JP2009300873A - Method for manufacturing new circuit substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a circuit substrate including a cured film of a photosensitive resin composition which can be microfabricated owing to its photosensitivity, can be developed with a diluted alkaline water solution, can be cured at a low temperature, is very flexible, is excellent in electrical insulation reliability, soldering heat resistance, resistance to an organic solvent, and property of adhesion with a sealant, and in which the warpage of a substrate after curing is small. <P>SOLUTION: The problems can be coped with by using the method for manufacturing a circuit substrate in which the cured film of the photosensitive resin composition is formed on a substrate at least by (1) a step in which a film is formed on a substrate using a photosensitive resin composition, (2) an exposure step, (3) an alkaline developing step, (4) an ionic impurity cleaning and removing step, and (5) a thermal curing step, wherein the photosensitive resin composition includes at least (A) an imidized tetracarboxylic acid, (B) a diamino compound and/or isocyanate compound, (C) a photosensitive resin, and (D) photopolymerization initiator. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  In the present invention, when a cured film of the photosensitive resin composition is formed on a substrate, at least the process of removing ionic impurities mixed in the coating film at the time of development is removed by washing, thereby improving the photosensitivity. It can be finely processed, can be developed with dilute alkaline aqueous solution, can be cured at a low temperature (200 ° C or less), has high flexibility, electrical insulation reliability, solder heat resistance, organic solvent resistance, sealing The present invention relates to a method for producing a circuit board, characterized by forming a cured film of a photosensitive resin composition that has excellent adhesion to a stopper and has little warpage of the substrate after curing.

  Polyimide resins are widely used in electrical and electronic applications because of their excellent heat resistance, electrical insulation reliability, chemical resistance, and mechanical properties. For example, it is used to form insulating films and protective coatings on semiconductor devices, base materials such as flexible circuit boards and integrated circuits, surface protective materials, and further, interlayer insulating films and protective films for fine circuits. .

  In particular, when used as a surface protection material for a flexible circuit board, a coverlay film obtained by applying an adhesive to a molded body such as a polyimide film has been used. When bonding this coverlay film on a flexible circuit board, there is a method in which an opening is provided in advance by a method such as punching in a terminal portion of a circuit or a joint portion with a component, and after aligning, a method of thermocompression bonding by a hot press or the like is used. It is common.

  However, it is difficult to provide a high-accuracy opening in a thin coverlay film, and since the alignment at the time of lamination is often performed manually, the positional accuracy is poor and the workability of the lamination is also poor. The cost was high.

  On the other hand, a liquid cover coat ink or the like may be used as a surface protection material for a circuit board. In particular, a liquid cover coat ink having a photosensitive function is preferably used when fine processing is required. Yes. As the liquid cover coat ink, a photosensitive ink mainly composed of epoxy resin or the like (generally also referred to as a solder resist) is used. This ink is excellent in electrical insulation reliability as an insulating material, but is bent. Therefore, when it is laminated on a thin and flexible circuit board such as a flexible circuit board, the warpage of the board becomes large and it is difficult to use it for a flexible circuit board.

  In recent years, various proposals have been made as liquid cover coat inks that can exhibit flexibility and high electrical insulation reliability.

  For example, a method for producing a circuit board using a photosensitive resin composition containing a terminal half-esterified imidosiloxane oligomer has been proposed (see, for example, Patent Documents 1 and 2).

In addition, a permanent mask resist is produced by irradiating a layer of a permanent mask resist or a photosensitive resin composition with actinic rays, and then washing and developing with a washing solution or a developer obtained by mixing or dissolving metal ions. And a multilayer substrate formed by laminating a permanent mask resist manufactured by the method (see, for example, Patent Document 3).
JP 2000-212446 A JP 2001-215702 A JP 2002-162739 A

  However, in the method for producing a circuit board using the resin composition containing the terminal half-esterified imide siloxane oligomer described in Patent Documents 1 and 2, the photosensitive resin composition containing the terminal half-esterified imide siloxane oligomer is used. Since the wettability of the surface of the cured film formed from is poor, the adhesion with various sealants is poor, and when forming a fine pattern by exposure / development treatment, it has a flexible siloxane skeleton, Since ionic impurities are taken up to a deep layer inside the coating film and the ionic impurities inhibit thermosetting, there is a problem that the electrical insulation reliability is poor.

  In the above-mentioned Patent Document 3, since a process of washing and developing with a washing solution or a developing solution in which metal ions are mixed or dissolved is passed, ionic impurities in the developing solution are hardly mixed in the cured film, and a thermosetting reaction is performed. However, since a photosensitive resin composition composed of a urethane resin and an acrylic resin is used, compared to the case where a polyimide type or polyamic acid type photosensitive resin composition is used as a cover coat ink, the temperature is increased. There is a problem of poor electrical insulation reliability and heat resistance under humidity.

  As a result of diligent research to solve the above problems, the present inventors have at least washed ionic impurities mixed in the coating film during development when forming a cured film of the photosensitive resin composition on the substrate. By passing through the removing process, it has photosensitivity, so it can be finely processed, can be developed with dilute alkaline aqueous solution, can be cured at low temperature (200 ° C or less), has high flexibility, and has high electrical insulation reliability. It has been found that a cured film of a photosensitive resin composition is obtained that has excellent properties, solder heat resistance, organic solvent resistance, and adhesiveness with a sealant, and has a small warpage of the substrate after curing.

  That is, the method for producing a circuit board according to the present invention comprises at least (1) a step of forming a coating film on the substrate using the photosensitive resin composition, (2) an exposure step, and (3) an alkali development step. (4) After passing through a step of removing ionic impurities mixed in the coating film during alkali development by washing, (5) Forming a cured photosensitive resin composition film on the substrate by a thermosetting step A method for producing a circuit board, wherein the photosensitive resin composition comprises (A) an imidized tetracarboxylic acid, (B) a diamino compound and / or an isocyanate compound, and (C) a photosensitive property. A method for producing a circuit board comprising at least a resin and (D) a photopolymerization initiator.

  In the method for producing a circuit board according to the present invention, the (A) imidized tetracarboxylic acid is preferably a tetracarboxylic acid urethane imide oligomer.

  In the method for producing a circuit board according to the present invention, the cleaning liquid used in the step (4) of removing the ionic impurities mixed in the coating film during alkali development is an aqueous solution containing an acidic compound. Preferably there is.

  Moreover, in the manufacturing method of the circuit board concerning this invention, it is preferable that the density | concentration of the aqueous solution containing the said acidic compound is 0.005-0.5M.

  In the method for producing a circuit board according to the present invention, the cleaning liquid used in the step (4) of removing the ionic impurities mixed in the coating film during alkali development is washed with calcium ions and / or magnesium ions. It is also preferable that the aqueous solution contains.

  Moreover, in the manufacturing method of the circuit board concerning this invention, it is preferable that the ion concentration of the aqueous solution containing the said calcium ion and / or magnesium ion is 50-5000 ppm.

  The method for producing a circuit board according to the present invention, as described above, removes at least ionic impurities mixed in the coating film during development when forming a cured film of the photosensitive resin composition on the substrate. By passing through this process, it can be finely processed because it has photosensitivity, it can be developed with dilute alkaline aqueous solution, it can be cured at low temperature (200 ° C or less), it is highly flexible, and it has electrical insulation reliability. In addition, it is possible to form a cured film of a photosensitive resin composition that is excellent in solder heat resistance, organic solvent resistance, and adhesiveness with a sealant and has a small warpage of the substrate after curing. Therefore, the circuit board manufacturing method of the present invention can be used for manufacturing various circuit boards, and has excellent effects.

  Hereinafter, the present invention will be described in detail.

<Circuit board manufacturing method>
The circuit board manufacturing method of the present invention comprises at least (1) a step of forming a coating film on a substrate using a photosensitive resin composition, (2) an exposure step, and further (3) an alkali development step, (4) After passing through a step of removing ionic impurities mixed in the coating film by washing during alkali development, (5) forming a cured photosensitive resin composition film on the substrate by a thermosetting step. Any other steps may be combined as long as they go through the steps (1) to (5).

  In addition, about the photosensitive resin composition in the manufacturing method of the circuit board of this invention, (A) imidized tetracarboxylic acid, (B) diamino compound and / or isocyanate type compound, (C) photosensitive resin, ( D) What is necessary is just to contain the photoinitiator at least.

  Here, the inventors of the present application have found that the cured film of the photosensitive resin composition formed using the method for manufacturing a circuit board of the present invention is excellent in various characteristics. This is because of the following reason. I guess that is due. In other words, in the process of forming the cured photosensitive resin composition film, the thermal curing reaction of the photosensitive resin composition is performed by going through a process of removing ionic impurities mixed in the coating film during alkali development by washing. Since it can proceed efficiently without being hindered by ionic impurities, not only can the mechanical strength, heat resistance, and chemical resistance of the cured film be dramatically improved, but also (A) imidization By using the photosensitive resin composition containing at least the tetracarboxylic acid, (B) diamino compound and / or isocyanate compound, (C) photosensitive resin, and (D) photopolymerization initiator, (A) Since the imide ring is contained in the molecular skeleton of the imidized tetracarboxylic acid, ionic impurities taken in during alkali development penetrate into the coating film. Hardly can further be readily removed in (A) for imidized tetracarboxylic acid is a low molecular weight of the oligomer region, washing process contaminating ionic impurities.

  In addition, since (A) an imidized tetracarboxylic acid has an imide skeleton in the molecule, it is excellent in heat resistance and electrical insulation reliability derived from the imide skeleton, and has a carboxyl group at the end, so it is represented by a dilute alkaline aqueous solution. It becomes soluble in a developing solution and can be finely processed by exposure and development. Furthermore, it reacts with the (B) diamino compound and / or isocyanate compound which is a chain extender by heating to increase the molecular weight while generating an imide group. For this reason, since the cured film obtained is rich in flexibility and has a small curing shrinkage rate, when used as an insulating protective film such as a flexible printed wiring board, it is resistant to bending when the flexible printed wiring board is bent. Excellent, lowering the height and stiffness.

  Furthermore, since the molecular skeleton does not contain a siloxane skeleton, the resulting cured film surface has good wettability, not only very good adhesion to various members, but also derived from the siloxane component from the cured film. Therefore, when a cured film is used as an insulating film of a printed wiring board, the semiconductor does not malfunction.

  Hereinafter, (1) a step of forming a coating film on a substrate using the photosensitive resin composition, (2) an exposure step, (3) an alkali development step, and (4) ionicity mixed in the coating during alkali development. A step of removing impurities by washing, (5) a thermosetting step, and (A) an imidized tetracarboxylic acid, (B) a diamino compound and / or an isocyanate compound in the photosensitive resin composition, (C) A photosensitive resin, (D) a photopolymerization initiator, other components, and a mixing method of (A) to (D) will be described.

<(1) The process of forming a coating film on a board | substrate using the photosensitive resin composition>
Examples of the process for forming a coating film on a substrate using the photosensitive resin composition of the present invention include, for example, screen printing, roller coating, curtain coating, spray coating, spin coating using a spinner. The photosensitive resin composition is applied onto the substrate by, for example, preferably, after forming a coating film of 5 to 100 μm, the coating film is dried at 120 ° C. or less, preferably 40 to 100 ° C. It is the process of removing the solvent and low volatile content contained in the conductive resin composition and forming a coating film on the substrate.

<(2) Exposure process>
The (2) exposure step of the present invention is (1) a negative or positive photomask on the coating film obtained in the step of forming a coating film on the substrate using the photosensitive resin composition. It is a process of irradiating actinic rays such as ultraviolet rays, visible rays, and electron beams. Irradiation with the actinic ray can be performed using a light source such as a high-pressure mercury lamp, a carbon arc lamp, a mercury vapor arc lamp, or a xenon lamp. A laser direct imaging method can also be used.

  When the photosensitive resin composition is negative, the exposed portion is cured by the exposure step, and the unexposed portion is removed by the developing step. Further, when the photosensitive resin composition is a positive type, the exposed portion is easily dissolved in the developer due to decomposition or the like, and the exposed portion is removed by the developing step.

<(3) Alkali development process>
The (3) alkali development step of the present invention includes, for example, a dilute aqueous solution of 0.1 to 5% by weight sodium carbonate, a dilute aqueous solution of 0.1 to 5% by weight potassium carbonate, and 0.1 to 5% by weight sodium hydroxide. This is a step of performing patterning by developing a coating film using a developer of a dilute alkaline aqueous solution such as dilute aqueous solution. Here, as a developing method, various methods such as shower, paddle, immersion, or ultrasonic wave can be used. Since the time until the pattern is exposed varies depending on the spray pressure and flow velocity of the developing device and the temperature of the developer, it is preferable to find the optimum device conditions as appropriate.

<(4) Step of removing ionic impurities mixed in the coating during alkali development by washing>
The step (4) of removing the ionic impurities mixed in the coating film during alkali development of the present invention is, for example, an aqueous solution containing an acidic compound, an aqueous solution containing calcium ions and / or magnesium ions, etc. This is a step of removing ionic impurities mixed in the coating film during alkali development using the cleaning solution. Here, as a cleaning method, various methods such as shower, paddle, immersion, or ultrasonic wave can be used. In addition, since the time until the ionic impurities are removed differs depending on the spraying pressure and flow rate of the cleaning device and the temperature of the cleaning solution, it is preferable to find optimal device conditions appropriately.

  The acidic compound is preferably an acidic compound having an acid dissociation constant PKa of an aqueous solution at 25 ° C. of 5.0 or less. For example, organic carboxylic acids such as formic acid, acetic acid, lactic acid, oxalic acid, trifluoroacetic acid, methanesulfonic acid, p -Inorganic acids, such as sulfonic acids, such as toluenesulfonic acid, hydrochloric acid, hydrogen bromide, hydrogen iodide, nitric acid, nitrous acid, sulfuric acid, sulfurous acid, etc. are mentioned, These can be used individually or in combination of 2 or more types.

  When the acid dissociation constant PKa of the aqueous solution at 25 ° C. of the above acidic compound is 5.0 or more, the acidic compound has a low acidity, and thus the effect of removing ionic impurities mixed in the coating film during alkali development is low. The heat resistance and electrical insulation reliability of the cured film may be inferior.

The concentration of the aqueous solution containing the acidic compound is preferably 0.005 to 0.5 M (mol / dm ³ ), more preferably 0.01 to 0.25 M, and particularly preferably 0.025 to 0.1 M. is there.

  By controlling the concentration of the aqueous solution containing an acidic compound within the above range, it becomes possible to efficiently remove ionic impurities mixed in the coating during alkali development, and the thermosetting reaction proceeds sufficiently, The cured film is preferable because it is excellent in heat resistance, chemical resistance and electrical insulation reliability.

  As the aqueous solution containing calcium ions and / or magnesium ions, for example, an aqueous solution in which calcium ions and / or magnesium ions are mixed or dissolved in tap water, pure water, ion-exchanged water or the like is preferable, and calcium ions and / or As a method for mixing or dissolving magnesium ions, for example, calcium sulfate, calcium hydrochloride, magnesium sulfate, magnesium chloride or the like is preferably mixed or dissolved in water.

  The ion concentration of the aqueous solution containing the calcium ions and / or magnesium ions is preferably 50 to 5000 ppm, more preferably 100 to 2500 ppm, and particularly preferably 250 to 1000 ppm on a weight basis.

  By controlling the ion concentration of the aqueous solution containing calcium ions and / or magnesium ions within the above range, it is possible to efficiently remove ionic impurities mixed in the coating during alkali development, and thermosetting reaction Is preferable because it proceeds sufficiently and the cured film has excellent heat resistance, chemical resistance and electrical insulation reliability.

<(5) Thermosetting process>
The (5) thermosetting step of the present invention means that the coating film is heat-treated and promotes the thermosetting reaction, thereby improving the cross-linking density of the coating film, resulting in heat resistance, chemical resistance, and electrical insulation reliability. It is a process for obtaining an excellent cured film. The heat treatment temperature at this time is preferably 100 ° C. or higher and 250 ° C. or lower, more preferably 120 ° C. or higher and 200 ° C. or lower, and particularly preferably 130 ° C. or higher and 180 ° C. or lower. When the heat treatment temperature is lower than the above range, the heat curing reaction of the coating film does not proceed sufficiently, and the heat resistance, chemical resistance, and electrical insulation reliability of the coating film may be poor. If it is higher than the range, when the cured film is used as an insulating material for a circuit board such as a flexible printed wiring board, the oxidative degradation of the wiring may proceed, and the adhesion between the cured film and the wiring may decrease. .

<Photosensitive resin composition>
The photosensitive resin composition of the present invention contains at least (A) an imidized tetracarboxylic acid, (B) a diamino compound and / or an isocyanate compound, (C) a photosensitive resin, and (D) a photopolymerization initiator. It only has to be.

<(A) Imidized tetracarboxylic acid>
The (A) imidized tetracarboxylic acid used in the present invention is the following general formula (1).

(In the formula, each R independently represents a tetravalent organic group, each R ′ independently represents a divalent organic group, and l represents an integer of 0 to 20.)
As shown in the formula, it is a tetracarboxylic acid having a structure in which at least two imide bonds are included in the structural formula and the terminal is a tetracarboxylic acid. In addition, the imidized tetracarboxylic acid of the present invention is preferably as the molecular weight is short because the solubility in an organic solvent solution is improved. For example, a polymer called an oligomer having a relatively low molecular weight is preferable. Although it is imidized by setting it as such a tetracarboxylic acid structure, the solubility to a solvent can be improved. Moreover, since the bond in the structure is not an amide bond but an imide bond, the storage stability is excellent. Therefore, when the polyimide precursor composition solution is prepared, deterioration of the solution viscosity with time can be prevented, and a change in viscosity can be suppressed.

  In addition, about (A) imidized tetracarboxylic acid in the photosensitive resin composition of this invention, although the tetracarboxylic-acid urethane imide oligomer which contains a urethane bond in a molecule | numerator is used more, it is limited to this. It is not something.

<Tetracarboxylic acid urethane imide oligomer>
The tetracarboxylic acid urethane imide oligomer used in the present invention has a tetracarboxylic acid at the terminal, a urethane structure inside, a closed imide ring, and a number average molecular weight of 30,000 in terms of polyethylene glycol. Hereinafter, more preferably 20,000 or less oligomer.

  More specifically, the tetracarboxylic acid urethane imide oligomer in the present invention does not have a siloxane bond in the main chain skeleton, and the following general formula (2)

(In the formula, R ″ and X each independently represent a divalent organic group, and n represents an integer of 1 or more.)
It has at least one repeating unit having a urethane bond represented by the following general formula (1)

(In the formula, each R independently represents a tetravalent organic group, each R ′ independently represents a divalent organic group, and l represents an integer of 0 to 20.)
And a compound having a structure having at least two imide bonds and a tetracarboxylic acid at the terminal.

  The number average molecular weight of the tetracarboxylic acid urethane imide oligomer of the present invention is preferably 30,000 or less, more preferably 20,000 or less, and particularly preferably 15,000 or less in terms of polyethylene glycol. It is preferable to react by controlling the number average molecular weight within the above range because the solubility of the tetracarboxylic acid urethane imide oligomer in the organic solvent is improved.

  Moreover, since the tetracarboxylic acid urethane imide oligomer of the present invention has no siloxane bond in the structure, it has excellent wettability on the surface of a cured film formed using this, and has good adhesion to various sealants. It is. Furthermore, since the bond in the structure is not an amide bond but an imide bond, the storage stability is excellent. Therefore, it is possible to suppress a change in the viscosity of the solution with time when the photosensitive resin composition solution is prepared and stored.

  The tetracarboxylic acid urethane imide oligomer used in the present invention is not particularly limited as long as it has the above structure, but more preferably, at least (a) the following general formula (3)

(In the formula, R ′ ″ represents a divalent organic group, and p is an integer of 1 to 20.)
(B) the following general formula (4)

(In the formula, X represents a divalent organic group.)
The terminal isocyanate compound is synthesized by reacting with the diisocyanate compound represented by formula (c), and then (c) the following general formula (5)

(In the formula, R represents a tetravalent organic group.)
It is obtained by reacting a tetracarboxylic dianhydride represented by formula (1) to synthesize a terminal acid anhydride urethane imide oligomer, and (d) further reacting with water.

<(A) Diol compound>
The (a) diol compound used in the present invention is a branched or straight-chain compound having two hydroxyl groups in the molecule represented by the general formula (3). (A) The diol compound is not particularly limited as long as it has the above structure. For example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neo Pentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decane Diols, alkylene diols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol, dimethylolpropionic acid (2,2-bis (hydroxymethyl) propionic acid), dimethylolbutanoic acid (2,2-bis ( Hydroxymethyl) butanoic acid), 2,3-dihydroxybenzoic acid, 2 Carboxyl group-containing diols such as 4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, polyethylene glycol, polypropylene glycol, Polytetramethylene glycol, polyoxyalkylene diols such as random copolymers of tetramethylene glycol and neopentyl glycol, polyester diols obtained by reacting polyhydric alcohols with polybasic acids, polycarbonate diols having a carbonate skeleton, γ -Polycaprolactone diol obtained by ring-opening addition reaction of lactones such as butyl lactone, ε-caprolactone, δ-valerolactone, bisphenol A, ethylene oxide adduct of bisphenol A, bisphenol Examples include a propylene oxide adduct of Nord A, hydrogenated bisphenol A, an ethylene oxide adduct of hydrogenated bisphenol A, a propylene oxide adduct of hydrogenated bisphenol A, and these can be used alone or in combination of two or more. .

  (A) As a diol compound, following General formula (6)

(In the formula, plural R _{1 s} each independently represent a divalent organic group, and m is an integer of 1 to 20.)
It is particularly preferable to use a polycarbonate diol represented by This is preferable in that the heat resistance, flexibility, water resistance, chemical resistance, and electrical insulation reliability under high temperature and high humidity of the obtained cured film can be further improved.

  More specifically, examples of the polycarbonate diol include trade names PCDL T-4671, T-4672, T-4691, T-4692, T-5650J, T-5651, T-5651 manufactured by Asahi Kasei Chemicals Corporation. , T-6001, T-6002, Daicel Chemical Industries, Ltd. Product Name Plaxel CD CD205, CD205PL, CD205HL, CD210, CD210PL, CD210HL, CD220, CD220PL, CD220HL, Kuraray Co., Ltd. product name Kuraray Polyol C-1015N , C-1050, C-1065N, C-1090, C-2015N, C-2065N, C-2090, Nippon Polyurethane Industry Co., Ltd., trade names NIPPOLAN 981, 980R, 982R These can be used alone or in combinations of two or more. The number average molecular weight of the polycarbonate diol is preferably 500 to 5000, more preferably 750 to 2500, and particularly preferably 1000 to 2000 in terms of polystyrene. When the number average molecular weight of the polycarbonate diol is within the above range, it is preferable in that the chemical resistance and flexibility of the obtained cured film can be improved. When the number average molecular weight is less than 500, the flexibility of the resulting cured film may be reduced, and when it is 5000 or more, the solvent solubility of the tetracarboxylic acid urethane imide oligomer may be reduced.

  More preferably, a carboxyl group can also be introduced into the side chain of the tetracarboxylic acid urethane imide oligomer by combining the polycarbonate diol and the carboxyl group-containing diol. Thereby, the branch point of the main chain of a tetracarboxylic acid urethane imide oligomer increases, crystallinity falls, and it is preferable at the point which can improve the solvent solubility of a tetracarboxylic acid urethane imide oligomer.

<(B) Diisocyanate compound>
The (b) diisocyanate compound used in the present invention is a compound having two isocyanate groups in the molecule represented by the general formula (4).

  Examples of the (b) diisocyanate compound include diphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-dimethyldiphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4,3'- Or 5,2'- or 5,3'- or 6,2'- or 6,3'-diethyldiphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2 ' -Or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-dimethoxydiphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, Diphenylmethane-3,3'-diiso Anate, diphenylmethane-3,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, benzophenone-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, tolylene-2,4-diisocyanate, tolylene-2 , 6-diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, naphthalene-2,6-diisocyanate, 4,4 '-[2,2-bis (4-phenoxyphenyl) propane] diisocyanate Compounds, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, etc., hexamethylene diisocyanate Sulfonate, trimethyl hexamethylene diisocyanate, aliphatic diisocyanate compounds and the like such as lysine diisocyanate, and these may be used alone or in combinations of two or more. Use of these is preferable for increasing the heat resistance of the resulting cured film. Moreover, you may use what was stabilized with the blocking agent required in order to avoid a change over time. Such blocking agents include alcohol, phenol, oxime and the like, but are not particularly limited.

  (B) As the diisocyanate compound, diphenylmethane-4,4'-diisocyanate, diphenylmethane-3,3'-diisocyanate, diphenylmethane-3,4'-diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate It is particularly preferable to use norbornene diisocyanate. Thereby, it is preferable at the point which can improve the heat resistance of the cured film obtained, and water resistance further.

  Moreover, in order to improve the developability of the photosensitive resin composition, (b) tolylene-2,6-diisocyanate, tolylene-2,4-diisocyanate and 1,6-hexamethylene diisocyanate are suitable as the diisocyanate compound. Used for.

<Method for synthesizing terminal isocyanate compound>
The method for synthesizing a terminal isocyanate compound obtained by reacting (a) a diol compound and (b) a diisocyanate compound used in the present invention is the ratio of the number of hydroxyl groups to the number of isocyanate groups. Is reacted in a solvent-free or organic solvent such that isocyanate group / hydroxyl group = 1 or more and 2.10 or less, more preferably 1.10 or more and 2.10 or less, and further preferably 1.90 or more and 2.10 or less. Can be obtained.

  When two or more types of (a) diol compounds are used, the reaction with (b) diisocyanate compound may be carried out after mixing two or more types of (a) diol compounds. You may react a compound and (b) diisocyanate compound separately. Moreover, after reacting (a) diol compound and (b) diisocyanate compound, the obtained terminal isocyanate compound is further reacted with another (a) diol compound, and this is further reacted with (b) diisocyanate compound. May be. The same applies when two or more types of (b) diisocyanate compounds are used. In this way, a desired terminal isocyanate compound can be produced.

  The reaction temperature between (a) and (b) is preferably 40 to 160 ° C, more preferably 60 to 150 ° C. If it is less than 40 ° C., the reaction time becomes too long. If it exceeds 160 ° C., a three-dimensional reaction occurs during the reaction and gelation tends to occur. The reaction time can be appropriately selected depending on the scale of the batch and the reaction conditions employed. If necessary, the reaction may be performed in the presence of a catalyst such as a tertiary amine, an alkali metal, an alkaline earth metal, a metal such as tin, zinc, titanium, cobalt, or a metalloid compound.

  The above reaction can be carried out in the absence of a solvent. However, in order to control the reaction, it is desirable to carry out the reaction in an organic solvent system. For example, examples of the organic solvent include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, N , N-dimethylformamide, formamide solvents such as N, N-diethylformamide, N, N-dimethylacetamide, acetamide solvents such as N, N-diethylacetamide, N-methyl-2-pyrrolidone, N-vinyl-2 -Pyrrolidone solvents such as pyrrolidone, phenol solvents such as phenol, o-, m- or p-cresol, xylenol, halogenated phenol, catechol, hexamethylphosphoramide, γ-butyrolactone, and the like. Further, if necessary, these organic polar solvents can be used in combination with an aromatic hydrocarbon such as xylene or toluene.

  Furthermore, for example, methyl monoglyme (1,2-dimethoxyethane), methyldiglyme (bis (2-methoxyether) ether), methyltriglyme (1,2-bis (2-methoxyethoxy) ethane), methyltetraglyme (Bis [2- (2-methoxyethoxyethyl)] ether), ethyl monoglyme (1,2-diethoxyethane), ethyldiglyme (bis (2-ethoxyethyl) ether), butyldiglyme (bis (2 Symmetric glycol diethers such as -butoxyethyl) ether), methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether Cetate (also known as carbitol acetate, 2- (2-butoxyethoxy) ethyl acetate), diethylene glycol monobutyl ether acetate, 3-methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether Acetates such as acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripylene glycol n Propyl ether, propylene glycol phenyl ether, dipropylene glycol dimethyl ether, 1,3-dioxolane, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, a solvent may be used ethers such as ethyl ether also ethylene glycol. Of these, symmetrical glycol diethers are preferably used because side reactions are unlikely to occur.

  The amount of solvent used in the reaction is desirably such that the solute weight concentration in the reaction solution, that is, the solution concentration is 5% by weight or more and 90% by weight or less. The solute weight concentration in the reaction solution is more preferably 10 wt% or more and 80 wt% or less. When the solution concentration is 5% or less, the polymerization reaction is difficult to occur, the reaction rate is lowered, and a desired structural substance may not be obtained.

  Moreover, the terminal isocyanate compound obtained by the said reaction can also block the isocyanate group of the resin terminal after completion | finish of synthesis | combination with blocking agents, such as alcohol, lactams, and oximes.

<Method of synthesizing terminal acid anhydride urethane imide oligomer>
The terminal acid anhydride urethane imide oligomer used in the present invention can be obtained by reacting the terminal isocyanate compound obtained as described above with tetracarboxylic dianhydride. At this time, the blending amount of the terminal isocyanate compound and the tetracarboxylic dianhydride is preferably such that the ratio of the number of isocyanate groups to the number of acid dianhydride groups is acid dianhydride group / isocyanate group = 2.10 or less, It is more preferably 1.10 or more and 2.10 or less, and further preferably 1.90 or more and 2.10 or less. Moreover, the solvent used at the time of the synthesis | combination of the said terminal isocyanate compound may be used for reaction of a terminal isocyanate compound and tetracarboxylic dianhydride as it is, and also said solvent can be added in addition.

<Tetracarboxylic dianhydride>
Examples of the tetracarboxylic dianhydride used in the synthesis of the terminal acid anhydride urethane imide oligomer in the present invention include 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-oxydiphthalic dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis (4-hydroxyphenyl) ) Propane dibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4 ′ -Biphenyltetracarboxylic dianhydride, 2,3,3 ', 4-biphenyltetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene- 1, - it can be used tetracarboxylic acid dianhydride such as dicarboxylic anhydrides.

  More preferably, the tetracarboxylic dianhydride used for the synthesis of the terminal acid anhydride urethane imide oligomer is 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 3, 3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride and 3,3 ′, 4,4′-oxydiphthalic dianhydride. By using these, the solubility of the terminal carboxylic acid urethane imide oligomer obtained in an organic solvent can be improved, and the chemical resistance of the resulting cured film is improved.

  The tetracarboxylic dianhydride is 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride or 5- (2,5-dioxotetrahydro-3-furanyl). It is more preferable to use -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride from the viewpoint of compatibility with other materials in the photosensitive resin composition.

  The amount of the tetracarboxylic dianhydride used in the present invention is as follows when the amount of the polyol (more specifically, the diol compound) used in the production of the terminal isocyanate compound is 1 mol. It is preferably used in a proportion of 50 mol or more and 2.50 mol or less in order to arrange a carboxyl group at both ends of the terminal carboxylic acid urethane imide oligomer, and a particularly preferable use range is 1.90 mol or more and 2.10 mol or less. It is to use at the rate of. This is preferable because tetracarboxylic dianhydride that does not contribute to the reaction can be reduced.

<Method for producing terminal acid anhydride urethane imide oligomer>
Various methods are mentioned as a reaction method of a terminal isocyanate compound and tetracarboxylic dianhydride in the manufacturing method of a terminal acid anhydride urethane imide oligomer. The typical method is illustrated below. However, any method may be used as long as tetracarboxylic dianhydride is arranged at the terminal.

  Method 1: A terminal isocyanate compound is gradually added to a solution in which tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent. The reaction temperature at this time is 100 ° C. or higher and 300 ° C. or lower, more preferably 140 ° C. or higher and 250 ° C. or lower. It is preferred that the reaction occurs and imidization proceeds at the same time when the terminal isocyanate compound is added by heating to such a temperature. However, after the terminal isocyanate compound and tetracarboxylic dianhydride are completely dissolved at a low temperature, a method of imidizing by heating to a high temperature may be used.

  Method 2: A terminal isocyanate compound is gradually added and dissolved in a solution in which tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent. Imidization can be carried out by drawing a vacuum while heating and drying a uniformly dissolved solution heated to 100 ° C. or higher and 250 ° C. or lower.

<Synthesis of tetracarboxylic acid urethane imide oligomer>
A tetracarboxylic acid urethane imide oligomer can be obtained by reacting the terminal acid anhydride urethane imide oligomer obtained by the above method with water.

  As a method of reacting the terminal acid anhydride urethane imide oligomer with water, the molar amount of tetracarboxylic dianhydride used for the production of the terminal acid anhydride urethane imide oligomer is water for the terminal acid anhydride urethane imide oligomer. Is preferably added at a ratio of 2.0 times to 300 times, more preferably 2.0 times to 200 times, to open the ring. Although this reaction can be carried out without solvent, for example, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, N, N-dimethylacetamide , Acetamide solvents such as N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, o-, m- or p-cresol, xylenol, halogenated Phenol solvents such as phenol and catechol, or hexamethylphosphoramide, γ-butyrolactone, methyl monoglyme (1,2-dimethoxyethane), methyl diglyme (bis (2-methoxyether) ether), methyl triglyme ( 1,2-bis (2-mesh Xyloxy) ethane), methyltetraglyme (bis [2- (2-methoxyethoxyethyl)] ether), ethyl monoglyme (1,2-diethoxyethane), ethyldiglyme (bis (2-ethoxyethyl) ether) , Symmetric glycol diethers such as butyl diglyme (bis (2-butoxyethyl) ether), γ-butyrolactone, N-methyl-2-pyrrolidone, methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate , Propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate (also known as carbitol acetate, 2- (2-butoxyethoxy) ethyl acetate)), diethylene glycol Acetates such as nobutyl ether acetate, 3-methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, Propylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripylene glycol n-propyl ether, propylene glycol phenyl Ether, dipropylene glycol dimethyl ether, 1, - dioxolane, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, also be used solvents ethers such as ethyl ether also ethylene glycol. If necessary, low-boiling hexane, acetone, toluene, xylene and the like can be used in combination. Among them, symmetric glycol diethers are particularly preferable because of high solubility of oligomers.

  The above reaction is preferably heated within a range where the added water does not come out of the reaction system, and the reaction is facilitated by heating within a temperature range of 20 ° C. or higher and 150 ° C. or lower, more preferably 120 ° C. or lower. Therefore, it is preferable. The amount of water added is preferably large, but if it is too large, the solubility of other added resins is lowered, and therefore it is preferable to remove unreacted substances after the reaction. The temperature at which unreacted substances are removed after the reaction is preferably equal to or higher than the boiling point of the added water. Unreacted substances can be removed out of the system by heating at such a temperature.

<(B) Diamino compound and / or isocyanate compound>
The diamino compound used as the component (B) in the present invention is a compound having two or more amino groups. Preferably, general formula (7)

(In the formula, R ₂ is a divalent organic group.)
Is an aromatic diamine.

  More specific examples of the diamino compound include m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, bis (3-aminophenyl) sulfide, (3 -Aminophenyl) (4-aminophenyl) sulfide, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, (3-aminophenyl) (4-aminophenyl) sulfoxide, bis (4-aminophenyl) ) Sulphoxide, bis (3-aminophenyl) sulfone, (3-aminophenyl) (4-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone 3,3′-diaminobenzophenone, , 3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylether, 3,3′-diaminodiphenylether, 3,4′-diaminodiphenylether, bis [4 -(3-aminophenoxy) phenyl] sulfoxide, bis [4- (aminophenoxy) phenyl] sulfoxide, (4-aminophenoxyphenyl) (3-aminophenoxyphenyl) phenyl] sulfoxide, bis [4- (3-aminophenoxy) ) Phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, (4-aminophenoxyphenyl) (3-aminophenoxyphenyl) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfi Bis [4- (aminophenoxy) phenyl] sulfide, (4-aminophenoxyphenyl) (3-aminophenoxyphenyl) phenyl] sulfide, 3,3′-diaminobenzanilide, 3,4′-diaminobenzanilide, 4 , 4'-diaminobenzanilide, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, [4- (4-aminophenoxyphenyl)] [4- (3-aminophenoxyphenyl)] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1- [4- (4-Aminophenoxyphenyl)] [4- (3-aminophenoxyphenyl)] ethane, 1,2-bis [4- (3-a Nophenoxy) phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2- [4- (4-aminophenoxyphenyl)] [4- (3-aminophenoxyphenyl) ] Ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2- [4- (4-amino) Phenoxyphenyl)] [4- (3-aminophenoxyphenyl)] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2- [4- (4-aminophenoxyphenyl)] [4 -(3-Ami Phenoxyphenyl)]-1,1,1,3,3,3-hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4 -Bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl Bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4- Aminophenoxy) phenyl] ether, polytetramethylene oxide-di-P-aminobenzoate, poly (tetramethylene / 3-methyltetramethyl) Ether) glycol bis (4-aminobenzoate), trimethylene-bis (4-aminobenzoate), p-phenylene-bis (4-aminobenzoate), m-phenylene-bis (4-aminobenzoate), bisphenol A-bis ( 4-aminobenzoate), 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 3,3′-diamino-4,4′-dicarboxybiphenyl, 4,4 ′ -Diamino-3,3'-dicarboxybiphenyl, 4,4'-diamino-2,2'-dicarboxybiphenyl, [bis (4-amino-2-carboxy) phenyl] methane, [bis (4-amino- 3-carboxy) phenyl] methane, [bis (3-amino-4-carboxy) phenyl] methane, [bis (3-amino-5-carboxy) phenyl] methane, , 2-bis [3-amino-4-carboxyphenyl] propane, 2,2-bis [4-amino-3-carboxyphenyl] propane, 2,2-bis [3-amino-4-carboxyphenyl] hexafluoro Propane, 2,2-bis [4-amino-3-carboxyphenyl] hexafluoropropane, 3,3′-diamino-4,4′-dicarboxydiphenyl ether, 4,4′-diamino-3,3′-di Carboxydiphenyl ether, 4,4′-diamino-2,2′-dicarboxydiphenyl ether, 3,3′-diamino-4,4′-dicarboxydiphenyl sulfone, 4,4′-diamino-3,3′-dicarboxy Diphenylsulfone, 4,4′-diamino-2,2′-dicarboxydiphenylsulfone, 2,3-diaminophenol, 2, Diaminophenols such as 4-diaminophenol, 2,5-diaminophenol, 3,5-diaminophenol, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3 ′ Hydroxybiphenyl compounds such as -dihydroxybiphenyl, 4,4'-diamino-2,2'-dihydroxybiphenyl, 4,4'-diamino-2,2 ', 5,5'-tetrahydroxybiphenyl, 3,3' Dihydroxydiphenylmethanes such as -diamino-4,4'-dihydroxydiphenylmethane, 4,4'-diamino-3,3'-dihydroxydiphenylmethane, 4,4'-diamino-2,2'-dihydroxydiphenylmethane, 2,2- Bis [3-amino-4-hydroxyphenyl] propane, 2,2-bis [4-amino-3- Bis [hydroxyphenyl] propanes such as droxyphenyl] propane, 2,2-bis [3-amino-4-hydroxyphenyl] hexafluoropropane, 2,2-bis [3-amino-4-hydroxyphenyl] hexa Bis [hyhydroxyphenyl] hexafluoropropanes such as fluoropropane, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 4,4′-diamino-3,3′-dihydroxydiphenyl ether, 4,4′- Hydroxydiphenyl ethers such as diamino-2,2′-dihydroxydiphenyl ether, 3,3′-diamino-4,4′-dihydroxydiphenyl sulfone, 4,4′-diamino-3,3′-dihydroxydiphenyl sulfone, 4,4 '-Diamino-2,2'-dihydroxydiphenylsulfur Dihydroxydiphenyl sulphones such as 3,3′-diamino-4,4′-dihydroxydiphenyl sulfide, 4,4′-diamino-3,3′-dihydroxydiphenyl sulfide, 4,4′-diamino-2, Dihydroxydiphenyl sulfides such as 2′-dihydroxydiphenyl sulfide, 3,3′-diamino-4,4′-dihydroxydiphenyl sulfoxide, 4,4′-diamino-3,3′-dihydroxydiphenyl sulfoxide, 4,4′- Dihydroxydiphenyl sulfoxides such as diamino-2,2′-dihydroxydiphenyl sulfoxide, and bis [(hydroxyphenyl) phenyl] alkane compounds such as 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] propane 4,4′-bis (4- Bis [(hydroxyphenoxy) biphenyl compounds such as mino-3-hydroxyphenoxy) biphenyl, bis [(hydroxyphenoxy) such as 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] sulfone Phenyl] sulfone compound, 4,4′-diamino-3,3′-dihydroxydiphenylmethane, 4,4′-diamino-2,2′-dihydroxydiphenylmethane, 2,2-bis [3-amino-4-carboxy Bis (hydroxyphenoxy) biphenyl compounds such as phenyl] propane and 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl. These can be used alone or in combination of two or more.

  In particular, diamino compounds that can be suitably used for the photosensitive resin composition of the present invention include m-phenylenediamine, bis (3-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, and 3,3′-diaminodiphenylmethane. Bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] methane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3 -Bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, etc. It is an aromatic diamine. Since the heat resistance of the cured film obtained by using said aromatic diamine improves, it is desirable.

  The isocyanate compound used as the component (B) in the present invention is a compound having two or more isocyanate groups.

  Examples of such isocyanate compounds include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, tetramethylxylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated xylylene diisocyanate. Diisocyanates such as alicyclic diisocyanates such as isophorone diisocyanate and norbornene diisocyanate, and aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate and lysine diisocyanate. In particular, the isocyanate compounds suitably used in the present invention are aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, and tetramethylxylene diisocyanate.

  It is preferable to use the isocyanate compound because high heat resistance can be imparted to the cured film obtained when the photosensitive resin composition is cured.

  Moreover, in this invention, the blocked isocyanate compound etc. which stabilized the said isocyanate type compound with the blocking agent can be used. The blocked isocyanate compound is a compound that is inactive at room temperature, and is heated to dissociate a blocking agent such as oximes, diketones, phenols, caprolactams, and regenerate isocyanate groups. Product names Duranate 17B-60PX, Duranate TPA-B80E, Duranate MF-B60X, Duranate MF-K60X, Duranate E402-B80T, Asahi Kasei Chemicals Co., Ltd. Trade names Takenate B-830, Takenate B- 815N, Takenate B-846N, Takenate B-882N, trade names Coronate AP-M, Coronate 2503, Coronate 2507, Coronate 2513, Coronate 2515, Million Over preparative MS-50 and the like. In particular, the blocked isocyanate compound suitably used in the present invention is a block isocyanate compound such as a hexamethylene diisocyanate type isocyanurate type, biuret type, adduct type, etc. in which the dissociation temperature of the blocking agent is 160 ° C. or less, hydrogenated diphenylmethane diisocyanate type, water It is an additive xylylene diisocyanate block isocyanate compound.

  The use of the above-mentioned blocked isocyanate compound is preferable because it can impart high adhesion to a substrate to the cured film obtained when the photosensitive resin composition is cured.

  These isocyanate compounds can be used alone or in combination of two or more.

  As the component (B), the diamino compound and the isocyanate compound may be used alone or in combination.

The blending amount of (B) diamino compound and / or isocyanate compound in the present invention is such that (A) component and (B) component in the photosensitive resin composition are:
(A) molar amount of tetracarboxylic dianhydride as component (A),
(B) the molar amount of the terminal isocyanate compound of component (A),
(C) (a) / ((b) + (c)) is 0.80 or more and 1.20 or less when the molar amount of the diamino compound and / or isocyanate compound of component (B) is used. It is preferable that it is blended.

  (B) By making the compounding quantity of a diamino compound and / or an isocyanate type compound into the said range, when thermosetting a photosensitive resin composition, an imidation reaction becomes easy to advance and a high molecular weight polyimide resin is obtained. Therefore, it is preferable because the heat resistance is improved.

<(C) Photosensitive resin>
The photosensitive resin (C) in the present invention is a resin in which a chemical bond is formed by a photopolymerization initiator. Among these, a resin having at least one unsaturated double bond in the molecule is preferable. Furthermore, the unsaturated double bond is an acryl group (CH ₂ ═CH— group), a methacryloyl group (CH═C (CH ₃ ) — group), or a vinyl group (—CH═CH— group). Is preferred.

  Examples of the photosensitive resin (C) include bisphenol F EO modified (n = 2 to 50) diacrylate, bisphenol A EO modified (n = 2 to 50) diacrylate, and bisphenol S EO modified (n = 2 to 50). Diacrylate, bisphenol F EO modified (n = 2-50) dimethacrylate, bisphenol A EO modified (n = 2-50) dimethacrylate, bisphenol S EO modified (n = 2-50) dimethacrylate, 1,6-hexane Diol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tetramethyl Propane tetraacrylate, tetraethylene glycol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, dipenta Erythritol hexamethacrylate, tetramethylolpropane tetramethacrylate, tetraethylene glycol dimethacrylate, methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, β-methacryloyloxyethyl hydrogen phthalate, β-methacryloyloxyethyl hydrogen succinate, 3-chloro-2- Hide Xylpropyl methacrylate, stearyl methacrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy polyethylene glycol acrylate, β-acryloyloxyethyl hydrogen succinate, lauryl acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2-hydroxy-1,3-dimethacryloxypropane, 2,2-bis [4- (Methacryloxyethoxy ) Phenyl] propane, 2,2-bis [4- (methacryloxy diethoxy) phenyl] propane, 2,2-bis [4- (methacryloxy polyethoxy) phenyl] propane, polyethylene glycol diacrylate, tripropylene glycol diacrylate, Polypropylene glycol diacrylate, 2,2-bis [4- (acryloxydiethoxy) phenyl] propane, 2,2-bis [4- (acryloxypolyethoxy) phenyl] propane, 2-hydroxy-1-acryloxy-3-methacryl Roxypropane, trimethylolpropane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetraacrylate, methoxydipropylene glycol methacrylate, methoxytriethylene group Cole acrylate, nonylphenoxy polyethylene glycol acrylate, nonyl phenoxy polypropylene glycol acrylate, 1-acryloyloxypropyl-2-phthalate, isostearyl acrylate, polyoxyethylene alkyl ether acrylate, nonylphenoxyethylene glycol acrylate, polypropylene glycol dimethacrylate, 1,4 -Butanediol dimethacrylate, 3-methyl-1,5-pentanediol dimethacrylate, 1,6-mexanediol dimethacrylate, 1,9-nonanediol methacrylate, 2,4-diethyl-1,5-pentanediol di Methacrylate, 1,4-cyclohexanedimethanol dimethacrylate, dipropylene glycol diacrylate, Tricyclodecane dimethanol diacrylate, 2,2-hydrogenated bis [4- (acryloxy polyethoxy) phenyl] propane, 2,2-bis [4- (acryloxy polypropoxy) phenyl] propane, 2,4-diethyl -1,5-pentanediol diacrylate, ethoxylated tomethylolpropane triacrylate, propoxylated tomethylolpropane triacrylate, isocyanuric acid tri (ethane acrylate), pentathritol tetraacrylate, ethoxylated pentathritol tetraacrylate, propoxylation Pentathritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol polyacrylate, triallyl isocyanurate, glycidyl methacrylate, glycidyl ali Ether, 1,3,5-triacryloylhexahydro-s-triazine, triallyl1,3,5-benzenecarboxylate, triallylamine, triallyl citrate, triallyl phosphate, arborbital, diallylamine, diallyldimethylsilane, diallyl Disulfide, diallyl ether, zalyl sialate, diallyl isophthalate, diallyl terephthalate, 1,3-dialyloxy-2-propanol, diallyl sulfide diallyl maleate, 4,4′-isopropylidene diphenol dimethacrylate, 4,4′-isopropyl Redene diphenol diacrylate and the like are preferable, but are not limited thereto. In particular, the repeating unit of EO (ethylene oxide) contained in one molecule of diacrylate or methacrylate is preferably in the range of 2-50, more preferably 2-40. By using an EO repeating unit in the range of 2 to 50, the solubility of the photosensitive resin composition in an aqueous developer typified by an alkaline aqueous solution is improved, and the development time is shortened. Furthermore, it is difficult for stress to remain in the cured film obtained by curing the photosensitive resin composition. For example, among the printed wiring boards, when laminated on a flexible printed wiring board based on a polyimide resin, curling of the printed wiring board is prevented. Features such as being able to be suppressed.

  In particular, it is particularly preferable to use the EO-modified diacrylate or dimethacrylate together with an acrylic resin having 3 or more acrylic groups or methacrylic groups in order to improve developability. For example, ethoxylated isocyanuric acid EO-modified triacrylate, Ethoxylated isocyanuric acid EO modified trimethacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol tri Acrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, ditrimethyl Propanetetraacrylate, ditrimethylolpropane tetraacrylate, propoxylated pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, 2,2,2-trisacryloyloxymethyl ethyl succinic acid, 2,2, 2-trisacryloyloxymethylethylphthalic acid, propoxylated ditrimethylolpropane tetraacrylate, propoxylated dipentaerythritol hexaacrylate, ethoxylated isocyanuric acid triacrylate, ε-caprolactone modified tris- (2-acryloxyethyl) isocyanurate, Caprolactone-modified ditrimethylolpropane tetraacrylate, the following general formula (8)

(Wherein a + b = 6 and n = 12.) A compound represented by the following general formula (9)

(Wherein a + b = 4 and n = 4), a compound represented by the following formula (10)

A compound represented by the following general formula (11)

(Where m = 1, a = 2, b = 4, or m = 1, a = 3, b = 3, or m = 1, a = 6, b = 0, or m = 2, a = 6 , B = 0)), a compound represented by the following general formula (12)

(Wherein a + b + c = 3.6), a compound represented by the following formula (13)

A compound represented by the following general formula (14)

An acrylic resin such as a compound represented by the formula (where m · a = 3, a + b = 3, where “m · a” is a product of m and a) is preferably used.

  In addition, hydroxyl groups in the molecular structure skeleton such as 2-hydroxy-3-phenoxypropyl acrylate, monohydroxyethyl acrylate phthalate, ω-carboxy-polycaprolactone monoacrylate, acrylic acid dimer, pentaerythritol tri and tetraacrylate, Those having a carbonyl group are also preferably used.

  In addition, any photosensitive resin such as an epoxy-modified acrylic (methacrylic) resin, a urethane-modified acrylic (methacrylic) resin, or a polyester-modified acrylic (methacrylic) resin may be used.

  In addition, although it is also possible to use 1 type as a photosensitive resin, using 2 or more types together is preferable when improving the heat resistance of the cured film after photocuring.

<(D) Photopolymerization initiator>
The (D) photopolymerization initiator in the present invention is a compound that is activated by energy such as UV and starts and accelerates the reaction of the photosensitive resin. Examples of the (D) photopolymerization initiator include, for example, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 4,4 ′, 4 ″ -tris (dimethylamino) triphenylmethane, and 2,2 ′. -Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-diimidazole, acetophenone, benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, Benzoin isopropyl ether, benzoin isobutyl ether, 2-t-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, methylanthraquinone, thioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 1- Hydroxycyclohexyl phenyl ketone, diacetylbenzyl, benzyldimethyl Ketal, benzyldiethylketal, 2 (2′-furylethylidene) -4,6-bis (trichloromethyl) -S-triazine, 2 [2 ′ (5 ″ -methylfuryl) ethylidene] -4, 6-bis (trichloromethyl) -S-triazine, 2 (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,6-di (p-azidobenzal) -4-methylcyclohexanone, 4,4′-diazidochalcone, di (tetraalkylammonium) -4,4′-diazidostilbene-2,2′-disulfonate, 2,2-dimethoxy-1,2-diphenylethane-1-one 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy)- Enyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2- Dimethylamino-1- (4-morpholinophenyl) -butane-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4- Trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, bis (n5-2,4-cyclopentadiene -1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, iododi And (4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate (1-), ethyl-4-dimethylaminobenzoate, 2-ethylhexyl-4-dimethylaminobenzoate, and the like. .

  (A) component, (B) component, (C) component, and (D) component in the photosensitive resin composition of this invention are with respect to 100 weight part of solid content which totaled (A) component and (B) component. (C) It is preferable to mix | blend so that 10-200 weight part and (D) component may be 0.1-50 weight part.

  The blending ratio is preferable because various properties (such as electrical insulation reliability) of the cured product and insulating film finally obtained are improved.

  (C) When the photosensitive resin is less than the above range, it is preferable because the heat resistance of the cured film after photocuring the photosensitive resin composition is lowered and the contrast when exposed and developed is difficult to be obtained. There may not be. For this reason, it is possible to set the resolution at the time of exposure / development to an optimal range by setting the value within the above range.

  (D) When there are few photoinitiators than the said range, the hardening reaction of the acrylic resin at the time of light irradiation hardly occurs, and hardening may become inadequate in many cases. Moreover, when there is too much, adjustment of light irradiation amount becomes difficult and may be in an overexposure state. Therefore, in order to advance the photocuring reaction efficiently, it is preferable to adjust within the above range.

<Thermosetting resin>
For the photosensitive resin composition of the present invention, a thermosetting resin can be used for the purpose of improving heat resistance, chemical resistance and electrical insulation reliability.

  The thermosetting resin in the present invention is a compound that generates a crosslinked structure by heating and functions as a thermosetting agent. For example, thermosetting resins such as epoxy resin, bismaleimide resin, bisallyl nadiimide resin, acrylic resin, methacrylic resin, hydrosilyl cured resin, allyl cured resin, unsaturated polyester resin; allyl on the side chain or terminal of polymer chain A side chain reactive group type thermosetting polymer having a reactive group such as a group, a vinyl group, an alkoxysilyl group, and a hydrosilyl group can be used. The thermosetting resin may be used alone or in combination of two or more.

  Among these, it is more preferable to use an epoxy resin as the thermosetting resin. By containing an epoxy resin component, heat resistance can be imparted to a cured film obtained by curing the photosensitive resin composition, and adhesion to a conductor such as a metal foil or a circuit board can be imparted.

  The epoxy resin is a compound containing at least two epoxy groups in the molecule. For example, as a bisphenol A type epoxy resin, product names jER828, jER1001, jER1002, and ADEKA manufactured by Japan Epoxy Resin Co., Ltd. Trade names of Adeka Resin EP-4100E, Adeka Resin EP-4300E, trade names RE-310S and RE-410S manufactured by Nippon Kayaku Co., Ltd., trade names Epicron 840S, Epicron 850S, Epicron 1050 and Epicron 7050 manufactured by Dainippon Ink, Inc. The product names Epototo YD-115, Epototo YD-127, Epototo YD-128, and bisphenol F type epoxy resins manufactured by Toto Kasei Co., Ltd. are trade names jER806 and jER8 manufactured by Japan Epoxy Resin Co., Ltd. 7. Trade names Adeka Resin EP-4901E, Adeka Resin EP-4930, Adeka Resin EP-4950, manufactured by Adeka Co., Ltd., trade names RE-303S, RE-304S, RE-403S, RE-404S, manufactured by Nippon Kayaku Co., Ltd. Product names Epicron 830 and Epicron 835 manufactured by Nippon Ink Co., Ltd. Product names Epototo YDF-170, Epototo YDF-175S, Epototo YDF-2001, and Bisphenol S type epoxy resin manufactured by Toto Kasei Co., Ltd. Trade name Epiklon EXA-1514 manufactured by Japan, Hydrogenated bisphenol A type epoxy resin includes Japan Epoxy Resin Co., Ltd. trade names jERYX8000, jERYX8034, jERYL7170, ADEKA Co., Ltd. trade names Adeka Resin P-4080E, Dainippon Ink Co., Ltd. trade name Epicron EXA-7015, Toto Kasei Co., Ltd. trade name Epototo YD-3000, Epototo YD-4000D, biphenyl type epoxy resin, manufactured by Japan Epoxy Resin Co., Ltd. Trade names jERYX4000, jERYL6121H, jERYL6640, jERYL6677, trade names NC-3000 and NC-3000H manufactured by Nippon Kayaku Co., Ltd., and phenoxy type epoxy resins include trade names jER1256, jER4250, jER4275, and naphthalene manufactured by Japan Epoxy Resins Co., Ltd. As the type epoxy resin, trade names “Epicron HP-4032”, “Epicron HP-4700”, “Epicron HP-4200” manufactured by Dainippon Ink Co., Ltd., “NC-” manufactured by Nippon Kayaku Co., Ltd. As 7000L, phenol novolac type epoxy resin, trade names jER152 and jER154 manufactured by Japan Epoxy Resin Co., Ltd., trade name EPPN-201-L manufactured by Nippon Kayaku Co., Ltd., trade name Epicron N- manufactured by Dainippon Ink Co., Ltd. 740, Epicron N-770, Toto Kasei Co., Ltd. trade name Epototo YDPN-638, Cresol novolac type epoxy resin, Nippon Kayaku Co., Ltd. trade names EOCN-1020, EOCN-102S, EOCN-103S, EOCN -104S, trade names manufactured by Dainippon Ink Co., Ltd. Epicron N-660, Epicron N-670, Epicron N-680, Epicron N-695, and Trisphenolmethane type epoxy resin are trade names of Nippon Kayaku Co., Ltd. EPPN-501H, EPP -501HY, EPPN-502H, dicyclopentadiene type epoxy resin, Nippon Kayaku Co., Ltd. trade name XD-1000, Dainippon Ink Co., Ltd. trade name Epicron HP-7200, amine type epoxy resin, Product names of Toto Kasei Co., Ltd. Epototo YH-434, Epototo YH-434L, and flexible epoxy resins include trade names jER871, jER872, jERYL7175, jERYL7217, manufactured by Dainippon Ink, Inc. As the name Epicron EXA-4850, urethane-modified epoxy resin, trade names of Adeka Resin EPU-6, Adeka Resin EPU-73, Adeka Resin EPU-78-11 manufactured by ADEKA Corporation, and ADE Co., Ltd. as ADE Co., Ltd. Product names Adeka Resin EPR-4023, Adeka Resin EPR-4026, Adeka Resin EPR-1309, and chelate-modified epoxy resins manufactured by A include Adeka Resin EP-49-10, Adeka Resin EP-49-20, etc., manufactured by ADEKA Corporation. It is done.

  Although it does not specifically limit as a hardening | curing agent of the said thermosetting compound in the photosensitive resin composition of this invention, For example, phenol resins, such as a phenol novolak resin, a cresol novolak resin, a naphthalene type phenol resin, an amino resin, and a urea resin , Melamine, dicyandiamide and the like, and these can be used alone or in combination of two or more.

  Further, the curing accelerator is not particularly limited, but for example, phosphine compounds such as triphenylphosphine; amine compounds such as tertiary amine, trimethanolamine, triethanolamine and tetraethanolamine; 1,8- Borate compounds such as diaza-bicyclo [5,4,0] -7-undecenium tetraphenylborate, imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-un Imidazoles such as decylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole; 2-methylimidazoline, 2- Ethyl imidazoline, 2 Imidazolines such as isopropylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline; 2,4-diamino-6- [2′-methylimidazolyl- ( 1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2 ′ Examples include azine-based imidazoles such as -ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, and these can be used alone or in combination of two or more.

  The thermosetting resin in the photosensitive resin composition of the present invention is preferably 0.5 parts per 100 parts by weight of the sum of the components (A), (B), (C), and (D). -100 parts by weight, more preferably 1-50 parts by weight, particularly preferably 5-20 parts by weight.

  It is preferable because the heat resistance, chemical resistance, and electrical insulation reliability of the cured film obtained by curing the photosensitive resin composition can be improved by adjusting the amount of the thermosetting resin within the above range. .

  If the thermosetting resin is less than the above range, the cured film obtained by curing the photosensitive resin composition may be inferior in heat resistance and electrical insulation reliability. Moreover, when there are more thermosetting resins than the said range, the cured film obtained by hardening the photosensitive resin composition becomes weak, it is inferior to a softness | flexibility, and the curvature of a cured film may also become large.

  The photosensitive resin composition of the present invention has high solubility in various organic solvents, for example, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, and formamide systems such as N, N-dimethylformamide and N, N-diethylformamide. Solvents, acetamide solvents such as N, N-dimethylacetamide, N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, o-, m- or Phenolic solvents such as p-cresol, xylenol, halogenated phenol, catechol, or hexamethylphosphoramide, γ-butyrolactone, methylmonoglyme (1,2-dimethoxyethane), methyldiglyme (bis (2-methoxyether) ) Ether), Methylto Glyme (1,2-bis (2-methoxyethoxy) ethane), methyltetraglyme (bis [2- (2-methoxyethoxyethyl)] ether), ethyl monoglyme (1,2-diethoxyethane), ethyl dig Symmetric glycol diethers such as lime (bis (2-ethoxyethyl) ether), butyldiglyme (bis (2-butoxyethyl) ether), γ-butyrolactone, N-methyl-2-pyrrolidone, methyl acetate, ethyl acetate , Isopropyl acetate, n-propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate (also known as carbitol acetate, 2- (2-butoxyethoxy) acetate )), Acetates such as diethylene glycol monobutyl ether acetate, 3-methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate Dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripylene glycol n-propyl ether , Propylene glycol phenyl ether, dipropylene glycol Lumpur dimethyl ether, 1,3-dioxolane, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, can be used diethylene glycol monobutyl ether, a solvent of ethers such as ethyl ether also ethylene glycol. In addition, as said solvent, low boiling point hexane, acetone, toluene, xylene etc. can be used together as needed.

  Among these, symmetric glycol diethers are particularly preferable because the photosensitive resin composition has high solubility.

  The resin composition solution obtained by dissolving the photosensitive resin composition of the present invention in an organic solvent has an organic solvent content of 10 parts by weight or more with respect to 100 parts by weight of the total solid content of the components (A) to (D). It is preferable that it is blended at 100 parts by weight or less.

  A resin composition solution within this range is desirable because the film reduction rate after drying is reduced.

  In the photosensitive resin composition of the present invention, an inorganic filler can be used for the purpose of improving the adhesion and the hardness of the cured film. The inorganic filler is not particularly limited, and examples thereof include barium sulfate, barium titanate, talc, ultrafine anhydrous silica, synthetic silica, natural silica, calcium carbonate, magnesium carbonate, and aluminum oxide. It can be used alone or in combination of two or more.

  In the photosensitive resin composition of the present invention, additives such as an antifoaming agent, a leveling agent, a flame retardant, a colorant, an adhesion imparting agent, and a polymerization inhibitor can be used as necessary. These additives are not particularly limited. For example, as an antifoaming agent, a silicon compound, an acrylic compound, as a leveling agent, as a silicon compound, an acrylic compound, and as a flame retardant, for example, phosphoric acid Ester compounds, halogen-containing compounds, metal hydroxides, organophosphorus compounds, etc., as colorants, phthalocyanine compounds, azo compounds, carbon black, titanium oxide, as adhesion promoters, silane coupling agents Examples of the triazole compound, tetrazole compound, triazine compound, and polymerization inhibitor include hydroquinone and hydroquinone monomethyl ether, and these can be used alone or in combination of two or more.

  The photosensitive resin composition of the present invention is obtained by uniformly mixing the components (A) to (D). As a method of uniformly mixing, for example, a general kneading apparatus such as a three roll or bead mill apparatus may be used for mixing. Moreover, when the viscosity of a solution is low, you may mix using a general stirring apparatus.

  A pattern comprising a cured film formed from the photosensitive resin composition of the present invention is excellent in heat resistance, flame retardancy, electrical and mechanical properties, and is particularly excellent in flexibility. For example, the insulating film of the present invention preferably has a thickness of about 2 to 50 μm and a resolution of at least 10 μm after photocuring, and particularly a resolution of about 10 to 1000 μm. For this reason, the insulating film of the present invention is particularly suitable as an insulating material for a high-density flexible substrate. Furthermore, it is used for various photo-curing type wiring coating protective agents, photosensitive heat-resistant adhesives, electric wire / cable insulation coatings, and the like.

  In addition, this invention can provide the same insulating material even if it uses the photosensitive film obtained by apply | coating the said photosensitive resin composition to the base-material surface, and drying.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

<Synthesis of imidized tetracarboxylic acid>
[Synthesis Example 1]
In a separable flask pressurized with nitrogen, methyltriglyme (17.5 g) was charged as a solvent for polymerization, and 20.7 g (0.1004 mol) of norbornene diisocyanate was charged therein and heated to 80 ° C. And dissolved. To this solution, 50.0 g (0.025 mol) of polycarbonate diol (manufactured by Asahi Kasei Co., Ltd .: trade name PCDL T5652, polycarbonate diol represented by the following general formula (15), average molecular weight 2000) and dimethylolbutane A solution of 8.1 g (0.050 mol) of acid (2,2-bis (hydroxymethyl) butanoic acid) in methyltriglyme (50.0 g) was added over 1 hour.

(In the formula, q, r, and s are integers of 1 or more.)
This solution was heated to reflux for 5 hours. The above reaction solution is referred to as Intermediate A.

  In a reactor different from the reactor used for the above reaction, 52.0 g of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride (hereinafter abbreviated as BPADA) ( 0.100 mol) and methyltriglyme (52.0 g) were added, heated to 80 ° C. and dispersed in methyltriglyme.

  The intermediate A was added to the solution over 1 hour and allowed to react. After the addition, the mixture was heated to 200 ° C. and reacted for 3 hours. The terminal acid anhydride urethane imide oligomer solution was obtained by performing the said reaction. To this solution, 7.2 g (0.400 mol) of pure water was added and heated to reflux at 80 ° C. for 5 hours to obtain a terminal carboxylic acid urethane imide oligomer solution. This synthetic resin is abbreviated as resin A.

<Preparation of photosensitive resin composition>
Add (A) imidized tetracarboxylic acid solution obtained in Synthesis Example 1, (B) diamino compound and / or isocyanate compound, (C) photosensitive resin, (D) photopolymerization initiator and other components. Thus, a photosensitive resin composition was prepared. Table 1 shows the blending amount of each constituent raw material in the resin solid content and the kind of the raw material. In addition, 1,2-bis (2-methoxyethoxy) ethane which is a solvent in the table is the total amount of solvent including the solvent and the like contained in the above synthetic resin solution and the like. The following evaluation was carried out by completely defoaming the foam in the solution with a defoaming device.

<1> Product name NK ester A-9300 (ethoxylated isocyanuric acid triacrylate) manufactured by Nakamura Chemical Co., Ltd.
<2> Nakamura Chemical Co., Ltd. Product name NK ester BPE-1300 (bisphenol A EO-modified diacrylate) Molecular weight: 1684
<3> Product name of photopolymerization initiator manufactured by Ciba Specialty Chemicals <4> Product name of silica particles manufactured by Nippon Aerosil Co., Ltd.

[Example 1]
<Preparation of coating film on polyimide film>
The adjusted photosensitive resin composition was printed on a 75 μm polyimide film (manufactured by Kaneka Corporation: trade name 75NPI) in an area of 100 mm × 100 mm so that the final dry thickness was 25 μm, and dried at 80 ° C. for 20 minutes. Thereafter, a negative photomask with a line width / space width of 50 mm × 50 mm = 100 μm / 100 μm was placed and irradiated with ultraviolet rays with an integrated exposure amount of 300 mJ / cm ² to be exposed. Subsequently, spray development was performed for 60 seconds at a discharge pressure of 1.0 kgf / mm ² using a solution obtained by heating a 1.0 wt% sodium carbonate aqueous solution to 30 ° C. Next, after thoroughly washing with pure water, a spray solution of 0.05 M hydrochloric acid, which is an aqueous solution containing an acidic compound, is used as a cleaning solution and sprayed at 30 ° C. for 180 seconds at a discharge pressure of 1.0 kgf / mm ^2. Washing was performed. Next, after sufficiently washing with pure water, it was cured by heating in an oven at 160 ° C. for 90 minutes to produce a cured film of the photosensitive resin composition. Table 2 shows the concentration of the aqueous hydrochloric acid solution contained in the cleaning solution.

[Examples 2 to 4]
A cured film of the photosensitive resin composition was produced in the same manner as in the above item <Preparation of coating film on polyimide film> while changing the concentration and type of acidic compound contained in the cleaning liquid. Table 2 shows the concentrations and types of acidic compounds contained in the cleaning liquid.

[Examples 5 to 6]
The same method as the above item <Preparation of coating film on polyimide film> by changing calcium chloride to an aqueous solution in which calcium ions are dissolved in pure water in amounts of 500 ppm and 1000 ppm in the cleaning solution as the cleaning solution A cured film of the photosensitive resin composition was prepared. Table 3 shows the concentration of calcium ions contained in the cleaning liquid.

[Examples 7 to 8]
The same method as the above item <Preparation of coating film on polyimide film>, except that magnesium sulfate is changed to an aqueous solution in which magnesium ions are 500 ppm and 1000 ppm dissolved in pure water. A cured film of the photosensitive resin composition was prepared. Table 3 shows the concentration of magnesium ions contained in the cleaning liquid.

<Evaluation of cured film>
The obtained cured film was evaluated for the following items. The evaluation results are shown in Table 4.

(I) Photosensitivity evaluation The photosensitivity evaluation of the photosensitive resin composition was determined by observing the surface of the cured film obtained in the above item <Preparation of coating film on polyimide film>.
◯: A clear photosensitive pattern with a line width / space width = 100/100 μm is drawn on the polyimide film surface, the line does not shake due to the peeling of the line portion, and there is no residual residue in the space portion. Things Δ: A clear line width / space width = 100/100 μm photosensitive pattern is drawn on the surface of the polyimide film, and there is a fluctuation of the line due to peeling in the line portion, but there is a dissolution residue in the space portion. None x: Clear line width / space width = 100/100 μm photosensitive pattern is not drawn on the polyimide film surface, the line portion is peeled off, and dissolution residue is generated in the space portion thing

(Ii) Adhesiveness of cured film The adhesive strength of the cured film obtained in the above item <Preparation of coating film on polyimide film> was evaluated by a cross-cut tape method according to JIS K5400.
○: No peeling by cross-cut tape method Δ: 95% or more of the squares remain ×: The residual quantity of the squares is less than 80%

(Iii) Solvent resistance The solvent resistance of the cured film obtained in the above item <Preparation of coating film on polyimide film> was evaluated. In the evaluation method, the film was dipped in methyl ethyl ketone at 25 ° C. for 15 minutes and then air-dried to observe the state of the film surface.
○: There is no abnormality in the coating film.
X: Abnormality such as swelling or peeling occurs in the coating film.

(Iv) Flexibility A cured film laminated film of a photosensitive resin composition on the surface of a polyimide film having a thickness of 25 μm (Apical 25NPI manufactured by Kaneka Corporation) in the same manner as in the above item <Preparation of coating film on polyimide film>. Was made. The cured film laminated film was cut into a 30 mm × 10 mm strip, bent 10 times at 180 ° at 15 mm, and the coating film was visually confirmed to check for cracks.
○: The cured film has no cracks Δ: The cured film has some cracks ×: The cured film has cracks

(V) Insulation reliability Line width / space width = 100 μm on flexible copper-clad laminate (copper foil thickness 12 μm, polyimide film is Apical 25 NPI manufactured by Kaneka Co., Ltd., and copper foil is bonded with polyimide adhesive) A / 100 μm comb-shaped pattern was prepared, immersed in a 10% by volume sulfuric acid aqueous solution for 1 minute, washed with pure water, and subjected to a copper foil surface treatment. Then, the cured film of the photosensitive resin composition was produced on the comb pattern by the method similar to the above-mentioned <Preparation of the coating film on a polyimide film> method, and the test piece was adjusted. A 100 V direct current was applied to both terminals of the test piece in an environmental test machine at 85 ° C. and 85% RH, and changes in the insulation resistance value and occurrence of migration were observed.
○: A resistance value of 10 8 or more in 1000 hours after the start of the test and no occurrence of migration, dendrite, etc. ×: An occurrence of migration, dendrite, etc. in 1000 hours after the start of the test

(Vi) Wettability The wettability of the cured film obtained in the above item <Preparation of coating film on polyimide film> was evaluated according to JIS K6768.

(Vii) Solder heat resistance A cured film of a photosensitive resin composition is laminated on the surface of a 75 μm-thick polyimide film (Apical 75NPI manufactured by Kaneka Corporation) in the same manner as in the above item <Preparation of coating film on polyimide film>. A film was prepared.

The coated film was floated so that the surface coated with the cured film of the photosensitive resin composition was in contact with a solder bath completely dissolved at 260 ° C., and then pulled up 10 seconds later. The operation was performed three times, and the adhesive strength of the cured film was evaluated by a cross-cut tape method according to JIS K5400.
○: No peeling by cross-cut tape method Δ: 95% or more of the squares remain ×: The residual quantity of the squares is less than 80%

(Viii) Warpage A cured film laminated film of a photosensitive resin composition is applied to the surface of a 25 μm-thick polyimide film (Apical 25NPI manufactured by Kaneka Corporation) in the same manner as in the above item <Preparation of coating film on polyimide film>. Produced.

  The cured film was cut into a film having an area of 50 mm × 50 mm and placed on a smooth table so that the coating film was on the upper surface, and the warp height of the film edge was measured. A schematic diagram of the measurement site is shown in FIG. The smaller the amount of warpage on the polyimide film surface, the smaller the stress on the surface of the printed wiring board and the lower the amount of warping of the printed wiring board. The warp amount is preferably 5 mm or less.

[Comparative Example 1]
A glass flask having a capacity of 2000 ml was charged with 176.09 g (598.5 mmol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 254.26 g of methyltriglyme under a nitrogen atmosphere at 180 ° C. And stirred with heating. α, ω-bis (3-aminopropyl) polydimethylsiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., KF8010, average molecular weight 830) 250.25 g (301.5 mmol) and 100 g of methyltriglyme were added and stirred uniformly at 180 ° C. for 60 minutes. Went. Further, 42.51 g (148.5 mmol) of bis (3-carboxy, 4-aminophenyl) methane and 100 g of methyltriglyme were added to this reaction solution, and the mixture was heated and stirred at 180 ° C. for 6 hours. This solution is a half-esterified solution.

  Separately from the above reaction apparatus, in a glass container with a capacity of 500 ml blocked from light, isocyanuric acid tris (2-acryloyloxyethyl) [manufactured by Toagosei Co., Ltd., M-315] 126.9 g (300 mmol) and methyl jig 120 g of lime was charged and stirred and dissolved at room temperature in a nitrogen atmosphere. Next, 83.0 g (100 mmol) of α, ω-bis (3-aminopropyl) polydimethylsiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., KF8010, average molecular weight 830) and 52.9 g of diglyme were added, and the mixture was further stirred for 2 hours. A reaction solution of a photosensitive monomer in which one tris (2-acryloyloxyethyl) isocyanurate was added to both ends of diaminopolysiloxane was obtained. This solution is used as a photosensitive monomer solution.

  Next, 1.25 g of 2-hydroxyethyl methacrylate and 15.39 g of a photosensitive monomer solution are added to 50 g of this half esterified solution, and 2.57 g and 2 of Irgacure 907 (manufactured by Ciba Specialty Chemicals Co., Ltd.) are used as a photopolymerization initiator. , 4-Diethylthioxanthone (Nippon Kayaku Co., Ltd., DETX) 0.51 g, p-dimethylaminobenzoic acid ethyl ester (Nippon Kayaku Co., Ltd., EDMAB) 1.02 g, Silicone defoamer (Dow Corning, (DB-100) 0.13 g, Aerosil (average particle size: 0.01 μm) 2.56 g, and talc (average particle size: 1.8 μm) 5.19 g were charged and stirred at room temperature (25 ° C.) for 2 hours. The mixture was allowed to stand for 1 hour, and then uniformly mixed by a three roll mill to obtain a photosensitive imidosiloxane oligomer composition.

  50 g of this photosensitive imidosiloxane oligomer composition, 3.2 g of epoxy resin (Japan Epoxy Resin Co., Ltd., Epicoat 152) and 0.032 g of 2-ethyl-4-methylimidazole were added and stirred at room temperature for 1 hour, A functional resin composition was obtained.

  The physical properties of this composition were evaluated in the same manner as in Example 1. The results are listed in Table 5.

[Comparative Example 2]
After introducing air into a reaction vessel equipped with a stirrer, a thermometer, a cooling tube and an air introduction tube, 196.8 parts of polycarbonate diol (Daicel Chemical Industries, Plaxel CD205PL, average molecular weight 500), dimethylolbutanoic acid ( (Mitsubishi Chemical Corporation) 58.3 parts, diethylene glycol (Nisso Maruzen Chemical Co., Ltd.) 37.6 parts, 1,4-cyclohexanedimethanol monoacrylate (Mitsubishi Chemical Corporation) 148.1 parts, 0.55 part of p-methoxyphenol (manufactured by Wako Pure Chemical Industries, Ltd.), 0.55 part of dibutyltin laurate (manufactured by Tokyo Fine Chemical Co., Ltd., L101) and 110.2 parts of methyl ethyl ketone (manufactured by Tonen Chemical Co., Ltd.) Was heated to 65 ° C. with stirring under an air stream. 305.9 parts of trimethylhexamethylene diisocyanate (manufactured by Huls Japan Co., Ltd., VESTANATMTMDI) was charged into the dropping container, and uniformly dropped into the reaction container over 3 hours while maintaining the temperature at 65 ± 3 ° C. After completion of the dropping, the dropping container was washed with 76.5 parts of methyl ethyl ketone, and the washing solution was directly put into the reaction container. The mixture was further kept warm for 2 hours with stirring, and then heated to 75 ° C. Thereafter, stirring and heating were continued at 75 ± 3 ° C. until the isocyanate peak in the infrared absorption spectrum disappeared. The isocyanate peak disappeared in about 6 to 8 hours. After confirming the disappearance of this peak, the temperature was lowered to 60 ° C., 9.3 parts of methanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was kept at 60 ± 3 ° C. for 30 minutes. Thereafter, 56.4 parts of methyl ethyl ketone was added to obtain a transparent resin solution. This resin had a solid content of 75.6%, an acid value of 22.2 mg KOH / g, and a viscosity of 1,810 cP. 62.5 g of the obtained resin solution (solid content 50 g), 2,2′-bis (4-methacryloxypentaethoxyphenyl) propane 30 g, (methacrylic acid, methyl methacrylate and butyl acrylate in a weight ratio of 22:71 : A copolymer having a weight average molecular weight of 80,000 and an acid value of 143 mgKOH / g copolymerized at a ratio of 7 was dissolved in methyl cellosolve / toluene (6/4, weight ratio) to a solid content of 40% by weight. 162.5 g (solid content 65 g), benzophenone 3.5 g, N, N′-tetraethyl-4,4′-diaminobenzophenone 0.1 g, hexamethylene-based isocyanurate type isocyanate compound is reacted with methyl ethyl ketone oxime. 20 g of a 75 wt% methyl ethyl ketone solution of the blocked isocyanate compound obtained 15g), CR747 (condensed phosphoric acid ester-based additive-type flame retardant) 40 g, and stirred for 1 hour at room temperature in acetone 85 g, to obtain a photosensitive resin composition.

  The physical properties of this composition were evaluated in the same manner as in Example 1. The results are listed in Table 5.

Schematic diagram measuring the amount of warping of the film

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Polyimide film which laminated the photosensitive resin composition 2 Warpage amount 3 Smooth stand

Claims (6)

  At least (1) a step of forming a coating film on the substrate using the photosensitive resin composition, (2) an exposure step, and further (3) an alkali development step, (4) A method of manufacturing a circuit board comprising: (5) forming a cured photosensitive resin composition film on a substrate by a thermosetting process after passing through a process of removing the mixed ionic impurities by washing. The photosensitive resin composition contains at least (A) an imidized tetracarboxylic acid, (B) a diamino compound and / or an isocyanate compound, (C) a photosensitive resin, and (D) a photopolymerization initiator. A method of manufacturing a circuit board.   The method for producing a circuit board according to claim 1, wherein the (A) imidized tetracarboxylic acid is a tetracarboxylic acid urethane imide oligomer.   3. The cleaning solution used in the step (4) of removing by washing ionic impurities mixed in the coating film during alkali development is an aqueous solution containing an acidic compound. Circuit board manufacturing method.   The method for manufacturing a circuit board according to claim 3, wherein the concentration of the aqueous solution containing the acidic compound is 0.005 to 0.5M.   The cleaning liquid used in the step (4) of removing the ionic impurities mixed in the coating during the alkali development by washing is an aqueous solution containing calcium ions and / or magnesium ions. Item 3. A circuit board manufacturing method according to Item 1 or 2.   6. The method of manufacturing a circuit board according to claim 5, wherein the ion concentration of the aqueous solution containing calcium ions and / or magnesium ions is 50 to 5000 ppm.