JP2011253044A - Photosensitive resin composition, its use and method of utilizing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition that gives a cured film free of bubbles, swelling, peeling or the like of a coating film during development and drying thereafter in a photolithographic process.SOLUTION: A photosensitive resin composition contains: an amid acid (A) obtained by allowing a compound (a) having two amino groups in one molecule to react with a compound (b) having two acid anhydride structures in one molecule; a reactive diluent (B) having one unsaturated double bond and 1 to 4 of aromatic hydrocarbon rings in one molecule, or a reactive diluent (B') having one unsaturated double bond and 1 to 4 of aliphatic heterocyclic rings in one molecule; and a photoacid generator (C).

Description

  The present invention relates to an amic acid (A) obtained by reacting a compound (a) having two amino groups in one molecule with a compound (b) having two acid anhydride structure moieties in one molecule. Reactive diluent (B) having one unsaturated double bond and one to four aromatic hydrocarbon rings in one molecule or one unsaturated double bond and one to four in one molecule The present invention relates to a photosensitive resin composition containing a reactive diluent (B ′) having one aliphatic heterocycle and a photoacid generator (C). The photosensitive resin composition is particularly suitably used as a molding material, a film forming material, and the like. Or it is used suitably for the material aiming at electrical insulation. Specifically, it can be used for solder resists, interlayer insulating materials, other resist materials that can be alkali-developed, adhesives, lenses, displays, optical fibers, optical waveguides, holograms, etc. in the production of printed circuit boards. .

  Printed circuit boards are required to have higher precision and higher density for the purpose of reducing the size and weight of portable devices and improving communication speed, and as a result, there is also a demand for so-called solder resists for film forming materials that cover circuits. It is getting higher and higher. For example, with regard to heat resistance that can withstand the heat generation of elements during board manufacturing and operation using solder etc., reliability by maintaining high insulation for a long time, performance that can withstand chemical treatment such as plating, etc. High performance is required, and a film-forming material having toughened cured product performance is demanded.

  On the other hand, in recent years, the use of flexible printed wiring boards such as flexible boards is also expanding. In the case of a flexible substrate, so-called cover lay film is generally laminated to protect the circuit. However, problems remain in productivity, such as time-consuming manufacturing.

  On the other hand, attempts have been made to use a solder resist type film-forming material that can be coated, photopatterned, and developed for laminating, but the film is rigid and is a material that can follow bending until now. At the same time, no material has been found that satisfies other required properties.

  Non-Patent Document 1 discloses an amic acid obtained by reacting a compound (a) having two amino groups in one molecule with a compound (b) having two acid anhydride structures in one molecule, and A photoacid generator is described. These compounds generally have low solubility in solvents, and it is necessary to use polar solvents such as N-methylpyrrolidone. Then, varnishes using these high-boiling solvent systems are applied to the substrate and dried. In the process, the poor volatility becomes a problem, and a large amount of the solvent remains in the dried coating film. Since these polar solvents are generally water-soluble, not only does the residual solvent flow out in the next development step, causing poor patterning, but the coating film remaining during development absorbs water, and when it is dried It tends to cause foaming, swelling and peeling of the coating film.

  Patent Document 1 discloses a composition comprising polyimide, a photoacid generator, and a reactive diluent having an unsaturated double bond. However, the reactive diluent used here is an aliphatic bifunctional acrylate for the purpose of improving plasticity as a dry film. Usually, the bifunctional acrylate has a problem in compatibility with amic acid, and the amount of the compound in the resin composition cannot be increased. With relatively high-polarity diluents such as polyalkylene glycol diacrylate having relatively good compatibility, the coating film tends to swell during development, and it is difficult to maintain good development characteristics. The remaining coating film absorbs water and may cause coating film defects such as foaming, blistering, and peeling when dried. As a result, insulation reliability that maintains insulation for a long time can be maintained. was difficult.

JP 2008-107419 A

The latest photosensitive polyimide (published January 28, 2002, edited by Japan Polyimide Research Association, published by NTS Corporation) Chapter 6

  The present invention obtains a cured film free from foaming, swelling, peeling, etc. of a coating film during development in a photolithography process, which is a process of forming a pattern by curing with active energy rays and then developing, and subsequent drying. It is an object.

In view of the above problems, the present inventors have found that a photosensitive resin composition containing amic acid, a reactive diluent having a specific structure and a photoacid generator has excellent performance, and has completed the present invention. .
That is, the present invention relates to an amic acid obtained by reacting a compound (a) having two amino groups in one molecule with a compound (b) having two acid anhydride structure parts in one molecule ( A) Photosensitive resin composition comprising a reactive diluent (B) having one unsaturated double bond and one to four aromatic hydrocarbon rings in one molecule and a photoacid generator (C) About.

  Furthermore, the amide acid (A) obtained by reacting the compound (a) having two amino groups in one molecule with the compound (b) having two acid anhydride structure parts in one molecule, 1 The present invention relates to a photosensitive resin composition comprising a reactive diluent (B ′) having one unsaturated double bond and 1 to 4 aliphatic heterocycles in the molecule, and a photoacid generator (C).

  Furthermore, it is related with the said photosensitive resin composition whose compound (a) which has two amino groups in 1 molecule is a compound which has two aromatic amino groups.

  Furthermore, it is related with the said photosensitive resin composition which is a molding material.

  Furthermore, it is related with the said photosensitive resin composition which is a film forming material.

  Furthermore, it is related with the said photosensitive resin composition which is an electrically insulating material composition.

  Furthermore, it is related with the said photosensitive resin composition which is a photosensitive soldering resist composition.

  Furthermore, it is related with the hardened | cured material obtained by irradiating the said photosensitive resin composition with an active energy ray.

  Furthermore, it is related with the multilayer material which has the layer of the hardened | cured material of the said photosensitive resin composition.

  Furthermore, after coating the photosensitive resin composition on a substrate, if necessary, the solvent is dried, then photopatterning is performed, and after development with an alkaline aqueous solution, the unsaturated double bond is polymerized by light or heat. It is related with the usage method of the photosensitive resin composition characterized by making it a cured film.

  The photosensitive resin composition of the present invention can provide a cured product having a tough cured product performance while being capable of photopatterning, and also having flexibility required for a flexible substrate. Therefore, film-forming materials, alkali-developable resist materials, such as solder resists, interlayer insulating materials, adhesives, and molding materials in the production of printed circuit boards, lenses, displays, optical fibers, optical waveguides, holograms Suitable as a component for equal use. Furthermore, since this composition has excellent insulation reliability, it can be suitably used as a material for the purpose of electrical insulation.

Hereinafter, the present invention will be described in detail.
The photosensitive resin composition of the present invention is obtained by reacting a compound (a) having two amino groups in one molecule with a compound (b) having two acid anhydride structures in one molecule. Amic acid (A) Reactive diluent (B) having one unsaturated double bond and one to four aromatic hydrocarbon rings in one molecule or one unsaturated double in one molecule A reactive diluent (B ′) having a bond and 1 to 4 aliphatic heterocycles, and a photoacid generator (C) are included.

  The compound (a) having two amino groups in one molecule used in the production of the amic acid (A) contained in the photosensitive resin composition of the present invention is used for the purpose of the resin composition of the present invention. It is appropriately selected depending on the situation and can be used alone or in combination of two or more.

  The compound (a) is preferably a compound having two aromatic amino groups in one molecule. For example, monocyclic aromatic diamines such as phenylenediamine and dimethylphenylenediamine, naphthalenediamine, biphenylenediamine, bis ( Hydroxyphenyl) diamine, dianisidine, bis (aminophenyl) ether, bis (methylaminophenyl) ether, bis (hydroxyaminophenyl) ether, bis (carboxyaminophenyl) ether, bis (aminophenyl) sulfone, bis (aminophenyl) Bicyclic aromatic diamines such as methane, bis (aminophenyl) propane, bis (aminophenyl) sulfide, bis (aminophenyl) hexafluoropropane, bis (hydroxyaminophenyl) benzene, bis (hydroxyamido) Phenoxy) benzene, bis aminophenyl fluorene, bis [[aminophenoxy] phenyl] propane, bis [[aminophenoxy] phenyl] polycyclic aromatic diamines such as sulfonic, and derivatives thereof.

  The compound (b) having two acid anhydride structures in one molecule used in the production of the amide acid (A) contained in the photosensitive resin composition of the present invention refers to the resin composition of the present invention. It is appropriately selected according to the purpose, and can be used alone or in combination of two or more.

  Examples of the compound (b) include monocyclic aromatic tetrabasic dianhydrides such as pyromellitic anhydride, biphenyltetracarboxylic anhydride, naphthyltetracarboxylic anhydride, benzophenonetetracarboxylic anhydride, Bicyclic aromatic tetramers such as diphenyl ether tetracarboxylic acid anhydride, diphenyl sulfone tetracarboxylic acid anhydride, ethylene glycol bistrimellitic acid anhydride, diol bistrimellitic acid anhydrides (for example, hexanediol bistrimellitic acid anhydride, etc.) Examples include basic acid dianhydrides, fluorene anhydrides of bisphthalic acid, polycyclic aromatic tetrabasic acid dianhydrides such as biphenol bistrimellitic acid anhydride, butanetetracarboxylic acid anhydride, and the like. Furthermore, alicyclic tetrabasic dianhydrides obtained by aromatic nucleus hydrogenation reaction of aromatic tetrabasic dianhydrides among these can also be suitably used.

  The amic acid (A) can be obtained by reacting the compound (a) with the compound (b). For this reaction, known general methods and reaction conditions can be used. In this reaction, a solvent can be appropriately used. The solvent is not particularly limited as long as it does not affect the reaction and can dissolve the raw material and the resulting amide acid (A).

  In general, amic acid (A) has poor solubility in a low-polarity solvent, and examples of the solvent include amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, ester solvents such as butyrolactone, and butylene glycol. So-called highly polar solvents such as glycol solvents are preferred.

  Reactive diluent (B) having one unsaturated double bond and 1 to 4 aromatic hydrocarbon rings in one molecule contained in the photosensitive resin composition of the present invention, or 1 in one molecule Reactive diluent (B ′) having 1 unsaturated double bond and 1 to 4 aliphatic heterocycles prevents foaming, swelling and peeling of the coating film during development and subsequent drying in the photolithography process. Used to

  Examples of the reactive diluent (B) include 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate. , Benzyl (meth) acrylate, EO (ethylene oxide) modified cresol (meth) acrylate, ethoxylated phenyl (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, phenylglycidyl ether (meth) Acrylate, phenoxypolyethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, ethoxylated pheny Phenol (meth) acrylate and the like. These may be used as a mixture of two or more may be used alone.

  Examples of the aliphatic heterocycle in the reactive diluent (B ′) include a 3- to 10-membered ring group containing one or more heteroatoms such as N, O, and S, and the reactive diluent (B ′). Examples thereof include (meth) acryloylmorpholine, pentamethylpiperidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, and these may be used alone or in combination of two or more. May be used in combination.

  The photoacid generator (C) contained in the photosensitive resin composition of the present invention is added for the purpose of, for example, generating an acidic group by irradiation with an active energy ray and causing a change in resin properties. is there. For example, the active energy ray irradiated portion and the non-irradiated portion of the resin composition of the present invention can be patterned by changing the solubility in a solvent or an alkaline aqueous solution.

  That is, by using a compound that generates an acid group upon irradiation with light, the irradiated portion is dissolved by improving the solubility of the irradiated portion in a developing solution such as an alkaline aqueous solution, while the non-irradiated portion is transferred to the developing solution. So-called positive-type photosensitive characteristics can be imparted by keeping the solubility of the toner low.

  Examples of the photoacid generator (C) include quinonediazide compounds that undergo a transfer reaction with light to generate a carboxy group. These are obtained by an esterification reaction from a polyhydroxy compound having a plurality of phenolic hydroxyl groups and a naphthoquinone diazide sulfonate, such as 1,2-naphthoquinone-2-diazide-5-sulfonate, 1,2- 6-diazo-dihydro-5-oxo-1-naphthalenesulfonic acid of naphthoquinone-2-diazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone or 2,3,4,4′-tetrahydroxybenzophenone Examples include esters. Examples of commercially available compounds include PC-5, NT-200, 4NT-300 manufactured by Toyo Gosei Co., Ltd., DTEP-300, DTEP-350, PA-6 manufactured by Daitokemix, and the like.

  The photosensitive resin composition of the present invention easily causes positive or negative characteristic changes by active energy rays. Examples of active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays, and laser rays, and particle rays such as alpha rays, beta rays, and electron beams. Of these, ultraviolet rays, laser beams, visible rays, or electron beams are preferred in view of suitable applications of the present invention.

  The molding material in which the photosensitive resin composition of the present invention is used is a positive type or negative type reaction using active energy rays after the uncured composition is put into a mold or an object is molded by pressing the mold. It refers to a material that is caused to cause molding, or a material that is irradiated with a focused light such as a laser beam to cause an uncured composition to cause a negative characteristic change and to be molded.

  A sheet formed into a flat shape; a sealing material for protecting the element; a so-called nanoimprint material that performs fine molding by pressing a “mold” that has been finely processed into an uncured composition; For example, a sealing material for the purpose of electrical insulation which requires high reliability and avoids halogen compounds can be used.

  The film forming material in which the photosensitive resin composition of the present invention is used is used for the purpose of coating the substrate surface. For example, ink materials such as gravure ink, flexo ink, silk screen ink, offset ink; coating materials such as hard coat, top coat, overprint varnish, clear coat; various adhesives and adhesives for laminating and optical disc Adhesive materials such as: Resist materials such as solder resist, etching resist, and micromachine resist. Furthermore, so-called dry film, in which a film-forming material is temporarily applied to a peelable substrate to form a film and then bonded to a target substrate to form a film, corresponds to the film-forming material.

The photosensitive resin composition of the present invention is preferably used in a positive type.
The present invention also includes a cured product obtained by irradiating the photosensitive resin composition with active energy rays, and also includes a multilayer material having a layer of the cured product.

  In general, an insulating material composition forms a film layer of the composition on a substrate, has a large electric resistance between two target areas in an electronic circuit or its components, and a current flows even when a voltage is applied. It refers to an active energy curable resin composition in a non-existing state. The photosensitive resin composition of the present invention includes an overcoat material for a flexible wiring board, an interlayer insulating film for a multilayer substrate, a molding material for an insulating film or a passivation film for a solid element in the semiconductor industry, a semiconductor integrated circuit, a multilayer printed wiring board, etc. It is used as an interlayer insulating material, a solder resist used for protecting a substrate, and the like. It is particularly suitable for flexible substrates that require particularly high flame retardancy. That is, not only can high flame retardancy be imparted, but also long-term insulation stability can be exhibited.

  In general, if there are parts that need insulation and parts that need to be electrically conductive on the substrate, and these must be patterned as necessary, the pattern can be formed by a printing method. Difficult and not suitable for making high-density substrates. In that case, the photosensitive resin composition of the present invention is used as an insulating material to form a film layer on the substrate, and then an active energy ray such as ultraviolet rays is partially irradiated to irradiate and unirradiate the irradiated portion Fine patterning can be made possible by drawing using the physical property difference. In particular, it is preferable to use it as an insulating material that requires patterning for permanent resist applications such as solder resist, taking advantage of the characteristics that can provide flame retardancy and high reliability.

  In addition, the photosensitive resin composition of the present invention can also be used for printed wiring boards, electrical / electronic / optical substrates such as optoelectronic substrates and optical substrates as optical waveguides that are similarly required to have high flame resistance. Is possible.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples. In the examples, “parts” represents parts by weight and “%” represents percent by weight unless otherwise specified. For measuring the viscosity at 25 ° C., an E-type viscometer was used.

Synthesis Example 1: Preparation of amic acid (A-1) 4,4′-oxy as compound (a) having two amino groups in one molecule in a 300 ml reactor equipped with a stirrer, a thermometer and a condenser Dianiline (18.00 g, 90.00 mmol) was dissolved in 87.8 g of N-methylpyrrolidone by stirring at 80 ° C. for 1 hour. Then, 19.63 g (90.00 mmol) of pyromellitic acid anhydride was charged as a compound (b) having two acid anhydride structures in one molecule, and further reacted at 80 ° C. for 5 hours to obtain amic acid ( A-1) was obtained. The viscosity (25 ° C.) of this amic acid compound (A-1) was 63 Pa · s.

Synthesis Example 2: Preparation of amic acid (A-2) In a 300 ml reactor equipped with a stirrer, a thermometer, and a condenser, 1,3-bis (1) as a compound (a) having two amino groups in one molecule 3-aminophenoxy) benzene (12.00 g, 41.05 mmol) was dissolved in 56.18 g of N-methylpyrrolidone at 80 ° C. for 1 hour. Thereafter, 12.08 g (41.05 mmol) of 3,3 ′, 4,4′-biphenyltetracarboxylic acid anhydride was charged as the compound (b) having two acid anhydride structures in one molecule. Reaction at 5 ° C. for 5 hours gave amido acid (A-2). The viscosity (25 ° C.) of this amic acid compound (A-2) was 30 Pa · s.

Synthesis Example 3: Preparation of amic acid (A-3) 4,4′-bis as compound (a) having two amino groups in one molecule in a 300 ml reactor equipped with a stirrer, a thermometer, and a condenser 20.00 g (100.9 mmol) of (aminophenyl) methane was stirred and dissolved in 93.31 g of N-methylpyrrolidone at 80 ° C. for 1 hour. Thereafter, 19.99 g (100.9 mmol) of butanetetracarboxylic anhydride was added as a compound (b) having two acid anhydride structures in one molecule, and further reacted at 80 ° C. for 5 hours to obtain amic acid. (A-3) was obtained. The viscosity (25 ° C.) of this amic acid compound (A-3) was 0.8 Pa · s.

ＤＴＥＰ−３５０ ：ダイトーケミックス製 ジアゾナフトキノン系感光剤
ＰＡ−６ ：ダイトーケミックス製 ジアゾナフトキノン系感光剤
ＲＭ−１００１ ：日本化薬製 アクリロイルモルフォリン
Ｒ−１２８Ｈ ：日本化薬製 フェニルグリシジルエーテルアクリレート
ライトエステルＴＨＦ：共栄社化学製 テトラヒドロフルフリルメタクリレート Examples 1-3, Comparative Examples 1-3
The amic acid obtained in Synthesis Examples 1 to 3 and other components were mixed in the composition shown in Table 1 to obtain a resin composition.
[Table 1]

DTEP-350: Daito Chemix diazonaphthoquinone photosensitizer PA-6: Daito Chemix diazonaphthoquinone photosensitizer RM-1001: Nippon Kayaku acryloylmorpholine R-128H: Nippon Kayaku Phenyl glycidyl ether acrylate Light ester THF: Kyoeisha Chemical tetrahydrofurfuryl methacrylate

Evaluation of composition for positive-type solder resist Each composition shown as Example 1 and Comparative Example 1 was applied to a copper circuit printed circuit board by a screen printing method so as to have a thickness of 25 microns. For 60 minutes. Next, the mask film on which the pattern was drawn was brought into close contact, and irradiated with ultraviolet rays using an ultraviolet exposure device (USHIO: 500 W multilight). Next, spray development (spray pressure: 0.2 MPa) was performed for 180 seconds using a 1% tetramethylammonium hydroxide aqueous solution (temperature: 30 ° C.) as a developer. After washing with water, heat treatment was performed for 60 minutes in a 200 ° C. hot air dryer to obtain a cured product. The obtained coating film was visually confirmed, and the results are shown in Table 2.

  Each composition shown as Example 2 and Comparative Example 2 was applied to a copper circuit printed circuit board by a screen printing method so as to have a thickness of 25 microns, and the coating film was dried in a hot air dryer at 80 ° C. for 60 minutes. It was. Next, the mask film on which the pattern was drawn was brought into close contact, and irradiated with ultraviolet rays using an ultraviolet exposure device (USHIO: 500 W multilight). Next, using a 1% aqueous sodium hydroxide solution (temperature: 30 ° C.) as a developer, spray development (spray pressure: 0.2 MPa) was performed for 180 seconds. After washing with water, heat treatment was performed for 60 minutes in a 200 ° C. hot air dryer to obtain a cured product. The obtained coating film was visually confirmed, and the results are shown in Table 2.

  Each composition shown as Example 3 and Comparative Example 3 was applied to a copper circuit printed circuit board to a thickness of 25 microns by a screen printing method, and the coating film was dried in a hot air dryer at 80 ° C. for 60 minutes. It was. Next, the mask film on which the pattern was drawn was brought into close contact, and irradiated with ultraviolet rays using an ultraviolet exposure device (USHIO: 500 W multilight). Next, spray development (spray pressure: 0.2 MPa) was performed for 240 seconds using a 1% aqueous sodium carbonate solution (temperature: 30 ° C.) as a developer. After washing with water, heat treatment was performed for 60 minutes in a 200 ° C. hot air dryer to obtain a cured product. The obtained coating film was visually confirmed, and the results are shown in Table 2.

○ ‥塗膜に異常は見られない
泡 ‥塗膜に発泡が見られる
ひび‥塗膜にひびが見られる [Table 2]

○ …… No abnormalities in the paint film Foam …… Bubble is seen in the paint film Cracks …… Cracks are seen in the paint film

  As is apparent from the above results, a good cured coating film can be obtained by incorporating a specific reactive diluent into the photosensitive resin composition.

  The use of the cured product of the photosensitive resin composition of the present invention dramatically improves the smoothness of the cured film, which is a basic characteristic as a solder resist, and the photosensitive resin composition of the present invention is suitable for use as a solder resist. Also suitable.

Claims (10)

Amide acid (A) obtained by reacting compound (a) having two amino groups in one molecule with compound (b) having two acid anhydride structures in one molecule, in one molecule A photosensitive resin composition comprising a reactive diluent (B) having one unsaturated double bond and 1 to 4 aromatic hydrocarbon rings and a photoacid generator (C). Amide acid (A) obtained by reacting compound (a) having two amino groups in one molecule with compound (b) having two acid anhydride structures in one molecule, in one molecule A photosensitive resin composition comprising a reactive diluent (B ′) having one unsaturated double bond and 1 to 4 aliphatic heterocycles, and a photoacid generator (C). The photosensitive resin composition according to claim 1 or 2, wherein the compound (a) having two amino groups in one molecule is a compound having two aromatic amino groups. It is a molding material, The photosensitive resin composition as described in any one of Claims 1-3. It is a film forming material, The photosensitive resin composition as described in any one of Claims 1-3. It is an electrically insulating material composition, The photosensitive resin composition as described in any one of Claims 1-3. It is a photosensitive soldering resist composition, The photosensitive resin composition as described in any one of Claims 1-3. Hardened | cured material obtained by irradiating an active energy ray to the photosensitive resin composition as described in any one of Claims 1-7. A multilayer material having a layer of a cured product of the photosensitive resin composition according to claim 8. After coating the photosensitive resin composition according to any one of claims 1 to 7 on a substrate, if necessary, the solvent is dried, then photo-patterning is performed, and after further development with an alkaline aqueous solution, light or A method of using a photosensitive resin composition, wherein a cured film is obtained by polymerizing an unsaturated double bond with heat.