WO2008018352A1

WO2008018352A1 - Photosensitive polyimide composition, positive photosensitive resin composition, and fpc

Info

Publication number: WO2008018352A1
Application number: PCT/JP2007/065135
Authority: WO
Inventors: Masaya Kakimoto; Shuhei Maeda; Akira Mizoguchi
Original assignee: Sumitomo Electric Industries, Ltd.
Priority date: 2006-08-08
Filing date: 2007-08-02
Publication date: 2008-02-14

Abstract

A photosensitive polyimide composition comprising a soluble polyimide resin which is a condensate of an aromatic tetracarboxylic dianhydride with diamines, a positive-acting photosensitizer, and a solvent in which the resin and photosensitizer are dissolved, the photosensitive polyimide composition having a pyridine content of 0.05 wt.% or lower. The photosensitive polyimide composition may be one in which the diamines comprise a siliconediamine and a hydroxylated diamine and the soluble polyimide resin has a weight-average molecular weight of 20,000-50,000 and a molecular-weight distribution which has one peak and a dispersity ratio of 2.0 or less. The positive photosensitive resin composition comprises a solvent-soluble heat-resistant resin which is a soluble polyimide resin or soluble polyamide-imide resin, a positive-acting photosensitizer, a heat-curing agent, and a solvent, and is characterized in that the heat-curing agent is a melamine-type curing agent.

Description

Specification

Photosensitive polyimide composition, positive photosensitive resin composition, and FPC technical field

The present invention relates to a photosensitive polyimide composition and a positive photosensitive resin composition used for forming a protective film or the like of an FPC (flexible printed wiring board). The present invention also relates to a method for producing the photosensitive polyimide composition and a method for producing a soluble polyimide resin used as a component of the photosensitive polyimide composition. The present invention further relates to a protective film that is formed of the photosensitive polyimide composition and functions as a cover lay of FPC, and an FPC having the protective film. The present invention further relates to a photosensitive resin film obtained from the positive photosensitive resin composition, an FPC production method using the positive photosensitive resin composition, and an FPC obtained by the production method.

Background art

[0002] In many cases, FPCs are provided with a protective film (coverlay) on the outer surface to protect the wiring. This protective film covers the wiring, the element portion, and the like, but on the other hand, it is necessary to expose the pad portion and the connection portion. In recent years, with the miniaturization and weight reduction of electronic devices, device wiring has been miniaturized, and the formation of an FPC insulating protective film (hereinafter simply referred to as “protective film”) is a sensitive process. A method using a conductive resin composition has been adopted. In this method, after forming a coating film of a photosensitive resin composition on an FPC substrate on which wiring or the like is formed, only a predetermined part is exposed and developed, and a coating film on a part such as a pad part or a connection part. This is a method for removing the protective film and enables fine processing of the protective film.

As such a photosensitive resin composition, a negative photosensitive resin composition called a solder resist (for example, acrylic epoxy type) is widely used. However, these have the disadvantage that the remaining film portion after development is crosslinked and cured, so that it has the disadvantage that it is hard and brittle and does not have sufficient flexibility. It is used. Therefore, recently, as an alternative, a flexible protective film having excellent heat resistance has been desired. From a resin (solvent soluble heat resistant resin) that has excellent heat resistance and solvent solubility (solvent soluble heat resistant resin) and a positive photosensitive agent. A method using a photosensitive resin composition is proposed. It has been proposed.

Here, as a solvent-soluble heat-resistant resin, a soluble polyimide resin using a hydroxyl-containing diamine is disclosed in Japanese Patent No. 2935994 (Patent Document 1) and Japanese Patent Application Laid-Open No. 10-224017 (Patent Document 2). Etc. are proposed. The polyimide resin is provided with solubility and alkali developability by using a monomer component which is inherently insoluble in a solvent and containing a certain proportion of diamine having a hydroxyl group.

[0005] Examples of the diamine having a hydroxyl group include a compound S represented by the following structural formula.

[0006] [Chemical 11

[0007] The soluble polyimide resin is obtained by condensing a diamine containing a diamine having a hydroxyl group as described above and an aromatic tetracarboxylic dianhydride in a molar ratio of approximately 1: 1. For example, pyridine is used as a catalyst for promoting the reaction.

[0008] Further, by adding a silicone diamine to the diamine component used for the synthesis of the soluble polyimide resin, the flame retardance of the protective film, the adhesion to the copper constituting the wiring, the flexibility, etc. are improved. That power S. Therefore, a soluble polyimide resin synthesized using a diamine component containing both a diamine having a hydroxyl group and a silicone diamine, and a positive photosensitive agent, A photosensitive resin composition (photosensitive polyimide composition) is proposed! (W099 / 19

771 Publication, Patent Document 3)

Patent Document 1: Japanese Patent No. 2935994

Patent Document 2: Japanese Patent Laid-Open No. 10-224017

Patent Document 3: WO 99/19771

Disclosure of the invention

Problems to be solved by the invention

[0009] When an FPC protective film is formed using a photosensitive polyimide composition containing a soluble polyimide resin, an adhesive is not required. Therefore, the thickness of the film is reduced, thereby reducing the rigidity of the FPC and reducing the low elastic modulus. It becomes possible and higher foldability is obtained. In addition, excellent effects such as fewer manufacturing processes can be obtained.

[0010] However, the photosensitive polyimide composition for forming a protective film has a characteristic that, in addition to the flexibility and heat resistance, development residue (remaining omission during development) hardly occurs in the exposed area ( Developability) and a force S that requires non-exposed portions (that is, portions that serve as a protective film) to be less susceptible to deterioration due to the meshing performed for the formation of connection portions, etc. When an FPC protective film is formed using a conventional photosensitive polyimide composition, there is a problem that it is difficult to achieve both developability and resistance to plating.

[0011] That is, if a residue (remaining omission) occurs in the exposed portion, the pad portion and the connecting portion become poorly exposed and cause a poor electrical connection with the outside. It is necessary to develop so as to completely remove the coating film on the light part. However, in this case, the surface of the coating film (protective film) in the unexposed area deteriorates in the gold plating process for forming the developer and the connection part, and a new defect is immediately generated. It's easy to do.

[0012] For example, when performing patterning by exposure and development, there is a problem that spot discoloration tends to occur on the surface of the coating film. This spot discoloration may deteriorate the characteristics of the protective film. Further, in the manufacture of FPC, gold plating may be necessary for forming connection portions and the like, but a protective film formed using a conventional photosensitive polyimide composition is easily deteriorated in the gold plating process.

[0013] More specifically, the unexposed area is likely to deteriorate during development, leading to whitening of the surface. Deteriorated by the pre-treatment liquid of the cookie. This phenomenon is greatly deteriorated in the force S generated by both electrolytic gold plating and electroless gold plating, particularly in the electroless gold plating process.

[0014] Furthermore, in order to increase the resistance to scratching, the protective film is required to improve the adhesive strength, particularly the adhesive strength with copper, but the conventional protective film is bonded to the copper foil constituting the FPC. There is also a problem that the force is not yet sufficient, and the developing solution may penetrate into the opening to cause deterioration of the film.

[0015] The first problem of the present invention is a photosensitive polyimide composition containing a soluble polyimide resin, which deteriorates even in the gold plating process <<, particularly, it is difficult to cause spot defects (that is, by exposure and development). (When patterning, there is little occurrence of spot discoloration on the coating surface), and furthermore, a protective film having sufficient adhesion to copper foil can be formed, and the same as conventional photosensitive polyimide compositions. It is to provide a photosensitive polyimide composition that maintains developability and hardly causes problems such as residue warpage. The present invention further provides a method for producing this photosensitive polyimide composition, a force formed by this photosensitive polyimide composition, which hardly resists deterioration in the gold plating process, and a sufficient adhesive strength to copper foil. It is providing the protective film of FPC which has these, and FPC which has this protective film.

[0016] Among conventional photosensitive resin compositions, if a protective film having a low softening temperature is used, excellent developability may be imparted and good adhesive force may be imparted. In this case, since the softening temperature of the protective film is low,

When the reinforcing plate is pressed (adhered) after the protective film is formed, wrinkles occur. The protective film is damaged during solder reflow or manual soldering.

There was a problem such as.

[0017] This problem can be prevented by introducing a rigid component into the soluble polyimide resin to improve the softening temperature. However, in this case, there is a problem that warpage is increased and peeling is likely to occur in a crosscut test due to a decrease in adhesion. The second problem of the present invention is to provide a positive-type photosensitive resin composition that does not cause such a problem of the prior art. Means for solving the problem

[0018] As a result of intensive studies, the present inventor has found water for imparting solubility to a soluble polyimide resin. As the diamine having an acid group, 2,2-bis (3-amino-4-hydroxyphenol) hexafluoropropane (hereinafter referred to as 6FAP) represented by the following structural formula (式) is used. By setting the copolymerization ratio within a predetermined range, it is possible to form a protective film having a power that hardly deteriorates even in the gold plating process and an even better adhesion to copper foil, and a conventional photosensitive polyimide composition. It has been found that the same developability as that of the product is maintained and problems such as warpage are unlikely to occur. The first aspect of the present invention, which will be described later, has been completed based on this finding.

Yes

[0019] [Chemical 2]

[0020] The present inventor has also shown that the soluble polyimide resin used as the base resin of the conventional photosensitive polyimide composition has a wide molecular weight distribution (dispersion) and two peaks in the low molecular weight region and the high molecular weight region. It was found to have a mountain distribution and a high content of low molecular weight components. And since the high molecular weight component is difficult to dissolve in the solvent, the low molecular weight component is easy to dissolve. Therefore, a residue (residual portion) is generated on the exposed portion of the FPC substrate. As a result of diligent investigation, the surface of the polyimide resin is considered to be easily degraded. I found out that they can be compatible.

[0021] The inventor further provides a method for synthesizing a soluble polyimide resin by condensation of an aromatic tetracarboxylic dianhydride and diamine! /, And the aromatic tetracarboxylic dianhydride and the above-mentioned Polymerization (condensation) is started in a state where a part of silicone diamine is insoluble and suspended in the reaction solvent, and these molecular weight ranges and molecular weight distributions are reduced by dissolving them as the polymerization proceeds. It has been found that a soluble polyimide resin can be easily synthesized. In the conventional synthesis method, the molecular weight and molecular weight distribution are easily changed for each synthesis (polymerization) lot. As a result, developability has also been a cause of lowering of resistance to scratches, but this problem can also be solved by this method. The photosensitive polyimide composition and the production method thereof according to the second aspect of the present invention to be described later have been completed based on these findings.

[0022] The present inventor further added a crosslinkable melamine as a thermosetting agent to a positive photosensitive resin composition comprising a solvent-soluble heat-resistant resin, for example, the above-described soluble polyimide resin, and a positive photosensitive agent. Even if a compound is added, a positive photosensitive patterning is possible in the same way as when it is not added, and when this melamine compound is added, a positive pattern is formed by an afterbeta after development. It is possible to crosslink the resin to increase the softening temperature and improve the high temperature elasticity. As a result, it is possible to generate creases when pressing the reinforcing plate after the protective film is formed, during solder reflow, It was found that problems such as damage to the protective film during correction by solder, problems such as warping and peeling in the cross-cut test can be solved. A third aspect of the present invention, which will be described later, has been completed based on this finding.

[0023] The present inventor further thought that spot discoloration is formed by the following mechanism. That is, at the time of development, the developing solution soaks into a defective portion on the coating film to form a minute crack or hole, and soaking further progresses between the coating film and the substrate. Conductor (copper, etc.) oxidation occurs at the part where the penetration occurred after baking after development. As a result, the conductor is colored and observed as spot discoloration. In addition, if pyridine used as a catalyst for the condensation reaction is present, the polymer constituting the coating film may interact with the pyridine to increase the affinity of the coating film for the developer, which may promote the penetration of the developer. I thought there was. Therefore, the cause of spot discoloration appears to be over-development and pyridine, and it was found that spot discoloration is less likely to occur by reducing the amount of pyridine in the photosensitive polyimide composition. The fourth aspect of the present invention, which will be described later, has been completed based on this finding.

[0024] The first aspect of the present invention is:

A photosensitive resin composition containing a soluble polyimide resin and a positive photosensitive agent, wherein the soluble polyimide resin is a condensate of aromatic tetracarboxylic dianhydride and diamine,

The diamine containing S, silicone diamine, and diamine having a hydroxyl group, and the diamine having a hydroxyl group is 6FAP. The photosensitive polyimide composition is characterized in that the content of 6FAP is 1 to 50 mol% with respect to the total diamine (Claim 1).

[0025] The photosensitive polyimide composition according to the first aspect contains a soluble polyimide resin, which is a condensate of aromatic tetracarboxylic dianhydride and diamine, as a base polymer. The condensate of aromatic tetracarboxylic dianhydride and diamine means a reaction product obtained by condensing aromatic tetracarboxylic dianhydride and diamine in an equimolar amount of about 1: 1. The diamine used for the synthesis of the soluble polyimide resin is a mixture of a silicone diamine and a diamine having a hydroxyl group, and other diamines added if necessary. The developability is obtained by the hydroxyl group of the diamine having a hydroxyl group.

[0026] In the photosensitive polyimide composition of the first aspect, Jiamin having a hydroxyl group is a 6FAP, and characterized in that the content of 6FAP is 1 to 50 mol ^_0/0 for all Jiamin To do. When the diamine having a hydroxyl group is 6FAP, developability is further improved. Further, by making the content of the hydroxyl group-containing diamine to 1 to 50 mol% with respect to the total diamine, the developability, heat resistance, and resistance to plating can be improved. Therefore, it is possible to obtain excellent developability, heat resistance, and meticulous resistance with the photosensitive polyimide composition of the first embodiment having both of the characteristics.

[0027] The soluble polyimide resin constituting the photosensitive polyimide composition of the first aspect comprises an aromatic tetracarboxylic dianhydride, silicone diamine, 6FAP, and other diamine added as necessary, as a solvent. It can be produced by dissolving and heating to cause a condensation reaction. If the same solvent as the solvent of the photosensitive polyimide composition is used as the solvent, it is preferable because a solvent replacement operation is not necessary in the production of the photosensitive polyimide composition. Accordingly, examples of the solvent include those described later as the solvent for the photosensitive polyimide composition.

Yes

[0028] The invention according to claim 2 is a preferred embodiment of the photosensitive polyimide composition of the first embodiment, and the weight average molecular weight of the soluble polyimide resin that is the base polymer of the photosensitive polyimide composition is 20000 to 50000 2. The photosensitive polyimide composition according to claim 1, wherein the molecular weight distribution is a single peak distribution.

[0029] In the first embodiment, the soluble polymer having such an average molecular weight and molecular weight distribution. By using a mid resin as a base polymer, it is difficult for the development residue to be generated during development, and the insulating film pattern obtained from the parenthesis composition has excellent heat resistance, solvent resistance, and mechanical strength. Insulating film patterns satisfying the required characteristics can be obtained. In particular, when the molecular weight distribution force distribution is small and the dispersion is small, the effect of hardly causing the development residue and excellent heat resistance, solvent resistance, and mechanical strength becomes remarkable.

[0030] The single peak distribution means that the molecular weight distribution curve has substantially one peak.

The dispersion represents the extent of the molecular weight distribution, and specifically is a value of (weight average molecular weight / number average molecular weight). The weight average molecular weight, number average molecular weight, and molecular weight distribution curve are values measured by GPC and calculated using standard polystyrene (TSK standard polystyrene). In addition, a soluble polyimide resin having such an average molecular weight and molecular weight distribution can be produced by the method described in claim 18 described later.

[0031] The second aspect of the present invention provides:

It contains the diamine power S, silicone diamine and diamine having a hydroxyl group, and the soluble polyimide resin has a weight average molecular weight of 20000 to 50,000, a molecular weight distribution of one peak distribution, and a dispersion of 2.0 or less. It is a photosensitive polyimide composition characterized in that (Claim 3).

[0032] The photosensitive polyimide composition of the second aspect also contains a soluble polyimide resin that is a condensate of aromatic tetracarboxylic dianhydride and diamine as a base polymer, and the diamine includes silicone diamine and hydroxyl group. Containing diamine. The meaning and action of the condensate of aromatic tetracarboxylic dianhydride and diamine are the same as in the first embodiment.

[0033] In the photosensitive polyimide composition of the second aspect, the soluble polyimide resin as the base polymer has a weight average molecular weight in the range of 20000 to 50000, a molecular weight distribution of one peak distribution, and a dispersion of 2. It is 0 or less. By adding a photosensitizer to a soluble polyimide resin having such an average molecular weight, molecular weight distribution, and dispersion, As a photosensitive polyimide composition, high photosensitivity and developability are obtained, and development residues are less likely to occur during development, and the coating film obtained from the parenthesis composition has excellent heat resistance, solvent resistance, and resistance to plating. Thus, a protective film satisfying the required characteristics can be easily obtained. In particular, when the weight average molecular weight is in the range of 25,000 to 45000, a protective film having further excellent characteristics can be obtained.

[0034] The photosensitive polyimide composition of the second aspect is

A condensation reaction step of condensing an aromatic tetracarboxylic dianhydride with a diamine containing a silicone diamine and a diamine having a hydroxyl group;

In the condensation reaction step, the aromatic tetracarboxylic dianhydride and the silicone diamine are condensed in a solvent that dissolves only a part of the aromatic tetracarboxylic dianhydride and the silicone diamine. And then, it is produced by a method for producing a soluble polyimide resin, characterized in that it is carried out by dissolving aromatic tetra force rubonic acid dianhydride and silicone diamine in the solvent while raising the temperature. Yes (claim 18).

[0035] This soluble polyimide resin production method is the same as the conventional polyimide resin production method in that it has a condensation reaction step of condensing aromatic tetracarboxylic dianhydride and diamine. In this process, the aromatic tetracarboxylic dianhydride and diamine are condensed in a solvent that dissolves only a part of the aromatic tetracarboxylic dianhydride and silicone diamine. Then, condensation is started in a state where the aromatic tetracarboxylic dianhydride and the silicone diamine are suspended, and then the aromatic tetracarboxylic acid 2 anhydrous and the silicone diamine are used in the solvent while raising the temperature. It is characterized in that it is dissolved and further condensed.

[0036] Examples of the solvent that dissolves only a part of the aromatic tetracarboxylic dianhydride and the silicone diamine include γ-petit-mouth rataton. The invention according to claim 19 is a preferred embodiment of the method for producing the soluble polyimide resin, wherein the aromatic tetracarboxylic acid 2 anhydrous is 4,4′-oxydiphthalic acid dianhydride ( 19. The production method according to claim 18, characterized in that it comprises OPDA), is a diamine force 6FAP having a hydroxyl group, and the solvent is γ-butyroratatone. Detailed explanation of OPDA will be described later.

[0037] In the method of claim 19, first, γ-butyrolatatone in which silicone diamine is a solvent is used. The aromatic tetracarboxylic dianhydride OPDA is then added gradually and then stirred for a predetermined time to initiate the polymerization. Alternatively, the aromatic tetracarboxylic dianhydride may be first added to the solvent γ-butyrolatatone, and then the silicone diamine may be gradually added to initiate the polymerization. At this time, because it is room temperature, a part of the silicone diamine and aromatic tetracarboxylic dianhydride OPDA that is difficult to dissolve dissolves and the rest suspends. Thereafter, the reaction system is heated and heated. Silicone diamine and OPDA react gradually and dissolve in y-petit mouth ratatones as the temperature rises. When the temperature is raised to a predetermined temperature, the reaction is performed at that temperature for a predetermined time. After that, stop heating and let it cool naturally to near room temperature.

[0038] Thereby, it is possible to easily obtain a soluble polyimide resin (polyimide silicone) having a weight average molecular weight in the range of 20000 to 50,000, a molecular weight distribution of one peak distribution, and a dispersion of 2.0 or less. I'll do it.

[0039] Instead of γ-petit-mouth rataton alone, a solvent mixture of γ-petit-mouth rataton with methinole benzoate, ethyl benzoate, methyl ethyl ketone (ΜΕΚ), acetone, etc. was used as the solvent. If all of the amine and OPDA are dissolved from the beginning of the reaction and the reaction proceeds in a homogeneous system, the molecular weight distribution becomes a two-peak distribution with another peak on the high molecular weight side. As a result, developability deteriorates and a residue tends to remain in the exposed area.

[0040] The fourth aspect of the present invention is as follows.

A photosensitive polyimide composition containing a soluble polyimide resin, a positive photosensitive agent and a solvent for dissolving them,

The soluble polyimide resin is a condensate of aromatic tetracarboxylic dianhydride and diamine,

The diamine contains a diamine having a hydroxyl group.

A photosensitive polyimide composition (claim 9), wherein the content power of pyridine contained in the photosensitive polyimide composition is 0.05% by weight or less.

[0041] The photosensitive polyimide composition of the fourth embodiment contains a soluble polyimide resin that is a condensate of aromatic tetracarboxylic dianhydride and diamine, and the diamine contains diamine having a hydroxyl group. The meaning of aromatic tetracarboxylic dianhydride and diamine condensate and its The action and the like are the same as in the first embodiment.

[0042] The photosensitive polyimide composition according to the fourth aspect is characterized in that the content of pyridine contained therein is 0.05% by weight or less. Pyridine is used as a catalyst for the condensation reaction of aromatic tetracarboxylic acid dihydrate and diamine. As a result, the conventional photosensitive polyimide composition contains pyridine. It was found that the problem of spot discoloration can be greatly reduced by removing from the photosensitive polyimide composition and making its content 0.05% by weight or less based on the total weight of the photosensitive polyimide composition.

[0043] The photosensitive polyimide composition of the fourth aspect,

A condensation step of condensing aromatic tetracarboxylic dianhydride and diamine in the presence of pyridine to synthesize a soluble polyimide resin;

After the condensation step, pyridine removal step for removing pyridine from the reaction system until the content is 0.05% by weight or less, and

It can be produced by a production method (Claim 17) comprising a step of mixing the soluble polyimide resin, a positive photosensitive agent and a solvent.

[0044] In this production method, a condensation reaction step of condensing an aromatic tetracarboxylic dianhydride and diamine to obtain a soluble polyimide resin, and mixing the obtained soluble polyimide resin and a positive photosensitive agent are performed. The point which has a process is the same as the manufacturing method of the conventional photosensitive polyimide composition. However, the production method of the present invention is characterized by having a pyridine removal step of removing pyridine from the reaction system after the condensation step until the content thereof is 0.05% by weight or less.

[0045] The method for removing pyridine is not particularly limited. For example, the condensation of aromatic tetracarboxylic dianhydride and diamine is usually carried out using a solvent, and after completion of the reaction, the solvent S is removed to remove pyridine and adjust the concentration. By evaporating the solvent for a longer time, the amount of pyridine in the system can be reduced, and the content can be reduced to 0.05% by weight or less by adjusting the conditions. After the reaction is completed, pyridine can also be removed by a method of reprecipitation and purification using a solvent insoluble in the resin such as methanol and again dissolving in a solvent such as γ-petit-mouth rataton.

[0046] The invention according to claim 10 is a preferred embodiment of the photosensitive polyimide composition of the fourth embodiment. 10. The photosensitive polyimide composition according to claim 9, wherein the weight average molecular weight of the soluble polyimide resin that is a base polymer of the photosensitive polyimide composition is 20000 to 50000. By using a soluble polyimide resin having such an average molecular weight as a base polymer, it is difficult for development residue to occur during development, and the heat resistance, solvent resistance, and mechanical strength of the insulating film pattern obtained from the parenthesis composition are reduced. Therefore, an insulating film pattern that easily satisfies the required characteristics can be obtained. More preferably, the weight average molecular weight is in the range of 25000-45000.

[0047] In both the second aspect and the fourth aspect, the copolymerization ratio of the diamine having a hydroxyl group used in the production of the photosensitive polyimide composition, that is, the hydroxyl group in the total diamine used in the condensation. The ratio of diamine having a dimer is preferably in the range of 1 to 50 mol%. (Claim 1 The smaller the copolymerization ratio of diamine having a hydroxyl group, the smaller the copolymerization ratio of the obtained photosensitive polyimide composition is used. In order to achieve a sufficient image, the developing property of the film pattern is low, and a concentrated alkaline solution or an organic solvent is required as a developer, while copolymerization of a diamine having a hydroxyl group. The higher the ratio, the lower the heat resistance of the coating film formed by applying the composition to a substrate or the like and curing it, and the lower the coating resistance of the coating film. Deterioration of the protective film is likely to occur Therefore, the range of 1 to 50 mol% is preferable from the viewpoints of image resistance, matt resistance and the like.

[0048] The invention according to claim 12 is characterized in that the diamine having a hydroxyl group is 6FAP, or the photosensitive polyimide according to any one of claims 9 to 11 It is a composition. In either of the second aspect and the fourth aspect, the diamine having a hydroxyl group used in the production of the photosensitive polyimide composition is the one used in the conventional photosensitive polyimide composition, that is, the above-described examples. Although compounds can be mentioned, 6FAP is preferable in order to obtain excellent developability. By using 6FAP, film deterioration and film loss during development can be reduced.

[0049] The diamine component used for the synthesis of the soluble polyimide resin of the fourth aspect can further contain a silicone diamine, and is synthesized using the diamine component containing both the diamine having a hydroxyl group and the silicone diamine. The soluble polyimide resin is preferably used. In addition, the diamond used for the synthesis of the soluble polyimide resin of the first and second embodiments. The silicone component contains silicone diamine. By containing silicone diamine, it is possible to improve the flame retardance of the protective film, the adhesion to copper constituting the wiring, the flexibility, etc. with the force S.

[0050] Here, the silicone diamine is a compound having a siloxane group in the skeleton and two primary amino groups at its ends and the like, for example, represented by the following structural formula (III) Is widely adopted.

[0051] [Chemical 3]

H ₂ N—

In the formula, a represents a number of 1 to about 10,000. In addition to the above, those represented by the following structural formulas are also exemplified.

[0052] [Chemical 4]

(CH ₂ ) ₃ — NH ₂

In the formula, a + b (a if not including formula force ¾) is a number from 1 to about 10,000.

[0053] Specific examples of silicone diamines include: Toray Dow Cowing. Silicone BY16 — 853U, BY16-853C, Shin-Etsu Chemical X—22—1660B—3, KF—8010, X—22—161A X-22-161B and the like.

[0054] The invention according to claim 13 is a preferred embodiment of the photosensitive polyimide composition of the first, second and fourth aspects, wherein the diaminergic silicone diamine is all diamine. The photosensitive polyimide composition according to any one of claims 1 to 3, or the photosensitive polyimide composition according to any one of claims 9 to 12, wherein the photosensitive polyimide composition is contained in an amount of 5 to 60 mol% based on

[0055] In any of the first aspect, the second aspect, and the fourth aspect, the content of the silicone diamine is preferably 5 to 60 mol% with respect to the total diamine. In particular, when the molecular weight of silicone diamine is about 500 to about 1000, it is preferably 10 to 60 mol% with respect to the total diamine! /. If it exceeds 60 mol%, the glass transition temperature of the film decreases and heat resistance decreases, whereas if it exceeds 5 mol%, the warpage of the film tends to increase. The More preferably, it is the range of 30-50 mol%. However, heat resistance and film warpage are also affected by the structure and content of other diamines.

That is, in any of the first aspect, the second aspect, and the fourth aspect, as the photosensitive polyimide composition, the above-mentioned diamine power silicone diamine is used in an amount of 5 to 60 And containing 1 to 50 mol% of diamine having a hydroxyl group based on the total diamine.

[0057] The invention of claim 14 is a preferred embodiment of the photosensitive polyimide composition of the first, second and fourth embodiments, wherein the silicone diamine has a weight average molecular weight. 14. The photosensitive polyimide composition according to claim 13, wherein the photosensitive polyimide composition is 1000 or less. If the weight average molecular weight of the silicone diamine exceeds 1000, the adhesive strength with copper foil or the like tends to decrease, so it is preferably 1000 or less. At this time, a in the structural formula (III) is about 8 to 9 or less.

[0058] In the first aspect, the second aspect, and the fourth aspect,! /, In the deviation! /, The diamine that can be used in the production of the photosensitive polyimide composition has the above-mentioned hydroxyl group. In addition to the diammine and silicon diamine which are included, other diamines can be included within the scope not departing from the gist of the present invention.

[0059] Other diamines include, for example, bis (3aminopropyl) ether ethane, 3,3, -diamino-4,4'dihydroxydiphenylsulfone, 4,4'diamino3,3'dihydroxybiphenyl, 2,2bis. [4- (4 aminophenoxy) fenenole] hexafluoropropane, siloxane diamine, bis (3-aminopropinole) ether ethane, N, N bis (3-aminopropyl) ether, 1, 4 bis (3 —Aminopropyl) piperazine, isophorone diamine, 1,3 ′ bis (aminomethyl) cyclohexane, 3,3 ′ dimethyl-4,4′-diaminodicyclohexylmethane, 4,4′-methylene bis (cyclohexylamine), 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diamino -Diphenyl sulfone, 3,4'-diamino-diphenyl sulphone, 3,3'-diamino-diphenyl sulfone, 2,4'-diaminodiphenyl ether, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 2,2 bis [4 (4-aminophenoxy) phenol] propane, 2,2 bis [4-1 (4-1 Nophenoxy) fenenole] hexafluoropropane, bis [4- (4-aminophenoxy) phenol binole] sulfone, bis [4 (3-aminophenoxy) phenenole] sulfone, 4, 4′bis (4 -Aminophenoxy) biphenyl, 1,4-bis (4-aminophenoxy) benzene, 4,4'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 3 , 3 'diamine, 4, 4' dihydroxydiphenyl sulfone, 2,4 diaminotoluene, 2,5 diaminotoluene, 3,5 diamineaminobenzoic acid, 2,6 diamineaminopyridine, 4, 4 'diamine, 3, 3' dimethoxybiphenyl, 4 , 4, diamine, 3, 3 'dimethylenobiphenyl, 9, 9, and bis (4-aminophenyl) fluorene.

[0060] Among them, 1,3-bis (3-aminophenoxy) benzene (hereinafter referred to as “1,3-APB”) represented by the following structural formula (IV) is a viewpoint of transparency and flexibility. More preferably used.

[0061] [Chemical 5]

[0062] In addition, bis [4- (3aminophenoxy) phenyl] sulfone (hereinafter referred to as “: BAPSM”) and 1,4-bis (3-aminophenoxy) benzene (hereinafter referred to as “1, 4 APB”). The use of) is also preferred. In addition, 1,3-APB and diammine represented by the following structural formula can also be used.

[0063] [Chemical 6]

The invention according to claim 15 is a preferred embodiment of the photosensitive polyimide composition according to the first, second and fourth embodiments, wherein the aromatic tetracarboxylic dianhydride is 4, Four The photosensitive polyimide according to claim 1, characterized in that it contains oxydiphthalic acid dianhydride, V, deviation, or claim 9! It is a composition.

[0065] In the first aspect, the second aspect, and the fourth aspect,! /, In fact, the aromatic tetracarboxylic dianhydride constituting the soluble polyimide compound is 3, 3 ', 4, 4' biphenyltetracarboxylic dianhydride, 3, 3 ', 4, 4'-benzophenone tetracarboxylic dianhydride, 4, 4'-oxydiphthalic dianhydride, 3, 3' , 4, 4'-diphenylsulfone tetracarboxylic dianhydride, bicyclo (2, 2, 2) -otato 7-ene 2, 3, 5, 6 tetracarboxylic dianhydride, 1, 2, 4, 5 Cyclohexanetetracarboxylic dianhydride, pyromellitic dianhydride, 2,2 bis (3,4 dicarboxylicoxyphenyl) hexafluoropropane dianhydride, 5 (2,5 dixotetrahydro) Furyl) -3 methyl-3 cyclohexene mono 1,2 dicarboxylic acid dianhydride and the like.

[0066] Among them, OPDA force represented by the following structural formula (V) is preferable from the viewpoint of transparency and flexibility, and therefore, an aromatic tetracarboxylic dianhydride containing OPDA is preferably used.

[0067] [Chemical 7]

[0068] In many cases, the soluble polyimide resin used in the photosensitive polyimide composition of the present invention has already been imidized at the stage of synthesis. Therefore, heating for forming an imide ring is unnecessary, and a heat treatment step may be performed if necessary after pattern formation. This is done to evaporate residual solvent contained in the pattern. Therefore, heating at a high temperature necessary to form an imide ring is not necessary.

[0069] The photosensitive polyimide composition of the present invention contains a positive-type photosensitive agent and a solvent that dissolves the soluble polyimide resin and the positive-type photosensitive agent together with the soluble polyimide resin. Po Examples of di-type photosensitizers include naphthoquinone diazide compounds, and particularly preferred are naphthoquinone diazide sulfonyl esters of aromatic polyhydroxy compounds.

16).

[0070] Examples of aromatic polyhydroxy compounds include 2, 3, 4-trihydroxybenzophenone, 2, 3, 4, monotrihydroxybenzophenone, 2, 4, 6 trihydroxybenzophenone, 2, 3 , 4, 4, —tetrahydroxybenzophenone, nopolac resin and the like. The naphthoquinone diazide sulfonyl compounds that form esters with aromatic polyhydroxy compounds include 1,2-naphthoquinone-1,2 diazide-1,5 sulfonic acid, 1,2 naphthoquinone-1,2 diazido-1,4-sulfonic acid, 6-diazodihydro 5-oxo1 naphthalene Examples include sulfonic acid. Specific product names include PC-5, NT-200, 4N T-300 manufactured by Toyo Gosei Co., Ltd., DTEP-300, DTEP-350 manufactured by Daito Chemix.

[0071] The amount of the positive photosensitive agent needs to be adjusted depending on the film thickness of the coating film, the type of the photosensitive agent, etc., but it is 5 to 30 parts by weight based on 100 parts by weight of the soluble polyimide resin. It is preferable to do this. If the amount is less than 5 parts by weight, sufficient sensitivity may not be obtained and a residue may be generated. If the amount exceeds 30 parts by weight, the heat resistance and solvent resistance of the resin film formed by curing of the composition will decrease. There is a case. 10 to 20 parts by weight is more preferable.

[0072] The photosensitive polyimide composition of the present invention can be obtained by mixing the soluble polyimide resin thus produced and a positive photosensitive agent. This mixing step can be performed in the same manner as in the case of a conventional photosensitive polyimide composition, for example, by dissolving the soluble polyimide resin and the positive photosensitive agent in a solvent.

[0073] As a solvent for dissolving the soluble polyimide resin and the positive photosensitive agent,

N-methyl-2-pyrrolidone, N, N'-dimethylacetamide, dimethylformamide, dimethyl sulfoxide, acetonitrile, diglyme, _{Ίbutyrolataton} , _Ύ- valerolataton, _phenol , toluene, dioxane, tetrahydrofuran, Examples include sulfolane and hexamethylphosphoramide. Among these, 7 petit-mouth rataton is preferably used from the viewpoint of high volatility and odor. The amount used is preferably 1 to 20 times (weight ratio) of the soluble polyimide resin. Soluble polyimide resin as solvent It is preferable to use the same solvent as that used for the synthesis because the solvent replacement operation is not necessary in the production of the photosensitive polyimide composition. Therefore, like the case where the soluble polyimide resin is synthesized by the method of claim _19, Ί - if petit port la out emissions is used in the synthesis, also γ- Petit port as a solvent of a photosensitive polyimide composition Rataton Is preferred.

[0074] The photosensitive polyimide composition of the present invention obtained as described above can be used for forming a protective film of FPC. The present invention further provides a protective film for covering the wiring of the FPC, the curing of the photosensitive polyimide composition according to any one of claims 1 to 3 or claim 9 to claim 16. There is provided a protective film (claim 20) characterized by comprising a material.

[0075] This protective film is provided on the outer surface of the FPC and covers them in order to protect the wiring, the element portion, and the like. On the other hand, since it is necessary to expose the connection part, the pad part, etc., first, the photosensitive polyimide composition is applied to the entire surface of the FPC, and if necessary, the solvent is removed by heating (prebaking) to remove the solvent. After the film is formed, a pattern is formed (patterned) through an exposure process in which only a predetermined portion is irradiated with an actinic ray such as ultraviolet rays through a mask or the like, and a development process in which development is performed with an alkaline developer. It is formed by the method of removing.

[0076] Examples of the alkali developer include sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonium hydrogen carbonate, tetramethyl ammonium hydroxy. A basic solution in which a salt (ΤΜΑΗ) or the like is dissolved in water or alcohol, or a solution in which a basic compound is increased by further adding an amine compound to this solution is used.

[0077] When the development is performed at room temperature, the development time is suitably about 4 to 30 minutes. In less than 4 minutes, it is difficult to obtain good development results. On the other hand, if it exceeds 30 minutes, pattern peeling or the like tends to occur. In addition, the power that can further reduce the occurrence of spot discoloration by setting the development time within 30 minutes When the photosensitive polyimide composition of the fourth aspect is used, even if the development time exceeds 30 minutes. The occurrence of spot discoloration can be reduced to a practical level.

The present invention further provides FPC (Claim 21) having the protective film according to Claim 20. [0079] The third aspect of the present invention provides:

A positive photosensitive resin composition comprising a solvent-soluble heat-resistant resin, a positive photosensitive agent, a thermosetting agent, and a solvent,

The thermosetting agent is a melamine-based curing agent,

The solvent-soluble heat-resistant resin is a positive photosensitive resin composition characterized in that it is a polyimide resin or a polyamide-imide resin containing diamine having a hydroxyl group as a structural unit (claim 4).

[0080] The positive-type photosensitive resin composition of the third aspect includes a thermosetting agent that causes a crosslinking reaction by heating to cure the resin. When this is used, patterning is performed by exposure and development. Heat curing can be performed later. As a result, a protective film that is resistant to thermal deformation can be obtained, and when a reinforcing plate is pressed after the protective film is formed (for example, adhesion is performed under conditions of about 180 ° C × 30 minutes), In addition, it is possible to suppress damage to the protective film during solder reflow or during manual solder correction.

[0081] The positive photosensitive resin composition of the third aspect is characterized by using a melamine curing agent as the thermosetting agent. Other possible thermo-curing agents include epoxy-based curing agents and isocyanate-based curing agents. When epoxy-based curing agents are used, development that shortens the life of the positive photosensitive resin composition. There are problems such as possible deterioration due to alkali at the time. Also, when an isocyanate curing agent is used, there are problems such as poor storage stability. On the other hand, when a melamine curing agent is used, it is preferable because it has characteristics such as excellent storage stability of the positive photosensitive resin composition!

[0082] The invention according to claim 6 is the positive photosensitive resin composition according to the third aspect, wherein the melamine-based curing agent power is a methylolmelamine-based compound represented by the following structural formula (I). It is characterized by this.

[0083] [Chemical 8]

N 丫 N

W

[Wherein, W represents —NY Y, Y and Y are each independently hydrogen, —CH—ΟΖ.

5 6 5 6 2 or a phenyl group, and Υ to 独立 each independently represent hydrogen or —CH 、,

1 4 2

Ζ represents hydrogen or an alkyl group having 6 to 6 carbon atoms. )

[0085] The methylol melamine-based compound represented by the above formula is particularly excellent in storage stability, excellent developability, and resistance to mesh as compared with an epoxy-based curing agent and an isocyanate-based curing agent. This is preferable. Examples of the methylone melamine compound represented by the above formula include hexamethylol melamine, alkylated hexamethylol melamine, partially methylolated melamine and its alkylated product, tetramethylol benzoguanamine, alkylated tetramethylol benzoguanamine, It is possible to list partially methylolated benzoguanamine and its alkylated compounds.

[0086] These compounds may be used alone or in combination of two or more. Furthermore, other thermosetting agents such as an epoxy-based curing agent and an isocyanate-based curing agent may be used in combination as long as the gist of the present invention is not impaired.

[0087] The solvent-soluble heat-resistant resin constituting the positive photosensitive resin composition of the present invention is soluble in an alkaline aqueous solution used as an organic solvent developer and has excellent heat resistance. Specifically, it is a soluble polyimide resin or a soluble polyamideimide resin containing diamine having a hydroxyl group in its constituent unit.

[0088] As in the case of the first, second and fourth embodiments, the soluble polyimide resin comprises an aromatic tetracarboxylic dianhydride and a diamine containing a diamine having a hydroxyl group. It can be obtained by condensation in equimolar amounts. Soluble polyamideimide resin consists of aromatic tetracarboxylic dianhydride plus aromatic tricarboxylic anhydride and diamine containing hydroxyl-containing diamine, acid anhydride: diamin = approximately 1: 1 equimolar amount Obtained by condensation with It is a resin having an imide bond and an amide bond in the molecule.

[0089] As the acid anhydride as a raw material of the soluble polyamideimide, generally used is an aromatic tricarboxylic rubonic acid anhydride as described below, with an aromatic tetracarboxylic dianhydride added. The invention of claim 5 is the positive photosensitive resin composition according to the third aspect, wherein the polyimide resin or polyamideimide resin strength S, the aromatic tetracarboxylic dianhydride, or the aromatic tricarboxylic anhydride. The present invention provides a positive photosensitive resin composition characterized by being a condensed product of an acid anhydride obtained by adding aromatic tetracarboxylic dianhydride to diamine and diamine.

[0090] Examples of the diamine having a hydroxyl group include compounds represented by the following structural formulas as in the first, second and fourth embodiments (claim 7).

[0091] [Chemical 9

[0092] Among these, the use of 6FAP is preferable because film deterioration during development can be further reduced.

[0093] The copolymerization ratio of the diamine having a hydroxyl group, that is, the ratio of the diamine having a hydroxyl group in the total diamine used for the condensation is also the same as in the first, second and fourth embodiments; A range of 50 mono% is preferable, and the reason is the same. [0094] As in the first, second, and fourth aspects, in the third aspect, the diamine constituting the soluble polyimide resin or the soluble polyamideimide resin may contain a silicone diamine. Examples of the silicone diamine that are similar to each other include the silicone diamines exemplified above, and the effects of the blending are also the same. Furthermore, the diamine may contain other diamines in addition to the diammine having a hydroxyl group and the silicone diamine, as long as the gist of the present invention is not impaired. The diamine exemplified in the case of the fourth embodiment can be used in the same manner.

[0095] When the solvent-soluble heat-resistant resin is a soluble polyamideimide resin, examples of the aromatic tricarboxylic acid anhydride that is a raw material of the soluble polyamideimide resin include trimellitic anhydride (TMA), 2- (3 , 4 dicarboxyphenyl) -2- (3 carboxyphenyl) propan anhydride, (3, 4-dicarboxyphenyl) (3-carboxyphenyl) methane anhydride, (3,4-dicarboxy) Phenyl) (3-carboxyphenyl) ether anhydride, 3, 3,, 4 tricarboxybenzophenone anhydride, 1,2,4-butanetricarboxylic acid anhydride, 2,3,5-naphthalenetricarboxylic acid anhydride 2, 3, 6-naphthalene tricarboxylic acid anhydride, 1, 2, 4 naphthalene tricarboxylic acid anhydride, 2, 2 ', 3 biphenyl tricarboxylic acid anhydride, etc. That. It is preferable to use TMA from the viewpoint of heat resistance and cost!

[0096] The weight average molecular weight by GPC measurement of the soluble polyimide and / or soluble polyamideimide constituting the positive photosensitive resin composition of the third aspect is preferably in the range of 20000 to 50000. When the weight average molecular weight exceeds this range, the printability of the composition may be deteriorated, or the remaining portion may be lost during development. On the other hand, if the weight average molecular weight is less than this range, problems such as film deterioration during development and insufficient mechanical strength of the film may occur.

[0097] The soluble polyimide resin-soluble polyamideimide constituting the positive photosensitive resin composition of the third aspect includes an acid component such as aromatic tetracarboxylic acid dianhydride and aromatic tricarboxylic acid anhydride exemplified above. It is possible to obtain diamine by condensing it in a reaction solvent. This condensation reaction is carried out under the same conditions as in the synthesis of conventional polyimide-polyamideimide. [0098] For example, as a reaction solvent, methyl benzoate, ethyl benzoate, methyl ethyl ketone

(MEK), acetone, γ-butyrolatatane, Ν-methylpyrrolidone, Ν, ジメチル -dimethylacetamide, toluene, xylene and the like.

[0099] In the positive photosensitive resin composition of the third aspect, the solvent-soluble heat-resistant resin and the positive photosensitive agent produced as described above are mixed in a solvent constituting the positive photosensitive resin composition. It is obtained by doing.

[0100] The invention according to claim 8 is characterized in that the positive photosensitive agent is a quinonediazide compound. It is a photosensitive resin composition. When a quinonediazide compound is used as a positive photosensitive agent, even if a melamine curing agent is included in the composition, patterning is possible with the same sensitivity and developability as in the case where the melamine curing agent is not included. Preferred examples of the quinonediazide compound used as the positive photosensitive agent include naphthoquinonediazide compounds exemplified in the case of the first, second and fourth embodiments, particularly naphthoquinonediazidesulfonyl esters of aromatic polyhydroxy compounds.

[0101] As the solvent constituting the positive photosensitive resin composition of the third aspect, the same solvents as those exemplified in the case of the first, second and fourth aspects are preferably exemplified. It is preferable to use the same solvent as the solvent used for the synthesis of the solvent-soluble heat-resistant resin as the solvent does not require a solvent replacement operation in the production of the positive photosensitive resin composition.

[0102] The content of the thermosetting agent in the positive photosensitive resin composition is preferably in the range of 1 part by weight to 50 parts by weight with respect to 100 parts by weight of the solvent-soluble heat-resistant resin. 2 to 20 parts by weight. If the thermosetting agent is less than 1 part by weight, curing will be insufficient, and it will be easy to cause scratches during pressing (adhesion) of the reinforcing plate and damage to the protective film during solder reflow. On the other hand, if it exceeds 50 parts by weight, the shrinkage due to curing increases, and the substrate tends to warp.

[0103] The positive photosensitive agent is preferably in the range of 5 to 50 parts by weight, more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the solvent-soluble heat-resistant resin. If it is less than 5 parts by weight or more than 50 parts by weight, patterning may be difficult.

[0104] The concentration of the solids such as a solvent-soluble heat-resistant resin, positive photosensitive agent and thermosetting agent (solid content concentration) is 10 to 50% by weight, and the amount of the solvent is within this range. It is determined. [0105] The positive photosensitive resin composition obtained in this way has developability comparable to that of conventional positive photosensitive resin compositions and is less likely to cause problems such as residues. It is. On the other hand, it is also excellent in resistance to scratches, and it is difficult for deterioration and defects to occur in the plating process.

[0106] The invention described in claim 22 is obtained by forming the positive photosensitive resin composition of the third aspect and heating the resulting film to remove the solvent. This is a photosensitive resin film.

[0107] The positive photosensitive resin composition of the third aspect can be used for forming a protective film of FPC and also for forming a photosensitive resin film. This photosensitive resin film is formed by depositing a positive photosensitive resin composition by, for example, a method such as coating on a PET film which has been subjected to an appropriate release treatment, and the resulting film is then heated to 90 ° C. It is possible to manufacture by removing the solvent in the composition by heating to the extent. This photosensitive resin film can be used as a photosensitive dry film resist.

[0108] A method for producing an FPC protective film (coverlay) using the positive-type photosensitive resin composition of the third aspect comprises applying this composition onto an FPC substrate on which wiring is formed. After film formation, the obtained film is heated to remove the solvent, then exposed through a mask and further developed to obtain a positive pattern, and then heated to a temperature higher than the curing temperature of the melamine curing agent, Solvent soluble It is carried out by crosslinking a heat resistant resin.

[0109] The invention of claim 23 provides the positive photosensitive resin composition of the third aspect, that is, the positive photosensitive resin composition of claim 4 to claim 8, or the wiring of the positive photosensitive resin composition of any one of claims 4 to 8. A step of coating on an FPC substrate formed with a film, a step of heating the obtained film to remove the solvent, and exposing the positive photosensitive resin composition from which the solvent has been removed through a mask A method for producing an FPC comprising: a step, a step of developing after exposure, and a step of heating after development to a temperature equal to or higher than a curing temperature of the melamine curing agent.

[0110] Here, the method of applying the positive photosensitive resin composition onto the FPC substrate is not particularly limited, and can be performed, for example, by screen printing. Besides, spin coating, spray coating, die coating, doctor Examples include knife coating and flexographic printing. The step of heating the obtained film to remove the solvent (so-called pre-beta), the step of exposing the positive photosensitive resin composition from which the solvent has been removed through a mask, and the step of developing after exposure are generally followed. This can be done under the same conditions as when manufacturing protective films for FPC using conventional positive photosensitive resin compositions. Developers and the like are the same alkaline developers as conventional ones, for example, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water, ethylamine, n-propylamine and the like. 1st amine, such as dimethylamine, triethanolamine, 3rd amine such as triethylamine, triethanolamine, tetramethylammonium hydroxide, tetraethyl Aqueous solutions of ammonium hydroxide and corin can be used.

[0111] This FPC manufacturing method has a step of heating a film remaining after development to a temperature higher than the curing temperature of the melamine curing agent. By this heating, the solvent-soluble heat-resistant resin forming this film is cross-linked with a melamine curing agent, the softening temperature and the high temperature elastic modulus are improved, and the excellent effects as described above are obtained.

[0112] Therefore, the heating temperature is equal to or higher than the temperature at which crosslinking with the melamine curing agent is performed, and is usually in the range of about 130 to 200 ° C. This temperature range is almost the same as the after-beta temperature when an FPC protective film is produced using a conventional positive photosensitive resin composition. When the resin constituting the positive photosensitive resin composition of the present invention is a soluble polyimide, the soluble polyimide is often already imidized at the stage of synthesis. Therefore, heating at a high temperature necessary for imide ring formation is unnecessary.

[0113] The present invention further provides, as claim 24, an FPC manufactured by the method for manufacturing an FPC according to claim 23. This FPC has a protective film with an improved softening temperature and high-temperature elastic modulus. It can be used to generate scratches during pressing (adhesion) of the reinforcing plate, as well as during protective reflow or manual soldering. Damage is suppressed. The invention's effect

[0114] When the photosensitive polyimide composition of the first aspect is used for forming a protective film of FPC, etc., it has developability comparable to that of conventional photosensitive polyimide compositions, and is not warped. It is difficult to cause problems. In addition, the protective film formed using the photosensitive polyimide composition of the first aspect hardly deteriorates even in the gold plating process and has a sufficient adhesive force to the copper foil. [0115] The photosensitive polyimide composition of the second embodiment is used for forming a protective film of FPC, etc., and in the process of forming the protective film of FPC, the development is comparable to the conventional photosensitive polyimide composition. It is difficult for problems such as residues to occur. On the other hand, an FPC protective film with excellent adhesion resistance, resistance to deterioration even in the gold plating process, especially resistance to spot discoloration, and sufficient adhesion to copper foil. Can do. In other words, the photosensitive polyimide composition of the second embodiment makes it possible to achieve both excellent developability and matt resistance. The photosensitive polyimide composition of the second aspect can be easily produced by the method for producing a photosensitive polyimide composition according to claims 18 and 19.

[0116] The positive-type photosensitive resin composition of the third aspect has developability comparable to that of conventional positive-type photosensitive resin compositions and is less likely to cause problems such as residues. It is also excellent in the plating property, and it is difficult for deterioration and defects to occur in the plating process. Furthermore, by applying this positive photosensitive resin composition onto a substrate and crosslinking the resin by heating, a protective film having a high softening temperature and a high high temperature elastic modulus can be formed. It is possible to suppress problems such as the occurrence of wrinkles during pressing (adhesion) of the reinforcing plate, damage to the protective film during solder reflow or correction by hand solder.

[0117] The use of the photosensitive polyimide composition of the fourth aspect reduces the occurrence of spot discoloration on the coating surface when patterning is performed by exposure and development to form a protective film for FPC. The power to lose S Further, the photosensitive polyimide composition of the fourth aspect can be easily produced by the method for producing a photosensitive polyimide composition according to claim 17. Brief Description of Drawings

FIG. 1 is a GPC chart of a varnish obtained in Example 2 or Comparative Example 5.

BEST MODE FOR CARRYING OUT THE INVENTION

[0119] Next, the best mode for carrying out the present invention will be described with reference to the following examples.

1S The present invention is not limited to this example.

Example

[0120] Example 1, Comparative Examples 1, 2, 3, 4

(Synthesis of soluble polyimide resin)

1. 1L separate flask equipped with a cooler, mechanical stirrer, and nitrogen inlet tube In a nitrogen atmosphere, add silicone diamine (Shin-Etsu Silicone KF8010, molecular weight: 830, amine equivalent: 415) 49.80 g (0.06 mol) to 210 g butyrolatatatone, a solvent, in addition to a catalyst. Add 2.0 g of pyridine and 100 g of toluene as an azeotropic solvent.

[0121] 2. Gradually add 37.22 g (0.12 mol) of OPDA (molecular weight: 310 · 2) as the aromatic tetracarboxylic dianhydride and add to the total amount. Stir for 15 minutes, and then heat to 160 ° C with a mantle heater while allowing toluene to circulate and react for 1 hour. After that, stop heating and let it naturally cool to around room temperature (50 ° C or less).

[0122] 3. Next, 1,3—APB (molecular weight: 292.3) 5. 85 g (0.02 mol) and 6F AP (molecular weight: 366) 14. 64 g (0.04 mol) as the diamine Furthermore, 48 g of solvent γ-petit mouth rataton is added so that the solid content is about 40%. Stir for 15 minutes after charging, then heat to 160 ° C in an oil bath and react for 3 hours to obtain a reaction solution. The resulting reaction solution was heated to about 70 ° C. under reduced pressure of about 100 mMHg for 40 to 50 minutes to remove toluene and pyridine from this reaction solution, and varnish 1 was obtained.

[0123] The concentration of pyridine in the varnish was determined using GC-MS (apparatus: Shimadzu GC17A, column: UA-1 (inner diameter 0.25 mm, film thickness 0.25 ^ 111, length 30 m), injection temperature: 250. C, injection amount: 2 Quantitative determination by 1) was 0. 02% by weight based on the total amount of varnish 1. Furthermore, varnishes 2 to 5 were produced in the same manner except that the pressure reducing time was changed. Similarly, the pyridine concentration was quantitatively determined as follows.

Varnish 2: 0.06 Weight ^_0/0

Varnish 3: 0.08 Weight ^_0/0

Varnish 4: 0. 10 weight ^_0/0

Varnish 5: 2.90 Weight ^_0/0

(All are percentages of the total amount of varnish.)

[0124] The varnish thus obtained was subjected to the following measurements. The results are shown in Table 1.

[0125] (Evaluation of Photosensitivity 1)

To the resulting varnish, 1, 2 naphthoquinone-2 diazido 5 sulfone as a photosensitizer Ester (Daito - Chemix Ltd., DTEP- 300) was added and mixed 15 weight ^_0/0 (15 phr) with respect to the resin solid content, a photosensitive polyimide composition (photosensitive ink 1-5) were formulated. The photosensitive polyimide composition was applied onto a copper foil having a thickness of 18 m by screen printing, and then pre-betaged at 90 ° C. for 30 minutes to obtain a film having a thickness of 12 to 15 m. This film was exposed to 800 mj / cm ^{2 of} ultraviolet rays through a predetermined mask.

[0126] Subsequently, a developer solution of 2.3% NaOH + 1.0% ethanolamine was placed in a stainless steel pad so that the depth was about 1 cm. The exposed sample was immersed in it and developed for 3 minutes while shaking gently in the developer. After development, the sample was thoroughly rinsed with pure water and afterbetad at 180 ° C for 30 minutes. When the condition of the dried film was visually observed, it was possible to clearly pattern up to L / S of 50 Hm or less! /.

[0127] The sample subjected to patterning was subjected to a general electrolytic gold plating treatment. That is, the steps shown below were performed in the order shown below, and the samples were sequentially stacked in the tank of each step and then dried.

Degreasing, water washing, soft etching, water washing, desmear treatment, water washing, nickel plating, water washing, strike gold plating, water washing, gold plating, water washing

[0128] (Evaluation of spot discoloration 1)

Each of the photosensitive inks 1 to 5 is applied onto a copper foil having a thickness of 18 111, 4 cm X 1.5 cm, and dried to form a coating film having a thickness of 12 to; After irradiating with light through a mask, development was performed with the developer described above, and the state after gold plating was observed by the above-described method to determine the number of spots per sample. In practice, 40 samples were evaluated and the average number of spots per piece was calculated. The results and evaluations based on the following criteria are shown in Table 1.

[0129] ○: Spot power observed, less than 0.5 per sample.

Δ: The number of observed spots is 0.5 to 1.0 per sample piece.

X: The number of spots observed is greater than 1.0 per sample piece.

[0130] [Table 1] Residual pyridine concentration in varnish (weight ¾ spot color change number evaluation

Based on the entire composition based on varnish

Concentrated concentration Standardized concentration

Example 1 Varnish 1 0. 02 0. 017 0. 2 〇 Comparative Example 1 Varnish 2 0. 06 0. 052 0. 9 Δ Comparative Example 2 Varnish 3 0. 08 0. 07 2. 8 X Comparative Example 3 Varnish 4 0. 10 0. 09 1. 1 X Comparative Example 4 Varnish 5 2. 90 2. 52 12.9 X

[0131] The spot discoloration numbers shown in Table 1 are the results when gold plating is further performed after development. In consideration of the fact that spot discoloration is newly formed by the gold plating process and that the spot discoloration does not disappear due to the gold plating process, the number of spot discoloration generated by development is a smaller value than that shown in Table 1. Become. As shown in Table 1, when the residual pyridine concentration is 0.02% by weight with respect to the varnish, the number of spot discoloration is low and practical use is possible, while the residual pyridine concentration is 0.06% by weight with respect to the varnish. In the case of 0.08% by weight, 0.10% by weight, and 2.90% by weight, the number of spot discoloration is large and cannot be used practically.

[0132] Example 2

(Synthesis of soluble polyimide resin)

1. In a 1L separate flask equipped with a condenser, mechanical stirrer, and nitrogen inlet tube, in a nitrogen atmosphere, the solvent Ί Butyrolatathon 140g, Silicone diamine (Ketsugo Silicone KF8010) 49.80g Add (0. O6mol) to dissolve a portion and suspend the rest. Furthermore, 2.0 g of pyridine as a catalyst and 100 g of toluene as an azeotropic solvent are prepared.

[0133] 2. Gradually add 37.22 g (0.1 2 mol) of OPDA (molecular weight: 310 · 2) as an aromatic tetracarboxylic dianhydride, and add the entire amount. At this time, a part of OPDA is dissolved and the rest is suspended. Stir for 15 minutes, then heat to 160 ° C with a mantle heater while refluxing toluene, and react for 1 hour. During this time, silicone diamine and OPDA are gradually dissolved and condensed. After that, stop heating and let it cool naturally to around room temperature (50 ° C or less) Reject.

[0134] 3. Next, 1, 3— APB (molecular weight: 292.3) 5. 85 g (0.02 mol) and 6F AP (molecular weight: 366) 14. 64 g (0.04 mol) as diamine Furthermore, 15 g of solvent γ-petit mouth rataton is added so that the solid content is about 40%. Stir for 15 minutes after charging, then heat to 160 ° C with an oil bath and react for 3 hours to obtain a reaction solution. Thereafter, the pressure was reduced and toluene and pyridine were removed from the reaction solution to obtain tuss.

The varnish thus obtained was subjected to the following measurements. The results are shown in Table 2.

[0135] (Molecular weight measurement)

The dispersion (Mw / Mn), which is the ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mn), of the obtained varnish was measured by GPC (HLC-8220GPC, manufactured by Tosoh Corporation). TSKgel GMHHR-H manufactured by Tosoh Corporation was used as the column, and the carrier solvent was LiMP dissolved in NMP at a concentration of 0.1 N. The molecular weight is a converted value calculated using standard polystyrene (TSK standard polystyrene). Figure 1 shows the GPC chart of the varnish obtained.

[0136] (Evaluation of photosensitive developability 2)

The resulting varnish was mixed with 15 phr of 1,2-naphthoquinone-2-diazido 5-sulfonic acid ester (manufactured by Toyo Gosei Co., Ltd., hereinafter referred to as PC 5) as a photosensitizer, and mixed with a photosensitive polyimide composition ( Photosensitive ink) was prepared. The photosensitive ink was applied on a copper foil having a thickness of l S ^ m by screen printing and then pre-betaged to obtain a coating having a thickness of 12 to 15 m. The film was exposed to 1000 mj / cm ^{2 of} mercury lamp light through a predetermined mask.

Development was carried out by showering the developer using a conveyor type development line. The developer used was 2 · 3% NaOH + 0.5% ethanolamine aqueous solution (40 ° C). The 2m development is rinsed pure and then dried at 80 ° C. The state of the dried film was visually observed and evaluated according to the following criteria. The results are shown in Table 2.

[0138] ©: It is possible to clearly pattern up to L / S of δΟ μm or less, and there is no deterioration of the film or penetration into the interface.

◯: Patterning up to 50 m L / S, no residue. Deterioration of the film is seen There is a case where some penetration into the interface is observed.

Δ: Force that can be put in the patterning area The power at which residues can be seen in the exposed area and the deterioration of the film can be seen.

X: The pattern cannot be put on or the deterioration is remarkable.

[0139] (Evaluation of resistance to scratching: Evaluation of spot discoloration 2)

Each photosensitive ink is applied onto a copper foil having a thickness of 18 m, dried to form a resist film having a thickness of 12 to 15 m, and irradiated with light through a predetermined mask. After developing on the development line, electroless gold plating is applied. The condition after the plating was observed and evaluated according to the following criteria. The results are shown in Table 2.

[0140] ○: Spot power S observed, 0.3 or less per sample piece.

Δ: The number of spots observed is greater than 0.3 and less than 1.0 per sample.

X: The number of spots observed is greater than 1.0 per sample piece.

[0141] Example 3

Except that ABPS was used instead of 6FAP, the same reaction as in Example 2 was performed to produce a varnish, and the same measurement was performed.

[0142] Comparative Example 5

A varnish was prepared in the same manner as in Example 2 except that a mixed solvent in which 40 g of methyl benzoate was mixed with 100 g of γ-butyral rataton instead of 140 g of γ-butyrolatatone as a solvent was used. In this reaction, the silicone diamine and OPDA were completely dissolved from the beginning of the reaction, and the suspended portion was not strong. The varnish of Comparative Example 5 thus obtained was measured in the same manner as the varnish of Example 2. The results are also shown in Table 2. Figure 1 shows the GPC chart of the varnish obtained.

[0143] Comparative Example 6

The reaction was the same as in Example 2 except that instead of 140 g of the solvent γ-butyroratatone 140 g, a mixed solvent of 100 g of γ-butyrolactaton mixed with 40 g of methyl benzoate was used, and ABPS was used instead of 6FAP. To produce a varnish. Also in this reaction, the silicone diamine and OPDA were completely dissolved from the beginning of the reaction, and the suspended portion was not strong.

[0144] [Table 2] Difficult line speed Developability Meat resistance

Mw distribution

Number of spots /

<m / min, evaluation evaluation

Piece

1. 1 X 0. 1 〇

0. 9 △ 0. 2 〇

Example

38, 000 1. 8 0. 7 ◎ 0. 2 o

2

0.5 ◎ 0.3 〇

0. 3 ○ 0. 4 Δ

1. 1 X 0. 2 O

0. 9 Δ 0.5 Δ

Example

40, 000 1. 8 0. 7 〇 1. 0 △

Three

0. 5 O 4.0 X

0. 3 Δ 10. 0 X

1. 1 X 0. 5 Δ

0. 9 Δ 1. 0 △

Comparative example

78, 000 2. 5 0. 7 △ 2. 0 X

Five

0.5 〇 4.0 0 X

0. 3 O 4.0 X

1. 1 X 4.0 X

0. 9 X 8. 0 X

Comparative example

69, 000 2. 4 0. 7 X 10. 0 X

6

0. 5 Δ 1 5. 0 X

0. 3 〇 1 5. 0 X

As shown in Table 2, according to the photosensitive polyimide compositions of Examples 2 and 3 which are the products of the present invention, it is possible to achieve both excellent developability and scratch resistance. With a photosensitive polyimide composition, it is difficult to achieve both excellent developability and resistance to plating. In particular, in the case where 6FAP is not used and in Comparative Example 6, the resistance to the plating is inferior. [0146] Example 4

(Synthesis of soluble polyimide resin)

1. In a 1L separate flask equipped with a condenser, mechanical stirrer, and nitrogen inlet tube, in a nitrogen atmosphere, the solvent 溶媒 Butyroratatone 140g, Silicone diamine (KF8010, Shin-Etsu Silicone Co., Ltd., molecular weight: 830, Amine equivalent: 415) 33. 20 g (0.04 mol) is added and dissolved. Furthermore, 2.0 g of pyridine as a catalyst and 100 g of toluene as an azeotropic solvent are calorieated.

[0147] 2. Slowly add OPDA (molecular weight: 310.2) 37.22g (0.12mol) as acid dianhydride, stir for 15 minutes after adding the whole amount, and then 160 ° C with mantle heater Heat to react for 1 hour. During this time, the cooling water is poured and toluene is circulated. Then stop heating and let it cool naturally to near room temperature (50 ° C or less).

[0148] 3. Next, 1, 3— APB (molecular weight: 292.3) 20.46 g (0.07 mol) and 6 FAP (molecular weight: 366) 3.66 g (0. Olmol) were added as diamines. In addition, 51 g of solvent γ petit rataton is added so that the solid content is about 32%. Stir for 15 minutes after charging, then heat to 160 ° C in an oil bath and react for 3 hours to obtain a reaction solution. Thereafter, the pressure was reduced and toluene and pyridine were removed from the reaction solution to obtain tuss.

[0149] The molecular weight of the varnish thus obtained was measured in the same manner as described above.

The following measurements were performed. The results are shown in Table 4.

[0150] (Glass transition temperature measurement)

Using a dynamic viscoelasticity measuring device (DMS6100, manufactured by Seiko Instruments Inc.), tan δ is measured in an air atmosphere at a heating rate of 10 ° C / min, and the temperature at the maximum value of tan δ is measured. The lath transition temperature (Tg) was used.

[0151] (Thermogravimetric analysis)

TG DTA (differential heat .simultaneous thermogravimetric measuring device: Seiko Instruments Inc., TG / DT

A220), a temperature that reduces 5% weight (Td) at a heating rate of 10 ° C / min in an air atmosphere.

5) was measured.

[0152] (Warpage measurement) After applying the varnish obtained on 18 m thick copper foil and drying to form a 20 m thick film, this composite was cut into 100 mm squares and placed on a horizontal surface. The height of the warp at 4 points was measured and the average was obtained.

[0153] (Evaluation of photosensitive developability 3)

To the obtained varnish, 15 phr of 1,2-naphthoquinone-2-diazido 5-sulfonic acid ester (Toyo Gosei Co., Ltd., PC5) was added and mixed as a photosensitizer, and a photosensitive polyimide composition (photosensitive ink) was added. Prepared. The photosensitive ink was applied on a copper foil having a thickness of 18 m by screen printing and then pre-betated to obtain a film having a thickness of 12 to 15 m. This film was exposed to 800 mj / cm ^{2 of} ultraviolet rays through a predetermined mask.

[0154] Development was performed at room temperature for 7 minutes using a developer, rinsed with pure water, and then dried. Three types of imaging solutions were used: (a) 3% NaOH + 3% ethanolamine, (b) 3% NaOH + 0.5% ethanolamine, and (c) 3% NaOH. The state of the dried film was visually observed and evaluated according to the same criteria as in Photosensitive Development Evaluation 2. The results are shown in Table 4.

[0155] Examples 5 to; 12, Comparative Examples 7 to 15;

Based on the formulation shown in Table 3, the varnishes of Examples 5 to 12 and Comparative Examples 7 to 15 were obtained in the same manner as Example 4, and the same measurements as those of Example 4 were performed. The results are also shown in Table 4. In Table 3, SiOn represents silicone diamine, the molar ratio is the molar ratio of each component in the diamine, and mol% is the molar ratio expressed in%. The total number of moles of diamine is the same as that of OPDA.

[0156] [Table 3]

Molar ratio mol% (vs total diamine)

S i On APB 6FAP or BPS * S i On APB 6 FAP or BPS Comparative example 7 1 2 33 67

Example 4 4 7 1 33 58 8 Comparative example 8 4 7 (1) 33 58 8 Example 5 2 3 1 33 50 17 Comparative example 9 2 3 (1) 33 50 17 Example 6 1 1 1 33 33 33 Comparison Example 10 1 1 (1) 33 33 33 Comparative example 11 1 1 50 50

Example 7 6 5 1 50 42 8 Comparative example 12 6 5 (1) 50 42 S Example 8 3 2 1 50 33 17 Comparative example 13 3 2 (1) 50 33 1 7 Example 9 3 I 2 50 17 33 Comparative example i41 3 1 (2) 50 17 33 Comparative example 15 2 1 67 33

Example 10 8 3 1 67 25 8 Example IV 4 I 1 67 17 17 Example IV 2 8 1 3 j 67 8 25

* In “6 FAP or ABP S”, when it is shown within 0, it indicates that ABPS was used, and in other cases, 6 FAP was used.

Four] Tg Td 5 Warpage Development

Mw Mw / Mn

(° C) C) (mm) (a) (b) (c) Comparative example 7 33000 1. 8 97 4 1 5 13. 2 XXX Example 4 41000 2. 1 104 391 12.5 XXX Comparative example 8 54 100 1. 9 1 1 1 14.2 XXX Example 5 35000 2. 0 1 15 386 13.5 O Δ X Comparative example 9 43300 1. 9 1 14 14.1 O △ X Example 6 34000 2. 0 137 365 1 1.5 O O Comparative Example 10 41000 1. 9 144 14.0 Δ △ Δ Comparative Example 11 33900 2. 0 47 425 2. 1 XXX Example 7 39200 2. 1 58 379 1.9 O △ X Comparative Example 12 53000 1. 5 67 3.5 OOX Example 8 33 100 2. 1 76 387 2. 5 ◎ ○ X Comparative Example 13 22400 1. 7 56 4. 7 ○ ○ .X Example 9 28000 1. 9 96 347 1 8 ○ ◎ o Comparative Example 14 42 800 2. 2 98 4. 2 △ Δ Δ Comparative Example 15 35 800 2. 0 43 425 0. 0 XXX Example 10 39 800 2. 9 45 362 0. 4 XXX Example 11 32 800 1 9 46 351 0. 4 〇 OX Example 12 27300 1. 9 45 338 0. 6 OO Δ The results in Table 4 show that when 6FAP is used (Example), ABPS is used (Comparative Example). It shows that almost the same warp and glass transition temperature can be obtained. The results in Table 4 show that the warpage and glass transition temperature are greatly influenced by the amount of silicone diamine. When the amount of silicone diamine is small, the warpage increases. However, even in the case of about 33 mol% with respect to the total diamine (Examples 4 to 6), the warpage is not significant, and it can be used for applications such as a protective film. On the other hand, when the amount of silicone diamine is large, the glass transition temperature is lowered. In the case of about 67 mol% with respect to the total diamine (Examples 10 to 12), the glass transition temperature is about 45 ° C. A certain force that can be used In order to obtain better heat resistance, a higher glass transition temperature is desired. The results in Table 4 indicate that about 60 mol% or less is preferable based on the total diamine.

[0159] The results in Table 4 indicate that when 6FAP is used (Example), almost the same developability is obtained as when ABPS is used (Comparative Example). However, when the amount of ABPS is large, film loss occurs and tends to deteriorate. Photosensitive developability is greatly influenced by the amount of 6FAP (OH group). Photosensitivity depends largely on the concentration of the developer, but 3% NaOH + 3% ethanolamine or 3% NaOH + 0.5% ethanolamine. It is indicated that the amount is preferably in the range of 10 to 40 mol% (corresponding to Examples 5, 6, 8, 9, 11, 12) with respect to the total diamine.

[0160] Examples 13 to; 19, Comparative Examples 16 to 17;

Based on the formulation shown in Table 5, the varnishes of Examples 13 to 19 and Comparative Examples 16 to 17 were obtained in the same manner as in Example 4 (as shown in Table 5, some examples and comparisons). In the example, APB was replaced with BA PSM, OPDA was replaced with benzophenone tetracarboxylic acid (BTDA), and 6FAP was replaced with ABPS. In the same manner, a photosensitive polyimide composition (photosensitive ink) was prepared. Further, in the same manner, screen printing, pre-beta, exposure, and development (developer: 3% NaOH + 3% ethanolamine aqueous solution) of the photosensitive ink are performed, and then after-beta (160 ° C, 30 minutes) is performed. FPC for evaluation was obtained.

[0161] Using the above FPC for evaluation, migration resistance and mesh resistance were evaluated by the following methods. Table 6 shows the results. In Table 5, SiOn represents silicone diamine, the molar ratio is the molar ratio of each component in the diamine, and mol% is the molar ratio expressed in%. The total number of moles of diamine is the same as the number of moles of OPDA or BTDA.

[0162] [Table 5] Molar ratio (mol%)

APB or 6 FAP notes *

S i On

BAP SM or AB P S

Example 1 3 2 (50) 1 (25) 1 (25) AP B is replaced with BAP SM Example 14 6 (5, 0) 5 (42) 1 (8)

Example 1 5 3 (50) 2 (33) 1 (1 7)

Example 1 6 3 (50) 1 (1 7) 2 (33)

Example 1 7 2 (33) 3 (50) 1 (1 7)

Example 1 8 1 (25) 1 (25) OPDA replaced with BTDA Example 1 9 2 (50) 1 (25) 1 (25)

Comparative example 1. 6 22 (44) 1 1 (22) 1 7 (34) 6 FAP replaced with ABP S Comparative example 1 7 3 (50) 2 (33) 1 (1 7) 6 FAP replaced with ABP S

* APB, OPDA, 6 FAP are used unless otherwise specified.

[0163] (Evaluation of migration resistance)

Each of the photosensitive inks was applied onto a migration evaluation double-sided plate having a copper foil pattern of 18 m in thickness, and dried to form an insulating film having a thickness of 12 to 15 πι After irradiating with light through a mask, development with a developer was performed to create an FPC for evaluation. This was placed under a high temperature and high humidity of 85 ° C and relative humidity of 85% RH, a 50V DC voltage was applied between the conductors for 1000 hours, the state of the resist film was observed, and the following criteria were evaluated. The results are shown in Table 6.

[0164] ○: No abnormality at all.

Δ: No abnormality was observed in the current value, but minute dendrite formation was observed.

X: There was no abnormality in the current, but a large dendrite formation was observed.

X X: Dendrite formation was observed on the entire surface, and an abnormality occurred in the current value.

[0165] (Evaluation of anti-sticking property)

Each photosensitive ink is applied onto a copper foil having a thickness of 18 m, dried to form a resist film having a thickness of 12 to 15 m, irradiated with light through a predetermined mask, and then developed. After developing with the solution, (a) electroless gold plating, (b) electrolytic gold plating. Observe the post-mesh condition and Evaluation was based on the criteria shown. The results are shown in Table 6.

[0166] ○: No abnormality.

Δ: Slight or slight penetration of the terminal portion was observed on the film surface.

X: The surface of the film was deteriorated, and soaking of the terminals was observed.

X X: The film was cracked and peeled, and the insulation part was also partially scratched.

[0167] The developers used in (Evaluation of migration resistance) and (Evaluation of scratch resistance) are shown below.

Examples 13, 14, 15 and 17: 3% NaOH + 3% ethanolamine

Examples 16, 18 and 19 and comparative example: 3% NaOH + 0.5% ethanolamine

[0168] [Table 6]

[0169] As shown in the results of Table 6, 6FAP was used as a component of diamine, and its content was 1 to

When it is in the range of 50 mol% (Example), it is excellent in migration resistance and matt resistance. In particular, Examples 14 and 15 in which APB and OPDA are used, the content of 6FAP is 20 mol% or less, and the content of Si On is 50 mol%, show excellent resistance to plating even in the case of electroless gold plating. . On the other hand, when ABPS is used as the component of diamine (comparative example), both migration resistance and galling resistance are far inferior to those of the example (using 6FAP). [Synthesis Example 1]

In a 1 L separate flask equipped with a cooler, mechanical stirrer, and nitrogen inlet tube, in a nitrogen atmosphere, 140 g of butyrolatatane, a solvent, is represented by silicone diamine (formula (III) above). Compound, KF8010 manufactured by Shin-Etsu Silicone Co., Ltd., molecular weight: 830, amine equivalent: 415) 49.80 g (0.06 mol) is added to dissolve part, and the rest is suspended. Add 0.5 g of pyridine as catalyst and 50 g of toluene as azeotropic solvent.

Yes

[0171] As an aromatic tetracarboxylic dianhydride, 37.22 g (0.12 mol) of OPDA (molecular weight: 310 · 2) is gradually added, and the whole amount is charged. At this time, a part of OPDA is dissolved and the rest is suspended. Stir for 15 minutes, then heat to 160 ° C with a mantle heater while refluxing toluene, and react for 1 hour. Then, stop heating and let it cool naturally to near room temperature (50 ° C or less).

[0172] Next, 1,3—APB (molecular weight: 292.3) 5.85 g (0.02 mol) and 6FA P (molecular weight: 366) 14.64 g (0.04 mol) were mixed as diamine, and about 40% solids. Add 15 g of solvent γ-petit-mouthed rataton to make a minute. Stir for 15 minutes after charging, then heat to 160 ° C in an oil bath and react for 3 hours to obtain a reaction solution. Thereafter, the pressure was reduced and toluene and pyridine were removed from the reaction solution to obtain a pale yellow transparent varnish (OPDA: silicone diamine: 1,3-APB: 6FAP = 6: 3: 1: 2).

[Synthesis Example 2]

The amount of silicone diamine KF8010 is 33.20 g (0.04 mol), the amount of 1,3—APB is 11.69 g (0.04 mol), the solvent added to adjust the solid content concentration γ butyrolatatone amount is 50 g, solid content A pale yellow transparent varnish (OPDA: silicone diamine: 1, 3—APB: 6FAP = 6: 2: 2: 2 under the same conditions as in Synthesis Example 1 except that the concentration was changed to about 35%. )

[0174] (Synthesis Example 3)

As aromatic tetracarboxylic dianhydride, instead of OPDA37.22g (0.12mol), OPDA is 18.61g (0.06mol) and DSDA (3, 3, 4, 4, 4, dipheninores norephone tetracarboxylic acid 2 anhydride) was used in the same conditions as in Synthesis Example 2 except that 21 · 50 g (0.06 mol) was used. As a result, a brown transparent varnish (OPDA: DSDA: silicone diamine: 1, 3—APB: 6FA? = 3: 3: 2: 2: 2) was obtained.

[0175] (Synthesis Example 4)

Add 99.60 g (0.12 mol) of silicone diamine (KF8010) to 300 g of γ-butyrolatatone under a nitrogen atmosphere in a 1 L separatory flask equipped with a condenser, mechanical stirrer, and nitrogen inlet tube. Dissolve a portion and suspend the rest. Add 0.5 g of pyridine as a catalyst and 50 g of toluene as an azeotropic solvent.

[0176] As aromatic tetracarboxylic dianhydride, OPDA (molecular weight: 310.2) 46.53 g (0.15 mol) and DSDA (3, 3 ', 4, 4'-diphenylsulfone tetracarboxylic dianhydride) 53. Add 74g (0.15mol) gradually, and add the whole amount. At this time, part of OPDA is dissolved and the rest is suspended. Stir for 15 minutes, then heat to 160 ° C with a mantle heater while refluxing toluene, and react for 1 hour. Then stop heating and let it naturally cool to around room temperature (below 50 ° C).

[0177] Next, as diamine, 1,3-APB (molecular weight: 292.3) 17.54 g (0.06 mol), TPE —R (molecular weight: 292.3) 5.85 g (0.02 mol) and 6FAP36.60 g (0. lOmol) Add 160g of solvent γ-petit mouth rataton to a solid content of about 35%. After the addition, stir for 15 minutes, then heat to 160 ° C in an oil bath and react for 3 hours to obtain a reaction solution. Then, the pressure is reduced to remove toluene and pyridine from the reaction solution, and a brown transparent varnish (OPDA: DSDA: silicone diamine: 1,3-APB: TPE-R: 6FAP = 15: 15: 12: 6: 2: I got 10).

[0178] (Molecular weight measurement, viscosity measurement)

Molecular weight measurement was performed as described above. The viscosity of the varnish thus obtained at 25 ° C was measured with a B-type viscometer. These results are shown in Table 7.

[0179] [Table 7] Solid content,%, Mw Mw / M n Viscosity (P a 's) Synthesis example 1 4 0 3 8, 0 0 0 1. 8 2 1 0

Synthesis Italy J 2 3 5 3 6, 0 0 0 1 .9 3 2 0

Synthesis example 3 3 5 3 3, 5 0 0 1 .8 1 8 0

Synthesis example 4 3 5 3 4, 1 0 0 1 .8 1 2 4

[0180] Examples 20 to 34, Comparative Examples 18 to 21

(Manufacture of positive photosensitive resin composition)

In each of the varnishes (base varnishes) obtained in Synthesis Examples 1 to 4, naphthoquinone diazide sulfonic acid ester (manufactured by Daito Chemix, DTEP-300) as a photosensitizer is 15 wt% based on the polymer solid content, Melamine resin (low molecular weight methoxy melamine resin, product name: Cymel 303, manufactured by Mitsui Cytec Co., Ltd.) is mixed and mixed as shown in Table 8 with respect to the polymer solid content, and photosensitive polyimide composition (photosensitive ink). Was formulated. An antifoaming agent was added in an amount of about 1 wt% based on the solid content of the polymer. After the final stirring and mixing, defoaming was performed under vacuum to obtain a positive photosensitive resin composition.

[0181] (Developability evaluation: photosensitive development experiment)

Each positive photosensitive resin composition obtained in this way was applied on a 38 m thick copper foil by screen printing, and then pre-beta (90 ° C x 30 minutes). The solvent was removed to obtain a film having a thickness of 12 to 15 m. This film was exposed to 1000 mj / cm ^{2 of} mercury lamp light through a predetermined mask. Then, develop for 7 minutes at room temperature using a developer that is 2.3% NaOH + 0.5% ethanolamine aqueous solution (40 ° C), rinse with pure water, and dry. The developability was evaluated.

◯: Patterning up to L / S of about 100 m with no residue There is no deterioration of the film.

Δ: The power that can be applied to L / S patterning of about 100 m Deterioration of the film is observed.

X: No notching is possible, or the film is significantly deteriorated.

[0183] (Measurement of film properties)

Each of the positive photosensitive resin compositions obtained in the above (Preparation of positive photosensitive resin composition) was applied on a copper foil having a thickness of 38, im by screen printing, and then pre-beta (90 ° CX 30 minutes), the solvent in the composition was removed, and a film having a thickness of about 25 ^ 111 was obtained. This film was immersed in a developing solution of 2.3% NaOH + 0.5% ethanolamine aqueous solution (40 ° C.) at room temperature for 7 minutes. After washing with pure water, after-beta was performed at 120 ° C for 1 hour + 220 ° C for 30 minutes, and the copper foil was dissolved with an acid to obtain a film having a thickness of about 25 m. The resulting film was subjected to dynamic viscosity measurement, and the softening temperature, the elastic modulus at 180 ° C. (Ε ′ @ 180 ° C.), and the tan δ peak temperature were measured by the following methods. These results are shown in Table 8.

[0184] (Softening temperature) (Ε '@ 180 ° C) (tan δ peak temperature)

It calculated | required from the measurement result of dynamic viscoelasticity. The temperature at which the elastic modulus begins to decrease was defined as the softening temperature, and the elastic modulus at 180 ° C was defined as E '@ 180 ° C.

[0185] (Warpage)

After coating each positive photosensitive resin composition on a copper foil with a thickness of 38 am by screen printing, pre-beta (90 ° CX 30 minutes) was used to remove the solvent in the composition, and the thickness was about 12 ~; 15 111 films were obtained. This film was immersed in a developer solution of 2.3% NaOH + 0.5% ethanolamine aqueous solution (40 ° C) for 7 minutes at room temperature, and developed as it was. 120 ° CX for 1 hour + 220 ° CX 30 minutes after beta. This sample was cut into a 100 mm × 100 mm square and its warpage was measured. The warpage was obtained by measuring and averaging the height from the bottom of the four corners of the square. These results are shown in Table 8.

[0186] [Table 8] Base Melami «& Soften t ani5

E @ 180t

Temperature peak warping *

Varnish ί 娜分 (MP a) (mm) Developability

wt CC) C)

Synthesis example 1 6 100 71 164 3 l¾W21 Synthesis example 1 12. 5 102 180 193 4 ◎

赚 ί22 Synthesis example 1 25 -105 330 203 5 o

娜 23 Synthesis example 1 50 to 110 530 None 7 Δ

U! U 9 Composite Italy J 2 None 130 15 154 12 O

¾ »! | 24 Synthesis example 2 2. 5 1 30 34 173-〇

Composite 锊 2 5 to 135 90 180-〇

Synthesis example 2 12.5 to 13 5 200 207 14 o

t Translator 20 Composition example 3 None 1 58 100 184 20 o

-i27 Synthesis example 3 2. 5 160 120 186 o

Synthesis example 3 5 1 57 200 191 14 o

霞 9 Synthesis example 3 7.5 -160 280 200 ― o

¾ »ί | 30 Synthesis example 3 10 to 160 500 239 1 5 〇

卿 1 Synthesis example 4 None 143 60 176 1 1 ◎

¾SPJ31 Synthesis example 4 2. 5 145 70 188-◎

雾删 32 Synthesis example 4 5 148 90 190 13 ◎

33 Synthesis example 4 7.5 -150 150 197 1 0 Synthesis example 4 10 to 150 400 233 13 〇

[0187] From the results in Table 8, in the examples where the melamine-based curing agent was added, the softening temperature, the elastic modulus at high temperature, and the tan δ peak temperature increased, and this positive photosensitive resin composition was used. For example, it has been shown that it is possible to form a protective film that suppresses the occurrence of cracks during pressing (adhesion) of the reinforcing plate in FPC manufacturing, and damage during solder reflow or manual soldering. Further, it has been shown that even when a melamine curing agent is added, there is no significant reduction in warpage or developability.

[0188] (FPC production)

The positive photosensitive resin compositions of Examples 21, 27, 32, and 34 and Comparative Examples 18, 19, 20, and 21 were screen-printed as photosensitive coverlays on the FPC substrate, pre-beta, and then sequentially exposed. Development, drying, and after-beta (180 ° CX30min) were performed, and then an FPC with a protective film for electrolytic gold plating was produced. When the FPC obtained in this way was subjected to a reinforcing plate adhesion simulation press test in the subsequent process, in Comparative Examples 18, 19, and 21, a wrinkle was observed in the protective film around the reinforcing plate. Force In Examples 21, 27, 32, and 34 and Comparative Example 20, no wrinkles were observed in the periphery of the reinforcing plate. Also each When the high-temperature flux resistance of the FPC protective film was compared, Examples 21, 27, 32, and 34 showed better flux resistance than Comparative Examples 18-21.

Claims

The scope of the claims

[1] A photosensitive resin composition containing a soluble polyimide resin and a positive photosensitive agent, wherein the soluble polyimide resin is a condensate of aromatic tetracarboxylic dianhydride and diamine,

The diamine containing S, silicone diamine, and diamine having a hydroxyl group, and the diamine having a hydroxyl group is hexafluoro 2 2 bis (3 amino-4-hydroxyphenylenole) propane.

Hexafluoro 2,2 bis (3 amino-4-hydroxyphenenole) propane content force S, 150 mol% with respect to all diamines, photosensitive polyimide composition

[2] The photosensitive polyimide composition according to claim 1, wherein the soluble polyimide resin has a weight average molecular weight in the range of 20000 50000 and a molecular weight distribution of a single peak distribution.

[3] A photosensitive resin composition containing a soluble polyimide resin and a positive photosensitive agent, wherein the soluble polyimide resin is a condensate of aromatic tetracarboxylic dianhydride and diamine,

The soluble amine resin contains diamine power S, silicone diamine and hydroxyl group-containing diamine, the weight-average molecular weight is 20000 50000, the molecular weight distribution is a single peak distribution, and the dispersion is 2.0 or less. A photosensitive polyimide composition characterized by comprising:

[4] A positive photosensitive resin composition comprising a solvent-soluble heat-resistant resin, a positive photosensitive agent, a thermosetting agent, and a solvent,

The thermosetting agent is a melamine-based curing agent,

The positive-type photosensitive resin composition, wherein the solvent-soluble heat-resistant resin is a polyimide resin or a polyamide-imide resin containing diamine having a hydroxyl group as a structural unit

[5] The polyimide resin or the polyamideimide resin is an acid-free product obtained by adding an aromatic tetracarboxylic dianhydride to an aromatic tetracarboxylic dianhydride or an aromatic tricarboxylic anhydride. 5. The positive photosensitive resin composition according to claim 4, wherein the positive photosensitive resin composition is a condensate of water and diamine.

6. The positive photosensitive resin composition according to claim 4, wherein the melamine curing agent is a methylol melamine compound represented by the following structural formula (I).

[Chemical 1]

In the formula, W represents —NY Y, Y and Y are each independently hydrogen, —CH 2 —OZ

5 6 5 6 2 or a phenyl group, Y to Y each independently represent hydrogen or —CH 2,

1 4 2

Ζ represents hydrogen or an alkyl group having 6 to 6 carbon atoms. )

[7] The diamine having a hydroxyl group has the following structural formula:

[Chemical 2]

7. The positive photosensitive resin composition according to claim 4, wherein the positive photosensitive resin composition is selected from the group of compounds represented by:

[8] The positive photosensitive resin composition according to any one of [4] to [7], wherein the positive photosensitive agent is a quinonediazide compound.

[9] A photosensitive polyimide composition containing a soluble polyimide resin, a positive photosensitive agent and a solvent for dissolving them,

The diamine contains a diamine having a hydroxyl group.

The photosensitive polyimide composition, wherein the content power of pyridine contained in the photosensitive polyimide composition is 0.05% by weight or less.

10. The photosensitive polyimide composition according to claim 9, wherein the soluble polyimide resin has a weight average molecular weight of 20000 to 50000.

[11] The photosensitive polyimide composition according to [3], [9] or [10], wherein the diamine having a hydroxyl group is contained in an amount of 1 to 50 mol% based on the total diamine.

[12] The diamine having a hydroxyl group is hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane, which is characterized in that the diamine has a hydroxyl group. /, The photosensitive polyimide composition as described in any of the above.

[13] according to claim 1 of Les characterized in that it contains 5 to 60 mole ^_0/0 the Jiamin force silicone di § Minh for all Jiamin, teeth of claim 3! /, Displacement or claim 9 The photosensitive polyimide composition according to any one of Claims 12 and 12.

[14] The photosensitive polyimide composition according to claim 13, wherein the silicone diamine has a weight average molecular weight of 1000 or less.

[15] The aromatic tetracarboxylic acid dianhydride contains 4, 4'-oxydiphthalic acid dianhydride, and the! /, Deviation or claim of claim 3 9!

15. The photosensitive polyimide composition according to any one of 14.

[16] The positive photosensitive agent is naphthoquinone diazide sulfonyl ester of an aromatic polyhydroxy compound, and is! / In claim 3, or in claim 9, or in claim 9. The photosensitive polyimide composition according to claim 15.

[17] A method for producing a photosensitive polyimide composition comprising a soluble polyimide resin, a positive photosensitive agent and a solvent for dissolving them,

A method for producing a photosensitive polyimide composition, comprising: mixing the soluble polyimide resin, a positive photosensitive agent and a solvent.

[18] a condensation reaction step of condensing an aromatic tetracarboxylic dianhydride with a diamine containing a silicone diamine and a diamine having a hydroxyl group,

In the condensation reaction step, the aromatic tetracarboxylic dianhydride and the silicone diamine are condensed in a solvent that dissolves only a part of the aromatic tetracarboxylic dianhydride and the silicone diamine. Then, the temperature is raised and the aromatic tetra force rubonic acid dianhydride and silicone diamine are dissolved in the solvent. A method for producing a soluble polyimide resin.

[19] The aromatic tetracarboxylic dianhydride contains 4,4′-oxydiphthalic dianhydride, and the diamine having a hydroxyl group is hexafluoro-2,2bis (3-amino-4-hydroxy 19. The method for producing a soluble polyimide resin according to claim 18, wherein the solvent is phenyl propane, and the solvent is _{butyrolatatatone} .

[20] A protective film covering the wiring of the flexible printed circuit board, which is claimed in claim 1! /, Claim 3! /, Or in claim 9! /, And claim 16! A protective film comprising a cured product of the photosensitive polyimide composition described in any one of the above.

[21] An FPC comprising the protective film according to claim 20.

[22] By forming the positive photosensitive resin composition according to claim 4! / And claim 8 // according to claim 8, and heating the resulting film to remove the solvent. A photosensitive resin film characterized by being obtained.

[23] A step of applying the positive photosensitive resin composition according to claim 4! /, Or claim 8 of claim 8 on the FPC substrate on which the wiring is formed to form a film. A step of removing the solvent by heating the formed film, a step of exposing the positive photosensitive resin composition from which the solvent has been removed through a mask, a step of developing after exposure, and a development, A method for producing an FPC, comprising a step of heating to a curing temperature or higher.

[24] An FPC manufactured by the method for manufacturing an FPC according to claim 23.