coverlay and the adhesive layer can be formed. In this case, the ketone group of the polyimide siloxane and the primary amino group of the amino compound can be heat-condensed by using the heat at the time of thermocompression bonding. Also, even when the heat condensation at the time of thermocompression bonding is not sufficient, heat-condensation may be performed again after thermocompression bonding to perform heat condensation. When heat treatment is performed after thermocompression bonding, the heat treatment temperature is preferably, for example, 60 to 220 占 폚, more preferably 80 to 200 占 폚. Further, the adhesive resin composition of the present invention is applied on an arbitrary substrate in a solution state (for example, a varnish containing a solvent), dried at a temperature of, for example, 80 to 180 ° C, The cover layer film of the present invention having a film material for coverlay and an adhesive layer can be formed by thermally pressing the adhesive film at a temperature of, for example, 60 to 220 DEG C, . Also in this case, the ketone group of the polyimide siloxane and the primary amino group of the amino compound can be heat-condensed using heat at the time of thermocompression bonding. As described above, the adhesive resin composition of the present invention can be used by processing the ketone group of the polyimide siloxane and the primary amino group of the amino compound into various forms in the unreacted state. In addition, the adhesive resin composition of the present invention may be formed by forming a coating film in a solution state by screen printing on an arbitrary substrate, and drying it at a temperature of, for example, 80 to 180 ° C. Preferably at 130 to 220 DEG C for a predetermined period of time to completely cure the coating film to form a cured product. Also in this case, heat-condensation may be performed using heat at the time of curing.

[Coverage film, bonding sheet]

Examples of the film material used for the coverlay in the coverlay film of the present invention include, but not limited to, polyimide resin films such as polyimide resin, polyetherimide resin and polyamideimide resin, A resin film, a polyester-based resin film, or the like can be used. Among them, it is preferable to use a polyimide-based resin film having excellent heat resistance. The thickness of the film material used for covering is not particularly limited, but is preferably 5 占 퐉 or more and 100 占 퐉 or less, for example. The thickness of the adhesive layer is not particularly limited, but is preferably 10 탆 or more and 50 탆 or less, for example.

It is also possible to use the adhesive resin composition of the present invention in the form of a film, for example, as a bonding sheet of a multilayer FPC. In the case of using a bonding sheet, the adhesive resin composition of the present invention is applied on an arbitrary substrate film in a solution state, dried at a temperature of, for example, 80 to 180 ° C and then peeled off to obtain an adhesive film Or the adhesive film may be used in a state of being laminated with an arbitrary base film. Also in the case of using as the bonding sheet, the ketone group of the polyimide siloxane and the primary amino group of the amino compound can be heat-condensed using heat at the time of thermocompression bonding, and heat-condensation can be carried out again after thermocompression bonding.

Further, the coverlay film or the bonding sheet may be in the form of having a releasing material layer by bonding the releasing material to the adhesive surface. The material of the release material is not particularly limited as long as it can be peeled without inhibiting the shape of the coverlay film or the bonding sheet. For example, a resin film such as polyethylene terephthalate, polyethylene or polypropylene, And the like may be used.

The coverlay film or the bonding sheet obtained by molding the adhesive resin composition of the present invention and generating the heat condensation reaction by heat treatment contains the polyimide resin obtained by the reaction of the polyimide siloxane and the amino compound, And has excellent solder heat resistance. More specifically, as shown in the later embodiments, the solder heat resistance (dry) is preferably 260 占 폚 or higher, preferably 280 占 폚 or higher, more preferably 300 占 폚 or higher, and the solder heat resistance 260 DEG C or higher, and more preferably 280 DEG C or higher. By having such excellent solder heat resistance, occurrence of deformation and peeling in the soldering process can be prevented, and the yield and reliability of the produced circuit board and the like can be improved.

[Circuit board]

The circuit board of the present invention is not particularly limited as long as it includes a coverlay film or a bonding sheet obtained as described above. For example, a preferred form of the circuit board of the present invention comprises at least a substrate, a wiring layer formed of a metal such as copper formed in a predetermined pattern on the substrate, and a coverlay film of the present invention covering the wiring layer. The base material of the circuit board is not particularly limited, but in the case of FPC, it is preferable to use the same material as the above-mentioned cover material, and it is preferable to use a base made of a polyimide resin.

In the circuit board of the present invention, by using the coverlay film of the present invention, an adhesive layer having excellent flexibility and thermoplasticity is filled between wirings, and a high adhesion between the coverlay film and the wiring layer is obtained. Further, by forming an adhesive layer containing a polyimide resin obtained by the reaction of a polyimide siloxane and an amino compound, the diffusion of copper from the copper wiring is suppressed, and even if the use in a high temperature environment is repeated, . More specifically, after the long-term heat resistance test at 150 占 폚 for 1000 hours in the atmosphere, the amount of copper diffused into the adhesive layer by the measurement by an energy dispersive X-ray (EDX) analyzer Can be suppressed to 2.5% or less. As a result, it is possible to maintain the peel strength between the copper wiring layer and the cover material for coverlay after the long-term heat resistance test at 0.2 kN / m or more. Particularly, it is possible to obtain a very high peel strength of 0.4 kN / m or more by selecting the groups Ar, R ₁ and R ₂ in the general formulas (1) and (2). In addition, by making the mixing ratio of the diaminosiloxane to the total diamine component of the raw material 75 mol% or more, excellent solubility can be obtained, and warpage of the coverlay film can be prevented even without adding a plasticizer.

Further, the circuit board of the present invention may be configured as a multilayer circuit board. In this case, an adhesive film obtained from the adhesive resin composition of the present invention can be used for not only the coverlay film but also the bonding sheet.

The production of the circuit board of the present invention is not particularly limited. For example, a metal foil of a metal laminated board such as a copper clad laminate is subjected to circuit processing in a predetermined pattern by chemical etching or the like, A method of laminating a coverlay film and thermocompression bonding using, for example, a hot press apparatus or the like. In this case, the pressing conditions are not particularly limited. For example, the pressing temperature is preferably 130 占 폚 or more and 220 占 폚 or less, more preferably 140 占 폚 or more and 200 占 폚 or less, and the pressure is 0.1 MPa or more and 4 MPa or less . When the ketone group of the polyimide siloxane and the primary amino group of the amino compound are unreacted in the state of the coverlay film, the condensation reaction can be caused by using the heat at the time of thermally bonding the coverlay film to the circuit wiring have. That is, the step of arranging the adhesive layer of the coverlay film so as to be in contact with the wiring layer, the step of thermocompression bonding both members and the condensation reaction of the ketone group of the component (A) and the primary amino group of the component To form a C = N bond.

Example

Hereinafter, the present invention will be described concretely with reference to Examples, but the present invention is not limited at all by these Examples. In the following examples, unless otherwise stated, various measurements and evaluations are made as follows.

[Measurement of Adhesive Strength]

The adhesive strength was measured by placing the adhesive surface of a test piece cut into a width of 10 mm and a length of 100 mm on a glossy surface (with a rustproof metal removed) of a copper foil (35 占 퐉 thickness) under conditions of a temperature of 170 占 폚, a pressure of 1 MPa, And then heated in an oven under the conditions of a temperature of 150 占 폚 for 24 hours under the conditions of a temperature of 200 占 폚 and a pressure of 1 MPa for a time of 60 minutes for Example 21, The adhesive strength is defined as the force at the time of peeling at a rate of 50 mm / min in the direction of 180 DEG by using a tensile tester (Strogo Graph M1 manufactured by Toyooka Kogyo Co., Ltd.). In the present experiment, the case where the bonding strength was 0.2 kN / m or more was judged as "possible" and the case where the bonding strength was 0.35 kN / m or more was judged as "good".

[Measurement of weight average molecular weight (Mw)] [

The weight average molecular weight was measured by gel permeation chromatograph (HLC-8220GPC manufactured by Tosoh Corporation). Polystyrene was used as a standard substance and N, N-dimethylacetamide was used as a developing solvent.

[Evaluation method of bending]

The evaluation of the warpage was carried out in the following manner. A polyimide adhesive was applied on a 25 mu m thick Capton film so that the thickness after drying was 35 mu m. In this state, the capton film was placed on the underside, and the average height of the bent portions of the film at four corners was measured to be "good" for 5 mm or less, and "poor" for cases exceeding 5 mm.

[Evaluation method of soldering heat resistance (drying)] [

A printed circuit board on which circuits were formed with wiring width / wiring interval (L / S) = 1 mm / 1 mm was prepared by circuit processing a polyimide copper clad laminate (trade name: Espanex MC18 -25-00FRM, , The adhesive side of the test piece was placed on the wiring of the printed circuit board and pressed under the conditions of a temperature of 170 DEG C, a pressure of 1 MPa, and a time of 1 minute, and then heated in an oven at a temperature of 150 DEG C for 24 hours For Example 21, thermocompression was performed under the conditions of a temperature of 200 占 폚, a pressure of 1 MPa, and a time of 60 minutes, and the subsequent heat treatment was omitted. The test piece to which the copper foil was attached was allowed to stand at 105 DEG C and 50% RH for 1 hour, then immersed in a solder bath set at each evaluation temperature for 10 seconds, and the adhesion state was observed to find problems such as foaming, Respectively. Heat resistance is expressed by the upper limit temperature at which no problem occurs. For example, "320 ° C" means that the problem is not confirmed by evaluating the solder bath at 320 ° C (see Tables 2 to 4).

[Evaluation method of solder heat resistance (humidity)] [

A printed circuit board on which circuits were formed with wiring width / wiring interval (L / S) = 1 mm / 1 mm was prepared by circuit processing a polyimide copper clad laminate (trade name: Espanex MC18 -25-00FRM, , The adhesive side of the test piece was placed on the wiring of the printed circuit board and pressed under the conditions of a temperature of 170 DEG C, a pressure of 1 MPa, and a time of 1 minute, and then heated in an oven at a temperature of 150 DEG C for 24 hours For Example 21, thermocompression was performed under the conditions of a temperature of 200 占 폚, a pressure of 1 MPa, and a time of 60 minutes, and the subsequent heat treatment was omitted. The test piece to which the copper foil was attached was allowed to stand at 85 캜 and 85% relative humidity for 24 hours, and then immersed in a solder bath set at each evaluation temperature for 10 seconds to observe the state of adhesion thereof to find problems such as foaming, Respectively. The heat resistance is expressed by an upper limit temperature at which no problem occurs. For example, " 280 占 폚 " is evaluated in a soldering bath at 280 占 폚 to indicate that no problem is identified (see Tables 2 to 4 below).

[Tensile test]

A sample made of a polyimide resin film having a thickness of 35 mu m was cut into a rectangular shape having a width of 12.5 mm and a length of 120 mm to prepare a test piece. Using a tensile tester (Strograph R1, manufactured by Toyobo Co., Ltd.) 25 mm / min, and the chuck distance of 101.6 mm, and the value obtained by dividing the measured load by the cross sectional area (0.31 mm 2) of the test piece is taken as the tensile strength.

The following abbreviations are used in this embodiment.

BTDA: 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride

 (Polar group of BTDA: 1, p value = 0.56)

BPDA: 3,3 ', 4,4'-diphenyltetracarboxylic acid dianhydride

 (Polar group of BPDA: 0, p value = 0)

BAPP: 2,2-bis (4-aminophenoxyphenyl) propane

 (Polar group of BAPP; 2, p value = 0.53)

DAPE: 4,4'-diaminodiphenyl ether

TPE-R: 1,3-bis (4-aminophenoxy) benzene

p-PDA: p-phenylenediamine

m-TB: 2,2'-dimethyl-4,4'-diaminobiphenyl

BAFL: Bisaniline fluorene

HMDA: 1,6-hexamethylene diamine

PSX-A: diaminosiloxane represented by the above formula (5)

(Provided that the number average value of m ₁ is in the range of 1 to 20 and the weight average molecular weight is 740)

N-12: Dodecane dianhydride

(R ₁₇ in the formula (15) This C ₁₀ H ₂₀ )

ADH: adipic acid dihydrazide

(The C ₄ H ₈ R ₁₇ in the formula (15))

Synthesis Example 1

In a 1000 ml separable flask, 71.30 g of PSX-A (0.0964 mole), 9.89 g of BAPP (0.0241 mole), 38.66 g of BTDA (0.120 mole), 168 g of N-methyl- 112 g of xylene was charged and mixed well at room temperature for 1 hour to obtain a polyamic acid solution. The polyamic acid solution was heated to 190 캜 and heated and stirred for 20 hours to obtain a polyimide solution a in which the imidization was completed. The weight average molecular weight (Mw) of the polyimide resin in the obtained polyimide solution a was 122,000. The mole% of the diaminosiloxane component relative to the total diamine component is 80% (m value = 0.8). The " m value " means the molar ratio of the structural unit represented by the general formula (1) contained in the obtained polyimide resin (hereinafter the same). The P value, which is an index indicating the amount of polar groups contained in the obtained polyimide resin, is 0.55.

Synthesis Example 2

In a 1000 ml separable flask, 71.30 g of PSX-A (0.0964 mole), 9.89 g of BAPP (0.0241 mole), 38.66 g of BTDA (0.120 mole), 168 g of N-methyl- 112 g of xylene was charged and mixed well at room temperature for 1 hour to obtain a polyamic acid solution. The polyamic acid solution was heated to 190 캜 and heated and stirred for 6 hours to obtain a polyimide solution b in which imidization was completed. The weight average molecular weight (Mw) of the polyimide resin in the obtained polyimide solution b was 36,700. The mole% of the diaminosiloxane component relative to the total diamine component at this time is 80% (m value = 0.8). The P value, which is an index indicating the amount of polar groups contained in the obtained polyimide resin, is 0.55.

Synthesis Example 3

In a 1000 ml separable flask, 73.41 g of PSX-A (0.0992 mole), 10.21 g of BAPP (0.0249 mole), 36.46 g of BPDA (0.1239 mole), 168 g of N-methyl- 112 g of xylene was charged and mixed well at room temperature for 1 hour to obtain a polyamic acid solution. The polyamic acid solution was heated to 190 ° C and heated and stirred for 6 hours to obtain a polyimide solution c in which imidization was completed. The weight average molecular weight (Mw) of the polyimide resin in the obtained polyimide solution c was 27,900. The mole% of the diaminosiloxane component relative to the total diamine component is 80% (m value = 0.8). The P value, which is an index indicating the amount of polar groups contained in the obtained polyimide resin, is 0.18.

Synthesis Examples 1 to 3 are summarized in Table 1.

Reference Example 1

The polyimide solution a obtained in Synthesis Example 1 was applied to one side of a polyimide film (trade name: Capton ENS, length × width × thickness = 200 mm × 300 mm × 25 μm) manufactured by DuPont) and dried at 80 ° C. for 15 minutes To form a coverlay film having an adhesive layer thickness of 35 mu m. The infrared absorption spectrum of the adhesive layer in the coverlay film was measured using a Fourier transform infrared spectrophotometer (commercial product: FT / IR620, manufactured by Nihon Spectroscopy) to confirm absorption of the ketone group derived from BTDA near 1673 cm ^-1 Respectively. Next, the obtained coverlay film was placed on a copper foil on which a rust-preventive metal layer was removed from the surface, pressed under the conditions of a temperature of 170 占 폚, a pressure of 1 MPa, and a time of 1 minute, and then heated in an oven at a temperature of 150 占 폚 for 24 hours To obtain an evaluation sample. The evaluation results are shown in Table 2.

[Example 1]

5.78 g of BAPP (0.014 mol) was added to the polyimide solution a obtained in Synthesis Example 1 and further stirred for 1 hour to obtain polyimide solution 1.

The resulting polyimide solution 1 was applied to one side of a polyimide film (product name: Capton ENS, length × width × thickness = 200 mm × 300 mm × 25 μm, manufactured by DuPont) and dried at 80 ° C. for 15 minutes, Thereby forming a coverlay film 1 having an adhesive layer thickness of 35 mu m. The coverlay film 1 was placed on a copper foil on which a rust-preventive metal layer was removed, and pressed under the conditions of a temperature of 170 占 폚, a pressure of 1 MPa, and a time of 1 minute, and then heated in an oven at a temperature of 150 占 폚 for 24 hours, Evaluation sample 1 was obtained. The adhesive strength between the copper foil and the coverlay film after curing of the adhesive layer was 1.9 kN / m. Also, there was no problem with the warpage of the coverlay film. The infrared absorption spectrum of the adhesive layer in the evaluation sample 1 was measured using a Fourier transform infrared spectrophotometer (commercial product: FT / IR620, manufactured by Nihon Spectroscopy). As a result, absorption of the ketone group derived from BTDA was observed near 1673 cm ^-1 , And absorption of imine group was confirmed near 1635 cm ^-1 .

Next, the evaluation sample 1 was subjected to heat treatment in an oven at 150 캜 for 1000 hours in the air. The adhesion strength between the treated copper foil and the coverlay film was measured and found to be 0.80 kN / m. The peeling surface at this time was the interface between the copper and the adhesive layer.

A printed circuit board on which a circuit (wiring width / wiring interval (L / S) = 25 占 퐉 / 25 占 퐉) was formed on both sides of the polyimide film by copper was prepared and the coverlay film 1 obtained in Example 1 was mounted on a printed substrate And pressed under the conditions of a temperature of 170 DEG C, a pressure of 1 MPa, and a time of 1 minute, and then heated in an oven under the conditions of a temperature of 150 DEG C for 24 hours to obtain a wiring board 1 having a coverlay film .

[Example 2]

A polyimide solution 2 was obtained in the same manner as in Example 1 except that 5.78 g of DAPE (0.029 mole) was used instead of 5.78 g of BAPP in Example 1, 2 was obtained, and evaluation sample 2 was obtained. The adhesion strength between the copper foil and the coverlay film after curing of the adhesive layer was 1.55 kN / m. Also, there was no problem with the warpage of the coverlay film.

Next, the evaluation sample 2 was subjected to heat treatment in an oven at 150 캜 for 1000 hours in the air. The bonding strength between the treated copper foil and the coverlay film was measured and found to be 0.63 kN / m. The peeling surface at this time was the interface between copper and the adhesive layer.

A printed board on which a circuit (wiring width / wiring interval (L / S) = 25 占 퐉 / 25 占 퐉) was formed was prepared in the same manner as in Example 1 to prepare a coverlay film 2 obtained in Example 2, And placed on a circuit surface and thermocompression-bonded to obtain a wiring board 2 having a coverlay film.

[Example 3]

A polyimide solution 3 was obtained in the same manner as in Example 1 except that 5.78 g of p-PDA (0.053 mole) was used instead of 5.78 g of BAPP in Example 1, Ray film 3 was obtained, and evaluation sample 3 was obtained. The adhesion strength between the copper foil and the coverlay film after curing of the adhesive layer was 1.0 kN / m. Also, there was no problem with the warpage of the coverlay film.

Next, Evaluation Sample 3 was subjected to a heat treatment in an oven at 150 ° C for 1000 hours in an oven. The adhesion strength between the treated copper foil and the coverlay film was measured and found to be 0.54 kN / m. The peeling surface at this time was the interface between copper and the adhesive layer.

A printed board on which a circuit (wiring width / wiring interval (L / S) = 25 占 퐉 / 25 占 퐉) was formed was prepared in the same manner as in Example 1 to prepare a coverlay film 3 obtained in Example 3 Placed on a circuit surface and thermocompression-bonded to obtain a wiring board 3 having a coverlay film.

[Example 4]

A polyimide solution 4 was obtained in the same manner as in Example 1 except that 5.78 g of m-TB (0.027 mol) was used instead of 5.78 g of BAPP in Example 1, Ray film 4 was obtained, and evaluation sample 4 was obtained. The adhesion strength between the copper foil of the cover layer film and the copper foil after curing of the adhesive layer was 1.18 kN / m. Also, there was no problem with the warpage of the coverlay film.

Next, Evaluation Sample 4 was subjected to a heat treatment in an oven at 150 ° C for 1000 hours in an oven. The bonding strength between the treated copper foil and the coverlay film was measured and found to be 0.46 kN / m. The peeling surface at this time was the interface between copper and the adhesive layer.

A printed board on which a circuit (wiring width / wiring interval (L / S) = 25 占 퐉 / 25 占 퐉) was formed was prepared in the same manner as in Example 1, and the coverlay film 4 obtained in Example 4 was mounted on a printed board And placed on the circuit surface and thermocompression bonded to obtain a wiring board 4 having a coverlay film.

[Example 5]

A polyimide solution 5 was obtained in the same manner as in Example 1 except that 5.78 g of TPE-R (0.020 mol) was used instead of 5.78 g of BAPP in Example 1, Ray film 5 was obtained, and evaluation sample 5 was obtained. The adhesion strength between the copper foil and the coverlay film after curing of the adhesive layer was 2.0 kN / m. Also, there was no problem with the warpage of the coverlay film.

Next, Evaluation Sample 5 was subjected to a heat treatment in an oven at 150 ° C for 1000 hours in an oven. The bonding strength between the treated copper foil and the coverlay film was measured and found to be 0.66 kN / m. The peeling surface at this time was the interface between copper and the adhesive layer.

A printed board on which a circuit (wiring width / wiring interval (L / S) = 25 占 퐉 / 25 占 퐉) was formed was prepared in the same manner as in Example 1 to prepare a coverlay film 5 obtained in Example 5, And placed on the circuit surface and thermocompression bonded to obtain a wiring board 5 having a coverlay film.

[Example 6]

A polyimide solution 6 was obtained in the same manner as in Example 1 except that 5.78 g of BAFL (0.017 mol) was used instead of 5.78 g of BAPP in Example 1, 6 was obtained, and evaluation sample 6 was obtained. The adhesion strength between the copper foil and the coverlay film after curing of the adhesive layer was 1.22 kN / m. Also, there was no problem with the warpage of the coverlay film.

Next, Evaluation Sample 6 was subjected to a heat treatment in an oven at 150 ° C for 1000 hours in an oven. The bonding strength between the treated copper foil and the coverlay film was measured and found to be 0.65 kN / m. The peeling surface at this time was the interface between copper and the adhesive layer.

A printed board on which a circuit (wiring width / wiring interval (L / S) = 25 占 퐉 / 25 占 퐉) was formed was prepared in the same manner as in Example 1 to prepare the coverlay film 6 obtained in Example 6 And placed on the circuit surface and thermocompression-bonded to obtain a wiring board 6 having a coverlay film.

Reference Example 2

A polyimide solution to which BAPP had been added was obtained in the same manner as in Example 1 except that the polyimide solution c obtained in Synthesis Example 3 was used instead of the polyimide solution a in Example 1. This polyimide solution was applied to one side of a polyimide film (product name: Capton ENS, length × width × thickness = 200 mm × 300 mm × 25 μm) manufactured by DuPont) and dried at 80 ° C. for 15 minutes, Thereby forming a coverlay film having a layer thickness of 35 mu m. The coverlay film was evaluated in the same manner as in Example 1. [

The results of Examples 1 to 6 and Reference Examples 1 to 2 are summarized in Table 2. In Table 2, the bonding strength 1 indicates the bonding strength between the copper foil and the coverlay film after curing of the adhesive layer, and the bonding strength 2 indicates the bonding strength between the copper foil and the coverlay film after the heat treatment at 150 ° C for 1000 hours in air (The same applies to Tables 4 and 5). The molar ratio in Table 2 means the total molar ratio of primary amino groups in the amino compound to 1 mole of the ketone group in the polyimide siloxane (the same applies in Tables 3, 4 and 5).

[Example 7]

A polyimide solution 7 was obtained in the same manner as in Example 1 except that the polyimide solution b obtained in Synthesis Example 2 was used instead of the polyimide solution a in Example 1 to obtain a coverlay film 7, Evaluation sample 7 was obtained. The evaluation results are shown in Table 3.

A printed board on which a circuit (wiring width / wiring interval (L / S) = 25 占 퐉 / 25 占 퐉) was formed was prepared in the same manner as in Example 1 to prepare a coverlay film 7 obtained in Example 7, Placed on the circuit surface, and thermocompression-bonded to obtain a wiring board 7 having a coverlay film.

[Example 8]

A polyimide solution 8 was obtained in the same manner as in Example 2 except that the polyimide solution b obtained in Synthesis Example 2 was used instead of the polyimide solution a in Example 2 to obtain a coverlay film 8, Evaluation Sample 8 was obtained. The evaluation results are shown in Table 3.

A printed board on which a circuit (wiring width / wiring interval (L / S) = 25 占 퐉 / 25 占 퐉) was formed was prepared in the same manner as in Example 1, and the coverlay film 8 obtained in Example 8 was mounted on a printed board Placed on the circuit surface and thermocompression bonded to obtain a wiring board 8 having a coverlay film.

[Example 9]

A polyimide solution 9 was obtained in the same manner as in Example 3 except that the polyimide solution b obtained in Synthesis Example 2 was used instead of the polyimide solution a in Example 3 to obtain a coverlay film 9, Evaluation sample 9 was obtained. The evaluation results are shown in Table 3.

A printed board on which a circuit (wiring width / wiring interval (L / S) = 25 占 퐉 / 25 占 퐉) was formed was prepared in the same manner as in Example 1, and the coverlay film 9 obtained in Example 9 was laminated on the printed substrate Placed on the circuit surface, and thermocompression-bonded to obtain a wiring board 9 having a coverlay film.

[Example 10]

A polyimide solution 10 was obtained in the same manner as in Example 4 except that the polyimide solution b obtained in Synthesis Example 2 was used instead of the polyimide solution a in Example 4 to obtain a coverlay film 10, Evaluation sample 10 was obtained. The evaluation results are shown in Table 3.

A printed board on which a circuit (wiring width / wiring interval (L / S) = 25 占 퐉 / 25 占 퐉) was formed was prepared in the same manner as in Example 1 to prepare a coverlay film 10 obtained in Example 10 Placed on the circuit surface and thermocompression bonded to obtain a wiring board 10 having a coverlay film.

[Example 11]

A polyimide solution 11 was obtained in the same manner as in Example 5 except that the polyimide solution b obtained in Synthesis Example 2 was used instead of the polyimide solution a in Example 5 to obtain a coverlay film 11, Evaluation Sample 11 was obtained. The evaluation results are shown in Table 3.

A printed board on which a circuit (wiring width / wiring interval (L / S) = 25 占 퐉 / 25 占 퐉) was formed was prepared in the same manner as in Example 1 to prepare a coverlay film 11 obtained in Example 11, And placed on the circuit surface and thermocompression bonded to obtain a wiring board 11 having a coverlay film.

[Example 12]

A polyimide solution 12 was obtained in the same manner as in Example 6 except that the polyimide solution b obtained in Synthesis Example 2 was used instead of the polyimide solution a in Example 6 to obtain a coverlay film 12, Evaluation sample 12 was obtained. The evaluation results are shown in Table 3.

A printed board on which a circuit (wiring width / wiring interval (L / S) = 25 占 퐉 / 25 占 퐉) was formed was prepared in the same manner as in Example 1 to prepare a coverlay film 12 obtained in Example 12 And placed on the circuit surface and thermocompression bonded to obtain a wiring board 12 having a coverlay film.

Reference Example 3

The polyimide solution b obtained in Synthesis Example 2 was applied to one side of a polyimide film (trade name: Capton ENS, length × width × thickness = 200 mm × 300 mm × 25 μm) manufactured by DuPont), dried at 80 ° C. for 15 minutes To form a coverlay film having an adhesive layer thickness of 35 mu m. The coverlay film was evaluated in the same manner as in Example 1. [ The evaluation results are shown in Table 3.

The results of Examples 7 to 12 and Reference Example 3 are summarized in Table 3.

[Example 13]

A polyimide solution 13 was obtained in the same manner as in Example 1 except that 0.12 g of BAPP (0.28 mmol) was used instead of 5.78 g of BAPP in Example 1, 13 was obtained, and evaluation sample 13 was obtained. The evaluation results are shown in Table 4.

[Example 14]

A polyimide solution 14 was obtained in the same manner as in Example 1, except that 0.58 g of BAPP (1.4 mmol) was used instead of 5.78 g of BAPP in Example 1, 14 was obtained, and evaluation sample 14 was obtained. The evaluation results are shown in Table 4.

[Example 15]

A polyimide solution 15 was obtained in the same manner as in Example 1 except that 1.15 g of BAPP (2.8 mmol) was used instead of 5.78 g of BAPP in Example 1, 15 was obtained, and evaluation sample 15 was obtained. The evaluation results are shown in Table 4.

[Example 16]

A polyimide solution 16 was obtained in the same manner as in Example 1 except that 3.46 g of BAPP (8.4 mmol) was used instead of 5.78 g of BAPP in Example 1, 16 was obtained, and evaluation sample 16 was obtained. The evaluation results are shown in Table 4.

[Example 17]

A polyimide solution 17 was obtained in the same manner as in Example 1 except that 11.53 g of BAPP (0.028 mol) was used instead of 5.78 g of BAPP in Example 1, 17 was obtained, and evaluation sample 17 was obtained. The evaluation results are shown in Table 4.

[Example 18]

A polyimide solution 18 was obtained in the same manner as in Example 1 except that 17.29 g of BAPP (0.042 mole) was used instead of 5.78 g of BAPP in Example 1, 18 was obtained, and evaluation sample 18 was obtained. The evaluation results are shown in Table 4.

[Example 19]

A polyimide solution 19 was obtained in the same manner as in Example 1 except that 23.05 g of BAPP (0.056 mol) was used instead of 5.78 g of BAPP in Example 1, 19 was obtained, and evaluation sample 19 was obtained. The evaluation results are shown in Table 4.

[Example 20]

A polyimide solution 20 was obtained in the same manner as in Example 1 except that 28.82 g of BAPP (0.070 mol) was used instead of 5.78 g of BAPP in Example 1, 20 was obtained, and evaluation sample 20 was obtained. The evaluation results are shown in Table 4.

[Example 21]

5.78 g of BAPP (0.014 mol) was added to the polyimide solution a obtained in Synthesis Example 1 and further stirred for 1 hour to obtain a polyimide solution 21.

The resulting polyimide solution 21 was applied to one side of a polyimide film (manufactured by DuPont, trade name: Capton ENS, length × width × thickness = 200 mm × 300 mm × 25 μm) and dried at 80 ° C. for 15 minutes, Thereby forming a coverlay film 21 having an adhesive layer thickness of 35 mu m. The coverlay film 21 was placed on a copper foil having a rust-proof metal layer removed therefrom, and thermally bonded under the conditions of a temperature of 200 캜, a pressure of 1 MPa, and a time of 60 minutes to obtain an evaluation sample 21. The adhesion strength between the copper foil and the coverlay film after curing of the adhesive layer was 2.0 kN / m. Also, there was no problem with the warpage of the coverlay film. The infrared absorption spectrum of the adhesive layer in the evaluation sample 21 was measured. As a result, it was confirmed that the absorption of the BTDA-derived ketone group was reduced around 1673 cm ^-1 , and the absorption of the imine group was confirmed near 1635 cm ^-1 . From the measurement results, it is estimated that in the evaluation sample 21, a condensation reaction of the ketone group in the polyimide resin and the amino compound (BAPP) occurred simultaneously with the thermal compression of the coverlay film and the copper foil. Evaluation results of the evaluation sample 21 are shown in Table 4.

The results of Examples 13 to 21 are summarized in Table 4.

From the Tables 2 to 4, the coverlay films of Examples 1 to 21 in which the amino compound was added to the polyimide resin and then the condensation reaction of the ketone group and the amino compound in the polyimide resin were caused, And excellent solder heat resistance (humidity resistance) of 260 占 폚 or higher and an excellent bonding strength remarkably exceeding 0.2 kN / m even after heat treatment at 150 占 폚 for 1000 hours in the atmosphere. In addition, warpage of the coverlay film was also suppressed.

[Example 22]

1.16 g of N-12 (0.004 mol) was added to the polyimide solution a obtained in Synthesis Example 1 and further stirred for 1 hour to obtain a polyimide solution 22.

The resulting polyimide solution 1 was applied to one side of a polyimide film (product name: Capton ENS, length × width × thickness = 200 mm × 300 mm × 25 μm, manufactured by DuPont) and dried at 80 ° C. for 15 minutes, Thereby forming a coverlay film 22 having an adhesive layer thickness of 35 mu m. The coverlay film 22 was placed on a copper foil on which a rust preventive metal layer was removed and pressed under the conditions of a temperature of 170 DEG C and a pressure of 1 MPa for a time of 1 minute and then heated in an oven at a temperature of 150 DEG C for 6 hours, Evaluation Sample 22 was obtained. The warpage of the coverlay film was satisfactory. The infrared absorption spectrum of the adhesive layer in the evaluation sample 1 was measured using a Fourier transform infrared spectrophotometer (commercial product: FT / IR620, manufactured by Nihon Spectroscopy). As a result, absorption of the ketone group derived from BTDA was observed near 1673 cm ^-1 , Respectively.

The adhesive strength of the copper foil and the coverlay film after the curing of the adhesive layer of the evaluation sample 22 was 1.85 kN / m. Next, the evaluation sample 22 was subjected to heat treatment in an oven at 150 캜 for 1000 hours in the air. The bonding strength between the treated copper foil and the coverlay film was measured and found to be 0.73 kN / m.

[Example 23]

A polyimide solution 23 was obtained in the same manner as in Example 22 except that 3.47 g of N-12 (0.013 mol) was used instead of 1.16 g of N-12 in Example 22 , And a coverlay film 23 were obtained, and an evaluation sample 23 was obtained.

The adhesive strength of the copper foil and the coverlay film after the curing of the adhesive layer of the evaluation sample 23 was 1.62 kN / m. Next, the evaluation sample 23 was subjected to a heat treatment in an oven at 150 캜 for 1000 hours in the air. The bonding strength between the treated copper foil and the coverlay film was measured and found to be 0.62 kN / m.

[Example 24]

A polyimide solution 24 was obtained in the same manner as in Example 22 except that 5.78 g of N-12 (0.022 mol) was used instead of 1.16 g of N-12 in Example 22 , And a coverlay film 24 were obtained, and an evaluation sample 24 was obtained.

The adhesive strength of the copper foil and the coverlay film after the curing of the adhesive layer of the evaluation sample 24 was 1.36 kN / m. Next, the evaluation sample 24 was subjected to a heat treatment in an oven at 150 DEG C for 1000 hours in the oven. The adhesive strength of the treated copper foil and coverlay film was measured and found to be 0.58 kN / m.

[Example 25]

A polyimide solution 25 was obtained in the same manner as in Example 22 except that 1.16 g of ADH (0.007 mol) was used instead of 1.16 g of N-12 in Example 22, Ray film 25 was obtained, and evaluation sample 25 was obtained.

The adhesive strength of the copper foil and the coverlay film after the curing of the adhesive layer of the evaluation sample 25 was 1.65 kN / m. Next, the evaluation sample 25 was subjected to a heat treatment in an oven at 150 캜 for 1000 hours in the air. The adhesion strength between the treated copper foil and the coverlay film was measured and found to be 0.7 kN / m.

[Example 26]

A polyimide solution 26 was obtained in the same manner as in Example 22 except that 3.47 g of ADH (0.020 mol) was used instead of 1.16 g of N-12 in Example 22, Ray film 26 was obtained, and evaluation sample 26 was obtained.

The adhesive strength of the copper foil and the coverlay film after the curing of the adhesive layer of the evaluation sample 26 was 1.32 kN / m. Next, the evaluation sample 26 was subjected to heat treatment in an oven at 150 캜 for 1000 hours in the air. The bonding strength between the treated copper foil and the coverlay film was measured and found to be 0.56 kN / m.

[Example 27]

A polyimide solution 27 was obtained in the same manner as in Example 22 except that 5.78 g of ADH (0.033 mole) was used instead of 1.16 g of N-12 in Example 22, Ray film 27 was obtained, and evaluation sample 27 was obtained.

The adhesion strength of the copper foil and the coverlay film after the curing of the adhesive layer of the evaluation sample 27 was 1.02 kN / m. Next, the evaluation sample 27 was subjected to a heat treatment in an oven at 150 DEG C for 1000 hours in an oven. The bonding strength between the treated copper foil and the coverlay film was measured and found to be 0.48 kN / m.

Reference Example 4

A coverlay film was obtained in the same manner as in Example 1. The obtained coverlay film was placed on a copper foil on which a rust preventive metal layer was removed and pressed under the conditions of a temperature of 170 占 폚, a pressure of 1 MPa, and a time of 1 minute, and then heated in an oven at a temperature of 150 占 폚 for 6 hours, A sample was obtained. The evaluation results are shown in Table 5.

The results of Examples 22 to 27 and Reference Example 4 are summarized in Table 5.

From Table 5, the coverlay films of Examples 22 to 27 in which the condensation reaction of the ketone group and the amino compound in the polyimide resin after the addition of the dihydrazide compound to the polyimide resin significantly shortened the curing time after pressing (Dry) of 260 ° C or higher, solder heat resistance (moisture resistance) of 200 ° C or higher, and even after heat treatment at 150 ° C for 1000 hours in the air, an excellent adhesion strength exceeding 0.2 kN / m . In addition, warpage of the coverlay film was also suppressed.

Although the embodiment of the present invention has been described in detail for the purpose of illustration, the present invention is not limited to the above embodiment. Those skilled in the art will understand that many changes can be made without departing from the spirit and scope of the present invention, and they are also included in the scope of the present invention. For example, in the above embodiment, a coverlay film of a circuit board such as an FPC or an adhesive for a bonding sheet is taken as an example of the use of the polyimide resin of the present invention. However, other applications such as tape automotive bonding TAB), a chip size package (CSP), and the like.

Claims (20)

The structural unit represented by the following general formulas (1) and (2)
[Chemical Formula 1]

Wherein Ar is a tetravalent aromatic group derived from an aromatic tetracarboxylic acid anhydride, R ₁ is a divalent diaminosiloxane residue derived from a diaminosiloxane, R ₂ is a divalent aromatic diamine residue derived from an aromatic diamine each represents, while Ar and / or R ₂ contains a ketone group, and, m, n denotes the molar ratio of the structural units present, m is in the range of 0.75 ~ 1.0 I, n is in the range of 0 to 0.25. Provided that, when n is 0, the ketone group is contained in Ar.
In the polyimide siloxane having a weight average molecular weight of 10,000 to 200,000, the amino group of the amino compound having at least two primary amino groups as a functional group in a total amount of 0.004 to 1.5 mol Wherein the amino compound is reacted with the amine group to form a C = N bond, whereby the polyimide siloxane is crosslinked with the amino compound. The method according to claim 1,
In the general formula (2), n is at least 0.2. 3. The method according to claim 1 or 2,
Wherein the amino compound is a dihydrazide compound. 3. The method according to claim 1 or 2,
Wherein Ar is a group represented by the following formula (3)
(2)

Wherein the polyimide resin is a tetravalent aromatic group derived from an aromatic tetracarboxylic acid anhydride. 3. The method according to claim 1 or 2,
Wherein R ₂ is the following formula (10) or (11)
(3)

Wherein R ₉ independently represents a monovalent hydrocarbon group or alkoxy group having 1 to 6 carbon atoms, X represents CO, and n ₁ independently represents an integer of 0 to 4.
Lt; / RTI > The following components (A) and (B),
(A) a structural unit represented by the following general formulas (1) and (2):
[Chemical Formula 4]

Wherein Ar is a tetravalent aromatic group derived from an aromatic tetracarboxylic acid anhydride, R ₁ is a divalent diaminosiloxane residue derived from a diaminosiloxane, R ₂ is a divalent aromatic diamine residue derived from an aromatic diamine each represents, while Ar and / or R ₂ contains a ketone group, and, m, n denotes the molar ratio of the structural units present, m is in the range of 0.75 ~ 1.0 I, n is in the range of 0 to 0.25. Provided that, when n is 0, the ketone group is contained in Ar.
A polyimide siloxane having a weight average molecular weight of 10,000 to 200,000, and
(B) an amino compound having at least two primary amino groups as a functional group, wherein the total amount of the primary amino groups is in the range of 0.004 mol to 1.5 mol based on 1 mol of the ketone group in the component (A) The adhesive resin composition containing the component (B). The method according to claim 6,
Wherein in the general formula (2), n is at least 0.2. 8. The method according to claim 6 or 7,
Wherein the amino compound is a dihydrazide compound. 8. The method according to claim 6 or 7,
Wherein Ar is a group represented by the following formula (3)
[Chemical Formula 5]

Is a tetravalent aromatic group derived from an aromatic tetracarboxylic acid anhydride. 8. The method according to claim 6 or 7,
Wherein R ₂ is the following formula (10) or (11)
[Chemical Formula 6]

Wherein R ₉ independently represents a monovalent hydrocarbon group or alkoxy group having 1 to 6 carbon atoms, X represents CO, and n ₁ independently represents an integer of 0 to 4.
. A cured product obtained by curing the adhesive resin composition according to claim 6 or 7. A coverlay film comprising a laminate of an adhesive layer and a film material for a coverlay,
Wherein the adhesive layer is formed using the adhesive resin composition according to claim 6 or 7. A circuit board comprising a substrate, a wiring layer formed on the substrate, and a coverlay film according to claim 12 which covers the wiring layer. 14. The method of claim 13,
Wherein the peel strength of the wiring layer and the coverlay film after the long-term heat resistance test at 150 占 폚 in the atmosphere is 0.2 kN / m or more. The structural unit represented by the following general formulas (1) and (2)
(7)

Wherein Ar is a tetravalent aromatic group derived from an aromatic tetracarboxylic acid anhydride, R ₁ is a divalent diaminosiloxane residue derived from a diaminosiloxane, R ₂ is a divalent aromatic diamine residue derived from an aromatic diamine each represents, while Ar and / or R ₂ contains a ketone group, and, m, n denotes the molar ratio of the structural units present, m is in the range of 0.75 ~ 1.0 I, n is in the range of 0 to 0.25. Provided that, when n is 0, the ketone group is contained in Ar.
A polyimide siloxane having a weight average molecular weight of 10,000 to 200,000,
An amino compound having at least two primary amino groups as functional groups in the polyimide solution is added to the polyimide solution in such an amount that the amount of the amino compound having at least two primary amino groups as a functional group relative to 1 mole of the ketone group in the polyimide siloxane Adding the amino compound so that the total of the amino groups is in the range of 0.004 to 1.5 moles,
And a condensation reaction of the ketone group of the polyimide siloxane with the primary amino group of the amino compound. 16. The method of claim 15,
Wherein, in the general formula (2), n is at least 0.2. 17. The method according to claim 15 or 16,
Wherein the amino compound is a dihydrazide compound. 17. The method according to claim 15 or 16,
Wherein Ar is a group represented by the following formula (3)
[Chemical Formula 8]

Wherein the aromatic tetracarboxylic acid anhydride is a tetravalent aromatic group derived from an aromatic tetracarboxylic acid anhydride represented by the following formula. 17. The method according to claim 15 or 16,
Wherein R ₂ is the following formula (10) or (11)
[Chemical Formula 9]

Wherein R ₉ independently represents a monovalent hydrocarbon group or alkoxy group having 1 to 6 carbon atoms, X represents CO, and n ₁ independently represents an integer of 0 to 4.
Wherein the polyimide resin is a polyimide resin. A circuit board manufacturing method comprising a substrate, a wiring layer formed on the substrate, and a coverlay film covering the wiring layer,
A process for preparing a coverlay film having an adhesive layer by applying the adhesive resin composition according to claim 6 or 7 on a film material for use as a cover layer in a solution state and drying the same,
Disposing the coverlay film so that the adhesive layer is in contact with the wiring layer, and thermally compressing the coverlay film,
Wherein a ketone group of the component (A) and a primary amino group of the component (B) are subjected to a condensation reaction simultaneously with the thermocompression bonding to form a C = N bond.