JP2001007486A - Usage of laminated body and circuit board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing an insulating protective layer for a circuit, very easily, which is excellent in work precision and reliability. SOLUTION: Film-like laminated bodies comprising at least a photo-sensitized resin layer 2 and polyimide precursor resin layer 3 are so laminated on a circuit board 5 that the polyimide precursor resin layer 3 contacts the circuit board 5, which is processed with exposure, development, etching, release of remaining photo-sensitized resin layer, and solidification of a patterned polyimide precursor resin layer, providing a circuit board comprising a patterned insulating protective film 5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for using a laminate useful as an insulating protective material for a circuit board and a method for manufacturing a circuit board.

[0002]

2. Description of the Related Art Heretofore, as a method for insulating and protecting a circuit board, a method of protecting the circuit board with screen-printed ink (Japanese Patent Application Laid-Open No. 62-263892) and a method of laminating a film with an adhesive called a coverlay film (particularly, No. 63-110224) have already been implemented.

The former is generally made of a resin having no heat resistance, and is provided by using a screen, so that there is a face that it cannot cope with recent fine patterns due to its printing accuracy. Although the latter is excellent in terms of reliability by using a polyimide film having excellent heat resistance, the processing step requires a complicated step of laminating by hot pressing after punching with a mold, and There is also a problem that it is difficult to cope with a fine pattern due to low punching accuracy.

[0004] On the other hand, a method of directly providing a polyimide resin on a circuit by various methods and then patterning by etching with a chemical (Japanese Patent Application Laid-Open No. 62-113494, etc.) has been partially implemented. In this case, there are problems that dangerous chemicals such as hydrazine and ethylenediamine must be used, and that the etching takes a long time.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an insulating protective material for a circuit board which is excellent in reliability, processing accuracy and workability, and provides a method of using the same and a method of manufacturing the circuit board. Is to do.

[0006]

That is, the present invention provides a film-like laminate having at least two layers of a photosensitive resin layer and a polyimide precursor resin layer on a circuit board such that the polyimide precursor resin layer is in contact with the circuit board. And expose this,
This is a method for using the laminate, which comprises developing, etching, peeling off the remaining photosensitive resin layer, and curing the polyimide precursor resin. Further, the present invention is to laminate a film-like laminate having at least two layers of a photosensitive resin layer and a polyimide precursor resin layer on a circuit board such that the polyimide precursor resin layer is in contact with the circuit board, and exposure,
A method for producing a circuit board having a patterned insulating protective film, comprising performing development, etching, peeling of a remaining photosensitive resin layer, and curing treatment of a polyimide precursor resin. Further, the present invention is a circuit board having a patterned insulating protective film obtained by the above manufacturing method.

As the photosensitive resin layer, any structure can be selected, and both negative and positive types can be used. The photosensitive resin is generally of an ultraviolet reactive type, an electron beam reactive type, or the like, and is composed of a base oligomer, a reactive diluent, a photoinitiator, a photosensitizer, a pigment, a polymerization inhibitor and the like. Examples of the base oligomer include epoxy acrylate, urethane acrylate, and polyester acrylate.

The thickness is preferably from 2 μm to 100 μm. If the thickness is less than that, processing accuracy is high, but the film strength is insufficient, and problems such as peeling when etching the polyimide precursor resin layer are likely to occur. If it exceeds 100 μm, the strength is large and the reliability is high, but the processing accuracy is lowered and the cost is high.

The polyimide precursor resin is synthesized by reacting a diamine compound and an acid anhydride compound at 0 to 200 ° C. in a polar solvent. In this case, if an imidization reaction occurs, the solubility decreases, and the etching time in patterning becomes long, which is not preferable.

As the polar solvent, N-methylpyrrolidone (N
MP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethylsulfoxide (D
MSO), dimethyl sulfate, sulfolane, butyrolactone, cresol, phenol, halogenated phenol,
Cyclohexanone, dioxane, tetrahydrofuran,
Diglyme and the like.

As the diamine compound, p-phenylenediamine, m-phenylenediamine, 2'-methoxy-4,4 '
-Diaminobenzanilide, 4,4'-diaminodiphenyl ether, diaminotoluene, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4 ' -Diaminodiphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,2-bis (anilino) ethane, diaminodiphenylsulfone, diaminobenzanilide, diaminobenzoate, diaminodiphenylsulfide, 2,2 -
Bis (p-aminophenyl) propane, 2,2-bis (p-aminophenyl) hexafluoropropane, 1,5-diaminonaphthalene, diaminotoluene, diaminobenzotrifluoride, 1,4-bis (p-aminophenoxy) benzene,
4,4 '-(p-aminophenoxy) biphenyl, diaminoanthraquinone, 4,4'-bis (3-aminophenoxyphenyl) diphenyl sulfone, 1,3-bis (anilino) hexafluoropropane, 1,4-bis ( Anilino) octafluoropropane, 1,5-bis (anilino) decafluoropropane, 1,7-bis (anilino) tetradecafluoropropane, the following general formula

Embedded image (Where R ₂ represents a divalent organic group, R ₁ represents a monovalent organic group, and p represents an integer greater than 1), 2,2-bis [4- ( p-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane,
2,2-bis [4- (2-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] hexafluoropropane, 2,2- Bis [4- (4-aminophenoxy) -3,5-ditrifluoromethylphenyl] hexafluoropropane, p-
Bis (4-amino-2-trifluoromethylphenoxy) benzene, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluoro Methylphenoxy) biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4,4'-bis (4-amino-5-trifluoromethylphenoxy) diphenylsulfone, 2,2 -Bis [4-
(4-amino-3-trifluoromethylphenoxy) phenyl] hexafluoropropane, benzidine, 3,3 ', 5,5'-
Tetramethylbenzidine, octafluorobenzidine,
3,3'-methoxybenzidine, o-tolidine, m-tolidine,
Diamines such as 2,2 ', 5,5', 6,6'-hexafluorotrizine, 4,4 ''-diaminoterphenyl, 4,4 '''-diaminoquarterphenyl, and these diamines and phosgene And diisocyanates obtained by such a reaction.

The tetracarboxylic anhydrides and derivatives thereof include the following. Here, tetracarboxylic acid is exemplified, but of course, these esterified products, acid anhydrides, and acid chlorides can also be used. Pyromellitic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid,
3,3 ', 4,4'-benzophenonetetracarboxylic acid, 3,3', 4,
4'-diphenylsulfonetetracarboxylic acid, 3,3 ', 4,4'-
Diphenyl ether tetracarboxylic acid, 2,3,3 ', 4'-benzophenone tetracarboxylic acid, 2,3,6,7-naphthalene tetracarboxylic acid, 1,2,5,6-naphthalene tetracarboxylic acid,
3,3 ', 4,4'-diphenylmethanetetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) propane, 2,2-bis (3,
4-dicarboxyphenyl) hexafluoropropane, 3,
4,9,10-tetracarboxyperylene, 2,2-bis [4- (3,4-
Dicarboxyphenoxy) phenyl] propane, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid and the like. Moreover, trimellitic acid and its derivatives are also included.

It is also possible to modify with a compound having a reactive functional group to introduce a crosslinked structure or a ladder structure. For example, there is the following method. (A) A pyrrolone ring or an isoindoloquinazolinedione ring or the like is introduced by modification with a compound represented by the following general formula (3). H ₂ N—Ar (Z) _x —NH ₂ (3) (provided that Ar represents a 2 + x-valent aromatic residue and x represents 1 or 2
Wherein Z is a substituent selected from a —NH ₂ group, a —CONH ₂ group or a —SO ₂ NH ₂ group and is located at the o-position with respect to the amino group.) (B) a polymerizable unsaturated bond It is modified with a derivative of amine, diamine, dicarboxylic acid, tricarboxylic acid or tetracarboxylic acid to form a crosslinked structure upon curing. As the unsaturated compound, maleic acid, nadic acid, tetrahydrophthalic acid, ethynylaniline and the like can be used. (C) The compound is modified with an aromatic amine having a phenolic hydroxyl group or a carboxylic acid to form a crosslinking agent that can react with the hydroxyl group or the carboxyl group.

According to the present invention, the polyimide precursor thus obtained is provided in the form of a film in contact with the photosensitive resin layer, and the resin layer has a coefficient of thermal expansion of 3 × 1 after curing.
It is preferably at most 0 ^-5 / ° C. In particular, when provided on a flexible circuit such as a flexible printed circuit board, if the coefficient of thermal expansion exceeds 3 × 10 ⁻⁵ / ° C., the circuit warps during cooling after a high-temperature heat treatment such as an imidization reaction, which causes a practical problem. Cheap.

Further, a polyimide precursor having a repeating unit represented by the following formula (1) or (2) is preferable, and has a small coefficient of thermal expansion and excellent mechanical properties such as flexibility. .

Embedded image

Embedded image

In addition to these repeating units, it is also possible to copolymerize or blend with the above compounds for the purpose of controlling the thermal expansion coefficient or adjusting the mechanical properties. For the purpose of improving various properties, powders of inorganic, organic, or metal, fibers, chopped strands, and the like can be mixed and used. It is also possible to add an additive such as an antioxidant for the purpose of preventing the circuit from being oxidized during curing, or a silane coupling agent for the purpose of improving the adhesiveness. It is also possible to blend different polymers for the purpose of improving flexibility, flowability, adhesiveness, and the like.

The thickness of the polyimide precursor resin layer is preferably from 2 μm to 300 μm. If the thickness is less than 2 μm, the reliability of circuit insulation is poor and mechanical properties such as bending are low. If it exceeds 300 μm, a degradation reaction is apt to occur during the imidization reaction, which is not preferable.

The polyimide precursor thus obtained is brought into contact with the photosensitive resin layer to form a layer. The layer can be formed by any method. A more excellent workability is a method of applying a photosensitive resin on a release film and then applying a polyimide precursor resin solution.

As the release film, a general film such as a polyester film, a polypropylene film or a polyimide film can be selected, and a film having a surface coated with a release agent such as a silicone compound to further enhance the release property. Is more preferred.

The drying of the polyimide precursor resin solution after coating can be selected within a range that does not cause deterioration of the photosensitive resin or the release film, but is preferably 180 ° C. or lower. If the temperature is exceeded, an imidization reaction takes place, and when laminating to a circuit thereafter, the flowability of the resin is reduced, so that the filling property is reduced, or the etching time is longer at the time of patterning, which is not preferable.

The dry state can be adjusted in consideration of the filling property at the time of lamination or the tack property with the circuit. Further, for the purpose of protecting the surface of the polyimide precursor resin layer, a release film can be further laminated thereon in contact therewith.

The laminate obtained in this manner is laminated on a circuit board on which an arbitrary circuit pattern is drawn so that the polyimide precursor resin layer is in contact with the circuit board. As the circuit board, any circuit board such as a hard board such as a glass epoxy or a flexible printed board using a polyimide film can be used. However, since the polyimide precursor resin layer needs to be cured at a high temperature thereafter, the glass / A circuit board excellent in heat resistance such as a maleimide hard board or a non-adhesive flexible printed board is more preferable. The laminating method can be performed by a hot press machine or a roll-to-roll laminator. At this time, in order to increase the filling property of the resin, 200
It is more preferable to perform heating at a temperature of not more than ℃. Further, a dipping liquid such as an organic solvent may be used at the interface to further improve the adhesion to the substrate.

Next, in order to process the polyimide precursor resin layer, which is an insulating layer, into an arbitrary shape, an arbitrary negative pattern or positive pattern is overlaid on the release film or directly on the photosensitive resin layer, and exposure is performed. Further, after developing the photosensitive resin, the polyimide precursor is etched with an alkaline solution. Heating can be performed to increase the etching speed. Finally,
The remaining photosensitive resin layer is peeled off to obtain a patterned polyimide precursor insulating resin layer.

The circuit thus obtained is subjected to a high-temperature heat treatment in order to carry out a curing reaction which is an imidization reaction.
The highest heat treatment temperature is 200 ° C. or higher, preferably 250 ° C. or higher. The heating can be either batch heat treatment using a hot air oven or the like or heating of roll to roll. Further, it is more preferable to perform the reaction in an inert atmosphere because the oxidation of the circuit is suppressed.

[0025]

The present invention will be described in more detail with reference to the following examples.

The coefficient of thermal expansion was determined by using a thermomechanical analyzer (T
MA), and after raising the temperature to 250 ° C., 10 ° C./min.
And the average coefficient of thermal expansion from 240 ° C to 100 ° C was calculated and determined.

The solder resistance was determined by immersing a circuit left at 76% RH for 24 hours in a solder bath for 1 minute, and examining the maximum temperature at which blistering and peeling did not occur at intervals of 10 ° C.

The processing accuracy was determined by etching the polyimide precursor resin layer using circular patterns having different diameters in increments of 10 μm and visually observing the size of the diameter having a good shape.

Synthesis Example 1 2'-methoxy-4,4'-diaminobenz was fed into a 300 ml four-necked flask equipped with a thermometer, a calcium chloride tube, a stirring bar and a nitrogen inlet at a flow rate of 200 ml / min. 0.07 mol of anilide and 0.03 mol of 4,4'-diaminodiphenyl ether were dissolved under stirring in 220 ml of DMAc (dimethylacetamide). While cooling this solution to 10 ° C. or lower in a water-cooled bath, 0.10 mol of PMDA (pyromellitic anhydride) was gradually added and reacted. Thereafter, stirring was continued at room temperature for about 2 hours to carry out a polymerization reaction.
A brown transparent viscous polyimide precursor solution was obtained.

Synthesis Example 2 Paraphenylenediamine, 0.08 mol, and 4,8 mol of nitrogen were fed into a 300 ml four-necked flask equipped with a thermometer, a calcium chloride tube, a stirring bar, and a nitrogen inlet at a flow rate of 200 ml / min. 4'-diaminodiphenyl ether, 0.02
The mole is 220 ml of NMP (N-methyl-2-pyrrolidone)
Was stirred and dissolved therein. While cooling this solution to 10 ° C. or lower in a water-cooled bath, 0.10 mol of 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride was gradually added and reacted. Thereafter, stirring was continued at room temperature for about 2 hours to carry out a polymerization reaction. A brown transparent viscous polyimide precursor solution was obtained.

Synthesis Example 3 While flowing 200 ml of nitrogen per minute into a 300 ml four-necked flask equipped with a thermometer, a calcium chloride tube, a stirring bar and a nitrogen inlet, 4,4'-diaminodiphenylmethane was added.
0.10 mol was dissolved under stirring in 220 ml of DMAc (dimethylacetamide). This solution was placed in a water-cooled bath for 10 minutes.
0.10 mol of BTDA (3,3 ′, 4,4′-benzophenonetetracarboxylic anhydride) was gradually added to the mixture while cooling the mixture to a temperature of not more than 0 ° C. or lower. Thereafter, stirring was continued at room temperature for about 2 hours to carry out a polymerization reaction. A yellow transparent viscous polyimide precursor solution was obtained.

Example 1 Commercially available direct emulsion film emulsion [manufactured by Murakami Screen Co., Ltd.
MS-FILM (diazo emulsion 30 μm / release polyester film 75 μm)], the polyimide precursor resin solution obtained in Synthetic Example 1 was dried to a thickness of 50 μm.
The coating was performed using an applicator so as to have a thickness of μm. 1
The resultant was dried in a hot-air circulation oven at 30 ° C. for 4 minutes to obtain a laminate having a three-layer structure of a release polyester film / photosensitive resin layer / polyimide precursor resin layer.

This laminate was laminated with a non-adhesive copper-clad laminate (ESPANEX (rolled copper foil: 35 μm / polyimide: 35 μm), manufactured by Nippon Steel Chemical Co., Ltd.) which had been subjected to circuit processing in advance. The circuit is 300μm in line width / 300μ between lines
In a parallel circuit of m, using a laminator (ST Laminator 8B-550ID, manufactured by Taisei Laminator Co., Ltd.), a solution obtained by mixing DMAc and ethyl alcohol at a ratio of 1: 3 was wetted on the circuit surface by spraying, and then 90 ° C. At the temperature of the roll. The polyimide precursor resin layer was cleanly filled between the circuits, and no entrapment of air bubbles was observed.

Further, it comes into contact with the release film and has a size of 3 cm ×
A negative film having a pattern of 10 cm is placed, and after performing exposure of about 1000 mmNJ / cm ² using a discharge lamp exposure apparatus (3000 NEL manufactured by Hitec Co., Ltd.), the release film is peeled off, and a simple vertical shower apparatus is mounted. Developed with water at a water temperature of 23 ° C. and a water pressure of 1 kg / cm ² for 80 seconds.

Further, after drying at 80 ° C. for about 1 minute, 5%
Etching was performed at a liquid temperature of 33 ° C. and a water pressure of 1.5 kg / cm ² for 60 seconds with a simple vertical shower apparatus using a sodium hydroxide solution. The exposed polyimide precursor resin layer was removed by etching without any residue.

Subsequently, a stripping solution (manufactured by Murakami Screen Co., Ltd.)
1.0 kg / cm ² using STRIP SUPER)
For 2 minutes to remove the remaining photosensitive resin layer. Next, the obtained substrate was subjected to a heat treatment at 130 ° C. for 10 minutes in a hot air oven.
Heat treatment was performed stepwise at 00, 250 and 300 ° C. for 2 minutes each.

The obtained flexible printed circuit board had a 33 μm polyimide layer as an insulating layer, and when its cross section was observed with a microscope, it was found that the circuit had a uniform thickness and no gap. Moreover, the appearance of the substrate had extremely good flatness. As the characteristics, the soldering resistance was high up to a high temperature of 350 ° C., and it did not break even when it was bent by hand along a circuit, and had high mechanical properties.

Further, the processing accuracy was evaluated by using the above-mentioned pattern for determining the processing accuracy.
It was processed finely up to the circle of, and was far superior to the processing accuracy of the coverlay film punching. When the thermal expansion coefficient of this insulating resin layer was separately examined, it was found that 2.0 × 1
0 ^-5 / ° C.

Example 2 Using the polyimide precursor resin solution obtained in Synthesis Example 2, processing and evaluation were performed in the same manner as in Example 1. The solder resistance was 330 ° C., the bendability was good, and the flatness of the substrate was excellent. The processing accuracy was also 100 μm. The coefficient of thermal expansion was 2.2 × 10 ⁻⁵ / ° C.

Example 3 Using the polyimide precursor resin solution obtained in Synthesis Example 3, processing and evaluation were performed in the same manner as in Example 1. Although the solder resistance was good at 330 ° C. and the bendability was good, the flatness of the substrate was 10 mm on a test bench in a pattern of 3 cm × 10 cm.
There was about a corner rise. However, it is at a level that does not interfere with use. Processing accuracy is also 10
It was 0 μm. The coefficient of thermal expansion was 5.0 × 10 ⁻⁵ / ° C.

[0041]

The laminate used in the present invention has a high processing accuracy and can provide an insulating protective layer of a circuit with excellent reliability very easily. Therefore, the processing accuracy is high and the reliability is high. A circuit board having an excellent insulating protective film is provided.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing a layer structure of a laminate.

FIG. 2 is a conceptual diagram showing a state of an insulating protective layer after etching.

[Explanation of symbols]

 1 Release film layer 2 Photosensitive resin layer 3 Polyimide precursor resin layer 4 Circuit 5 Substrate resin surface 6 Polyimide insulating protective layer

Claims (3)

[Claims] 1. A film-like laminate having at least two layers, a photosensitive resin layer and a polyimide precursor resin layer, is laminated on a circuit board so that the polyimide precursor resin layer is in contact with the circuit board. , Development, etching, peeling of the remaining photosensitive resin layer, and curing treatment of the polyimide precursor resin. 2. A film-like laminate having at least two layers, a photosensitive resin layer and a polyimide precursor resin layer, is laminated on a circuit board so that the polyimide precursor resin layer is in contact with the circuit board. , Development, etching, peeling of the remaining photosensitive resin layer, and curing treatment of the polyimide precursor resin. 3. A circuit board having a patterned insulating protective film obtained by the method according to claim 2.