JP2009109591A - Photosensitive polyamide resin composition, photosensitive dry film and coverlay using those - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyamide resin composition and a photosensitive polyamide resin composition having an effect to suppress warpage. <P>SOLUTION: There are also provided a photosensitive dry film, a photosensitive laminated film and a resin pattern using a resin composition containing a polyamide resin having a specific structure. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polyamide resin composition, a photosensitive polyamide resin composition, a photosensitive dry film using the same, a laminated film, and a resin pattern.

  In recent years, a film-like printed board called a flexible printed board (hereinafter referred to as FPC) has gained popularity. This board has a structure that has a coverlay made of polyimide film on the FCCL (Flexible Copper Clad Laminate) that has been processed by wiring. It has been. Since FPC maintains its function even when it is bent, it is an indispensable material for reducing the size and weight of equipment. Particularly, in recent years, various electronic devices have been reduced in size and weight, and the adoption of FPC for such products contributes to the reduction of the size and weight of the devices, the reduction of product cost, and the simplification of design. ing.

  As a coverlay material provided in this FPC, a polyimide film provided with an adhesive is used from the viewpoint of bending resistance, heat resistance, and electrical insulation. However, in the case of using the polyimide film, there is a problem in terms of alignment accuracy and cost because the bonding and punching are performed manually. Therefore, various methods have been devised in which polyimide is formed by imparting photosensitivity to the polyimide precursor and forming a wiring pattern, and then heating the polyimide precursor (Patent Documents 1 and 2).

However, when these polyimide precursors are made of polyimide, high temperatures of 300 ° C. or higher are required, so use them in applications where high temperatures cannot be applied, such as coverlay materials for FPCs used in electronic devices. Is difficult. Further, when the polyimide precursor is converted to polyimide, the FPC warps due to the stress accompanying the solvent removal or the ring closure reaction of the polyamic acid. When warpage occurs in the FPC, problems such as poor adhesion between the FCCL and the coverlay and an increase in driving power of an electronic device equipped with the FPC arise. Therefore, it is required to improve the warpage of the FPC having a coverlay on the copper wiring.
Further, in the production of the photosensitive dry film, there is a problem that the photosensitive layer of the wound photosensitive dry film is in close contact with the support film. Therefore, it is possible to prevent adhesion to the support film by laminating the cover film, but it cannot be laminated unless the photosensitive layer has tackiness.
Patent No. 3064579 JP 2002-278061 A

  In the present invention, in view of solving the above-described problems, there is no warp even when a coverlay is formed on a flexible substrate such as FCCL, and the surface of the photosensitive dry film using the photosensitive polyamide resin composition is tacked. It aims at providing the photosensitive polyamide resin composition which can comprise a cover film by leaving, the photosensitive dry film using the said photosensitive polyamide resin composition, the photosensitive laminated | multilayer film, and a resin pattern.

As a result of intensive studies, the present inventor has solved the above-mentioned problems by using a resin composition containing a polyamide resin having a specific structure. That is, the object of the present invention can be achieved by the following configuration.
I. A photosensitive polyamide resin composition comprising (A) a polyamide resin represented by the following general formula (1) and (B) a photosensitizer.

(R ₁ represents an alkylene group having 2 or more carbon atoms, R 2 to R 4 represent divalent to tetravalent organic groups, m and n represent mole percentages, and m + n = 100, 0 <n <100.)
II. R _{1 in} said (A) polyamide resin is following General formula (2), The photosensitive polyamide resin composition of I characterized by the above-mentioned.
[Chemical 2]
C ₄ H ₈ (2)
III. Wherein (A) R ₂ in the polyamide resin, photosensitive polyamide resin composition according to I or II, characterized in that a following general formula (3).
[Chemical 3]
_{R 6 OOC-R 5 -COOR 7} ··· (3)
(R ₅ represents a tetravalent organic group. R ₆ and R ₇ represent a hydrogen atom or an organic group having 1 to 20 carbon atoms, which may be the same or different.)

IV. The photosensitive polyamide resin composition according to any one of I to III, wherein the photosensitive agent (B) is a quinonediazide compound.
V. A photosensitive dry film comprising a layer of the photosensitive polyamide resin composition according to any one of I to IV and a support film layer. VI. A photosensitive laminated film comprising the photosensitive dry film according to V and a cover film for protecting the photosensitive layer.
VII. The (A) polyamide resin is imidized and contains a polyamide resin according to any one of I to IV.

  By using the photosensitive polyamide resin composition of the present invention, warpage of the photosensitive dry film and laminated film after baking can be suppressed.

Hereinafter, the present invention will be specifically described.
The polyamide resin used in the present invention is synthesized by a known method from a compound having a carboxyl group and a compound having an amino group. As the polyamide resin, a polyimide precursor is preferable from the viewpoint of solubility in an alkaline aqueous solution, and polyamic acid is more preferable.
Examples of the compound having a carboxyl group and the compound having an amino group used as a monomer for the polyamide resin include the following.

(A) Polyamide resin
Specific examples of the compound having a carboxyl group include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic Acid dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3 ′ -Benzophenone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1 -Bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, Bis (2,3-dicarbox Phenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,3′-oxydiphthalic dianhydride, 4,4′-oxydiphthalic dianhydride, 2,2-bis ( 4- (4-aminophenoxy) phenyl) propane, 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4-phenylene ester, 4- (2,5-dioxotetrahydrofuran-3 -Yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetra Carboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarbo Ciphenyl) hexafluoropropane dianhydride, 2,2-bis (4- (3,4-dicarboxyphenoxy) phenyl) hexafluoropropane dianhydride, 2,2-bis (4- (3,4-dicarboxy) And benzoyloxy) phenyl) hexafluoropropane dianhydride, 2,2′-bis (trifluoromethyl) -4,4′-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride, and the like.

  Aliphatic tetracarboxylic dianhydrides include cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5,6-cyclohexanetetracarboxylic dianhydride 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylicsan dianhydride, ethylene glycol-bis-trimellitic anhydride ester, butanediol- Bis-trimellitic anhydride ester, pentanediol-bis-trimellitic anhydride ester, bicyclo [2,2,2] oct-7-ene-2,3,5,6 tetracarboxylic dianhydride, 1,2 3,4-butanetetracarboxylic dianhydride and the like. These may be used alone or in combination of two or more.

Of these, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic acid is used from the viewpoint of lowering the glass transition temperature (Tg-2) of the film obtained by baking the photosensitive layer. Dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′- Benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride Bis (3,4- Dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,3′-oxydiphthalic dianhydride, 4,4′-oxydiphthalic dianhydride, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1, 4-phenylene ester, ethylene glycol-bis-trimellitic anhydride ester, butanediol-bis-trimellitic anhydride ester, pentanediol-bis-trimellitic anhydride ester are preferred.
As a compound which has an amino group, the compound represented by General formula (4) is preferable.

(R ₁ represents an alkylene group having 2 or more carbon atoms, and n represents an integer of 1 or more.)
_{Specifically,} a compound represented by _{R 1 = C 2 H 4,} t-C 3 H 6, C 4 H 8 and the like.
Moreover, it is possible to use the compound which has the said amino group, and the compound which has the other amino group simultaneously. Specifically, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3 , 3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 3, , 7-diamino-dimethylbenzothiophene-5,5-dioxide, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 4,4′-bis (4-aminophenyl) sulfide, 4,4′- Diaminodiphenylsulfone, 4,4′-diaminobenzanilide, 1, n-bis (4-aminophenoxy) alkane, 1,3-bis (4- Minophenoxy) -2,2-dimethylpropane, 1,2-bis [2- (4-aminophenoxy) ethoxy] ethane, 9,9-bis (4-aminophenyl) fluorene, 5 (6) -amino-1 -(4-aminomethyl) -1,3,3-trimethylindane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3 -Aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, 2,2-bis (4-aminophenoxyphenyl) propane, bis [ 4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) Enyl] hexafluoropropane, 3,3′-dicarboxy-4,4′-diaminodiphenylmethane, 4,6-dihydroxy-1,3-phenylenediamine, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 1,4-bis (4-aminophenoxy) pentane, 1,5-bis (4′-aminophenoxy) pentane, bis (γ-aminopropyl) tetramethyldisiloxane, 1,4-bis (γ-aminopropyldimethyl) Examples thereof include silyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetraphenyldisiloxane, and a diaminosiloxane compound represented by the formula (5). These may be used alone or in combination of two or more.

(R is an integer of 2 to 12)
Among these, from the viewpoint of lowering Tg-2, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-dimethyl-4,4′-dianobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3,7-diamino-dimethylbenzothiophene-5 , 5-dioxide, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 4,4′-bis (4-aminophenyl) sulfide, 4,4′-diaminodiphenylsulfone, 4,4′-diamino Benzanilide, 1, n-bis (4-aminophenoxy) alkane, 1,3-bis (4-aminophenoxy) -2,2-dimethyl Rupropane, 1,2-bis [2- (4-aminophenoxy) ethoxy] ethane, 9,9-bis (4-aminophenyl) fluorene, 5 (6) -amino-1- (4-aminomethyl) -1 , 3,3-trimethylindane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 4,4 '-Bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, 2,2-bis (4-aminophenoxyphenyl) propane, bis [4- (4-aminophenoxy) phenyl ] Sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,6-dihydroxy-1,3-phenylenediamine, 3,3′-dihydroxy- , 4′-diaminobiphenyl, 1,4-bis (4-aminophenoxy) pentane, 1,5-bis (4′-aminophenoxy) pentane, bis (γ-aminopropyl) tetramethyldisiloxane, 1,4- Bis (γ-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetraphenyldisiloxane, and a diamine represented by formula (5) are preferred.

(R is an integer of 2 to 12.) Tg (Tg-1) of the photosensitive layer obtained by removing the solvent from the photosensitive polyamide resin composition of the present invention is preferably 120 ° C or lower, and 100 ° C or lower. It is more preferable that it is 90 degreeC or less. By setting Tg-1 to 120 ° C. or lower, it is possible to remove the stress associated with solvent removal, and to reduce the warp of the support film and the film composed of the photosensitive layer (hereinafter referred to as photosensitive dry film).
When synthesizing a polyimide precursor, a polymer terminal may be sealed with a monofunctional acid anhydride, a monofunctional carboxylic acid, or a monofunctional amine as necessary.
Moreover, it is also possible to esterify a part of carboxyl group of the polyimide precursor used for this invention using well-known compounds, such as an alcohol compound, and a method.

(B) Photosensitizer (B) The photosensitizer used in the present invention is preferably a compound that generates an acid upon irradiation with actinic rays. Of these, quinonediazide compounds are preferred. For example, those described in US Pat. No. 2,797,213, 3669658 can be used. Among these, an ester compound of a phenol compound and 1,2-naphthoquinone-2-diazide-4-sulfonic acid or 1,2-naphthoquinone-2-diazide-5-sulfonic acid is preferable. These may be used alone or in combination of two or more.
The blending amount of the photosensitive agent (B) used in the present invention is preferably 5 to 30 parts by weight, more preferably 10 to 20 parts by weight, based on 100 parts by weight of the (A) polyamide resin. The blending amount of the photosensitive agent is preferably 5 parts by weight or more from the viewpoint of sensitivity and 30 parts by weight or less from the viewpoint of light absorption.

(C) Organic solvent The photosensitive polyamide resin composition of the present invention may contain (C) an organic solvent. (C) As the organic solvent, ester compounds such as γ-butyrolactone and ethyl lactate and ether compounds such as tetrahydrofuran are preferable from the viewpoint of solubility in an alkali developer. These organic solvents may be used alone or in combination of two or more. The organic solvent that can be used in the present invention is preferably 120 to 900 parts by weight with respect to 100 parts by weight of the polyamide resin.

In the organic solvent used in the present invention, a solvent having a boiling point lower than that of γ-butyrolactone can be blended as necessary. By blending a low boiling point solvent, foaming during drying can be suppressed.
Specific examples of the low boiling point solvent include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ethyl alcohol, isopropyl alcohol, n-butanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and hexylene glycol. Alcohols, 1,4-dioxane, trioxane, diethyl acetal, 1,2-dioxolane, ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, anisole, ethyl acetate, methyl benzoate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate , Ethylene glycol monopropyl ether acetate, ethylene glycol diacetate, propylene glycol Monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol diacetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diacetate and other esters, n -Hydrocarbons such as heptane, n-octane, cyclohexane, benzene, toluene, xylene, ethylbenzene and diethylbenzene.

(Plasticizer)
A plasticizer can be mix | blended with the photosensitive polyamide resin composition of this invention as needed. The plasticizer is preferably a compound represented by the general formula (6) from the viewpoint of reducing warpage of a sheet composed of a film after baking and a substrate.

(U is an integer greater than or equal to 0. R < ₁₃ >, R < ₁₄ > is a single bond, an oxygen atom, and a bivalent or more organic group.
X1 to X14 represent a hydrogen atom, a hydroxyl group, or an organic group, and may be the same or different. )
Specifically, dihydroxydiphenylmethane, 4,4′-dioxyphenol, 1,4-bis- (3-hydroxyphenoxy) -benzene, 1,3-bis- (4-hydroxyphenoxy) -benzene, 1,5 -Binuclear compounds such as bis- (o-hydroxyphenoxy) -3-oxapentane, α, α′-bis- (4-hydroxyphenyl) -1,4-diisopropylbenzene, tris (hydroxyphenyl) methane, tris ( And trinuclear compounds such as hydroxyphenyl) ethane and 4- {4- [1,1-bis (4-hydroxyphenyl) ethyl] -α, α-dimethylbenzyl} phenol. These phenol compounds may be used alone or in combination of two or more.

  As the plasticizer that can be used in the present invention, a compound represented by the general formula (7) can also be suitably used.

(R ₁₅ to R ₁₇ are organic groups containing an ethylene glycol chain and / or a propylene glycol chain, which may be the same or different.)
Specific examples include compounds represented by general formula (8) and general formula (9), but are not limited thereto.

(N is an integer greater than or equal to 0)

(N is an integer greater than or equal to 0)
These compounds may be used alone or in combination of two or more.
Moreover, you may use combining the compound represented by General formula (6) and General formula (7).

(Dissolution inhibitor)
The photosensitive polyamide resin composition of the present invention may contain a dissolution inhibitor as necessary. By blending a dissolution inhibitor, the solubility of the polyamide resin in an alkaline developer can be suppressed. The dissolution inhibitor used in the present invention refers to a compound that forms a hydrogen bond with a carboxyl group of a polyamide resin. When the carboxyl group of the polyamide resin is hydrogen-bonded with the dissolution inhibitor, the polyamide resin is shielded from the developer, and dissolution can be suppressed.

Examples of the compound having a group capable of hydrogen bonding with a carboxyl group include a carboxylic acid compound, a carboxylic acid ester compound, an amide compound, and a urea compound. An amide compound and a urea compound are preferable from the viewpoint of the effect of inhibiting dissolution in an alkaline aqueous solution and storage stability.
Examples of the amide compound include N, N-diethylacetamide, N, N-diisopropylformamide, N, N-dimethylbutyramide, N, N-dibutylacetamide, N, N-dipropylacetamide, N, N-dibutylformamide. N, N-diethylpropionamide, N, N-dimethylpropionamide, N, N′-dimethoxy-N, N′-dimethyloxamide, N-methyl-ε-caprolactam, 4-hydroxyphenylbenzamide, salicylamide, salicylanilide , Acetanilide, 2′-hydroxyphenylacetanilide, 3′-hydroxyphenylacetanilide, 4′-hydroxyphenylacetanilide.

Among these, an amide compound containing an aromatic hydroxyl group is more preferable from the viewpoints of lowering the Tg of the photosensitive layer and the film obtained by baking the photosensitive layer, increasing the sensitivity of the photosensitive layer, and increasing the residual film ratio. Specific examples include 4-hydroxyphenylbenzamide, 3′-hydroxyphenylacetanilide, and 4′-hydroxyphenylacetanilide. These may be used alone or in combination of two or more.
Examples of the urea compound include 1,3-dimethylurea, tetramethylurea, tetraethylurea, 1,3-diphenylurea, and 3-hydroxyphenylurea. Among these, a urea compound containing an aromatic hydroxyl group is more preferable from the viewpoint of increasing sensitivity, increasing the residual film ratio, reducing the Tg of the photosensitive layer and the film obtained by baking the photosensitive layer. Specific examples include 3-hydroxyphenylurea. These may be used alone or in combination of two or more.

When the amide compound is used as the dissolution inhibitor that can be used in the present invention, (A) 0.1 mol to 1.5 mol may be blended with respect to 1 mol of the carboxyl group of the polyamide resin in terms of the dissolution inhibition effect. Preferably, 0.15-1.0 mol is blended.
In the case of using a urea compound, the (B) dissolution inhibitor used in the present invention is preferably 0.1 mol to 1.5 mol in terms of the dissolution inhibition effect with respect to 1 mol of the carboxyl group of (A) the polyimide precursor. From the viewpoint of the dissolution inhibiting effect and the mechanical properties of polyimide obtained by baking after alkali development, it is more preferable to add 0.15 to 0.5 mol.

Moreover, when using both an amide compound and a urea compound, the total amount of an amide compound and a urea compound is 0.1 mol-1 with respect to 1 mol of carboxyl groups of the (A) polyimide precursor from a viewpoint of a dissolution inhibitory effect. A range of .5 mol is preferred.
In this invention, a crosslinking agent can be mix | blended in order to improve the mechanical physical property of the film after baking. As the crosslinking agent, a tetracarboxylic acid compound or a tetracarboxylic acid ester compound represented by the formula (10), a polyamic acid compound represented by the formula (11) or a carboxyl group-containing polyamic acid ester compound is preferable.

(R ₁₈ is a tetravalent organic group, and R _{19 to} R ₂₂ are hydrogen or an organic group having 1 to 20 carbon atoms, which may be the same or different.)

(R ₂₃ , R ₂₅ and R ₂₇ are tetravalent organic groups which may be the same or different. R24 and R ₂₆ are divalent to tetravalent organic groups which may be the same or different. R _{28 to} R ₃₃ are hydrogen or an organic group having 1 to 20 carbon atoms, and may be the same or different, and v is an integer of 0 to 100.)

The amount of the crosslinking agent that can be used in the present invention is preferably from 0.1 mol to 1.5 mol, preferably from 0.5 mol to 1. 1 mol is more preferable.
The amount of residual amino groups can be calculated using high performance liquid chromatography.
The photosensitive polyamide resin composition of the present invention can contain a thermal base generator, if necessary. A thermal base generator is a compound that generates a base by heating. For example, a base such as an amine is protected with an acid chloride compound, which is protected with a dicarbonate compound, which forms a salt structure with an acid such as a sulfonic acid. Thereby, it is stable without exhibiting basicity at room temperature, and can be a thermal base generator that generates a base by deprotection by heating.

By blending the thermal base generator, when a polyamic acid or a carboxyl group-containing polyamic acid ester is used as the polyamide resin, the temperature of the heating imidization after development can be made relatively low.
Specific examples of the thermal base generator include U-CAT (registered trademark) SA810, U-CAT SA831, U-CAT SA841, U-CAT SA851 (trade name, manufactured by San Apro), N- (isopropoxycarbonyl). -2,6-dimethylpiperidine, N- (tert-butoxycarbonyl) -2,6-dimethylpiperidine, N- (benzyloxycarbonyl) -2,6-dimethylpiperidine, 1,3-bis (4-aminophenoxy) Examples include compounds in which both amines of benzene are protected with dibutyl dicarbonate.

N- (isopropoxycarbonyl) -2,6-dimethylpiperidine, N- (tert-butoxycarbonyl) from the viewpoints of storage stability of the photosensitive polyamide resin composition, stability by solvent removal, alkali solubility, and ion migration ) -2,6-dimethylpiperidine, N- (benzyloxycarbonyl) -2,6-dimethylpiperidine, 1,3-bis (4-aminophenoxy) benzene, both amines protected with dibutyl dicarbonate are preferred. . The compounds are described, for example, in Chemistry Letters Vol. 34, no. 10 (2005).
The blending amount of the thermal base generator is preferably from 1 to 30 parts by weight, more preferably from 1 to 20 parts by weight, based on 100 parts by weight of the alkali-soluble resin, from the viewpoint of promoting imidization and developing performance.

The photosensitive polyamide resin composition of the present invention includes alcohols such as ethanol, 2-propanol and ethylene glycol, ethyl lactate, methyl benzoate and ethylene glycol as necessary for the purpose of improving the wettability with the support film. Mixing esters such as monopropyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ethers such as n-butyl ether, tetrahydrofuran and dioxane, glycol ethers such as ethylene glycol monoethyl ether and propylene glycol monoethyl ether I can do it.
In the photosensitive polyamide resin composition of the present invention, an imidazole compound, a triazole compound, a tetrazole compound, and a sulfide compound can be blended as necessary. By blending these compounds, the adhesion to the copper substrate can be improved.

(Production of photosensitive dry film)
It is possible to produce a photosensitive dry film using the photosensitive polyamide resin composition of the present invention. The photosensitive dry film is obtained by applying the photosensitive polyamide resin composition to a support film and drying the solvent. As the support film, low density polyethylene, high density polyethylene, polypropylene, polyester, polycarbonate, polyarylate, polyacrylonitrile, ethylene / cyclodecene copolymer (trade name: APEL, manufactured by Mitsui Chemicals) and the like can be used. The thickness of the carrier film is usually from 15 to 100 μm, preferably from 15 to 75 μm, in consideration of coatability, adhesion, rollability, toughness, cost and the like.

The photosensitive polyamide resin composition can be applied to the above support film using a known method such as a reverse roll coater, a gravure roll coater, a comma coater, a lip coater, or a slot die coater.
Drying of the solvent can be performed at a temperature of 50 to 120 ° C. with a dryer using hot air drying, far infrared rays, or near infrared rays. The thickness of the photosensitive layer obtained by solvent removal is preferably 5 to 100 μm, more preferably 5 to 50 μm. The film thickness is preferably 5 μm or more from the viewpoint of insulation reliability, and preferably 100 μm or less from the viewpoint of obtaining a good line image.

A cover film can be laminated on the photosensitive dry film to form a photosensitive laminated film. By laminating the cover film, adhesion of the photosensitive layer to the support film can be prevented. As the cover film, low density polyethylene, high density polyethylene, polypropylene, polyester, polycarbonate, polyarylate, polyacrylonitrile, ethylene / cyclodecene copolymer (product name: APEL, manufactured by Mitsui Chemicals) can be used.
The photosensitive polyamide resin composition of the present invention can be used as a coverlay. A coverlay refers to a protective film that protects wiring formed on a silicon wafer, a copper clad laminate, an FPC, or the like.

(Coverlay production)
A photosensitive dry film can be produced from the photosensitive polyamide resin composition of the present invention, and a coverlay can be formed on the FPC. For example, it can be formed by the following steps.
1. A step of laminating a photosensitive dry film composed of the photosensitive polyamide resin composition of the present invention on a circuit-formed surface such as an FPC to form a photosensitive layer.
The photosensitive dry film is superposed on a circuit-formed surface such as FPC, and heated to 40 to 120 ° C., preferably 60 to 110 ° C. by a known method such as flat lamination, roll lamination, or vacuum press. The photosensitive layer can be laminated by laminating at a pressure of 2 to 4 MPa. At this time, when the photosensitive dry film is a photosensitive laminated film in which a cover film is laminated, the cover film is peeled off before lamination. By setting the temperature at which lamination is possible to 40 ° C or higher, there is no need to take time and labor when aligning before lamination, and by setting it to 120 ° C or lower, imidization does not proceed too much, allowing for a sufficient laminating time and process margin. Can be taken widely. Note that the temperature at which lamination is possible is that there is no problem such as remaining bubbles, and the pattern can be sufficiently embedded, and at the same time, the photosensitive layer can be controlled to a viscosity at which the resin does not flow out of the pattern. It means temperature. Moreover, the photosensitive dry film can be suitably laminated by lowering the Tg of the photosensitive layer below the laminating temperature. After lamination of the photosensitive layer, the support film may or may not be peeled off. When not peeling off a support film, it peels after an exposure process.

2. A step of irradiating the photosensitive layer obtained in this step with actinic rays.
The photosensitive layer is exposed through a photomask on which an arbitrary pattern is drawn in order to form fine holes and fine width lines. The exposure amount varies depending on the composition of the photosensitive polyamide resin composition, but is usually 100 to 3,000 mJ / cm ² . Examples of actinic rays used at this time include X-rays, electron beams, ultraviolet rays, and visible rays. As the light source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a halogen lamp, or the like can be used. In the present invention, it is preferable to use i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp. As a method of irradiating with actinic rays, either contact exposure or projection exposure may be used.

3. Development and rinsing process of the portion irradiated with actinic rays.
After the exposure, development can be performed by a known method such as a dipping method or a spray method using a developer, and a line image can be obtained. As the developer, an aqueous alkali solution such as an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous sodium carbonate solution, or an aqueous potassium carbonate solution can be used. After development, washing is performed using a rinse solution. Examples of the rinsing liquid include water and water obtained by adding an organic solvent.

4). Resin pattern formation by baking.
A resin pattern is formed by baking the line image obtained by development. Baking is performed continuously or stepwise at a temperature of 100 ° C. to 200 ° C. for 5 minutes to 5 hours. And the processed product is completed. Moreover, when using the said photosensitive polyamide resin composition, an actinic ray is irradiated to the line image obtained at the said process, and it can also bake after that.
Examples of the processed product thus obtained include FPC and multilayer printed wiring boards.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, it is not limited at all by these examples.
(Synthesis of polyimide precursor)
(Synthesis Example 1) Synthesis of Polyamic Acid (I) 13.7 g of polytetramethylene oxide-di-p-aminobenzoate and 93 g of γ-butyrolactone were placed in a three-necked separable flask and stirred at room temperature until a homogeneous solution was obtained. Next, 5 g of pentanediol-bis-trimellitic anhydride ester was added, and the mixture was stirred for 1 hour while cooling with ice and then for 6 hours at room temperature. Next, the product was subjected to pressure filtration with a 5 μm filter to obtain polyamic acid (I).

Synthesis Example 2 Synthesis of Polyamic Acid (II) In a three-necked separable flask, 6.8 g of polytetramethylene oxide-di-p-aminobenzoate, 1.6 g of 1,3-bis (3-aminophenoxy) benzene, γ- 50.6 g of butyrolactone was added and stirred at room temperature until a homogeneous solution was obtained. Next, 5 g of pentanediol-bis-trimellitic anhydride ester was added, and the mixture was stirred for 1 hour while cooling with ice and then for 6 hours at room temperature. Next, the product was subjected to pressure filtration with a 5 μm filter to obtain polyamic acid (II).

(Synthesis Example 3) Synthesis of Polyamic Acid (III) Into a three-necked separable flask, 7.8 g of 1,3-bis (3-aminophenoxy) benzene and 74.3 g of γ-butyrolactone were added until a uniform solution was obtained at room temperature. Stir. Next, 12 g of pentanediol-bis-trimellitic anhydride ester was added, and the mixture was stirred for 1 hour while cooling with ice and then for 6 hours at room temperature. Next, the product was subjected to pressure filtration with a 5 μm filter to obtain polyamic acid (III).

(Observation of warping)
Coating: A polyimide film (Kapton EN-100 trade name, manufactured by Toray DuPont) was placed on a coating table (manufactured by Matsuki Kagaku Co., Ltd.) that can be vacuum-adsorbed and heated, and the polyimide film was adhered by vacuum adsorption. On the polyimide film, a photosensitive polyamide resin composition was applied using an applicator (manufactured by Matsuki Scientific Co., Ltd.) having a gap of 100 μm.
Solvent removal: Solvent removal was performed with a dryer (SPH-201, manufactured by Espec Corp.) at 60 ° C. for 30 minutes and then at 95 ° C. for 20 minutes. Baking: Using a dryer (SPH-201 manufactured by Espec Corp.), baking was performed under the conditions of a heating rate of 1 ° C./min, an air atmosphere at 110 ° C. for 60 minutes, and 140 ° C. for 60 minutes.
Measurement of warpage: The film obtained after baking was cut into a length of 5 cm and a width of 5 cm, and the warpage was measured using a ruler.

(Evaluation of surface tack)
Coating: A polyimide film (R-310-25, trade name, manufactured by Mitsubishi Polyester Co., Ltd.) was placed on a coating table (manufactured by Matsuki Kagaku Co., Ltd.) that can be vacuum-adsorbed and heated, and the polyester film was adhered by vacuum adsorption. On the polyester film, a photosensitive polyamide resin composition was applied using an applicator (manufactured by Matsuki Scientific Co., Ltd.) having a gap of 100 μm. Solvent removal: A photosensitive dry film was obtained by removing the solvent with a dryer (SPH-201, manufactured by Espec Corp.) at 60 ° C. for 30 minutes and then at 95 ° C. for 20 minutes.
The surface of the photosensitive dry film was evaluated for the presence or absence of tack by palpation. The case where there was a fingerprint on the film or the film was tacked was marked as ◯, and the case where there was no fingerprint was marked as x.

[Example 1]
10 g of the polyamic acid (I) obtained in Synthesis Example 1 and 0.42 g of a quinonediazide compound (formula 12) based on polyamic acid as a photosensitizer are placed in a 20 cc glass bottle, and a mix rotor (manufactured by MR-5 ASONE) To obtain a photosensitive polyamic acid composition (I). The evaluation results are shown in Table 1.

[Example 2]
10 g of polyamic acid (II) obtained in Synthesis Example 2 and 0.42 g of quinonediazide compound (Formula 12) with respect to polyamic acid as a photosensitizer are placed in a 20 cc glass bottle, and a mix rotor (manufactured by MR-5 ASONE) To obtain a photosensitive polyamic acid composition (II). The evaluation results are shown in Table 1.

[Comparative Example 1]
10 g of polyamic acid (III) obtained in Synthesis Example 3 and 0.42 g of quinonediazide compound (Formula 12) with respect to polyamic acid as a photosensitizer are placed in a 20 cc glass bottle, and a mixed rotor (manufactured by MR-5 ASONE) To obtain a photosensitive polyamic acid composition (III). The evaluation results are shown in Table 1.

The polyamide resin composition, the photosensitive polyamide resin composition, and the photosensitive dry film, laminated film, and resin pattern using the polyamide resin composition of the present invention can be suitably used for FPC applications.

FT-IR chart after removing the solvent from the composition obtained in Example 2

Claims (7)

A photosensitive polyamide resin composition comprising (A) a polyamide resin represented by the following general formula (1) and (B) a photosensitizer.

(R ₁ represents an alkylene group having 2 or more carbon atoms, R ₂ to R ₄ represent a divalent to tetravalent organic group. M and n represent mole percentages, and m + n = 100, 0 <n <100. .) The photosensitive polyamide resin composition according to claim 1, wherein R ₁ in the polyamide resin (A) is represented by the following general formula (2).
[Chemical 2]
C ₄ H ₈ (2) Wherein (A) R ₂ in the polyamide resin, photosensitive polyamide resin composition which is a following general formula (3).
[Chemical 3]
_{R 6 OOC-R 5 -COOR 7} ··· (3)
(R ₅ represents a tetravalent organic group. R ₆ and R ₇ represent a hydrogen atom or an organic group having 1 to 20 carbon atoms, which may be the same or different.) The photosensitive polyamide resin composition according to claim 1, wherein the photosensitive agent (B) is a quinonediazide compound. A photosensitive dry film comprising a layer of the photosensitive polyamide resin composition according to claim 1 and a support film layer. A photosensitive laminated film comprising the photosensitive dry film according to claim 5 and a cover film for protecting the photosensitive layer. The cover lay comprising the polyamide resin according to claim 1, wherein the (A) polyamide resin is imidized.

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