JP5362811B2 - Raw material liquid for protective film formation, protective film, wiring board with protective film - Google Patents

Description

  The present invention relates to a technique for forming a protective film for a wiring board, and more particularly, to a protective film having high adhesion, a raw material solution thereof, and a wiring board having the protective film.

Wiring boards are widely used in electronic devices, and a protective film is generally formed on the surface of the wiring board so that copper wiring is not exposed on the wiring board surface.
For example, the following Patent Document 4 (Japanese Patent Laid-Open No. 2002-12664) describes a protective film of a polyimide polymer. In this document, (a) a tetracarboxylic acid component capable of giving a heat-resistant polyimide, (b In an organic solvent using a reaction vessel equipped with a stirrer for polymerization with (i) diaminosiloxane, (c) an aromatic diamine having a polar group, and (d) a diamine composed of an aromatic diamine having a plurality of benzene rings. A synthesis method is described in which the synthesis is performed under the flow of humidified nitrogen.

  An invention of a composition for a polyimide-based insulating film comprising 1 to 100 parts by mass of an isocyanate and / or epoxy resin, particularly 2 to 40 parts by mass and an organic solvent with respect to 100 parts by mass of such a polyimide polymer is also described. Examples of the aromatic diamine having a polar group include hydroxydiamine. Block isocyanates are also described.

However, in recent years, photoreactivity is required for a film that is a precursor before patterning as a protective film. After exposing and developing a photoreactive film coated with a raw material solution, the protective film is formed by heating. To be done. There are advantages in that the number of steps is reduced compared to exposure, development, etching, and resist removal using a resist film, and pattern accuracy is also improved.
Patent Documents 1 to 3 below describe that a photosensitive polyimide composition is obtained when a photosensitive agent such as diazonaphthoquinone is contained in the polyimide composition.
JP 2008-38031 A JP 2008-37915 A WO2008 / 132914 JP 2002-12664 A JP-A-9-236916 Japanese translation of PCT publication No. 2002-544542

However, the protective film formed by exposure / development of the photoreactive film as described above has weak adhesion to the metal wiring, and has a strength of about 5 N / cm in the 90-degree peel test. This value indicates that there may be peeling in the cross-cut test when there is a blur between the processes. If the metal wiring is plated after patterning, the plating solution will be between the metal wiring and the protective film. There is a problem of intrusion and reducing reliability. Desirably, a peel strength of about 10 N / cm is desired.
In order to further improve the adhesion between the base material and the cover material, a new resin that is expected to be firmly bonded to both is required.

  The present invention was created to solve the above-described disadvantages of the prior art, and an object of the present invention is to provide a protective film with improved adhesion, a raw material solution thereof, and a wiring board having the protective film.

で表されるアミド基含有シロキサンジアミン化合物を含むジアミン成分と、ピロメリットテトラカルボン酸二無水物、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物、３，３’４，４’−ジフェニルエーテルテトラカルボン酸二無水物、３，３’，４，４’−ジフェニルスルホンテトラカルボン酸二無水物、２，２’−ビス（３，４−ジカルボキシフェニル）プロパン酸二無水物、１，４，５，８−ナフタレンテトラカルボン酸二無水物、４，４’−（ヘキサフルオロイソプロピリデン）ジフタル酸二無水物、９，９−ビス（３，４−ジカルボキシフェニル）フルオレン酸二無水物、９，９−ビス［４−（３，４−ジカルボキシフェノキシ）フェニル］フルオレン酸二無水物及び１，２，３，４−シクロブタン酸二無水物からなる群より選択される少なくとも一種の芳香族酸二無水物を含む酸二無水物成分とをイミド化して成るポリイミド樹脂を含み、前記ブロックイソシアネート成分は、ヘキサメチレンジイソシアネート化合物のイソシアネート基が封鎖されたブロックイソシアネート化合物を含有し、当該保護膜用原料液を塗布対象物に塗布し、前記溶剤を蒸発させて光反応性膜が形成されると、前記光反応性膜は光溶解性を有し、前記式（１）のアミド基含有シロキサンジアミン化合物は、ジアミンの合計量を１００モル％としたとき、０．１モル％以上２０モル％以下である保護膜用原料液である。
また、本発明は、前記ブロックイソシアネート化合物は、ポリイミド樹脂を１００質量部としたときに、２質量部以上１０質量部以下の範囲で含有された保護膜用原料液である。
また、本発明は、前記感光剤は、ポリイミド樹脂１００質量部に対し、５質量部以上３０質量部以下の範囲で含有された保護膜用原料液である。
また、本発明は、上記いずれかの保護膜用原料液が前記塗布対象物上に塗布され、露光・現像によってパターニングされ、前記塗布対象物上に配置された金属配線を覆い、部分的に露出させた保護膜である。
また、本発明は、基板と、前記基板上に配置された金属配線膜とを有する配線基板であって、基板上に金属配線膜を有する塗布対象物に、上記いずれかの保護膜用原料液が塗布され、露光・現像によってパターニングされ、前記基板上に配置された金属配線を覆いながら一部露出された配線基板である。 In order to solve the above problems, the present invention is a raw material liquid for a protective film containing a polyimide resin component, a photosensitizer, a crosslinking agent, and a solvent, wherein the crosslinking agent contains a blocked isocyanate component, The polyimide resin component has the following formula (1),

A diamine component containing an amide group-containing siloxane diamine compound represented by: pyromellitic tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3′4,4 '-Diphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 2,2'-bis (3,4-dicarboxyphenyl) propanoic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorenic acid The group consisting of anhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluoric acid dianhydride and 1,2,3,4-cyclobutanoic acid dianhydride A blocked isocyanate compound comprising a polyimide resin formed by imidizing an acid dianhydride component containing at least one selected aromatic acid dianhydride, wherein the blocked isocyanate component is a blocked isocyanate group of a hexamethylene diisocyanate compound containing, by applying the protective film raw material solution to the coating object, the solvent was evaporated when the photoreactive layer is formed, the photoreactive film have a light solubility, the formula ( 1 amide group-containing siloxane diamine compound) is, when the total amount of diamine and 100 mol%, a raw material liquid for the protective film Ru der than 20 mol% 0.1 mol%.
Moreover, this invention is a raw material liquid for protective films containing the said block isocyanate compound in the range of 2 mass parts or more and 10 mass parts or less, when a polyimide resin is 100 mass parts.
Moreover, this invention is the raw material liquid for protective films in which the said photosensitive agent was contained in 5 to 30 mass parts with respect to 100 mass parts of polyimide resins.
Further, the present invention provides any one of the above-described protective film raw material liquids coated on the object to be coated, patterned by exposure / development, covering the metal wiring disposed on the object to be coated, and partially exposed It is the made protective film.
Further, the present invention is a wiring board having a substrate and a metal wiring film disposed on the substrate, wherein any one of the above-described protective film raw material liquids is applied to a coating object having the metal wiring film on the substrate. Is a wiring substrate that is partially exposed by covering and covering the metal wiring arranged on the substrate by patterning by exposure and development.

  A blocked isocyanate is a structure in which an isocyanate group of a polyisocyanate (isocyanate compound having two or more isocyanate groups) is masked with a blocking agent (“isocyanate group is blocked by the blocking agent”). In this structure, H is bonded to N, and hydrocarbon is bonded to C via O.) If the temperature is equal to or lower than the temperature at which the blocking agent dissociates, it is mixed with a resin component having a hydroxyl group or a carboxyl group. Even if it does not respond. Since the temperature at which the blocking agent dissociates is usually 80 to 200 ° C., it does not react at room temperature and can be stored for a long time.

When heated to the dissociation temperature, the active isocyanate group is regenerated and reacts with a resin component having a hydroxyl group or a carboxyl group to obtain a tough resin.
As for the adhesiveness of the resin, a thermosetting resin having a high polarity has a high adhesiveness, and therefore, it is known to contain an epoxy resin, an acrylic resin, and a urethane resin. In order to enhance the adhesion to the metal, if there is a polar group such as OH, SH, NH, etc. in the resin, it becomes easy to bond to the metal, and in particular, it is preferable to have N · S atoms for bonding with Cu. (From HASB rule).

  In the present invention, a blocked isocyanate is blended with a hydroxyl group-containing polyimide compound having alkali solubility, and when the protective film is patterned and heated and thermally cured, the isocyanate group regenerated by heat becomes a resin component. By reacting with the contained hydroxyl group or carboxyl group, the resin components are crosslinked with each other, and a protective film stronger than the cured resin crosslinked by light can be obtained.

  By containing the blocked isocyanate compound, adhesion to metal is also improved. This is activated at the time of thermal curing at about 150 ° C., and it is considered that the cross-linking density of the main chain polyimide is increased and the adhesion with the base material is caused by the resulting urethane skeleton. A structure is formed, and the NH group of the generated urethane skeleton is easily bonded to a metal, and adhesion is improved.

When the blocked isocyanate compound is contained, unlike the case where the urethane resin is simply added, both the effect of urethane bonding and the effect of increasing the crosslinking density are obtained by bonding to the main chain PI (polyimide).
On the other hand, blocked isocyanate is a photosensitive composition cross-linking agent, it is easy to control the reactivity of the cross-linking agent and ensure the storage stability of the adhesive varnish, and induces deterioration of the properties of double-sided copper-clad films and multilayer printed wiring boards. do not do.

It is desirable to add 2 to 10 parts by mass of the blocked isocyanate with respect to 100 parts by mass of the polyimide resin.
The blocked isocyanate may be liquid or solid.
With respect to the polyisocyanate part of the blocked isocyanate, the adhesion effect can be obtained even with other types such as TDI / MDI type, but the effective content range is narrow and the HDI type having a wide range is desirable.

As for the block part of the blocked isocyanate, many have a dissociation temperature range of 80 to 200 ° C. In the present invention, it can be used within that range, but it is preferable that the dissociation temperature is desirably 100 to 180 ° C., and the photoreactive film is formed by drying the raw material liquid coated on the substrate at 80 ° C. The isocyanate group is not regenerated at that temperature, and a blocked isocyanate that is regenerated by the isocyanate group may be used when the patterned photoreactive film is thermally cured after development. Since thermosetting is performed by heating at 200 ° C. for 1 hour, the regeneration temperature of the blocked isocyanate needs to be lower than the thermosetting temperature.
Therefore, the regeneration temperature is higher than 80 ° C. and lower than 200 ° C. However, since a temperature margin is required, 100 ° C. or higher and 180 ° C. or lower is desirable.

When the protective film of the present invention is heated and thermally cured after patterning of the photoreactive film, the isocyanate group regenerated by heat reacts with the hydroxyl group or carboxyl group contained in the resin component in the protective film to crosslink. A protective film that is tougher than a cured resin crosslinked by light can be obtained.
Since the raw material liquid for the protective film of the present invention is light-soluble (positive type) that does not require a photopolymerization agent, the blocked isocyanate compound does not affect the reaction of exposure and development.

(A): Plan view of one embodiment of the present invention (b): A-A line cut cross-sectional view

10 ... Wiring board 11 ... Board 12 ... Metal wiring film 13 ... Protective film

  As a raw material liquid for the protective film, a resin having a nitrogen substituent that reacts with the polyimide in the protective film and has a strong binding force with the wiring film made of Cu can be mentioned, but as a practical resin, a glycidylamine type epoxy resin / isocyanate Resins and acrylamide resins are known.

When using a new additive, restrictions are imposed from the viewpoint of positive type, light, and thermal history. As the PSPI process, varnish application → 80 ° C. 10 min temporary drying → exposure → development → 200 ° C. baking is performed. Therefore, a reagent that does not cure before development (exposure and drying at 80 ° C.) but cures at 200 ° C. is desirable.
Based on the above, studies were conducted using glycidylamine type epoxy resin EP630 and isocyanate resin 17B-60PX.

<Compound for synthesizing polyimide resin>
The present invention provides the following formula (1),

A diamine component containing an amide group-containing siloxane diamine compound represented by: pyromellitic tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4, 4'-diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 2,2'-bis (3,4-dicarboxyphenyl) propanoic dianhydride 1,4,5,8-naphthalenetetracarboxylic dianhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorenic acid Dianhydrides, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorenic dianhydride and 1,2,3,4-cyclobutanoic dianhydride It is selected from Ranaru group containing a polyimide resin formed by imidizing an acid dianhydride component containing at least one aromatic dianhydride.

In the above formula (1), R ¹ and R ² are, for example, trimethylene.
m is an integer of 1 to 30, and n is preferably an integer of 0 to 20.
In the polyimide resin, the amide group-containing siloxane diamine compound of the formula (1) is preferably 40 to 90 mol%.
In addition to the formula (1), the diamine component preferably further contains 40 to 90 mol% of a siloxane diamine compound represented by the following formula (2).

Furthermore, it is preferable that the diamine component further contains 20 to 50 mol% of 3,3′-diamino-dihydroxydiphenylsulfone.
The acid dianhydride is preferably 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride.
The photosensitive agent is preferably contained in a range of about 5 to 30 parts by mass with respect to 100 parts by mass of the polyimide resin.
Furthermore, it is preferable to contain a crosslinking agent, and an epoxy resin or an oxazine resin is preferable as the crosslinking agent.

  The polyimide resin includes a diamine component containing an amide group-containing siloxane diamine compound represented by the following formula (1), pyromellitic tetracarboxylic dianhydride, 3,3 ′, 4 ′, 4-benzophenone tetracarboxylic dianhydride 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 2,2′-bis (3,4) Dicarboxyphenyl) propanoic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic dianhydride, 9,9-bis (3 , 4-dicarboxyphenyl) fluoric dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluoric dianhydride, and 1,2 An acid dianhydride component containing at least one aromatic dianhydride is selected from the group consisting of 3,4-cyclobutane dianhydride, it is preferable to use those formed by imidization.

  The amide group-containing siloxane diamine compound, which is an essential diamine component of the polyimide resin, has a chemical structure represented by the formula (1).

In the above formula (1), R ¹ and R ² are each an alkylene group which may be independently substituted. Specific examples thereof include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a pentamethylene group. And hexamethylene group. Examples of the substituent include a lower alkyl group such as a methyl group and an ethyl group, and an aryl group such as a phenyl group. Among these, a trimethylene group is desirable because of the availability of raw materials. R ¹ and R ² are the same and may be different from each other, but it is desirable that they are the same because it is difficult to obtain the raw materials.

  Moreover, although m is an integer of 1-30, Preferably it is 1-20, More preferably, it is an integer of 2-20. This is because when m is 0, it is difficult to obtain raw materials, and when m exceeds 30, it is separated without being mixed with the reaction solvent. On the other hand, n is an integer of 0 to 20, preferably 1 to 20, more preferably an integer of 1 to 10. This is because when n is 1 or more, a diphenylsiloxane unit excellent in flame retardancy is introduced, the flame retardancy is improved as compared with the case where it is not introduced, and when it exceeds 20, the elasticity is lowered. This is because the contribution becomes small.

The number average molecular weight of the amide group-containing siloxane diamine compound of the formula (1) varies depending on the number of m and n, but is preferably 500 to 3000, more preferably 1000 to 2000.
Since the amide group-containing siloxane diamine compound of the formula (1) has an amide bond at both ends of the molecule, the amide bond is succeeded to the polyimide resin prepared therefrom. For this reason, the adhesiveness with respect to conductor parts, such as copper, of the wiring board of a polyimide resin improves.

  In addition, it is known that an amide group undergoes an addition reaction or an insertion reaction with an epoxy group (Hitachi Chemical Technical Report No. 39 (2002-7)), page 29). If the epoxy resin generally used and the polyimide resin derived from the amide group-containing siloxane diamine compound represented by the formula (1) are used in combination, the reactive group constituting the crosslinking point where the amide group reacts with the crosslinking agent. Will function as. Therefore, the step of introducing a crosslinking group after isolating the polyimide resin becomes unnecessary.

  The novel amide group-containing siloxane diamine compound of the formula (1) can be produced according to the following reaction scheme.

<Reaction scheme>
In formulas (1) to (4), R ¹ , R ² , m and n are as already described in formula (1), and X is a halogen atom such as chlorine or bromine. In the method for producing the amide group-containing siloxane diamine compound of the formula (1), first, the diamine compound of the formula (2) and the nitrobenzoyl halide of the formula (3) are subjected to a nucleophilic substitution reaction to obtain an amide group of the formula (4). A containing dinitro compound is formed.

  In this case, for example, the dinitro compound of the formula (4) is formed by heating and mixing the compound of the formula (2) and the compound of the formula (3) in a solvent such as toluene in the presence of a base such as triethylamine. (See Organic Chemistry, 5th edition, page 283 (Ed. Stanley H. Pine)).

  Next, the nitro group of the dinitro compound of formula (4) is reduced to an amino group. Thereby, the novel amide group containing siloxane diamine compound of Formula (1) is obtained. The reduction method is not limited as long as the compound of formula (1) is obtained by converting the nitro group to an amino group. For example, in the mixed solvent of ethyl benzoate and ethanol, in the presence of a palladium carbon catalyst, the formula (4 )) With an excess of hydrogen (see Organic Chemistry, 5th edition, page 642 (Ed. Stanley H. Pine)).

If the content of the amide group-containing siloxane diamine compound represented by the formula (1) in the diamine component constituting the polyimide resin is too small, the electroless plating resistance is deteriorated. When the total amount of diamine is 100 mol%, it is 0.1 to 20 mol%, more preferably 0.1 to 15 mol%.
In addition to the amide group-containing siloxane diamine compound of the formula (1), which is an essential component, the diamine component can contain a siloxane diamine compound of the above formula (2) in order to reduce warpage.

When the content of the siloxane diamine compound of the formula (2) is too small, the effect of low warpage is not sufficient, and when it is too large, the flame retardancy is lowered, so that it is preferably 40 to 90 mol%, more preferably 50 to 80%. Mol%.
The siloxane diamine compound represented by the above formulas (1) and (2) is desirably contained in an amount of 65 mol% or more in a total of 100 mol of the diamine component and the acid anhydride component. "Example" is 65 mol% or less.

Further, in addition to the diamine compound of the formula (1), the diamine component is 3,3′-diamino-4,4′-dihydroxydiphenyl in order to achieve alkali solubility as a basis for imparting positive photosensitivity. Sulfones can be included.
If the content of 3,3′-diamino-4,4′-dihydroxydiphenylsulfone in the diamine component is too small, the alkali solubility cannot be obtained, and if it is too large, the alkali solubility becomes too high. It is -50 mol%, More preferably, it is 25-45 mol%.

  As a diamine component, in addition to the formula (2) and 3,3′-diamino-4,4′-dihydroxydiphenylsulfone, it is used as a diamine component of a general polyimide resin as long as the effects of the present invention are not impaired. A diamine compound similar to the one described above (see Japanese Patent No. 3363600, paragraph 0008) can be used in combination.

  Examples of the acid dianhydride component constituting the polyimide resin include pyromellitic tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′- Diphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 2,2′-bis (3,4-dicarboxyphenyl) propanoic dianhydride, 1, 4,5,8-naphthalenetetracarboxylic dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorenic dianhydride 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluoric acid dianhydride and 1,2,3,4-cyclobutanoic acid dianhydride Acid dianhydride component containing at least one aromatic dianhydride is can be exemplified. Of these, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride is preferably used from the viewpoint of enhancing alkali solubility, which is the basis for imparting positive photosensitivity.

  As an acid dianhydride component, in addition to the above-mentioned compounds, an acid dianhydride similar to that used as an acid dianhydride component of a general polyimide resin as long as the effects of the present invention are not impaired (patent No. 3363600, paragraph 0009) can be used in combination.

  The polyimide resin can be produced by imidizing a diamine component containing the amide group-containing siloxane diamine compound of the above formula (1) and an acid dianhydride component. Here, the molar ratio of the acid dianhydride component to 1 mol of the diamine component is usually 0.8 to 1.2, preferably 0.9 to 1.1. Moreover, in order to seal the molecular terminal of a polyimide resin, if necessary, a dicarboxylic acid anhydride or a monoamine compound can be allowed to coexist during imidization (see Japanese Patent No. 3363600, paragraph 0011).

  As conditions for imidization, any of known imidization conditions can be appropriately employed. In this case, conditions for forming an intermediate such as polyamic acid and then imidizing are also included. For example, it can be carried out under known solution imidization conditions, heat imidization conditions, and chemical imidization conditions (development of new polyimides for next-generation electronics and electronic materials and technology for imparting high functionality, Technical Information Association, 2003, P42).

  The preferable aspect of the polyimide resin demonstrated above contains the polyimide resin by which the repeating unit of a main skeleton is represented with the following structural formula (a) as an essential component. Moreover, it is preferable to further contain the polyimide resin of the following structural formula (b) and structural formula (c).

  The photosensitive resin composition used in the present invention contains the above polyimide resin and a photosensitive agent. By containing this photosensitizer, photosensitivity can be imparted to the formed polyimide composition.

  Examples of the photosensitive agent include diazonaphthoquinone compounds. The polyimide composition containing the diazonaphthoquinone compound changes its alkali solubility upon exposure. Before exposure, the solubility in an alkaline aqueous solution is low. On the other hand, after exposure, the molecular structure of the diazonaphthoquinone compound changes to produce ketene, which reacts with an aqueous alkaline solution to produce carboxylic acid. The produced carboxylic acid is further reacted with water and dissolved. Therefore, the solubility in alkaline aqueous solution becomes high by irradiating light.

  By containing the diazonaphthoquinone compound which is a photosensitizer, the hydroxyl group and the diazonaphthoquinone compound interact with each other in the polyimide structure composed of polyimide having a hydroxyl group. Thereby, the hydroxyl group which is easy to melt | dissolve in an alkali is protected, and alkali solubility falls. When the polyimide composition in this state is exposed, the molecular structure of the diazonaphthoquinone compound changes and alkali solubility is exhibited. Therefore, by containing a diazonaphthoquinone compound as a photosensitive agent, a pattern can be formed by developing with an aqueous alkali solution such as sodium hydroxide or tetramethylammonium hydroxide after exposure to the wiring board.

  The diazonaphthoquinone compound as a photosensitizer is not particularly limited as long as it is a compound having a diazonaphthoquinone skeleton, but 2,3,4-trihydroxybenzophenone o-naphthoquinonediazide-4-sulfonic acid ester, 2, Examples include 3,4-trihydroxybenzophenone o-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4-trihydroxybenzophenone o-benzoquinonediazide-4-sulfonic acid ester, and the like.

In the photosensitive resin composition, the blending amount of the photosensitive agent with respect to 100 parts by mass of the polyimide resin is preferably 5 to 30 parts by mass.
The photosensitive resin composition can contain a metal deactivator. As this metal deactivator, 2,3-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] propionohydrazide (CDA), which is a hydrazide metal deactivator, is used. -10, ADEKA Co., Ltd.), and when used for a wiring board, it is possible to prevent resin degradation of the polyimide composition that comes into contact with the metal.

  Examples of metal deactivators other than CDA-10 include decazethylene carboxylic acid disalicyloyl hydrazide as a hydrazide type, 3- (N-salicyloyl) amino-1,2,4-triazole as a triazole type, and the like. However, it is not limited to these.

  The photosensitive resin composition can contain a crosslinking agent in order to improve the adhesion between a conductor such as a copper foil and a polyimide resin, and also to improve the plating resistance. The cross-linking agent reacts with the amide group of the polyimide resin or with the cross-linking agents to form a three-dimensional cross-linked structure. As such a crosslinking agent, what is conventionally used for resin for electronic components can be used, and an epoxy type crosslinking agent and an oxazine type crosslinking agent can be mentioned preferably from a reactive point.

  As specific examples of the epoxy-based crosslinking agent, those showing good compatibility with the polyimide resin are preferable. Conventionally, various epoxy monomers, oligomers and polymers for forming an epoxy resin can be used. For example, bis-F type Epoxy compounds, bis-A type epoxy compounds, cycloaliphatic epoxy compounds such as 3,4-epoxycyclohexenylmethyl-3 ′, 4-epoxycyclohexenecarboxylate, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl Ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, polymethylolpropane polyglycidyl ether, resorcinol diglyceryl ether, neopentyl glycol diglycidyl ether, Glycidyl compounds such as 1,6-hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, polyethylene glycol glycidyl ether, polypropylene glycol glycidyl ether, hydroquinone diglycidyl ether, glycidyl phthalate, glycidyl terephthalate, etc. Halogenated flame retardant epoxy compounds such as esters, dibromoneopentylglycol glycidyl ether, cresol novolac epoxy resins, novolac epoxy resins such as phenol novolac epoxy resins, tetraglycidyldiaminodiphenylmethane, tetraglycidylmetaxylenediamine, triglycidylaminophenol, diglycerides Examples include glycidylamine compounds such as glycidylaniline. Kill.

  As the oxazine-based crosslinking agent, those originally used as thermosetting monomers that undergo ring-opening polymerization by heat can be used. For example, bisphenol F type benzoxazine (for example, 6,6′-1 -Methylidene) bis [3,4-dihydro-3-phenyl-2H-1,3-benzoxazine], etc.), bisphenol S-type benzoxazine (for example, 6,6′-sulfonylbis [3,4-dihydro-3) -Phenyl-2H-1,3-benzoxazine], bisphenol A-type benzoxazine (hereinafter, formula (d), phenol novolac-type benzoxazine (hereinafter, formula (e)) and the like.

  In the above formula (e), q is an arbitrary integer.

  In the photosensitive resin composition, additives, such as a solvent, a filler, and a pigment, can be contained as needed. The photosensitive resin composition can be prepared by uniformly mixing the above-described polyimide resin, a photosensitive agent, and optionally a metal deactivator, a crosslinking agent, and other additives by a conventional method. it can. The photosensitive resin composition can be preferably applied as the polyimide resin of a wiring board having a polyimide resin layer.

  The wiring board configured as described above is also within the range of the present invention. As an application method, a known method can be adopted. Here, as a polyimide resin layer, the dry film resist layer and a cover film layer can be mentioned from the functional surface. It can also be used as an interlayer insulating film, and can also be used as a passivation film for semiconductor chips.

<Synthesis example of amide group-containing siloxane diamine compound>
First, a method for synthesizing polyimide using the above formula (1) will be described.
To a 2 liter reactor equipped with a cooler, thermometer, dropping funnel and stirrer, 500 g of toluene, siloxane diamine of formula (2) (R ¹ , R ² = trimethylene; trade name X-22-9409, Shin-Etsu Chemical) 200 g (0.148 mol) and 30 g (0.297 mol) of triethylamine were added.
Subsequently, a solution in which 54.7 g (0.295 mol) of p-nitrobenzoyl chloride was dissolved in 300 g of toluene was charged into the dropping funnel. The temperature in the reactor was raised to 50 ° C. while stirring, and then the solution in the dropping funnel was added dropwise over 1 hour.

  After completion of the dropwise addition, the temperature was raised and the mixture was stirred for 6 hours and reacted under reflux. After completion of the reaction, the mixture was cooled to 30 ° C., 800 g of water was added and the mixture was strongly stirred, then transferred to a separatory funnel and allowed to stand for liquid separation. Washing with 300 g of 5% aqueous sodium hydroxide was performed 3 times, and washing with 300 g of saturated aqueous sodium chloride was performed twice.

  The organic layer was dried over magnesium sulfate, the toluene solvent was distilled off by heating under reduced pressure, concentrated and then dried under reduced pressure at 60 ° C. for 1 day. The obtained α- (p-nitrobenzoyliminopropyldimethylsiloxy) -ω- (p-nitrobenzoyliminopropyldimethylsilyl) oligo (dimethylsiloxane-co-diphenylsiloxane) (hereinafter, dinitro compound) was obtained in a yield of 235 g (yield). 96%). The dinitro product was a pale yellow oil.

  112 g (0.068 mol) of the obtained dinitro compound was placed in a 1 liter reactor equipped with a stirrer, a hydrogen introduction tube and a hydrogen bulb, 180 g of ethyl acetate, 320 g of ethanol, and 20 g of 2% palladium-carbon (water content 50). %).

  After replacing the inside of the reactor with a hydrogen gas atmosphere, stirring was continued for 2 days at room temperature under a hydrogen bulb pressure. The catalyst was removed by filtration from the reaction mixture, and the reaction mixture was concentrated under reduced pressure and then dried at 60 ° C. under reduced pressure for 2 days. Α- (p-aminobenzoyliminopropyldimethylsiloxy) was obtained as a pale yellow oil. A yield of 102 g (yield: 95%) of -ω- (aminobenzoyliminopropyldimethylsilyl) oligo (dimethylsiloxane-co-diphenylsiloxane) (amide group-containing siloxane diamine compound used in the present invention) was obtained.

  The amine value of the obtained amide group-containing siloxane diamine compound was 69.96 KOHmg / g, and the amino group equivalent was 802 g / mol. The amine value was measured using an automatic potentiometric titrator (AT-500, manufactured by Kyoto Electronics Industry). The amino group equivalent was calculated by 56.106 / (amine value) × 1000.

As a result of measuring the infrared absorption spectrum and ¹ H-NMR spectrum of this amide group-containing siloxane diamine compound, it was confirmed that the desired product was obtained. The infrared absorption spectrum was measured by a transmission method using a Fourier transform infrared spectrophotometer (FT-IR420, manufactured by JASCO Corporation). The ¹ H-NMR spectrum was measured in deuterated chloroform using an NMR spectrophotometer (MERCURY VX-300, Varian Technologies Japan Limited). These results are shown below.

IR spectrum:
3450 cm ⁻¹ (νN—H), 3370 cm ⁻¹ (νN—H), 3340 cm ⁻¹ (νN—H), 3222 cm ⁻¹ (νN—H), 1623 cm ⁻¹ (νC═O), 1260 cm ⁻¹ (νCH) ₃ ), 1000-1100 cm ⁻¹ (νSi—O)
¹ H-NMR (CDCl ₃ , δ):
-0.2 to 0.2 (m, methyl), 0.4 to 0.6 (m, 4H, methylene), 1, 4 to 1.8 (m, 4H, methylene), 3.2 to 3. 5 (m, 4H, methylene), 3.9 (bs, 4H, amino group hydrogen), 5.8 to 6.3 (m, 2H, amide group hydrogen), 6.4 (m, 4H, amino group adjacent) Aromatic ring hydrogen), 7.1-7.7 (m, aromatic ring hydrogen)

<Polyimide resin polymerization example>
(Example in which 1 mol% of the novel amide group-containing siloxane diamine compound of the formula (1) is contained in all diamine components)
4460.6 g (3.30 mol) of a siloxane diamine compound (X-22-9409, Shin-Etsu Chemical Co., Ltd.) in a 20 liter reaction vessel equipped with a nitrogen introduction tube, a stirrer, and a Dean-Stark trap. , 3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride (DSDA, Shin Nippon Rika Co., Ltd., purity 99.70%) 1912.7 g (5.34 mol), γ-butyrolactone 287 g, as described above A mixed solution of 89.0 g (54.3 mmol, purity 97.10%) of the amide group-containing siloxane diamine compound of formula (1) and 2870 g of triglyme were added, and the mixed solution was stirred. Further, 1100 g of toluene was added, and then the mixture was heated to reflux at 185 ° C. for 2 hours, followed by dehydration under reduced pressure and toluene removal to obtain an acid anhydride-terminated oligoimide solution.

  The obtained acid anhydride-terminated oligoimide solution was cooled to 80 ° C., and 3431 g of triglyme, 413 g of γ-butyrolactone, 3,3′-diamino-4,4′-dihydroxydiphenyl sulfone (BSDA, Konishi Chemical Industries, Ltd., A dispersion composed of 537.8 g (1.92 mol) of 99.70% purity was added and stirred at 80 ° C. for 2 hours.

524 g of triglyme was added thereto for adjusting the amount of solvent, and the mixture was heated to reflux at 185 ° C. for 2 hours. After cooling the obtained reaction mixture to room temperature, toluene and water accumulated in the trap were removed. By the above operation, an amide group-containing polyimide resin was synthesized.
The actually measured solid content of the obtained polyimide was 47.50%. Moreover, the polystyrene conversion molecular weight by GPC (gel permeation chromatography) was 63000 as a weight average molecular weight.

  Hereinafter, a case where polyimide is synthesized by changing the content of the novel amide group-containing siloxane diamine compound of formula (1) will be described.

<When changing the content 1>
(Example in which 5 mol% of the novel amide group-containing siloxane diamine compound of the formula (1) is contained in all diamine components)
In polymerization examples, 4099.8 g (3.04 mol) of a siloxane diamine compound (X-22-9409, Shin-Etsu Chemical Co., Ltd.), 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride (DSDA) Shin Nippon Rika Co., Ltd., purity 99.70%) 1907.0 g (5.32 mol), 443.7 g (270.5 mmol, purity 97.10) of the novel amide group-containing siloxane diamine compound obtained in Reference Example 1. %), 3,3′-diamino-4,4′-dihydroxydiphenylsulfone (BSDA, Konishi Chemical Co., Ltd., purity 99.70%) was changed to 549.5 g (1.96 mol), and polymerization examples The same operation as 1 was performed to synthesize a novel polyimide resin having an amide group. The measured solid content of the obtained polyimide was 47.4%. Moreover, the polystyrene conversion molecular weight by GPC (gel permeation chromatography) was 57000 as a weight average molecular weight.

<When changing the content 2>
(Example in which the novel amide group-containing siloxane diamine compound of the formula (1) is contained in an amount of 10 mol% in the total diamine components)
In the polymerization example, 3665.3 g (2.72 mol) of a siloxane diamine compound (X-22-9409, Shin-Etsu Chemical Co., Ltd.), 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride (DSDA) Shinnippon Rika Co., Ltd., purity 99.70%) (1895.1 g, 5.29 mol) and 881.9 g (537.7 mmol, purity 97.10) of the novel amide group-containing siloxane diamine compound obtained in Reference Example 1. %), 3,3′-diamino-4,4′-dihydroxydiphenyl sulfone (BSDA, Konishi Chemical Co., Ltd., purity 99.70%) was changed to 557.8 g (1.99 mol), and polymerization examples The same operation as 1 was performed to synthesize a novel polyimide resin having an amide group. The actually measured solid content of the obtained polyimide was 47.7%. Moreover, the polystyrene conversion molecular weight by GPC (gel permeation chromatography) was 77000 as a weight average molecular weight.

<When changing the content 3>
(Example not containing a novel amide group-containing siloxane diamine compound of formula (1))
In the polymerization examples, 4550.2 g (3.37 mol) of siloxane diamine compound (X-22-9409, Shin-Etsu Chemical Co., Ltd.), 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride (DSDA) , Shin Nippon Rika Co., Ltd., purity 99.70%), 1914.5 g (5.34 mol), 3,3′-diamino-4,4′-dihydroxydiphenyl sulfone (BSDA, Konishi Chemical Industries, Ltd., purity 99.70). 70%) was changed to 535.3 g (1.91 mol), and the same operation as in Polymerization Example 1 was performed except that the novel amide group-containing siloxane diamine compound obtained in Reference Example 1 was not added. Synthesized.
The actually measured solid content of the obtained polyimide was 47.3%. Moreover, the polystyrene conversion molecular weight by GPC (gel permeation chromatography) was 65000 as a weight average molecular weight.

<When changing the content ratio 4>
(Example in which 1 mol% of the novel amide group-containing siloxane diamine compound of the formula (1) is contained in all diamine components)
In Polymerization Example 1, 4289.6 g (3.18 mol) of a siloxane diamine compound (X-22-9409, Shin-Etsu Chemical Co., Ltd.), 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride ( 1988.4 g (5.62 mol) of DSDA, Shin Nippon Rika Co., Ltd., purity 99.70%), 90.5 g (54.8 mmol) of the novel amide group-containing siloxane diamine compound obtained in Reference Example 1, The same procedure was followed except that 3'-diamino-4,4'-dihydroxydiphenylsulfone (BSDA, Konishi Chemical Industries, Ltd., purity 99.70%) was changed to 631.5 g (2.25 mol). A novel polyimide having a group was synthesized. The actually measured solid content of the obtained polyimide was 49.50%. Moreover, the polystyrene conversion molecular weight by GPC (gel permeation chromatography) was 69000 as a weight average molecular weight.

<Example of adjustment of raw material liquid for protective film>
With respect to 100 parts by mass of the amide group-containing polyimide resin synthesized in “Polymer resin polymerization example”, diazonaphthoquinone (4NT-300, Toyo Gosei Kogyo Co., Ltd.) as a photosensitizer and epoxy resin, oxazine compound ( 6,6 ′-(1-methylidene) bis [3,4-dihydro-3-phenyl-2H-1,3-benzoxazine]) (BF-BXZ, Konishi Chemical Industries), Resole (Showa Polymer Co., Ltd.) "BRL-274"), blocked isocyanate compound, rust inhibitor CDA-10 (ADEKA Corporation), and antifoaming agent ("FA-600" of Shin-Etsu Chemical Co., Ltd.) are shown in Table 1 below. No. described in 1. Each of 1 to 13 was added in a predetermined amount and mixed until it was sufficiently uniform to prepare a photosensitive resin composition for a protective film.
In Table 1 below, regarding the amide group-containing polyimide resin, each diamine component and acid anhydride component constituting the polyimide resin are shown in molar ratios of each component when the total diamine component is 100 mol. It was.

(17B-60PX, TRA-B60PX: Asahi Kasei Chemicals Corporation, Coronate 2520: Nippon Polyurethane Industry Co., Ltd.)
A blocked isocyanate compound is also called a blocked isocyanate, a blocked polyisocyanate, or a blocked polyisocyanate. A polyisocyanate compound is reacted with a compound having a certain type of active hydrogen (block material or masking agent) at room temperature. It is a stabilized cyanate group-blocking compound. Here, a blocked isocyanate compound obtained by blocking an isocyanate compound of MDI (4,4′-diphenylmethane diisocyanate) and a blocked isocyanate compound obtained by blocking an isocyanate compound of HDI (hexamethylene diisocyanate) are crosslinking agents.

When polymerizing polyimide, a diamine of formula (1) is used.
The obtained raw material liquid for the protective film was observed, and the presence or absence of a blending abnormality was observed.
Table 2 below shows the manufacturing conditions and test results after adjustment of the raw material liquid for the protective film.

As shown in Table 2, since no abnormality was found in the composition, a bar coater was applied to the copper foil surface of the copper-clad substrate (ESPANEX), and the solvent was removed by drying to form a photoreactive film having an average film thickness of 15 μm. The film was formed, exposed to light of 1500 mJ / cm ² through a mask, and developed with a 3 wt% NaOH solution at 40 ° C. for 40 seconds.

The residue of exposure was not seen, and in Table 2, "(circle)" is described.
The photoreactive film has a positive photoreactivity in which a polymerization reaction does not occur during exposure and a dissolution reaction occurs in a portion irradiated with light, and an isocyanate is present between the exposure process and the development process. Does not affect the reaction.

Next, a 90 degree peel test was performed, and the average value of the test results of a plurality of measurements is shown in Table 2 as “average peel strength”.
When the average peel strength is less than 10 N / cm, there is a possibility of peeling in a cross cut test to FPC. Therefore, it exceeded No. 10 using blocked isocyanate that exceeded 10 N / cm. If it is this strength, even if it varies between processes, the possibility of peeling in a cross-cut test is eliminated.

The average peel strength in Table 2 is low when no epoxy resin is blended (No. 1), because no cross-linking is formed with the polyimide OH group. 2-4 are No.2. It is almost the same as 1 and does not improve adhesion.
No. As can be seen from the measurement results of 12, the raw material liquid containing the blocked isocyanate compound of MDI (diphenylmethane diisocyanate) may have a very strong peel strength depending on the isocyanate content. The range of addition amount is narrow.

In contrast, no. As can be seen from 5 to 9, when a blocked isocyanate compound of HDI (hexamethylene diisocyanate) is added, it is in the range of 5 to 10 parts by mass. The peel strength is 4 times or more than 1.
Therefore, it can be seen that if the polyimide resin polymerized using the diamine of formula (1) and another diamine contains an HDI blocked isocyanate compound, a protective film having a high peel strength can be obtained in a wide range of contents.

  FIGS. 1A and 1B show a wiring board 10 according to an example of the present invention. The wiring substrate 10 is a film made of a flexible resin (having flexibility or flexibility), or a substrate 11 made of a resin and glass fibers dispersed therein, and a patterning made of copper or another metal. The metal wiring film 12 and the protective film 13 are provided.

  The protective film raw material liquid is applied onto the surface of the wiring substrate 10 before the protective film is formed on the surface on which the metal wiring film 12 as the application target is disposed, and the solvent is evaporated by coating and drying. Then, a photopolymerizable film covering the metal wiring film 12 is formed, and the photopolymerized film is partially removed by exposure and development, cured by heating, and the metal wiring film 12 is partially exposed to another part. A protective film 13 is formed to cover the wiring board 10.

Although the protective film 13 covers the plurality of metal wiring films 12 here, the protective film 13 may be divided into a plurality of parts when patterning, and each metal wiring film 12 may be covered with a separate protective film 13.
The metal wiring film may be other metal such as nickel, or may be covered with gold or the like in addition to copper.

Claims (5)

A polyimide resin component;
A photosensitizer,
A crosslinking agent;
A raw material liquid for a protective film containing a solvent,
The crosslinking agent contains a blocked isocyanate component,
The polyimide resin component has the following formula (1),

A diamine component containing an amide group-containing siloxane diamine compound represented by: pyromellitic tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3′4,4 '-Diphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 2,2'-bis (3,4-dicarboxyphenyl) propanoic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorenic acid The group consisting of anhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluoric acid dianhydride and 1,2,3,4-cyclobutanoic acid dianhydride Includes a polyimide resin formed by imidizing an acid dianhydride component containing at least one aromatic dianhydride is selected,
The blocked isocyanate component contains a blocked isocyanate compound in which the isocyanate group of the hexamethylene diisocyanate compound is blocked,
Applying the protective film raw material solution to the coating object, the solvent was evaporated when the photoreactive layer is formed, the photoreactive film have a light solubility,
The amide group-containing siloxane diamine compound of formula (1) is, when the total amount of diamine and 100 mol%, the protective film raw material solution Ru der than 20 mol% 0.1 mol%.   The said block isocyanate compound is a raw material liquid for protective films of Claim 1 contained in the range of 2 mass parts or more and 10 mass parts or less, when a polyimide resin is 100 mass parts.   The protective film raw material solution according to claim 1, wherein the photosensitive agent is contained in an amount of 5 parts by mass to 30 parts by mass with respect to 100 parts by mass of the polyimide resin.   A protective film in which the raw material liquid for a protective film according to claim 1 is applied onto the object to be coated, patterned by exposure / development, covers the metal wiring disposed on the object to be coated, and is partially exposed. A substrate,
A wiring board having a metal wiring film disposed on the substrate,
A protective film raw material liquid according to claim 1 is applied to a coating object having a metal wiring film on a substrate, patterned by exposure / development, and partially exposed while covering the metal wiring arranged on the substrate. Wiring board.

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