JP2019032474A - Photosensitive resin composition, dry film, cured product, and printed wiring board - Google Patents

Abstract

A photosensitive resin composition, a dry film, and a photosensitive resin composition capable of suppressing clogging of a developing device due to contamination of a developing solution and precipitates in a developing process while satisfying high resolution of a coating film after main curing. To provide a cured product. A photosensitive resin composition containing an alkali-soluble resin, wherein the contact angle of water on the dried coating film when the coating film formed by applying the photosensitive resin composition is dried at 80 ° C. for 40 minutes. A (°), when the contact angle of water in the dried coating film when the coating film formed by applying the photosensitive resin composition is dried at 80 ° C. for 70 minutes is B (°), A is 75. 0.080 or more, and a rate of change R80 represented by R80 (%) = | (BA) / A | × 100 is 3.0 or less, which is a photosensitive resin composition. [Selection diagram] None

Description

  The present invention relates to a photosensitive resin composition, and more particularly to an alkali development type photosensitive resin composition containing an alkali-soluble resin, a dry film, a cured product, and a printed wiring board.

  In recent years, there has been an increasing demand for miniaturization, high density, high definition, etc. in mobile phones, personal computers, touch panel displays, etc., and insulation such as solder resist, coverlay and interlayer insulation of printed wiring boards formed on these. Refinement of layers, conductive circuits, electrodes, and the like has been increasingly demanded.

  In response to such a demand, in order to apply a photolithography method capable of high-definition patterning compared to the pattern printing method, an insulating layer or a conductive circuit using an insulating paste or a conductive paste made of a photosensitive resin composition is used. (For example, refer to Patent Documents 1 to 6). In consideration of environmental problems, both alkaline development type insulating pastes and conductive pastes using a dilute alkaline aqueous solution as a developing solution at the time of development are mainly used.

JP 2014-101212 A JP2013-137511A JP 2013-136727 A International Publication No. 2010/113287 Pamphlet JP 2014-167090 A Japanese Patent Laying-Open No. 2015-026013

  However, the alkali development type photosensitive resin composition used in the insulating paste and the conductive paste as described above, the components of the photosensitive resin composition dissolved in the developer in the development step are precipitated at the bottom of the developer, There was a problem of contaminating the developer. When the contamination of the developing solution proceeds, the developing device is also contaminated and the developing ability is lowered. In addition, there has been a problem that the component precipitated in the developer becomes a residue and the developing device is clogged. For this reason, there is a problem that workability is inferior because it is necessary to increase the replacement frequency of the developer or to clean the developing device in a short period of time in order not to lower the developing ability.

  Accordingly, an object of the present invention is to provide a photosensitive resin composition capable of suppressing contamination of the developing solution and clogging of the developing device due to precipitates in the developing process while satisfying the high resolution of the coating film after the main curing. It is in providing a dry film and hardened | cured material.

  By the way, when developing the dry coating film of the photosensitive resin composition, a development management width (hereinafter also referred to as development life) is provided. The development management width refers to the width of the drying time when the coating film formed by coating is dried. When the development control width of the dried coating film is wide, the drying time when drying the coating film formed by coating can be extended, and thus the residual solvent in the photosensitive resin composition can be sufficiently volatilized. Therefore, the coating film properties such as photocurability and finger drying are improved. Therefore, a development management width of a certain level or more is required for process management. The inventors of the present invention have stated that the development control range based on the thermal history when drying the coating film formed using the photosensitive resin composition is caused by contamination of the developer in the development process or clogging of the developing device due to precipitates. I found out. That is, when the development management width is narrow, the development state is worse than that with a wide development management width, and the state of the dry coating film to be developed is different, so that precipitates are easily generated, and the developer is contaminated. Furthermore, it has been found that clogging of the developing device occurs.

  Furthermore, as a result of diligent research, the present inventors focused on the contact angle of water in the dried coating film of the photosensitive resin composition, the contact angle of water shows a specific numerical value, and satisfies a specific formula, The inventors have obtained knowledge that a photosensitive resin composition can be provided with a certain development life or more and can solve the above-mentioned problems. The present invention is based on such knowledge.

That is, the photosensitive resin composition of the present invention is a photosensitive resin composition containing an alkali-soluble resin,
The contact angle of water in the dried coating film when the coating film formed by application of the photosensitive resin composition is dried at 80 ° C. for 40 minutes is A (°),
When the contact angle of water in the dry coating film when the coating film formed by application of the photosensitive resin composition is dried at 80 ° C. for 70 minutes is B (°),
A is 75.0 ° or more,
R ₈₀ (%) = | (B−A) / A | × 100
The change rate R ₈₀ represented by the _formula is 3.0 or less.

The photosensitive resin composition of the present invention is a photosensitive resin composition containing an alkali-soluble resin,
The contact angle of water in the dried coating film when the coating film formed by application of the photosensitive resin composition is dried at 90 ° C. for 20 minutes is C (°),
When the contact angle of water in the dry coating film when the coating film formed by application of the photosensitive resin composition is dried at 90 ° C. for 35 minutes is defined as D (°),
C is 75.0 ° or more,
R ₉₀ (%) = | (D−C) / C | × 100
The change rate R ₉₀ represented by the formula is characterized by being 3.0 or less.

  Moreover, the dry film by another aspect of this invention has a resin layer obtained by apply | coating the said photosensitive resin composition to a film, and drying, It is characterized by the above-mentioned.

  Moreover, the hardened | cured material by another aspect of this invention is obtained by hardening the said photosensitive resin composition or the said dry film, It is characterized by the above-mentioned.

  Furthermore, the printed wiring board by another aspect of this invention has the said hardened | cured material, It is characterized by the above-mentioned.

  According to the present invention, a photosensitive resin composition capable of suppressing clogging of a developing device due to contamination of a developing solution and a precipitate in a developing process while satisfying high resolution of a coating film after main curing, Dry films and cured products can be provided.

The photosensitive resin composition by the 1st Embodiment of this invention contains alkali-soluble resin, and the contact angle of water at the time of setting it as a dry coating film has a specific relationship. That is, the photosensitive resin composition of the present invention has a water contact angle A (°) in the dry coating film when the coating film formed by application of the photosensitive resin composition is dried at 80 ° C. for 40 minutes. When the contact angle of water in the dry coating film when the coating film formed by application of the conductive resin composition is dried at 80 ° C. for 70 minutes is B (°),
A is 75.0 ° or more,
R ₈₀ (%) = | (B−A) / A | × 100
The change rate R ₈₀ represented by the formula is characterized by being 3.0 or less.

Further, the photosensitive resin composition according to the second embodiment of the present invention contains an alkali-soluble resin, and when a coating film formed by applying the photosensitive resin composition is dried at 90 ° C. for 20 minutes. The contact angle of water in the dried coating film was C (°), and the contact angle of water in the dried coating film when the coating film formed by applying the photosensitive resin composition was dried at 90 ° C. for 35 minutes was D (° ), And
C is 75.0 ° or more,
R ₉₀ (%) = | (D−C) / C | × 100
The change rate R ₉₀ represented by the formula is characterized by being 3.0 or less.

  As a result of diligent research, the present inventors have been able to provide a development life of a certain level or more when the contact angle of water in the dry coating film of the photosensitive resin composition satisfies the relationship as described above. It has been found that the developing device is prevented from being clogged with contamination and precipitates. The reason for this is not necessarily clear, but is considered as follows. In general, a small contact angle with water is hydrophilic. However, in the case of a dry coating film, if the hydrophilicity is strong, there is a problem that the alkali developer is easily adapted to the dry coating film, which makes it difficult to develop. In the present invention, when the contact angle of water in the dry coating film of the photosensitive resin composition is 75.0 ° or more, the alkali developer becomes intimately compatible with the dry coating film of the composition and is easily developed. Become. Furthermore, even if the drying conditions when forming the dried coating film are changed, by maintaining the state, an appropriate development state can be maintained, and as a result, a precipitate due to the developed dried coating film is hardly generated. Thus, it is presumed that the developer is not contaminated and the developing device is not clogged. However, the mechanism described above is only a guess of the present inventors, and is not necessarily bound by this theory.

Here, the contact angle is defined in JIS R3257: 1999, and in the present invention, the contact angle is defined by the contact angle of water. In the present invention, water means ion-exchanged water. Specifically, the quality of treated water produced by an apparatus (Purelite PRO-0250-003 manufactured by Organo Corporation) is 1 μS / cm or less. Use water. The following method is mentioned as an example of the measuring method.
The contact angle of water can be measured and analyzed by a perfect circle fitting method under the following conditions using DropMaster DM300 as a contact angle meter and FAMS (both manufactured by Kyowa Interface Science Co., Ltd.) as an interface measurement analysis comprehensive system.
<Measurement conditions and measurement method>
First, start up the interface measurement analysis integrated system and start up the CA / PD controller. At that time, “standard” is selected as the “field of view” on the controller screen. Next, ion-exchanged water is put into a plastic syringe, and a stainless needle (22 gauge) is attached to the tip of the ion-exchanged water and dropped onto the surface of the test piece (the surface of the dried coating film). When dripping, make sure that the camera attached to the contact angle meter is in focus. Immediately after dropping, press the “Measure” button on the controller screen.
-Water used for measurement: Ion-exchanged water having a treated water quality of 1 µS / cm or less prepared with an apparatus (Purelite PRO-0250-003 manufactured by Organo Corporation)-Drop amount of water: 2 µL
・ Measurement temperature: 20 ℃
Lens field of view range: Standard Next, the contact angle immediately after dripping water is measured at any five locations on a horizontally placed test piece, and the average value of the measurement results is taken as the water contact angle. . Here, the values of the contact angles at five arbitrary positions are values automatically calculated by pressing the “measure” button.
In the present invention, A or C is 75.0 ° or more. A preferable value of A or C is 80.0 ° or more. Moreover, as an upper limit of A or C, it is preferable that it is 120.0 degrees or less, and it is more preferable that it is 110.0 degrees or less. In the present invention, the contact angle change rate R ₈₀ or R ₉₀ calculated from the above formula is 3.0% or less, preferably 2.5% or less.

  The photosensitive resin composition of the present invention is characterized by containing an alkali-soluble resin. Moreover, the photosensitive resin composition of this invention may contain arbitrary components as components other than alkali-soluble resin. For example, when using a photosensitive resin composition as an insulating resin composition such as a solder resist, a photopolymerization initiator, a filler, a reactive diluent, a thermosetting component, and the like may be included. Moreover, as a conductive resin composition, when using a photosensitive resin composition, each component, such as a photoinitiator, a filler, a reactive diluent, a thermosetting component, and an organic acid, is contained. Also good.

  On the other hand, when the coating film formed by coating the photosensitive resin composition was dried at 80 ° C. for 40 minutes, the contact angle A of water in the dried coating film and the coating film formed by coating were dried at 90 ° C. for 20 minutes. In order to set the contact angle C of water in the dry coating film at 75.0 ° or more, it is necessary to adjust the composition of the photosensitive resin composition. The method of adjustment is not particularly limited, but for the adjustment of the organic component, for example, a compound having a methyl group or a fluorene skeleton, an organic acid, a higher fatty acid type, a styrene / acrylic type, a styrene / Maleic acid-based, polyacrylamide-based, alkyl ketene dimer-based, alkenyl succinic anhydride-based additives, petroleum-based additives, and silicone-based antifoaming agents may be included, but are not limited thereto.

Moreover, even if the drying conditions at the time of forming the dry coating film of the photosensitive resin composition are changed, the contact angle is maintained in a certain range, that is, R ₈₀ or R ₉₀ may be 3.0% or less. It can be carried out by adjusting the composition of the photosensitive resin composition. The method of adjustment is not particularly limited, but for the photosensitive resin composition, for example, selection of a photosensitive component and a curing component that are not easily thermally decomposed, selection of an organic solvent having an appropriate boiling point, etc. Can be mentioned. This is presumed that the surface condition of the dried coating film may change due to the progress of the curing reaction under the drying conditions or volatilization of the solvent. Absent. Further, the adjustment method is not limited to these.

  Next, each component of the photosensitive resin composition of the present invention in which the contact angle of water of the dry coating film satisfies the above relationship will be described in detail. In addition, in this specification, (meth) acrylate is a term which generically refers to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.

[Alkali-soluble resin]
The photosensitive resin composition of the present invention contains an alkali-soluble resin. The alkali-soluble resin may be any resin that can be alkali-soluble, and a known and commonly used resin is used. An alkali-soluble resin can be used individually by 1 type or in combination of 2 or more types. Examples include water-soluble resins such as carboxyl group-containing resins and phenolic hydroxyl group-containing resins. Of these, carboxyl group-containing resins and phenolic hydroxyl group-containing resins are preferred, and carboxyl group-containing resins are more preferred because of their excellent developability. The carboxyl group-containing resin can be rendered alkali developable by containing a carboxyl group. Further, from the viewpoint of photosensitivity, in addition to the carboxyl group, it is preferable to have an ethylenically unsaturated bond in the molecule, but even if only a carboxyl group-containing resin having no ethylenically unsaturated double bond is used. Good. When the carboxyl group-containing resin does not have an ethylenically unsaturated bond, it is necessary to use a reactive diluent in combination in order to make the composition photocurable. As the ethylenically unsaturated double bond, those derived from acrylic acid, methacrylic acid or derivatives thereof are preferable.

  Specific examples of the carboxyl group-containing resin include compounds listed below (any of oligomers and polymers).

  (1) A carboxyl group-containing resin having an aromatic ring, obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene or α-methylstyrene. In this case, it suffices that at least one of the unsaturated group-containing compound and the unsaturated carboxylic acid has an aromatic ring.

  (2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers A carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group. When this carboxyl group-containing urethane resin has an aromatic ring, it is sufficient that at least one of diisocyanate, carboxyl group-containing dialcohol compound and diol compound has an aromatic ring.

  (3) Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A systems A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group. When this carboxyl group-containing urethane resin has an aromatic ring, it is sufficient that at least one of a diisocyanate compound, a diol compound, and an acid anhydride has an aromatic ring.

  (4) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( Photosensitive carboxyl group-containing urethane resin by polyaddition reaction of (meth) acrylate or its modified partial anhydride, carboxyl group-containing dialcohol compound and diol compound. When this photosensitive carboxyl group-containing urethane resin has an aromatic ring, at least one of diisocyanate, bifunctional epoxy resin (meth) acrylate or its partial acid anhydride modified product, carboxyl group-containing dialcohol compound and diol compound is aromatic. What is necessary is just to have a ring.

  (5) Bifunctional epoxy such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin Add a diol compound to the resin, and further add an acid anhydride to the end of the urethane epoxy (meth) acrylate resin obtained by reacting the urethane epoxy resin obtained by adding a diisocyanate compound with glycidyl (meth) acrylate. A terminal carboxyl group-containing urethane resin obtained by reaction. When this terminal carboxyl group-containing urethane resin has an aromatic ring, it is sufficient that at least one of a bifunctional epoxy resin, a diol compound, a diol compound, a diisocyanate compound, and an acid anhydride has an aromatic ring.

  (6) Bifunctional epoxy such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin Adding a diol compound having a carboxyl group such as a diisocyanate compound and 2,2-bis (dimethylol) -propionic acid to an epoxycarboxylate compound obtained by reacting a monocarboxylic acid having an ethylenically unsaturated group with a resin Carboxyl group-containing urethane resin obtained by When this carboxyl group-containing urethane resin has an aromatic ring, it is sufficient that at least one of a bifunctional epoxy resin, a monocarboxylic acid, a diisocyanate compound, and a diol compound having a carboxyl group has an aromatic ring.

  (7) During the synthesis of the resin of the above (2) or (4), a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate is added, and the terminal ( (Meth) acrylic carboxyl group-containing urethane resin. When this photosensitive carboxyl group-containing urethane resin has an aromatic ring, the compound having one hydroxyl group and one or more (meth) acryloyl groups in the molecule may have an aromatic ring.

  (8) During the synthesis of the resin of the above (2) or (4), one isocyanate group and one or more (meth) acryloyl groups are introduced into the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. The carboxyl group-containing urethane resin which added the compound which has and was terminally (meth) acrylated. When this photosensitive carboxyl group-containing urethane resin has an aromatic ring, the compound having one isocyanate group and one or more (meth) acryloyl groups in the molecule may have an aromatic ring.

  (9) Photosensitivity obtained by reacting polyfunctional epoxy resin with (meth) acrylic acid and adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride to the hydroxyl group present in the side chain Carboxyl group-containing resin. When this photosensitive carboxyl group-containing resin has an aromatic ring, it is sufficient that at least one of the polyfunctional epoxy resin and the dibasic acid anhydride has an aromatic ring.

  (10) A photosensitive carboxyl group in which (meth) acrylic acid is reacted with a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional epoxy resin with epichlorohydrin, and a dibasic acid anhydride is added to the resulting hydroxyl group. Containing resin. When this photosensitive carboxyl group-containing resin has an aromatic ring, it is sufficient that at least one of a bifunctional epoxy resin and a dibasic acid anhydride has an aromatic ring.

  (11) A carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group. When this photosensitive carboxyl group-containing polyester resin has an aromatic ring, it is sufficient that at least one of a polyfunctional oxetane resin, dicarboxylic acid and dibasic acid anhydride has an aromatic ring.

  (12) A reaction product obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a product with a polybasic acid anhydride.

  (13) Obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a reaction product obtained by reacting a cyclic carbonate compound such as ethylene carbonate or propylene carbonate with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.

  (14) An epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and (meth) Reacting with an unsaturated group-containing monocarboxylic acid such as acrylic acid, and then reacting with the alcoholic hydroxyl group of the resulting reaction product, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipine A carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride such as an acid. When this photosensitive carboxyl group-containing polyester resin has an aromatic ring, an epoxy compound, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in a molecule, an unsaturated group-containing monocarboxylic acid and a polybasic It suffices that at least one of the acid anhydrides has an aromatic ring.

  (15) One epoxy group and one or more (meth) acryloyl in a molecule such as glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate and the like in any one of the resins (1) to (12) above A photosensitive carboxyl group-containing resin obtained by adding a compound having a group. When this photosensitive carboxyl group-containing urethane resin has an aromatic ring, a compound having one epoxy group and one or more (meth) acryloyl groups in the molecule may have an aromatic ring.

  (16) A photosensitive carboxyl group-containing resin obtained by reacting a carboxyl group-containing (meth) acrylic copolymer resin with a compound having an oxirane ring and an ethylenically unsaturated group in one molecule.

  (17) A copolymer obtained by copolymerizing a compound having one epoxy group and an unsaturated double bond in each molecule and an unsaturated double bond of each compound of the compound having an unsaturated double bond. A photosensitive carboxyl group-containing resin obtained by reacting an unsaturated monocarboxylic acid, and reacting a saturated or unsaturated polybasic acid anhydride with the generated secondary hydroxyl group.

  (18) After reacting a hydroxyl group-containing polymer with a saturated or unsaturated polybasic acid anhydride, the resulting carboxylic acid is reacted with a compound having one epoxy group and an unsaturated double bond in each molecule. A photosensitive hydroxyl group- and carboxyl group-containing resin.

  Since the carboxyl group-containing resin as described above has a large number of carboxyl groups in the side chain of the backbone polymer, development with an alkaline aqueous solution becomes possible.

  Among the resins described above, it is preferable to use a carboxyl group-containing resin having an aromatic ring among the resins exemplified in (1) and the resins exemplified in (2) to (10). Among these resins, the resins illustrated in (2) to (8) and (10) are more preferable, and the resins illustrated in (2) to (8) are more preferable.

  The phenolic hydroxyl group-containing resin is not particularly limited as long as it has a phenolic hydroxyl group, that is, a hydroxyl group bonded to a benzene ring, in the main chain or side chain. Preferably, it is a resin containing two or more phenolic hydroxyl groups per molecule. As two or more phenolic hydroxyl group-containing resins in one molecule, catechol, resorcinol, hydroquinone, dihydroxytoluene, naphthalenediol, t-butylcatechol, t-butylhydroquinone, pyrogallol, phloroglucinol, bisphenol A, bisphenol F, Bisphenol S, biphenol, bixylenol, novolac-type phenol resin, novolac-type alkylphenol resin, bisphenol A novolak resin, dicyclopentadiene-type phenol resin, xylok-type phenol resin, terpene-modified phenol resin, polyvinylphenols, phenols Of aromatic aldehydes with phenolic hydroxyl groups, condensation of 1-naphthol or 2-naphthol with aromatic aldehydes Although and the like, not limited thereto.

  Further, the alkali-soluble resin has an acid dissociation constant (pKa) in an ethylene-glycol butyl ether solution at 25 ° C. of less than 9.5. This is preferable in that the contamination of the developer can be made highly compatible. In addition, when alkali-soluble resin is a mixture which combined 2 or more types of alkali-soluble resin, pKa as a mixture (whole alkali-soluble resin) is less than 9.5. The value of pKa is preferably 7.5 to 9.4, more preferably 8.2 to 9.0.

  The alkali-soluble resin may or may not have an aromatic ring in the structure, but is preferably an alkali-soluble resin having an aromatic ring. In particular, an alkali-soluble resin having a bisphenol structure is preferable.

Moreover, it is preferable that the alkali-soluble resin has a urethane bond from the viewpoint of further suppressing the contamination of the developing solution in the developing step and the clogging of the developing device due to the precipitate. In other words, when developability is imparted, for example, in the case of an alkali-soluble resin having a urethane bond, even if development is performed using an alkaline developer, development of development residues is suppressed regardless of the Na ₂ CO ₃ concentration, The resolution is also good. The suppression of the development residue is considered to be due to the fact that the urethane bond exhibits high wettability with other components, and as a result, it is difficult to produce a precipitate even when the drying conditions are changed. On the other hand, since it is developed with a dilute alkaline aqueous solution, it is possible to form an image with little damage to the exposed area, and the resolution of the alkaline developer in the exposed and unexposed areas is increased, resulting in resolution. About the property, it is estimated that it becomes favorable. However, it is just a guess and is not bound by this theory.

  The acid value of the alkali-soluble resin is desirably in the range of 20 to 200 mgKOH / g, more preferably in the range of 40 to 180 mgKOH / g, and still more preferably in the range of 50 to 160 mgKOH / g. When it is in the range of 20 to 200 mg KOH / g, the adhesion of the coating film after the main curing can be obtained, the alkali development becomes easy, the dissolution of the exposed portion by the developer is suppressed, and the line does not fade more than necessary. In addition, it is preferable because a normal resist pattern can be easily drawn. Further, it is preferable because the contrast between the development resistance of the exposed portion and the developability of the unexposed portion can be maintained, and the resolution is excellent.

  The weight average molecular weight of the alkali-soluble resin used in the present invention varies depending on the resin skeleton, but is preferably in the range of 2,000 to 150,000. Within this range, tack-free performance is good, the moisture resistance of the coated film after exposure is good, and film loss is less likely to occur during development. Further, when the weight average molecular weight is within the above range, the resolution is improved, the developability is good, and the storage stability is improved. More preferably, it is 5,000-100,000. The weight average molecular weight can be determined by gel permeation chromatography (GPC) method (polystyrene standard). In addition, when two or more alkali-soluble resins are contained in the photosensitive resin composition, it is preferable that each resin is within the above range, but measurement is performed in a state where each resin is mixed. It is also preferable that there is.

  The glass transition temperature of the alkali-soluble resin is preferably in the range of −10 to 60 ° C. In the case of −10 ° C. or higher, the tack-free performance is more excellent. In the case of 60 ° C. or lower, the crack resistance becomes better. More preferably, it is 0-40 degreeC. In addition, the glass transition temperature of alkali-soluble resin can be calculated | required by the differential scanning calorimeter (DSC) measurement of a photosensitive component. In addition, when 2 or more types of alkali-soluble resins are contained in the photosensitive resin composition, it is preferable that each resin is within the above range. Preferably there is. When measuring in the state which mixed each resin, it is preferable to measure in the state which made each resin varnished and stirred uniformly.

  The suitable compounding quantity of such alkali-soluble resin can be suitably adjusted with the use application of the photosensitive resin composition. For example, when used as an insulating resin composition such as a solder resist, the blending amount of the alkali-soluble resin is 10 to 60% by mass, preferably 15 to 50% by mass in the total composition in terms of solid content. is there. On the other hand, when using as a conductive resin composition, the compounding quantity of alkali-soluble resin is 5-50 mass% in the whole composition in conversion of solid content, Preferably it is 5-40 mass%. When the blending amount of the alkali-soluble resin is within the above range, the coating strength after the main curing does not decrease, and the increase in the viscosity of the composition and the decrease in the coating property can be suppressed.

  The photosensitive resin composition of the present invention may contain an arbitrary component as a component other than the alkali-soluble resin. Details of the optional components will be described below.

[Photopolymerization initiator]
The photosensitive resin composition of the present invention may contain a photopolymerization initiator. The photopolymerization initiator is not particularly limited. For example, bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, Bis- (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine Oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2 , 4,6-Trimethylbenzoyl) -phenylphos Bisacylphosphine oxides such as tin oxide; 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2-methyl Monoacylphosphine oxides such as benzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 1-hydroxy-cyclohexylphenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl) -Propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, hydroxyacetophenones such as 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzoin, benzyl, benzoin methyl ether, benzoin Benzoins such as ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether; benzoin alkyl ethers; benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4′-dichlorobenzophenone, 4,4 Benzophenones such as'-bisdiethylaminobenzophenone; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, , 1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl) -1- [4- (4-morpholinyl) phenyl] -1-butanone, N, N-dimethyl Acetophenones such as aminoacetophenone; thioxanthones such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; anthraquinone , Chloroant Anthraquinones such as quinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone and 2-aminoanthraquinone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; Benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethylbenzoate, p-dimethylbenzoic acid ethyl ester; 1,2-octanedione, 1- [4- (phenylthio)-, 2- Oxime esters such as (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime); Bis (η5-2,4-cyclope Tadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2 -Titanocenes such as-(1-pyr-1-yl) ethyl) phenyl] titanium; phenyl disulfide 2-nitrofluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, etc. it can. Any of the above photopolymerization initiators may be used alone or in combination of two or more.

  Commercially available products of photopolymerization initiators of phosphine oxides such as bisacylphosphine oxides and monoacylphosphine oxides include IRGACURE TPO manufactured by BASF Japan, Omnirad manufactured by IGM Resins (Omnilad) ) 819 and the like. Examples of commercially available acetophenone photopolymerization initiators include IRGACURE 369, IRGACURE 379EG manufactured by BASF Japan, and Omnirad 907 manufactured by IGM Resins. Furthermore, commercially available products of photopolymerization initiators of oxime esters include CGI-325, IRGACURE OXE01, IRGACURE OXE02 manufactured by BASF Japan, N-1919, NCI-831 manufactured by ADEKA, and TOE manufactured by Nippon Chemical Industry Co., Ltd. -004, TR-PBG-304 manufactured by Changzhou Power Electronics New Materials Co., Ltd.

  The blending amount of the photopolymerization initiator is not particularly limited, but the blending amount when using the photopolymerization initiator of oxime esters is preferably 0.01 with respect to 100 parts by mass of the alkali-soluble resin in terms of solid content. It is 10 mass parts, More preferably, it is the range of 0.1-5 mass parts. By setting it as 0.01 mass part or more, the photocurability on copper becomes more reliable and it is preferable at the point which the coating-film characteristics after this hardening, such as chemical resistance, improve. Moreover, by setting it as 5 mass parts or less, it is preferable at the point which the light absorption in the coating-film surface after exposure is suppressed, and the sclerosis | hardenability of a deep part improves.

  On the other hand, the content of the photopolymerization initiator other than the photopolymerization initiator of the oxime ester is preferably 0.1 to 30 parts by mass, more preferably 100 parts by mass in terms of solid content, and more preferably. It is 0.5-25 mass parts, More preferably, it is the range of 1-15 mass parts. It is preferable from a viewpoint of photocurability, chemical resistance, etc. as it is 0.1 mass part or more. On the other hand, if it is 30 parts by mass or less, light absorption on the surface of the coating film after the main curing by the photopolymerization initiator is controlled, and this is preferable from the viewpoint of improving the deep curability.

[Filler]
The photosensitive resin composition of the present invention may contain a filler. It does not specifically limit as a filler, A well-known and usual inorganic or organic filler can be used. The purpose of blending the filler is not particularly limited, and may be for increasing the physical strength of the coating film after the main curing. When imparting conductivity, it is preferable to use a conductive filler, and when using the photosensitive resin composition of the present invention for forming an insulating layer, it is preferable to use an insulating filler.

Any conductive filler can be used as long as it is a filler that imparts conductivity to the photosensitive resin composition of the present invention. Examples of such conductive fillers include Ag, Au, Pt, Pd, Ni, Cu, Al, Sn, Pb, Zn, Fe, Ir, Os, Rh, W, Mo, Ru, and the like. Among these, Ag is preferable. These conductive fillers may be used in the form of the above component alone, but may be used in the form of an alloy or oxide. Further, tin oxide (SnO ₂ ), indium oxide (In ₂ O ₃ ), ITO (Indium Tin Oxide), or the like can also be used. The conductive filler may be carbon powder such as carbon black, graphite, or carbon nanotube. However, care should be taken because the light transmittance is lowered.

  The shape of the conductive filler is not particularly limited, but is preferably other than flakes, particularly preferably acicular or spherical. As a result, light transmission is improved, and a conductive circuit or electrode having excellent resolution can be formed.

  In order to form a fine line, the conductive filler preferably has a maximum particle size of 30 μm or less. By setting the maximum particle size to 30 μm or less, the resolution of the conductive circuit and the electrode is improved.

The particle diameter of the conductive filler is 0.1 to 10 μm as the average particle diameter of 10 random conductive fillers observed at 10,000 times using an electron microscope (SEM). It is preferable. It is preferable from an electroconductive viewpoint that an average particle diameter is 0.1 micrometer or more. On the other hand, when the average particle size is 10 μm or less, it is preferable from the viewpoint of preventing clogging of the screen. In addition, it is preferable to use the thing of the magnitude | size of 0.5-3.5 micrometers in the average particle diameter measured with the micro track | truck. The conductive filler preferably has a volume resistivity (JIS K 6911) of 10 ⁻³ Ω · cm or less.

The insulating filler preferably has an insulating property with a volume resistivity (JIS K 6911) of 10 ¹⁰ Ω · cm or more. Examples of the insulating filler include amorphous silica, fused silica, spherical silica and the like, barium sulfate, hydrotalcite, talc, clay, magnesium carbonate, calcium carbonate, alumina, titanium oxide, aluminum hydroxide, silicon nitride, Examples thereof include aluminum nitride, boron nitride, and Neuburg silica particles.

  A filler can be used individually by 1 type or in combination of 2 or more types.

  The suitable compounding quantity of a filler can be suitably adjusted with the use application of the photosensitive resin composition. For example, when used as an insulating resin composition such as a solder resist, the blending amount of the insulating filler is preferably 50 to 500 parts by mass with respect to 100 parts by mass of the alkali-soluble resin in terms of solid content. More preferably, it is -300 mass parts. It is preferable from a printable viewpoint that the compounding quantity of an insulating filler is 50 mass parts or more. Moreover, it is preferable from a viewpoint of printability and light transmittance that the compounding quantity of an insulating filler is 500 mass parts or less. On the other hand, when using as a conductive resin composition, it is preferable that the compounding quantity of a conductive filler is 700-1300 mass parts with respect to 100 mass parts of alkali-soluble resin in conversion of solid content. It is preferable from an electroconductive viewpoint that the compounding quantity of an electroconductive filler is 700 mass parts or more. Moreover, it is preferable from a viewpoint of printability and light transmittance that the compounding quantity of an electroconductive filler is 1300 mass parts or less.

(Reactive diluent)
Since the photosensitive resin composition of the present invention can be effectively cross-linked by light, a reactive diluent may be contained. As the reactive diluent, it is preferable to use a (meth) acrylate compound. The reactive diluent is preferably bifunctional or more, that is, polyfunctional. The reason why polyfunctionality is preferable is that the photoreactivity is improved and the resolution is excellent as compared with the case where the number of functional groups is one. In addition, in this specification, (meth) acrylate is a term that collectively refers to acrylate and methacrylate, and the same applies to other similar expressions.

  Examples of the (meth) acrylate compound include polyfunctional (meth) acrylate monomers or oligomers (bifunctional or higher functional (meth) acrylate monomers or oligomers). Specific examples include conventionally known polyester (meth) acrylates, poly Examples include ether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, and epoxy (meth) acrylate. Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; N, N-dimethylacrylamide Acrylamides such as N-methylol acrylamide and N, N-dimethylaminopropyl acrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, Polyhydric alcohols such as pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or the like Multivalent acrylates such as thyloxide adducts, propylene oxide adducts, or ε-caprolactone adducts; polyvalent acrylates such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide or propylene oxide adducts of these phenols Acrylates; glyceryl diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyglycerides of glycidyl ether such as triglycidyl isocyanurate; not limited to the above, polyether polyol, polycarbonate diol, hydroxyl-terminated polybutadiene, Polyurethane polyol such as polyester polyol is directly acrylated or urethane acrylate via diisocyanate And at least one of acrylates and melamine acrylates, and methacrylates corresponding to the acrylates.

  Further, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, or a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin. An epoxy urethane acrylate compound reacted with a half urethane compound, and each methacrylate resin or compound corresponding to the acrylate may be used as a reactive diluent. Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.

Especially, it is preferable to use a polyfunctional (meth) acrylate monomer, and especially a tetrafunctional (meth) acrylate monomer is preferable. Examples of the tetrafunctional (meth) acrylate monomer include pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and urethane (meth) acrylate. Among these, urethane is used for the same reason as the alkali-soluble resin. Those having a bond, that is, urethane (meth) acrylate are preferred. Any urethane (meth) acrylate may be used as long as it has a urethane bond, and examples thereof include those represented by the following formula (I).

In the above formula (I), Z ¹ represents an alkylene group, R ¹ represents a hydrogen atom, R ² represents a methyl group, R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, However, at least one of R ³ and R ⁴ represents a methyl group.

  As the above-described tetrafunctional urethane (meth) acrylate, urethane (meth) acrylate or ester (meth) acrylate in which acryl and methacryl are 1: 1 is preferable.

  As such tetrafunctional urethane (meth) acrylate or ester (meth) acrylate, for example, acrylic acid is added to glycidyl methacrylate, and a hydroxyl group generated at that time is reacted with diisocyanate or dicarboxylic acid.

  A reactive diluent can be used individually by 1 type or in combination of 2 or more types.

  The suitable compounding quantity of a reactive diluent can be suitably adjusted with the use application of the photosensitive resin composition. For example, when used as an insulating resin composition such as a solder resist, the compounding amount of the reactive diluent is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the alkali-soluble resin in terms of solid content, and 2 to 20 Part by mass is more preferable. When the amount is 1 part by mass or more, the photocurability is good, and it is easy to form a pattern line in alkali development after irradiation with active energy rays. Moreover, when it is 30 mass parts or less, the solubility with respect to aqueous alkali solution is favorable, and a pattern film | membrane becomes difficult to become weak. On the other hand, when using as a conductive resin composition, the compounding amount of the reactive diluent is preferably 1 to 40 parts by mass and more preferably 5 to 40 parts by mass with respect to 100 parts by mass of the alkali-soluble resin in terms of solid content. preferable. When the amount is 1 part by mass or more, the photocurability is good, and it is easy to form a pattern line in alkali development after irradiation with active energy rays. In the case of 40 parts by mass or less, the solubility in an alkaline aqueous solution is good, and the pattern film is not easily brittle.

(Thermosetting component)
The photosensitive resin composition of the present invention may further contain a thermosetting component because crack resistance is further improved. Examples of thermosetting components used in the present invention include amine resins such as melamine resins and benzoguanamine resins, block isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, melamine derivatives, and the like. A thermosetting resin can be used. A thermosetting component can be used individually by 1 type or in combination of 2 or more types. In the present invention, a thermosetting component having at least one selected from the group consisting of two or more cyclic ether groups and cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether group) in the molecule, or A thermosetting component having two or more isocyanate groups or blocked isocyanate groups in one molecule is preferable.

  The thermosetting component having two or more cyclic (thio) ether groups in the molecule contains either one of the three, four or five-membered cyclic ether groups, or the cyclic thioether group or two kinds of groups in the molecule. Two or more compounds, for example, a compound having at least two or more epoxy groups in the molecule, that is, a polyfunctional epoxy compound, a compound having at least two or more oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, Examples include compounds having two or more thioether groups in the molecule, that is, episulfide resins.

  Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, Epicron 840 manufactured by DIC Corporation, Epicron 850, Epicron 1050, Epicron 2055, Epototo YD manufactured by Nippon Steel & Sumitomo Metal Corporation. -011, YD-013, YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Sumitomo Chemical Industries, Ltd. Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, A.A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. Bisphenol A type epoxy resin such as 664; jERYL903 manufactured by Mitsubishi Chemical Corporation, Epicron 152, Epicron 165 manufactured by DIC Corporation, Epotote YDB-400, YDB-500 manufactured by Nippon Steel & Sumitomo Metal Corporation, manufactured by Dow Chemical Co., Ltd. D. E. R. 542, Sumitomo Epoxy ESB-400, ESB-700, manufactured by Sumitomo Chemical Co., Ltd., A. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714; jER152 and jER154 manufactured by Mitsubishi Chemical Corporation, and D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865 manufactured by DIC Corporation, Epototo YDCN-701, YDCN-704 manufactured by Nippon Steel & Sumitomo Metal Corporation, EPPN-201 manufactured by Nippon Kayaku Co., Ltd. EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Chemical Co., Ltd. Sumi-epoxy ESCN-195X, ESCN-220, Asahi Kasei Kogyo Co., Ltd. E. R. Novolak type epoxy resins such as ECN-235 and ECN-299; Epicron 830 manufactured by DIC Corporation, jER807 manufactured by Mitsubishi Chemical Corporation, Epototo YDF-170, YDF-175, YDF-2004 manufactured by Nippon Steel & Sumitomo Metal Corporation Bisphenol F type epoxy resin such as EPOTOTO ST-2004, ST-2007, ST-3000, etc. manufactured by Nippon Steel & Sumikin Co., Ltd .; jER604 manufactured by Mitsubishi Chemical Co., Ltd., NS Glycidylamine type epoxy resin such as Epototo YH-434 manufactured by Sumitomo Chemical Co., Ltd., Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd .; Hydantoin type epoxy resin; Alicyclic epoxy resin such as Celoxide 2021P manufactured by Daicel Corporation ; YL- manufactured by Mitsubishi Chemical Corporation 33, Dow Chemical Co., Ltd. of T. E. N. Trihydroxyphenylmethane type epoxy resins such as EPPN-501 and EPPN-502; Bixylenol type or biphenol type epoxy resins such as YL-6056, YX-4000 and YL-6121 manufactured by Mitsubishi Chemical Corporation, or a mixture thereof; Bisphenol S epoxy resin such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by ADEKA Co., Ltd., EXA-1514 manufactured by DIC Co., Ltd., etc .; Bisphenol A novolak such as jER157S manufactured by Mitsubishi Chemical Corporation Type epoxy resin; tetraphenylolethane type epoxy resin such as jERYL-931 manufactured by Mitsubishi Chemical Corporation; heterocyclic epoxy resin such as TEPIC manufactured by Nissan Chemical Industries, Ltd .; dimer such as Blemmer DGT manufactured by Nippon Oil & Fats Co., Ltd. Glycidylphthale Resin; Tetraglycidylxylenoylethane resin such as ZX-1063 manufactured by Nippon Steel & Sumikin Co .; ESN-190, ESN-360 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., HP-4032 manufactured by DIC Co., Ltd. Naphthalene group-containing epoxy resins such as EXA-4750 and EXA-4700; Epoxy resins having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC Corporation; CP-50S and CP- manufactured by NOF Corporation 50M glycidyl methacrylate copolymer epoxy resin; cyclohexylmaleimide and glycidyl methacrylate copolymer epoxy resin; epoxy-modified polybutadiene rubber derivative (for example, Epode PB-3600 manufactured by Daicel Corporation), CTBN-modified epoxy resin ( For example, Nippon Steel & Sumitomo Metal And YR-102, YR-450, etc. manufactured by Kagaku Co., Ltd.), and the like. These epoxy resins can be used alone or in combination of two or more. Among these, a novolak type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is preferable.

Further, it may have a methyl group or a fluorene skeleton in that the contact angle value of the dried coating film can be easily adjusted to a constant value. The epoxy resin having a methyl group may be any as long as it has a methyl group, and examples thereof include those represented by the following formula (II). In the following formula (II), the n number is preferably 5 to 10.

On the other hand, the epoxy resin having a fluorene skeleton may be any as long as it has a fluorene skeleton, and examples thereof include those represented by the following formula (III).

  Polyfunctional oxetane compounds include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl- 3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin, poly (P-hydroxystyrene), cardo-type bisphenol S, calixarenes, calix resorcin arenes, or the like ethers of a resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

  Examples of the episulfide resin having two or more cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.

  In addition, the photosensitive resin composition of the present invention includes two or more isocyanate groups or blocked isocyanate in one molecule in order to improve the curability of the photosensitive resin composition and the toughness of the resulting cured film. It is preferable to add a compound having a group. Such a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is a compound having two or more isocyanate groups in one molecule, that is, a polyisocyanate compound, or two in one molecule. Examples thereof include compounds having the above blocked isocyanate groups, that is, blocked isocyanate compounds.

  As the polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanate include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m- Examples include xylylene diisocyanate and 2,4-tolylene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. In addition, adduct bodies, burette bodies and isocyanurate bodies of the isocyanate compounds mentioned above may be mentioned.

  The blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by reaction with a blocking agent and temporarily deactivated. When heated to a predetermined temperature, the blocking agent is dissociated to produce isocyanate groups.

  As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. Examples of the isocyanate compound that can react with the blocking agent include isocyanurate type, biuret type, and adduct type. As this isocyanate compound, for example, the same aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate as described above is used.

  Examples of isocyanate blocking agents include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-valerolactam, γ-butyrolactam and β-propiolactam. Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, Benzyl ether, methyl glycolate, butyl glycolate, diacetone alcohol, Alcohol blocking agents such as methyl acid and ethyl lactate; oxime blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol Mercaptan blocking agents such as methylthiophenol and ethylthiophenol; acid amide blocking agents such as acetic acid amide and benzamide; imide blocking agents such as succinimide and maleic imide; xylidine, aniline, butylamine, dibutylamine, etc. Amine-based blocking agents; imidazole-based blocking agents such as imidazole and 2-ethylimidazole; imine-based blocks such as methyleneimine and propyleneimine Agents and the like.

  The block isocyanate compound may be commercially available, for example, 7950, 7951, 7960, 7961, 7982, 7990, 7991, 7992 (above, manufactured by Baxenden) Sumijour BL-3175, BL-4165, BL-1100 , BL-1265, Death module TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Desmotherm 2170, Desmotherm 2265 (manufactured by Sumitomo Bayer Urethane Co., Ltd.), Coronate 2512, Coronate 2513, Coronate 2520 (above, Tosoh Corporation), B-830, B-815, B-846, B-870, B-874, B-882 (Mitsui Takeda Chemical Co., Ltd.), DURANATE TPA-B80E, 17B-60PX E402-B80T, MF-B60B, MF-K60B, SBN-70D (manufactured by Asahi Kasei Chemicals Corporation), Karenz MOI-BM (manufactured by Showa Denko KK) and the like. Sumijoules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent.

  The compounds having two or more isocyanate groups or blocked isocyanate groups in one molecule can be used singly or in combination of two or more.

  The compounding amount of the compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the alkali-soluble resin in terms of solid content. -70 mass parts is more preferable. It is preferable from 1 mass part or more from a viewpoint of the toughness of the coating film after this hardening. On the other hand, it is preferable from a viewpoint of storage stability that it is 100 mass parts or less.

(Organic acid)
The photosensitive resin composition of the present invention may contain an organic acid. As an organic acid, it also effectively functions as a development aid. In addition, since it is easy to adjust the contact angle of the dried coating film to a certain value, the components contained in the dissolved photosensitive resin composition do not precipitate at the bottom of the developer, resulting in contamination or precipitation of the developer in the development process. This is effective in that clogging of the developing device due to an object can be suppressed. Especially, when it contains, it is preferable to contain dicarboxylic acid from showing this effect notably. In particular, it is more preferable to use a photosensitive resin composition as the conductive resin composition because it further improves low resistance, that is, conductivity. Moreover, as an organic acid, the organic acid which does not have an aromatic ring is preferable. By blending an organic acid having no aromatic ring, the light absorption of the organic acid itself is suppressed, the photoreactivity of the photosensitive component is relatively improved, and excellent resolution can be obtained.

  Specific examples of organic acids include 2,2′-thiodiacetic acid, adipic acid, isobutyric acid, formic acid, citric acid, glutaric acid, acetic acid, oxalic acid, tartaric acid, lactic acid, pyruvic acid, malonic acid, butyric acid, Carboxylic acids such as malic acid, salicylic acid, benzoic acid, phenylacetic acid, acrylic acid, maleic acid, fumaric acid, crotonic acid; dibutyl phosphite, butyl phosphite, dimethyl phosphite, methyl phosphite, phosphorous acid Mono- or diesters of phosphorous acid such as dipropyl, propyl phosphite, diphenyl phosphite, phenyl phosphite, diisopropyl phosphite, isopropyl phosphite, phosphite-n-methyl-2-ethylhexyl; phosphorus Dibutyl phosphate, butyl phosphate, dimethyl phosphate, methyl phosphate, dipropyl phosphate, propyl phosphate, diphenyl phosphate, phenyl phosphate, Phosphate diisopropyl, isopropyl phosphoric acid, mono- or diesters of phosphoric acid such as phosphoric acid -n- butyl-2-ethylhexyl, and the like. Among these, 2,2′-thiodiacetic acid is advantageous in that it has more excellent effects in terms of suppressing contamination of the developing solution in the developing process and clogging of the developing device due to precipitates, conductivity, and resolution. Preferably there is.

  As a compounding quantity of the said organic acid, it is preferable that it is the range of 1-10 mass parts with respect to 100 mass parts of said alkali-soluble resin in conversion of solid content, and 1-5 mass parts is more preferable. When the amount is 1 part by mass or more, the effect as a development aid is more easily exhibited. On the other hand, when the amount is 10 parts by mass or less, the resolution is excellent.

(Dispersant)
The photosensitive resin composition of the present invention may contain a dispersant. By blending a dispersant, the dispersibility and precipitation of the photosensitive resin composition can be improved. Examples of the dispersant include DISPERBYK-191 (manufactured by Big Chemie Japan).

(Photopolymerization inhibitor)
The photosensitive resin composition of the present invention may contain a photopolymerization inhibitor. By adding the photopolymerization inhibitor, it is possible to suppress a certain amount of radical polymerization in accordance with the type of polymerization inhibitor and the amount of the addition among the radical polymerization that occurs inside the photosensitive resin composition by exposure.

(Thermosetting catalyst)
When the photosensitive resin composition of the present invention contains a thermosetting component having two or more cyclic (thio) ether groups in the molecule, a thermosetting catalyst may be included. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N -Amine compounds such as dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide, sebacic acid dihydrazide; And phosphorus compounds. Moreover, as what is marketed, for example, Cure Sole 2MZ-A, Cure Sole 2P4MHZ, Cure Sole 2PHZ-PW (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., U-CAT3503N manufactured by San Apro Co., Ltd., U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like. In particular, it is not limited to these, as long as it promotes the reaction of a carboxyl group with at least one selected from a thermosetting catalyst of an epoxy resin or an oxetane compound, or an epoxy group and an oxetanyl group, You may use individually by 1 type or in mixture of 2 or more types. Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine and isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine and isocyanuric acid adducts can also be used. A compound that also functions in combination with the thermosetting catalyst.

  The blending amount of these thermosetting catalysts is sufficient at a normal quantitative ratio, for example, 0.1 to 20 parts by weight is preferable with respect to 100 parts by weight of the alkali-soluble resin in terms of solid content, and 0.5 to 10 parts by weight. Part is more preferred.

(Thermal polymerization inhibitor)
The photosensitive resin composition of the present invention may contain a thermal polymerization inhibitor. The thermal polymerization inhibitor can be used to prevent thermal polymerization or temporal polymerization of the photosensitive resin composition of the present invention.

(Chain transfer agent)
In order to improve sensitivity, the photosensitive resin composition of the present invention may contain known N-phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole and the like as chain transfer agents.

(Organic solvent)
The photosensitive resin composition of the present invention may contain an organic solvent in order to obtain a good coating state. As the organic solvent, known and commonly used solvents can be used. Examples of organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve (ethylene glycol monoethyl ether), methyl cellosolve, butyl cellosolve, carbitol, methylcarbitol, butyl Glycol ethers such as carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether (DPGME), dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate (ethylene glycol monoethyl ether) Acetate), butyl cellosolve acetate, carbitol acetate (diethylene glycol monoethyl) Ether acetate; EDGAC), butyl carbitol acetate, propylene glycol monomethyl ether acetate (PMA), dipropylene glycol monomethyl ether acetate, esters such as propylene carbonate; aliphatic hydrocarbons such as octane and decane; petroleum ether, petroleum naphtha, Known and commonly used solvents such as solvent naphtha and petroleum solvents such as aromatic petroleum solvents can be used. These solvents can be used alone or in combination of two or more.

(Other additive components)
In the photosensitive resin composition of the present invention, in addition to the above-mentioned components, known and commonly used components such as thickeners, higher fatty acid series, styrene / acrylic series, styrene / maleic acid series, polyacrylamide series, alkyl ketene dimer series, Defoaming agents such as alkenyl succinic anhydride, petroleum and silicone, leveling agents, coupling agents, antioxidants, rust preventives, colorants, etc. may be blended as necessary. Needless to say.

  In the photosensitive resin composition of the present invention, a machine such as a three-roller or a blender is used for kneading and dispersing the above-described essential components and optional components. The photosensitive resin composition in which the respective components are dispersed in this manner is applied onto the substrate by an appropriate application method such as a screen printing method, a bar coater, or a blade coater.

  After coating, it is preferable to dry the coating film formed by coating in order to obtain touch dryness. The drying condition of the photosensitive resin composition of the present invention is characterized by drying at 80 ° C. to 40 to 70 ° C. in order to obtain a good dry coating film and developability thereafter. Although it does not specifically limit as a drying method, If an example is given, a hot-air circulation type drying furnace will be mentioned. Specifically, a sample such as a substrate to be dried is placed in the center of the furnace by using a shelf board or the like. The temperature inside the device is kept constant within a range of ± 1 ° C for both 80 ° C and 90 ° C by air circulation and duct adjustment. Examples of the device name include DF610 manufactured by Yamato Scientific Co., Ltd. Further, a far-infrared drying furnace or the like may be used as long as the same effect as described above, that is, the temperature in the apparatus can be kept constant within a range of ± 1 ° C. for both 80 ° C. and 90 ° C. The film thickness after drying, that is, the dry film thickness is not particularly limited, but the insulating resin composition such as a solder resist ink is 10 to 150 μm in that it is more excellent in printability in addition to being easier to develop. It is preferable and it is more preferable that it is 20-60 micrometers. On the other hand, the conductive resin composition such as a conductive paste is more preferably 1 to 20 μm, and more preferably 1 to 10 μm.

Next, contact exposure or non-contact exposure is performed using a negative mask having a predetermined exposure pattern. As the exposure light source, a halogen lamp, a high-pressure mercury lamp, a laser beam, a metal halide lamp, a black lamp, an electrodeless lamp, or the like is used. As the exposure amount, the integrated light amount can be a low light amount of 200 mJ / cm ² or less. In addition, you may form a pattern in a dry coating film with a laser direct imaging apparatus, without using a mask.

  Next, the coated film after exposure is formed into a pattern by development such as spraying or dipping. As a developing solution for a dry coating film formed using the photosensitive resin composition of the present invention, an aqueous alkali solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, or the like can be used. In particular, a dilute alkaline aqueous solution having a concentration of about 1.5% by mass or less is preferably used, as long as the carboxyl group in the photosensitive resin composition is saponified and the uncured part (unexposed part) is removed. The developer is not limited to the above.

  According to the photosensitive resin composition of the present invention, by using a dilute alkaline aqueous solution as a developer, it is possible to obtain a coated film after exposure with little damage to the coated film after exposure and excellent resolution. .

Therefore, in one embodiment of the present invention, the developer used in the method for forming a coated film after exposure is a dilute alkaline aqueous solution having a Na ₂ CO ₃ concentration of 0.1 to 2.0% by mass in pattern formation after development. It is preferable that In particular, the insulating resin composition such as solder resist ink is more preferably a dilute alkaline aqueous solution having a Na ₂ CO ₃ concentration of 0.2 to 2.0 mass%. On the other hand, the conductive resin composition such as a conductive paste is more preferably a dilute alkaline aqueous solution having a Na ₂ CO ₃ concentration of 0.1 to 1.0% by mass.

  After development, it is preferable to perform water washing and acid neutralization in order to remove unnecessary developer.

And the obtained coating film after exposure is fully cured by heat or ultraviolet irradiation. Thereby, the hardened | cured material which is excellent in printability, and is a cured film excellent in adhesiveness and crack resistance can be formed. In the case of thermosetting, the thermosetting temperature is preferably 180 ° C. or lower, more preferably 150 ° C. or lower, further preferably 140 ° C. or lower, and particularly preferably 130 ° C. or lower. On the other hand, in the case of curing by ultraviolet irradiation, 500 to 3000 mJ / cm ² is preferable, and 500 to 2000 mJ / cm ² is more preferable.

  The photosensitive resin composition of the present invention may be used as a dry film or as a liquid. When used as a liquid, it may be one-component or two-component or more. When forming into a dry film, the photosensitive resin composition of this invention is apply | coated on a carrier film, and the resin layer obtained by drying is formed. The example in the case of using the photosensitive resin composition of this invention as a dry film is shown below.

  The dry film has a structure in which a carrier film, a resin layer, and a peelable protective film used as necessary are laminated in this order. The resin layer is a layer formed by applying and drying the photosensitive resin composition of the present invention on a carrier film or a protective film. After forming the resin layer on the carrier film, a protective film is laminated thereon, or a resin layer is formed on the protective film, and this laminate is laminated on the carrier film to obtain a dry film.

  As the carrier film, for example, a thermoplastic film such as a polyester film such as polyethylene terephthalate or polyethylene naphthalate having a thickness of 2 to 150 μm is used.

  The resin layer is formed by uniformly applying the photosensitive resin composition to a carrier film or a protective film with a blade coater, a lip coater, a comma coater, a film coater, or the like at a thickness of, for example, 10 to 150 μm and drying.

  As the protective film, for example, a polyethylene film, a polypropylene film or the like can be used, but a film having an adhesive force with the resin layer smaller than that of the carrier film is preferable.

  In order to produce a cured film that is a cured product on a base material using a dry film, for example, the protective film is peeled off, the resin layer and the base material on which the circuit is formed are overlapped, and a circuit is formed by laminating using a laminator or the like. A resin layer is formed on the substrate. If the formed resin layer is exposed, developed, and fully cured as described above, a cured product that is a cured film can be formed. The carrier film may be peeled off either before exposure or after exposure.

  In these processes, as a base material, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass, in addition to printed wiring boards and flexible printed wiring boards that have been previously formed with copper or the like All grades (FR-4, etc.) using materials such as cloth / paper epoxy, synthetic fiber epoxy, high-frequency circuit copper-clad laminates using fluororesin, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate, etc. Other examples include copper-clad laminates, metal substrates, polyimide films, polyethylene terephthalate (PET) films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, and wafer plates.

  In the present invention, in addition to the above base material, a resin base material having no heat resistance can also be used. Specifically, as a resin-made base material, for example, polyimide, polyester resin, polyethersulfone (PES), polystyrene (PS), polymethyl methacrylate (PMMA), polycarbonate (PC), polyamide (PA) , Polypropylene (PP), polyphenylene oxide (PPO), and the like, and a polyester-based resin can be preferably used.

The photosensitive resin composition or dry film of the present invention is preferably used for producing a printed wiring board, and more preferably used for forming a permanent film. At that time, a cured product is formed by the above-described production method using the photosensitive resin composition or dry film of the present invention. When the photosensitive resin composition of the present invention or the resin layer of the dry film is insulative, it is preferably used to form a solder resist or a cover lay or an interlayer insulating layer. In addition, you may use the photosensitive resin composition of this invention in order to form a solder dam.
On the other hand, when the photosensitive resin composition of the present invention or the resin layer of the dry film is conductive, it is suitably used for conductive circuits, electrodes, electromagnetic wave shield formation, conductive adhesives and the like.

  EXAMPLES Next, although an Example is given and this invention is demonstrated still in detail, this invention is not limited to these Examples.

[Preparation of photosensitive resin composition]
Each component described in Table 1 and Table 2 below was blended and stirred, and three passes were performed using a three-roll mill. Then, carbitol acetate was added as a solvent so that the paste viscosity would be 250 dPa · s ± 20 Pa · s, and each photosensitive resin composition described in the same table was obtained.

上記一般式（IV）においてＸがＣ（ＣＨ_３）_２、平均の重合度ｎが３．３であるビスフェノールＡ型エポキシ樹脂（エポキシ当量６５０ｇ／ｅｑ、軟化点８０℃）３７１部とエピクロルヒドリン９２５部をジメチルスルホキシド４６２．５部に溶解させた後、攪拌下７０℃で９８．５％ＮａＯＨ５２．８部を１００分かけて添加した。添加後さらに７０℃で３時間反応を行った。反応終了後、水２５０部を加え水洗を行った。油水分離後、油層よりジメチルスルホキシドの大半および過剰の未反応エピクロルヒドリンを減圧下に蒸留回収し、残留した副製塩とジメチルスルホキシドを含む反応生成物をメチルイソブチルケトン７５０部に溶解させ、更に３０％ＮａＯＨ１０部を加え、７０℃で１時間反応させた。反応終了後、水２００部で２回水洗を行った。油水分離後、油層よりメチルイソブチルケトンを蒸留回収して、エポキシ当量２８７ｇ／ｅｑ、軟化点６５℃のエポキシ樹脂（ａ）を得た。得られたエポキシ樹脂（ａ）は、エポキシ当量から計算すると、前記出発物質ビスフェノールＡ型エポキシ樹脂におけるアルコール性水酸基３．３個のうち約３．１個がエポキシ化されたものであった。このエポキシ樹脂（ａ）３１０部およびカルビトールアセテート２８２部をフラスコに仕込み、９０℃に加熱・攪拌し、溶解した。得られた溶液を一旦６０℃まで冷却し、アクリル酸７２部（１モル）、メチルハイドロキノン０．５部、トリフェニルホスフィン２部を加え、１００℃に加熱し、約６０時間反応させ、酸価が０．２ｍｇＫＯＨ／ｇの反応物を得た。これにテトラヒドロ無水フタル酸１４０部（０．９２モル）を加え、９０℃に加熱し、反応を行い、アルカリ可溶性樹脂１の樹脂溶液を得た。生成物の固形分濃度は６４質量％、固形分酸価は１００ｍｇＫＯＨ／ｇであった。 (Synthesis of alkali-soluble resin 1)

371 parts of a bisphenol A type epoxy resin (epoxy equivalent 650 g / eq, softening point 80 ° C.) having X of C (CH ₃ ) ₂ and an average polymerization degree n of 3.3 in the above general formula (IV) and 925 parts of epichlorohydrin Was dissolved in 462.5 parts of dimethyl sulfoxide, and 52.8 parts of 98.5% NaOH was added over 100 minutes at 70 ° C. with stirring. After the addition, the reaction was further carried out at 70 ° C. for 3 hours. After completion of the reaction, 250 parts of water was added and washed with water. After the oil / water separation, most of the dimethyl sulfoxide and excess unreacted epichlorohydrin were recovered by distillation from the oil layer under reduced pressure, and the reaction product containing the remaining by-product salt and dimethyl sulfoxide was dissolved in 750 parts of methyl isobutyl ketone, and further 30% NaOH 10 Part was added and reacted at 70 ° C. for 1 hour. After completion of the reaction, washing was performed twice with 200 parts of water. After the oil-water separation, methyl isobutyl ketone was distilled and recovered from the oil layer to obtain an epoxy resin (a) having an epoxy equivalent of 287 g / eq and a softening point of 65 ° C. When the epoxy resin (a) obtained was calculated from the epoxy equivalent, about 3.1 of the 3.3 alcoholic hydroxyl groups in the starting material bisphenol A type epoxy resin were epoxidized. 310 parts of this epoxy resin (a) and 282 parts of carbitol acetate were charged into a flask, and heated and stirred at 90 ° C. to dissolve. The obtained solution is once cooled to 60 ° C., 72 parts (1 mol) of acrylic acid, 0.5 part of methylhydroquinone and 2 parts of triphenylphosphine are added, heated to 100 ° C., reacted for about 60 hours, and acid value Yielded a reaction of 0.2 mg KOH / g. To this, 140 parts (0.92 mol) of tetrahydrophthalic anhydride was added and heated to 90 ° C. for reaction to obtain a resin solution of alkali-soluble resin 1. The solid content concentration of the product was 64% by mass, and the solid content acid value was 100 mgKOH / g.

(Synthesis of alkali-soluble resin 2)
In an 2 L flask equipped with a stirrer and a reflux tube, as an epoxy compound (a) having two or more epoxy groups in the molecule, EP-4300E (bifunctional bisphenol A type epoxy resin, epoxy equivalent: manufactured by ADEKA Corporation): 185.0 g / equivalent) is 370.0 g, 144.1 g of acrylic acid (molecular weight: 72.06) is used as the monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule, and hydroquinone monomethyl is used as the thermal polymerization inhibitor. 1.10 g of ether and 1.61 g of triphenylphosphine as a reaction catalyst were charged and reacted at a temperature of 98 ° C. until the acid value of the reaction solution became 0.5 mg · KOH / g or less, to obtain an epoxy carboxylate compound (theoretical molecular weight : 548.2).
Next, 627.6 g of methyl ethyl ketone as a reaction solvent, 3.59 g of hydroquinone monomethyl ether as a thermal polymerization inhibitor, and 2,2-bis (dimethylol) -propionic acid (molecular weight: 134 as a diol compound having a carboxyl group) were added to this reaction solution. .1) was added to 222.9 g and the temperature was raised to 45 ° C. To this solution, 394.4 g of isophorone diisocyanate (molecular weight: 222.3) was gradually added dropwise as a diisocyanate compound so that the reaction temperature did not exceed 65 ° C. After completion of the dropping, the temperature was raised to 80 ° C., and the reaction was carried out for 6 hours until the absorption in the vicinity of 2250 cm ⁻¹ disappeared by an infrared absorption spectrum measurement method to obtain a resin solution of alkali-soluble resin 2. The solid content was 65% by mass, and the solid content acid value was 80 mgKOH / g.

(Measurement method of acid dissociation constant (pKa) of alkali-soluble resin)
0.5 g of each of the resin solutions of alkali-soluble resins 1 to 3 prepared or prepared in a 100 ml beaker was precisely weighed and dissolved in 50 ml of an ethylene glycol butyl ether solution. This solution was titrated with a 0.1 mol / ethanolic potassium hydroxide solution. As a titration apparatus, an automatic titration apparatus (COM-1500) manufactured by Hiranuma Sangyo Co., Ltd. was used (semi-titration method). The acid dissociation constant (pKa) was taken as the half equivalent point (half the titration amount of the equivalent point). The pKa values of the alkali-soluble resins 1 to 3 were as shown in Table 1 below.

(Measurement of contact angle)
A copper foil base material having a copper thickness of 35 μm was polished with buffalo, washed with water and dried. On this base material, each composition of Examples 1-9 and Comparative Examples 1-5 was apply | coated to the whole surface by the screen-printing method. Then, about each composition of Examples 1-7 and Comparative Examples 1-3, drying time was changed into 40, 50, 60, and 70 minutes with a 80 degreeC hot-air circulation type drying furnace (DF610 by Yamato Scientific Co., Ltd.). For each of the compositions of Examples 8 to 9 and Comparative Examples 4 to 5, the drying time was changed to 20, 25, 30, and 35 minutes in a hot air circulating drying oven (DF610 manufactured by Yamato Scientific Co., Ltd.) at 90 ° C. Each was dried to obtain a dried coating film of 95 mm × 75 mm. Each base material to be dried is installed in the center of the furnace by using a shelf, and the temperature in the apparatus is 80 ° C drying or 90 ° C drying by air circulation or duct adjustment ± 1 It adjusted in the range of ° C.
The contact angle of water was measured and analyzed by a perfect circle fitting method using DropMaster DM300 as a contact angle meter and FAMAS (both manufactured by Kyowa Interface Science Co., Ltd.) as an interface measurement analysis integrated system under the following conditions and methods.
・ Launch interface measurement analysis integrated system and start CA / PD controller. At that time, “standard” is selected as the “field of view” on the controller screen. Next, water is put into a plastic syringe, and a stainless needle (22 gauge) is attached to the tip of the syringe and dropped onto the evaluation surface. When dripping, make sure that the camera attached to the contact angle meter is in focus. Immediately after dropping, press the “Measure” button on the controller screen.
-Water used for the measurement: Ion-exchanged water having a treated water quality of 0.7 µS / cm or less prepared by an apparatus (Purelite PRO-0250-003 manufactured by Organo Corporation)-Drop amount of water: 2 µL
・ Measurement temperature: 20 ℃
-Lens field of view range: Standard Subsequently, the contact angle immediately after dripping water is measured at any five locations on the dried coating film placed horizontally, and the average value is taken as the water contact angle. did. Here, the values of the contact angles at five arbitrary locations were values automatically calculated by pressing the “Measure” button.
Moreover, about each composition of Examples 1-7 and Comparative Examples 1-3, the contact angle of the water in the dry coating film at the time of drying at 80 degreeC for 40 minutes was A (degree), and it dried at 80 degreeC for 70 minutes. The following formula when the contact angle of water in the dry coating film is B (°):
R ₈₀ (%) = | (B−A) / A | × 100
The change rate R ₈₀ (%) represented by
Moreover, about each composition of Examples 8-9 and Comparative Examples 4-5, the contact angle of water in the dry coating film at the time of drying at 90 degreeC for 20 minutes was C (degree), and it dried at 90 degreeC for 35 minutes. When the contact angle of water in the dry coating film is D (°), the following formula:
R ₉₀ (%) = | (D−C) / C | × 100
The change rate R ₉₀ (%) represented by
The contact angle and rate of change of water were as shown in Table 1.

(Development management width)
A copper foil base material having a copper thickness of 35 μm was polished with buffalo, washed with water and dried. On this base material, each composition of Examples 1-9 and Comparative Examples 1-5 was apply | coated to the whole surface by the screen-printing method. Then, about each composition of Examples 1-7 and Comparative Examples 1-3, drying time was changed into 40, 50, 60, and 70 minutes with a 80 degreeC hot-air circulation type drying furnace (DF610 by Yamato Scientific Co., Ltd.). In each of the compositions of Examples 8 to 9 and Comparative Examples 4 to 5, the drying time was changed to 20, 25, 30, and 35 minutes in a hot air circulating drying oven (DF610 manufactured by Yamato Scientific Co., Ltd.) at 90 ° C. It dried and obtained the dry coating film. For the obtained dried coating films, Examples 1 to 4 and 8 and Comparative Examples 1 to _{2 and 4} were each 1% by weight Na ₂ CO ₃ aqueous solution at 30 ° C., Examples 5 to 7 and 9 and Comparative Examples 3 and 5 , Development is carried out for 60 seconds under the condition of a spray pressure of 0.2 MPa using a 0.2 mass% Na ₂ CO ₃ aqueous solution at 30 ° C., respectively, and whether or not the dry coating film obtained in each drying time can be developed, and The time when development failure due to heat covering did not occur when dried was tested. When copper was visually observed and the components of the curable resin composition did not remain as residues, development was possible, and the drying time at which development was possible was used as an evaluation criterion. The longest drying time during which development is possible is referred to as a development management width. The longer this is, the wider the margin for drying and the easier the manufacturing management in the substrate manufacturing process.
The evaluation criteria are as follows. The obtained results are shown in Table 1.
○: 80 ° C for 60 minutes or more or 90 ° C for 30 minutes or more ×: 80 ° C for less than 60 minutes or 90 ° C for less than 30 minutes

(Resolution 1 evaluation test piece preparation method)
A substrate having a circuit pattern containing 30 μm / 40 μm line and space (L / S) with a copper thickness of 35 μm was polished with buffalo, washed with water and dried. On this base material, among the photosensitive resin compositions described in Tables 1 and 2 below by screen printing, the compositions of Examples 1 to 4 and 8 and Comparative Examples 1 to 2 and 4 were mixed with 200 mesh polyester. It applied to the whole surface using the screen. Then, the drying time was dried for 30 minutes in an 80 ° C. hot-air circulating drying oven (DF610, manufactured by Yamato Scientific Co., Ltd.) to obtain a dried coating film having a thickness of 20 μm after drying. Then, using the exposure apparatus (HMW-680-GW20 manufactured by Oak Manufacturing Co., Ltd.) equipped with a metal halide lamp as a light source, the obtained dried coating film was passed through a 30 μm / 40 μm line and space (L / S) negative mask. Then, pattern exposure was performed with an optimum exposure amount. Here, the optimum exposure amount is obtained by exposing the dried coating film obtained above through a step tablet having a sensitivity of 21 using an exposure apparatus equipped with a metal halide lamp, and 1 mass% Na ₂ with a liquid temperature of 30 ° C. The exposure amount was such that the pattern of the step tablet remaining when developing for 60 seconds under the condition of a spray pressure of 0.2 MPa using a CO ₃ aqueous solution was 6 steps. Then, development is performed using a 1 wt% aqueous _Na 2 CO ₃ solution temperature 30 ° C., and washed with water. Finally, it was cured at 150 ° C. for 60 minutes to prepare a test piece for resolution 1 evaluation.

(Resolution 1)
The resolution was evaluated in a 30 μm / 40 μm line and space (L / S) of the test piece.
○: No line loss and no undercut.
×: Line missing or undercut

(Resolution 2 evaluation test piece preparation method)
Each composition of Examples 5 to 7, 9 and Comparative Examples 3 and 5 among the photosensitive resin compositions described in Tables 1 and 2 below on a PET film (Lumilar T60 manufactured by Toray Industries, Inc., thickness 125 μm). Each conductive resin composition for evaluation was applied to the entire surface using a 380 mesh polyester screen so that the film thickness after drying was 5 μm, and then each composition of Examples 5 to 7 and Comparative Example 3 For 30 minutes in a hot air circulating drying oven (DF610 manufactured by Yamato Scientific Co., Ltd.) at 80 ° C., and for each composition of Example 9 and Comparative Example 5, a hot air circulating drying oven (DF610 manufactured by Yamato Scientific Co., Ltd.). ) For 15 minutes to form a dry coating film having good dryness to the touch. Then, using the exposure apparatus (HMW-680-GW20 manufactured by Oak Manufacturing Co., Ltd.) equipped with a metal halide lamp as a light source, the obtained dried coating film was passed through a 30 μm / 40 μm line and space (L / S) negative mask. Then, pattern exposure was performed with an optimum exposure amount. Here, the optimum exposure amount is obtained by exposing the dried coating film obtained above through a step tablet having a sensitivity of 21 steps using an exposure apparatus equipped with a metal halide lamp, and 0.2% by mass at a liquid temperature of 30 ° C. The exposure amount was set so that the pattern of the step tablet remaining when developing for 60 seconds under a spray pressure of 0.2 MPa using an aqueous Na ₂ CO ₃ solution was 6 steps. Then, the concentration of the liquid temperature 30 ° C. then developed with aqueous _Na 2 CO ₃ 0.2% by weight, and washed with water. Finally, it was cured at 150 ° C. for 60 minutes to prepare a test piece for evaluation of resolution.

(Resolution 2)
The resolution was evaluated in a 30 μm / 40 μm line and space (L / S) of the test piece.
○: No line loss and no undercut.
×: Line missing or undercut

(Development solution contamination assessment)
After 4 g of each composition of Examples 1 to 9 and Comparative Examples 1 to 5 was precisely weighed into a 100 ml screw tube, Examples 1 to 7 and Comparative Examples 1 to 3 were heated at 80 ° C. in a hot air circulation drying oven (Yamato). DF610 manufactured by Kagaku Co., Ltd. for 70 minutes, and Examples 8-9 and Comparative Examples 4-5 were each dried for 35 minutes in a hot air circulating drying oven (DF610 manufactured by Yamato Scientific Co., Ltd.) at a temperature of 90 ° C. Obtained. Drying examples coated screw tube film enters 1～4,8 and Comparative Examples 1～2,4 is 1 wt% _Na and 2 CO ₃ aqueous solution, examples 5～7,9 and Comparative Examples 3 and 5 For each, 30 g of 0.2 mass% Na ₂ CO ₃ aqueous solution was added, and the mixture was covered and stirred for 8 minutes, and then allowed to stand at 20 ° C. for 40 minutes. Then, it was confirmed visually whether solid matter adhered to the liquid upper surface of the screw tube. The evaluation criteria are as follows. The obtained results are shown in the above table.
(Double-circle): There is no solid substance and the liquid in a screw tube is transparent.
○: There is no solid matter, but the liquid in the screw tube is not transparent.
Δ: There is a slight amount of solid matter, and the liquid in the screw tube is not transparent.
X: A large amount of solid matter is present, and the liquid in the screw tube is not transparent.

(Developer clogged)
In “Developer Contamination”, the evaluated screw tube was allowed to stand at 20 ° C. for an additional 40 minutes. Thereafter, a filter having an opening of 10 μm was passed through, and the degree of clogging of the solid content in the filter was visually evaluated.
A: No solid clogging in the filter.
○: Solid clogging of filter is slightly present.
X: The filter has a large amount of clogged solids.

  Table 1 summarizes the test results. In addition, what is not attached | subjected with the numerical value regarding each component in Table 1 shows a mass part.

＊１１：下記構造式で示されるエポキシ樹脂（エポキシ当量：３００〜３３０ｇ／ｅｑ）

＊１２：熱硬化性成分、共栄社化学株式会社製エポライト４０Ｅ、エチレングリコールジグリシジルエーテル
＊１３：熱硬化性成分、旭化成ケミカルズ株式会社製ＤＵＲＡＮＡＴＥ ＭＦ−Ｂ６０Ｂ、ブロックイソシアネート
＊１４：２−フェニル−４，５−ジヒドロキシメチルイミダゾール、四国化成工業株式会社製キュアゾール ２ＰＨＺ−ＰＷ
＊１５：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌｕｅ １５：３
＊１６：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ １４７
＊１７：シリコーン系消泡剤、信越化学工業株式会社製ＫＳ−６６
＊１８：分散剤、ビックケミー・ジャパン社製ＤＩＳＰＥＲＢＹＫ−１９１
＊１９：有機酸、関東化学株式会社製 ２，２'−チオ二酢酸
＊２０：フィラー、堺化学工業株式会社製バリエースＢ−３０、硫酸バリウム
＊２１：フィラー、株式会社アドマファイン製ＳＯ−Ｅ２、球状シリカ
＊２２：フィラー、日本タルク株式会社製ＳＧ−２０００、タルク
＊２３：フィラー、球状銀粉末（最大粒径３０μｍ以下、平均粒径２μｍ、なお、平均粒径は、電子顕微鏡（ＳＥＭ）を用いて１０，０００倍にて観察したランダムな１０個の粒子の平均粒径である。）
＊２４：溶剤、出光興産株式会社製イプゾール１５０、石油系溶剤 In Table 1, * 1 to * 24 represent the following components. Moreover, the notation of "-" in Table 1 represents that it has not been evaluated.
* 1: Carboxyl group-containing bisphenol A type epoxy acrylate resin, solid content 64% by mass, solid content acid value 100 mgKOH / g, reference to synthesis of alkali-soluble resin 1, compounding amount in table is compounding amount of resin solution * 2: carboxyl Group-containing bisphenol A type urethane epoxy acrylate resin, solid content 51% by mass, solid content acid value 85 mgKOH / g, reference to synthesis of alkali-soluble resin 2, blending amount in table is blending amount of resin solution * 3: cyclomer P ( ACA) Z230AA, a carboxyl group-containing photosensitive copolymer resin solution manufactured by Daicel Ornex Co., Ltd., solid content 53.0% by mass, solid content acid value 40 mgKOH / g, the compounding amount in the table is the compounding amount of the resin solution * 4: Reactive diluent, Nippon Kayaku Co., Ltd. KAYARAD DPHA, dipentaerythritol pentaacrylate and Mixture with pentaerythritol hexaacrylate * 5: Reactive diluent, KAYARAD DPCA-60 manufactured by Nippon Kayaku Co., Ltd. Caprolactone modified product of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate * 6: Reactive dilution Agent, NK Oligo U-4HA manufactured by Shin-Nakamura Chemical Co., Ltd., tetrafunctional urethane (meth) acrylate obtained by reacting hexamethylene diisocyanate and 2-hydroxy-3-acryloyloxypropyl methacrylate * 7: Bisacylphosphine oxide light Polymerization initiator, Omnirad manufactured by IGM Resins 819
* 8: Oxime ester photopolymerization initiator, IRGACURE OXE02 manufactured by BASF Japan
* 9: Thermosetting component, jER828 manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin * 10: Epoxy resin represented by the following structural formula (epoxy equivalent: 300 to 330 g / eq)

* 11: Epoxy resin represented by the following structural formula (epoxy equivalent: 300 to 330 g / eq)

* 12: Thermosetting component, Kyoeisha Chemical Co., Ltd. Epolite 40E, ethylene glycol diglycidyl ether * 13: Thermosetting component, Asahi Kasei Chemicals Co., Ltd. DURANATE MF-B60B, Block isocyanate * 14: 2-Phenyl-4, 5-dihydroxymethylimidazole, Cure Sole 2PHZ-PW manufactured by Shikoku Kasei Kogyo Co., Ltd.
* 15: C.I. I. Pigment Blue 15: 3
* 16: C.I. I. Pigment Yellow 147
* 17: Silicone antifoaming agent, KS-66 manufactured by Shin-Etsu Chemical Co., Ltd.
* 18: Dispersant, DISPERBYK-191 manufactured by Big Chemie Japan
* 19: Organic acid, 2,2′-thiodiacetic acid manufactured by Kanto Chemical Co., Ltd. * 20: Filler, Variace B-30 manufactured by Sakai Chemical Industry Co., Ltd., Barium sulfate * 21: Filler, SO-E2 manufactured by Admafine, Inc. , Spherical silica * 22: filler, Nippon Talc Co., Ltd. SG-2000, talc * 23: filler, spherical silver powder (maximum particle size 30 μm or less, average particle size 2 μm, the average particle size is an electron microscope (SEM) The average particle size of 10 random particles observed at 10,000 times using
* 24: Solvent, Idzol 150 manufactured by Idemitsu Kosan Co., Ltd., petroleum solvent

As shown in Table 1 above, the contact angle of water is such that A and C are 75.0 ° or more, and the change rate of contact angle R ₈₀ (Examples 1 to 7) and R ₉₀ (Examples 8 to 9). In the photosensitive resin compositions of Examples 1 to 9 having a viscosity of 3.0 or less, the developing device is clogged with developer and clogged with developer in the developing process while satisfying the high resolution of the coating film after the main curing. It turns out that the photosensitive resin composition which can prevent is obtained. On the other hand, in the photosensitive resin compositions of Comparative Examples 1 and 2, since the contact angles A and C of water are less than 75.0 °, the contact angle change rates R ₈₀ (Comparative Examples 1 to 2) and R ₉₀ ( Even if Comparative Example 4) is 3.0 or less, it is possible to prevent the developing device from being contaminated with developer and clogged with deposits in the developing process while satisfying the high resolution of the coating film after the main curing. It can be seen that a conductive resin composition cannot be obtained. Further, in the photosensitive resin compositions of Comparative Examples 3 and 5, the contact angles A and C of water were 75.0 ° or more, but the contact angle change rates R ₈₀ (Comparative Example 3) and R ₉₀ (Comparative Example). 5) exceeds 3.0, so that the photosensitive resin composition capable of preventing contamination of the developing solution and clogging of the developing device due to precipitates in the developing process while satisfying the high resolution of the coating film after the main curing. It turns out that things cannot be obtained.

(Specific resistance value)
Each composition of Examples 6 and 9 was applied to the entire surface of a PET film (Lumilar T60, manufactured by Toray Industries, Inc., 125 μm thick) using a 380 mesh polyester screen, and then a hot-air circulating drying oven (Yamato Scientific Co., Ltd.) It was dried at 80 ° C. for 30 minutes on a company DF610) to form a dry coating film having good touch-drying properties. Then, using the obtained dry coating film as a light source, an exposure apparatus equipped with a metal halide lamp (HMW-680-GW20 manufactured by Oak Manufacturing Co., Ltd.), through a negative mask for forming a conductive pattern circuit of 4 mm × 100 mm, Pattern exposure was performed at the optimum exposure amount. Here, the optimum exposure amount is obtained by exposing the dried coating film obtained above through a step tablet having a sensitivity of 21 steps using an exposure apparatus equipped with a metal halide lamp, and 0.2% by mass at a liquid temperature of 30 ° C. The exposure amount was set so that the pattern of the step tablet remaining when developing for 60 seconds under a spray pressure of 0.2 MPa using an aqueous Na ₂ CO ₃ solution was 6 steps. Then, the liquid temperature 30 ℃, _Na 2 CO ₃ concentration then developed using a 0.2 wt% sodium carbonate aqueous solution, and washed with water. Finally, it was cured at 150 ° C. for 60 minutes to produce a test piece for evaluating specific resistance. The specific resistance was calculated by measuring the resistance value and the film thickness using such a test piece. As a result of the calculation, in both Examples 6 and 9, a specific resistance value as low as 4.0 × 10 ⁻⁵ (Ω · cm) was obtained. From the above, it can be seen that when an organic acid such as 2,2′-thiodiacetic acid is used in the conductive resin composition, it becomes more conductive.

Claims (5)

A photosensitive resin composition containing an alkali-soluble resin,
The contact angle of water in the dried coating film when the coating film formed by application of the photosensitive resin composition is dried at 80 ° C. for 40 minutes is A (°),
When the contact angle of water in the dry coating film when the coating film formed by application of the photosensitive resin composition is dried at 80 ° C. for 70 minutes is B (°),
A is 75.0 ° or more,
R ₈₀ (%) = | (B−A) / A | × 100
The photosensitive resin composition in the rate of change R ₈₀ represented is equal to or more than 3.0. A photosensitive resin composition containing an alkali-soluble resin,
The contact angle of water in the dried coating film when the coating film formed by application of the photosensitive resin composition is dried at 90 ° C. for 20 minutes is C (°),
When the contact angle of water in the dry coating film when the coating film formed by application of the photosensitive resin composition is dried at 90 ° C. for 35 minutes is defined as D (°),
C is 75.0 ° or more,
R ₉₀ (%) = | (D−C) / C | × 100
A photosensitive resin composition having a change rate R ₉₀ represented by the formula of 3.0 or less.   A dry film comprising a resin layer obtained by applying the photosensitive resin composition according to claim 1 or 2 to a film and drying the film.   A cured product obtained by curing the photosensitive resin composition according to claim 1 or 2 or the resin layer of the dry film according to claim 3.   A printed wiring board comprising the cured product according to claim 4.