JP2017037287A - Photosensitive resin composition, dry film, and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which has a high dielectric constant and is also excellent in resolution, and to provide a dry film and a printed wiring board using the photosensitive resin composition.SOLUTION: A photosensitive resin composition contains a carboxyl group-containing resin, a photopolymerization initiator, and at least two perovskite type compounds. One of the perovskite type compounds is barium titanate. The dry film has a resin layer obtained by applying the photosensitive resin composition onto a film and drying it. A cured product is obtained by curing the photosensitive resin composition or the resin layer of the dry film. The printed wiring board has a cured film obtained by curing the photosensitive resin composition or the dry film.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition (hereinafter, also simply referred to as “resin composition”), a dry film and a printed wiring board, and in particular, a photosensitive resin composition having a high dielectric constant and excellent resolution. The present invention relates to a dry film and a printed wiring board using the same.

  Conventionally, fingerprint detection devices have been used for applications such as entrance / exit management, but in recent years, they have attracted attention as personal authentication tools for portable terminals and security systems on computer networks. . In particular, recently, a capacitive fingerprint authentication sensor has been adopted for devices such as smartphones that require high fingerprint authentication accuracy. The principle of operation is to recognize the fingerprint by reading the difference in charge generated in the sensor due to the unevenness of the fingerprint with an electrode. For example, Patent Document 1 discloses a semiconductor device that can be used as a capacitive fingerprint detection device.

  The FC-BGA package used for such a fingerprint authentication sensor has a sensor surface on the top side (front side), a component such as an IC chip is mounted on the bottom side (back side), and solder balls are arranged. It has a structure. Since the sensor surface of the fingerprint authentication sensor requires high reading accuracy, the solder resist for the sensor surface requires high flatness and high dielectric constant. In particular, considering that this type of fingerprint authentication system will be changed from the current swipe method to the touch method in the future, the accuracy of fingerprint authentication is increasingly required. Such a fingerprint authentication sensor is required to have package-specific reliability such as HAST resistance.

JP 2002-71307 A

  Therefore, an object of the present invention is to provide a photosensitive resin composition having both high dielectric constant and high resolution applicable to a capacitive fingerprint authentication sensor while maintaining reliability such as HAST resistance, It is to provide a dry film and a printed wiring board using the same.

  As a result of intensive studies to achieve the above object, the present inventors have used at least two perovskite-type compounds and one of them as a resin composition containing barium titanate as an essential component. The inventors have found that a high dielectric constant and a high resolution can be achieved at a high level, and have completed the present invention.

That is, the photosensitive resin composition of the present invention is a photosensitive resin composition containing a carboxyl group-containing resin, a photopolymerization initiator, and at least two perovskite compounds,
One of the perovskite type compounds is barium titanate.

  In the photosensitive resin composition of the present invention, the absolute value of the difference between the refractive index of the carboxyl group-containing resin and the refractive index of the perovskite compound other than the barium titanate is 0.4 to 1.0. It is preferable.

  The dry film of the present invention is characterized in that the photosensitive resin composition has a resin layer that is applied and dried on the film.

  The cured product of the present invention is characterized in that the photosensitive resin composition or the resin layer of the dry film is cured.

  The printed wiring board of the present invention is characterized by having a cured film formed by curing the photosensitive resin composition or the dry film.

  According to the present invention, there are provided a photosensitive resin composition having a high dielectric constant and excellent resolution while maintaining reliability such as HAST resistance, and a dry film and a printed wiring board using the same. Can do. Moreover, the photosensitive resin composition of the present invention, the dry film using the same, and the printed wiring board can also be suitably applied to a capacitive fingerprint authentication sensor.

Hereinafter, embodiments of the present invention 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.

  The photosensitive resin composition of the present invention contains a carboxyl group-containing resin, a photopolymerization initiator, and at least two perovskite compounds. Further, the photosensitive resin composition of the present invention is characterized in that one of at least two perovskite compounds is barium titanate.

The photosensitive resin composition of the present invention contains at least two kinds of perovskite type compounds, and one of them contains barium titanate, so that a desired high dielectric constant and high resolution can be obtained. It became possible to achieve both. Since barium titanate is a high dielectric constant material, a desired high dielectric constant cannot be obtained unless the perovskite compound contains barium titanate. On the other hand, since barium titanate hardly transmits light having a wavelength of i-line (365 nm), when only one kind is used, sufficient resolution cannot be obtained. Here, the perovskite-type compound means a compound having a perovskite-type crystal structure generally found in complex oxides represented by the chemical formula ABO ₃ (both A and B represent metal atoms).

[Perovskite type compounds]
In the present invention, examples of perovskite type compounds that can be used with barium titanate include calcium titanate, strontium titanate, barium zirconate, calcium zirconate, strontium zirconate, and composite oxides containing these as main components. You can list things. Among these, it is preferable to use calcium titanate, strontium titanate, calcium zirconate, strontium zirconate, or a composite oxide containing these as a main component.

  Perovskite type compounds other than barium titanate may be used singly or in combination of two or more. Moreover, in order to obtain sufficient wettability to an organic compound such as a resin, such a perovskite type compound may be used which has been surface-treated with a coupling agent such as aminosilane, mercaptosilane, or vinylsilane. Good.

  Specific examples of commercially available perovskite compounds other than barium titanate used in the present invention include ST-03, CT-03, SZ-03, and CZ-03 manufactured by Sakai Chemical Industry Co., Ltd.

  Moreover, as a perovskite type compound other than barium titanate, it is preferable to use a compound having a refractive index of 0.4 to 1.0 as an absolute value of a difference from the refractive index of the carboxyl group-containing resin. If the difference between the refractive index of the carboxyl group-containing resin and the refractive index of the perovskite type compound other than barium titanate is within the above range, the resolution will be better. That is, the refractive index of the resin is generally 1.5 to 1.6, but if the refractive index of the perovskite type compound is close to the refractive index of the resin, the resulting resin composition has good resolution. ,preferable.

  In particular, it is preferable to use a combination of barium titanate and calcium zirconate as the perovskite type compound because a high dielectric constant and high resolution can be obtained well from the viewpoint of refractive index.

  Such a perovskite compound preferably has an average particle size of 0.01 to 1.0 μm, and more preferably 0.05 to 0.5 μm. By using a perovskite type compound having an average particle diameter within this range, the resolution can be further improved. An average particle diameter can be measured using a SEM (scanning electron microscope) photograph, for example.

Such a perovskite compound preferably has a specific surface area of 0.1 to 50 m ² / g, and more preferably ^{2 to} 30 m ² / g.

  Examples of the shape of such a perovskite type compound include a columnar shape, a ring shape, a spherical shape, a cubic shape, and a honeycomb shape. From the viewpoint of high filling with an inorganic filler, a spherical shape is preferable.

  In the present invention, the blending amount of the perovskite type compound is preferably 5 to 80% by mass, more preferably 20 to 80% by mass, and more preferably 30 to 70% by mass in the total composition. Is more preferable. If the blending amount of the perovskite compound is within such a range, the desired high dielectric constant and high resolution can be easily obtained.

  In the present invention, the mixing ratio of barium titanate and the perovskite type compound other than barium titanate is preferably barium titanate: perovskite type compound other than barium titanate = 1: 99 to 99: 1. It is more preferable that it is 10: 90-90: 10, and it is further more preferable that it is 25: 75-75: 25. If the blending ratio is within such a range, the desired high dielectric constant and high resolution can be easily obtained.

[Fillers other than perovskite type compounds]
In the curable resin composition of the present invention, a filler other than the perovskite type compound can be blended in order to increase the physical strength of the coating film. As such a filler, known and commonly used inorganic or organic fillers can be used. In particular, barium sulfate, spherical silica, talc, clay, kaolin, hydrotalcite, Neuburg siliceous particles and the like are preferably used. Furthermore, in order to obtain flame retardancy, metal hydroxides such as metal oxides and aluminum hydroxide can be used as extender pigment fillers. Among these, it is more preferable to use hydrotalcite because ionic impurities can be immobilized by ion exchange with a carbonate group and HAST resistance is more excellent. The amount of filler other than the perovskite type compound is preferably 20% by mass or less, more preferably 0.1 to 10% by mass, based on the total amount of the composition. When the blending amount of the filler is within such a range, it is excellent in coating and moldability, and a good cured product can be obtained.

[Carboxyl group-containing resin]
As the carboxyl group-containing resin constituting the curable resin composition of the present invention, a carboxyl group-containing resin having an ethylenically unsaturated group can be used. When such a carboxyl group-containing resin has alkali solubility and the resin composition of the present invention can be used as a patternable alkali-developable photocurable resin composition, when mounting components on the sensor surface Is also preferable from the viewpoint of productivity.

  In the present invention, it is particularly preferable to use a carboxyl group-containing resin having a polar group that contributes to a high dielectric constant such as a hydroxyl group. For example, a carboxyl group-containing resin using an epoxy resin as a starting material can contribute to the high dielectric constant of the resin composition because it has a hydroxyl group, but is a required performance when the resin composition is used for a solder resist for a package. It is thought that it is inferior to tolerance and PCT tolerance. On the other hand, when a copolymer resin is used as the carboxyl group-containing resin, HAST resistance and PCT resistance are improved. In addition, since the solder resist for a package affects the HAST resistance and PCT resistance, the content of chlorine as an impurity is small, that is, halogen-free may be required. When used for a solder resist, it is preferable to use a halogen-free resin.

Specific examples of the carboxyl group-containing resin having an ethylenically unsaturated bond include compounds as listed below (any of oligomers and polymers).
(1) Obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid, an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene, and a photosensitive monomer. A carboxyl group-containing resin having an ethylenically unsaturated group. The lower alkyl refers to an alkyl group having 1 to 5 carbon atoms.
(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 Of 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 During the synthesis, a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate For example, terminal (meth) were acrylated, carboxyl group-containing polyurethane resin having an ethylenically unsaturated group.
(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 During the synthesis of terminal carboxyl group-containing urethane resin by reacting acid anhydride with the terminal of urethane resin by polyaddition reaction of diol compounds such as alkylene oxide adduct diol, compounds having phenolic hydroxyl group and alcoholic hydroxyl group A compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate, and terminal (meth) acrylated, Carboxyl group-containing polyurethane resin having a down unsaturated group.
(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 ( A carboxyl group-containing polyurethane resin having an ethylenically unsaturated group by a polyaddition reaction of a meth) acrylate or a partially acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound and a diol compound.
(5) During the synthesis of the resin of (4) above, a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate is added, and terminal (meth) acrylation is performed. A carboxyl group-containing polyurethane resin having an ethylenically unsaturated group.
(6) 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 polyurethane resin which has the ethylenically unsaturated group which added the compound which has and was terminally (meth) acrylated.
(7) Ethylene in which (meth) acrylic acid is reacted with a polyfunctional epoxy resin, and a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride is added to the hydroxyl group present in the side chain A carboxyl group-containing resin having an unsaturated group. Here, the polyfunctional epoxy resin is preferably solid.
(8) A polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of a bifunctional epoxy resin with epichlorohydrin is reacted with (meth) acrylic acid, and a dibasic acid anhydride is added to the resulting hydroxyl group. A carboxyl group-containing resin having a saturated group. Here, the bifunctional epoxy resin is preferably solid.
(9) A carboxyl group-containing resin having an ethylenically unsaturated group obtained by reacting a dicarboxylic acid with a bifunctional oxetane resin and adding a dibasic acid anhydride to the resulting primary hydroxyl group.
(10) 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 resin having an ethylenically unsaturated group, obtained by reacting a product with a polybasic acid anhydride.
(11) Obtained by reacting an unsaturated group-containing monocarboxylic acid with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate. A carboxyl group-containing resin having an ethylenically unsaturated group, obtained by reacting a reaction product with a polybasic acid anhydride.
(12) 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 resin having an ethylenically unsaturated group, obtained by reacting a polybasic acid anhydride such as an acid.
(13) 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 carboxyl group-containing resin having an ethylenically unsaturated group, which is obtained by adding a compound having a group.

  Among the carboxyl group-containing resins having an ethylenically unsaturated group, a carboxyl group-containing resin that does not use an epoxy resin as a starting material can be suitably used. Therefore, among the specific examples of the carboxyl group-containing resin described above, a carboxyl group-containing resin having at least one ethylenically unsaturated group of (2), (3), (10), and (11) is preferably used. Can be used. Among these, it is particularly preferable to use the carboxyl group-containing resin (10) having an ethylenically unsaturated group.

  Thus, by not using an epoxy resin as a starting material, the amount of chlorine ion impurities can be suppressed to a very low value, for example, 100 ppm or less. The chlorine ion impurity content of the carboxyl group-containing resin having an ethylenically unsaturated group that is suitably used in the present invention is preferably 0 to 100 ppm, more preferably 0 to 50 ppm, and still more preferably 0 to 30 ppm. As a result of the chloride ion impurity content being suppressed to a small amount, high reliability is obtained in reliability tests such as HAST resistance.

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

  Moreover, the acid value of the said carboxyl group-containing resin has the preferable range of 20-200 mgKOH / g, More preferably, it is the range of 40-150 mgKOH / g. When the acid value of the carboxyl group-containing resin is 20 mgKOH / g or more, the adhesion of the coating film is good and the alkali developability is good. On the other hand, when the acid value is 200 mgKOH / g or less, it has excellent surface curability and can reduce development damage of the exposed portion by the developer.

  The weight average molecular weight of the carboxyl group-containing resin is preferably 2,000 to 150,000, although it varies depending on the resin skeleton. When the weight average molecular weight is 2,000 or more, a dry coating film excellent in dryness to touch can be obtained. On the other hand, when the weight average molecular weight is 150,000 or less, the alkali developability is good and the storage stability is also good. More preferably, it is 5,000-100,000.

  The amount of such a carboxyl group-containing resin is preferably 10 to 70% by mass, more preferably 10 to 50% by mass, and still more preferably 15 to 40% by mass based on the solid content in the entire composition. If the blending amount of the carboxyl group-containing resin is within such a range, the coating film strength does not decrease, and neither thickening nor workability deterioration occurs.

[Photopolymerization initiator]
As the photopolymerization initiator used in the curable resin composition of the present invention, any photopolymerization initiator known as a photopolymerization initiator or a photoradical generator can be used.

  Examples of the photopolymerization initiator include 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) -phenylphosphine oxide Bisacylphosphine oxides such as IRGACURE 819) manufactured by BASF Japan; 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, methyl 2,4,6-trimethylbenzoylphenylphosphinate Monoacylphosphine oxides such as ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (IRGACURE TPO manufactured by BASF Japan); 1-hydroxy-cyclohexyl phenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propyl Lopan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2-hydroxy-2 -Hydroxyacetophenones such as methyl-1-phenylpropan-1-one; benzoins such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether; benzoin alkyl Ethers; benzophenones such as benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone; acetophenone, 2,2-dimethoxy 2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-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 Acetophenones such as-(4-morpholinyl) phenyl] -1-butanone and N, N-dimethylaminoacetophenone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone 2-chlorothioxanthone, 2,4 Thioxanthones such as diisopropylthioxanthone; anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone; acetophenone dimethyl Ketals such as ketal and benzyldimethyl ketal; benzoates such as ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethylbenzoate and p-dimethylbenzoic acid ethyl ester; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, Oxime esters such as 1- (O-acetyloxime); bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl ) Titanocenes such as titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2- (1-pyr-1-yl) ethyl) phenyl] titanium; phenyl disulfide 2-nitrofluorene, Examples include butyroin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, and the like. Of these, monoacylphosphine oxides and oxime esters are preferable, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- 3-yl]-, 1- (O-acetyloxime) is more preferred. A photoinitiator may be used individually by 1 type and may be used in combination of 2 or more type.

  It is preferable to set it as 0.1-20 mass parts with respect to 100 mass parts of carboxyl group-containing resin, and, as for the compounding quantity of a photoinitiator, it is more preferable to set it as 0.5-15 mass parts. When the blending amount of the photopolymerization initiator is 0.1 parts by mass or more, the surface curability is good, and when the blending amount of the photopolymerization initiator is 20 parts by mass or less, halation hardly occurs and good resolution is obtained. It is done.

[Thermosetting component]
The resin composition of the present invention can contain a thermosetting component. The thermosetting component only needs to react with the carboxyl group-containing resin, and examples thereof include an epoxy compound, a compound having an amino group, an oxetane compound, and an isocyanate compound. Among these, an epoxy compound is preferable.

  Epoxy compounds include epoxidized vegetable oil, bisphenol A type epoxy resin, hydroquinone type epoxy resin, bisphenol type epoxy resin, thioether type epoxy resin, brominated epoxy resin, novolac type epoxy resin, biphenol novolac type epoxy resin, bisphenol F type epoxy. Resin, hydrogenated bisphenol A type epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin, alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bixylenol type or biphenol type epoxy resin or a mixture thereof, bisphenol S Type epoxy resin, bisphenol A novolac type epoxy resin, tetraphenylolethane type epoxy resin; heterocyclic epoxy resin, diglycidyl phthalate Resin, tetraglycidylxylenoylethane resin, naphthalene group-containing epoxy resin, epoxy resin having dicyclopentadiene skeleton, glycidyl methacrylate copolymer epoxy resin, cyclohexylmaleimide and glycidyl methacrylate copolymer epoxy resin, epoxy modified Examples thereof include, but are not limited to, polybutadiene rubber derivatives and CTBN-modified epoxy resins. From the viewpoint of reactivity, a bifunctional or higher functional epoxy compound is preferred.

  Examples of the compound having an amino group include amino resins such as melamine derivatives and benzoguanamine derivatives. For example, there are methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, methylol urea compounds, and the like. Furthermore, the alkoxymethylated melamine compound, alkoxymethylated benzoguanamine compound, alkoxymethylated glycoluril compound and alkoxymethylated urea compound have the methylol group of the respective methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound and methylolurea compound. Obtained by conversion to an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited, and can be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like. In particular, melamine derivatives having a formalin concentration of 0.2% or less that are friendly to the human body and the environment are preferable.

  Examples of the oxetane compound 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) methyl acrylate In addition to polyfunctional oxetanes such as (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 bisphenols, Calixarene compounds, calix resorcin arenes or etherified products such as the 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.

  As the isocyanate compound, a polyisocyanate compound having a plurality of isocyanate groups in the molecule can be used. 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. Moreover, the adduct body, burette body, and isocyanurate body of the isocyanate compound mentioned above are mentioned. The isocyanate compound may be a blocked isocyanate compound in which an isocyanate group is protected by a blocking agent and temporarily deactivated.

  The thermosetting component may be a compound other than those described above, and known and commonly used thermosetting components such as a maleimide compound, a benzoxazine resin, a carbodiimide resin, a cyclocarbonate compound, and an episulfide resin can be used. A thermosetting component may be used individually by 1 type, and may be used in combination of 2 or more type.

  The thermosetting component is blended so that the thermosetting reactive group of the thermosetting component that reacts with the carboxyl group is 0.1 to 5 equivalents with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing resin in terms of solid content. An amount is preferred. In particular, when the thermosetting component is an epoxy resin, a blending amount such that the epoxy group is 0.3 to 3 equivalents relative to 1 equivalent of the carboxyl group of the carboxyl group-containing resin is preferable. Within this range, curability is improved and general characteristics such as solder heat resistance are improved. Moreover, sufficient toughness is obtained and storage stability is not lowered.

[Photosensitive monomer]
The resin composition of the present invention may further contain a known and commonly used photosensitive monomer. The photosensitive monomer is a compound having one or more ethylenically unsaturated groups in the molecule. The photosensitive monomer assists photocuring of the carboxyl group-containing resin by irradiation with active energy rays.

  Examples of the compound used as the photosensitive monomer include known and commonly used polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, and the like. 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 side adducts, propylene oxide adducts, or ε-caprolactone adducts; phenoxy acrylate, bisphenol A diacrylate, and polyvalent acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols Polyglycerides of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate; other polyether polyols, polycarbonate diols, hydroxyl terminated polybutadienes, polyester polyols, etc. Acrylates obtained by direct acrylated polyol or urethane acrylated via diisocyanate And melamine acrylate, and methacrylates corresponding to the acrylate.

  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 obtained by reacting a half urethane compound may be used as a photosensitive monomer. Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.

  The compounding quantity of the photosensitive monomer is 0.1-20 mass parts suitably with respect to 100 mass parts of carboxyl group-containing resin in solid content conversion, More preferably, it is 1-10 mass parts. This is because, within this range, photocurability is improved, and pattern formation is facilitated and coating film strength is improved by alkali development after irradiation with active energy rays.

[Organic solvent]
The resin composition of the present invention may contain an organic solvent for the purpose of preparing the composition and adjusting the viscosity when applied to a substrate or a carrier film. Examples of organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether , Glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butylcarby Tall acetate, propylene glycol monomethyl ether acetate, dip Propylene glycol monomethyl ether acetate, esters such as propylene carbonate; octane, aliphatic hydrocarbons decane; petroleum ether, petroleum naphtha, and petroleum solvents such as solvent naphtha, organic solvents conventionally known can be used. These organic solvents can be used alone or in combination of two or more.

[Other optional ingredients]
Further, the resin composition of the present invention may be blended with other known and commonly used additives in the field of electronic materials. Other additives include thermosetting catalysts, thermal polymerization inhibitors, UV absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, anti-aging agents, antibacterial / antifungal agents, antifoaming agents, and leveling Agent, thickener, adhesion imparting agent, thixotropic agent, colorant, photoinitiator aid, sensitizer, thermoplastic resin, organic filler, mold release agent, surface treatment agent, dispersant, dispersion aid, Examples include surface modifiers, stabilizers, and phosphors.

  The 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.

  The dry film of the present invention has a resin layer obtained by applying and drying the resin composition of the present invention on a carrier film. Although flatness is required for the sensor surface of the fingerprint authentication sensor, it is preferable to use the resin composition of the present invention as a dry film because the flatness is improved.

  When forming a dry film, first, the resin composition of the present invention is diluted with the above organic solvent to adjust to an appropriate viscosity, and then a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse Apply a uniform thickness on the carrier film using a coater, transfer roll coater, gravure coater, spray coater or the like. Then, the resin layer can be formed by drying the applied composition at a temperature of 40 to 130 ° C. for 1 to 30 minutes. Although there is no restriction | limiting in particular about a coating film thickness, Generally, it is a film thickness after drying, and is suitably selected in the range of 5-150 micrometers, Preferably it is 15-60 micrometers.

  As the carrier film, a plastic film is used. For example, a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, or the like can be used. Although there is no restriction | limiting in particular about the thickness of a carrier film, Generally, it selects suitably in the range of 10-150 micrometers. More preferably, it is the range of 15-130 micrometers.

  After the resin layer made of the resin composition of the present invention is formed on the carrier film, a peelable cover film is further laminated on the film surface for the purpose of preventing dust from adhering to the film surface. It is preferable. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used. As a cover film, what is necessary is just a thing smaller than the adhesive force of a resin layer and a carrier film when peeling a cover film.

  In the present invention, a resin layer may be formed by applying and drying the resin composition of the present invention on the cover film and laminating a carrier film on the surface. That is, any of a carrier film and a cover film may be used as a film to which the resin composition of the present invention is applied when producing a dry film in the present invention.

The resin composition of this invention is used for manufacture of a printed wiring board by the following method, for example.
When the resin composition of the present invention is used in a liquid state, the resin composition is adjusted to a viscosity suitable for the coating method using, for example, the above organic solvent, and a dip coating method or a flow coating method is applied on the substrate. After coating by a method such as a roll coating method, a bar coater method, a screen printing method, or a curtain coating method, the organic solvent contained in the composition is evaporated and dried (temporarily dried) at a temperature of 60 to 100 ° C. A tack-free resin layer can be formed. In the case of a dry film obtained by applying the above composition on a carrier film or a cover film and drying and winding it as a film, the layer of the composition of the present invention is brought into contact with the substrate by a laminator or the like. After bonding together, the resin film can be formed by peeling off the carrier film.

  Examples of the base material include printed wiring boards and flexible printed wiring boards that have been previously formed with copper or the like, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy. It is made of materials such as copper-clad laminates for high-frequency circuits using synthetic fiber epoxy, fluororesin, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate, etc., and copper-clad laminates of all grades (FR-4 etc.) Examples thereof include a plate, a metal substrate, a polyimide film, a PET film, a polyethylene naphthalate (PEN) film, a glass substrate, a ceramic substrate, and a wafer plate.

  Volatile drying performed after applying the resin composition of the present invention is performed by using a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven or the like (using a heat source of an air heating method using steam, A counter-current contact method and a method of spraying the support from a nozzle).

  When the resin composition of the present invention contains a thermosetting component, for example, the resin composition of the present invention is heated to 100 to 220 ° C. to be thermally cured, whereby heat resistance, chemical resistance, moisture absorption resistance, adhesion, A cured film (cured product) excellent in various properties such as properties can be formed.

  When the resin composition of the present invention is photocurable, the resin layer obtained after applying the resin composition of the present invention and evaporating and drying the solvent is exposed (light irradiation), The exposed portion (the portion irradiated with light) is cured. Specifically, exposure is selectively performed with an active energy ray through a photomask on which a pattern is formed by a contact method or a non-contact method, or pattern exposure is directly performed by a laser direct exposure machine. A resist pattern can be formed by developing the unexposed portion with a dilute alkaline aqueous solution (for example, a 0.3 to 3 mass% sodium carbonate aqueous solution).

As an exposure machine used for the active energy ray irradiation, a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, and the like may be used as long as the apparatus irradiates ultraviolet rays in a range of 350 to 450 nm. Furthermore, a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer) can also be used. The lamp light source or laser light source of the direct drawing machine may have a maximum wavelength in the range of 350 to 410 nm. The amount of exposure for image formation varies depending on the film thickness and the like, but is generally 10 to 1000 mJ / cm ² , preferably 20 to 800 mJ / cm ² .

  The developing method can be a dipping method, a shower method, a spray method, a brush method, etc., and as a developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.

  Since the resin composition of the present invention has a high dielectric constant and high resolution, it can be suitably applied as a solder resist for printed wiring boards, a solder resist for packages, and the like, and in particular, a solder resist for fingerprint authentication sensors. As useful.

  EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following description, “parts” and “%” are all based on mass unless otherwise specified.

<Synthesis example of carboxyl group-containing resin solution>
(Synthesis Example 1)
In an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device, and a stirring device, 119.4 parts of a novolac type cresol resin (manufactured by Showa Denko KK, trade name “Shonol CRG951”, OH equivalent: 119.4), 1.19 parts of potassium hydroxide and 119.4 parts of toluene were charged, the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 parts of propylene oxide was gradually added dropwise and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The nonvolatile content was 62.1%, the hydroxyl value was 182.2 g / eq. A novolak-type cresol resin propylene oxide reaction solution was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.

  Next, 293.0 parts of an alkylene oxide reaction solution of the obtained novolak-type cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 part of methylhydroquinone and 252.9 parts of toluene were mixed with a stirrer. A reactor equipped with a thermometer and an air blowing tube was charged, air was blown at a rate of 10 ml / min, and the reaction was carried out at 110 ° C. for 12 hours while stirring. 12.6 parts of water was distilled from the water produced by the reaction as an azeotrope with toluene. Thereafter, the reaction solution was cooled to room temperature, neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution, and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 parts of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution.

  Next, 332.5 parts of the obtained novolak acrylate resin solution and 1.22 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min. While stirring, 60.8 parts of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 101 ° C. for 6 hours. A resin solution of a carboxyl group-containing photosensitive resin having a solid content acid value of 88 mgKOH / g, a carboxylic acid equivalent (solid content) of 638, a non-volatile content of 71%, and an Mw of about 10,000 was obtained. This resin solution is referred to as carboxyl group-containing resin solution A.

(Synthesis Example 2)
A flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser is charged with methyl methacrylate, ethyl methacrylate, and methacrylic acid in a molar ratio of 1: 1: 2, and dipropylene glycol monomethyl ether as a solvent, catalyst As a solution, azobisisobutyronitrile (AIBN) was added and stirred at 80 ° C. for 4 hours under a nitrogen atmosphere to obtain a resin solution. This resin solution is cooled, methylhydroquinone as a polymerization inhibitor, tetrabutylphosphonium bromide as a catalyst, and glycidyl methacrylate is added at 20% by mole to the carboxyl group of the resin at 95 to 105 ° C. for 16 hours. And cooled and then taken out. The thus obtained carboxyl group-containing photosensitive resin having both an ethylenically unsaturated bond and a carboxyl group has a solid content acid value of 120 mgKOH / g, a carboxylic acid equivalent (solid content) of 468, a non-volatile content of 71%, and an Mw of about 20 000. This resin solution is referred to as a carboxyl group-containing resin solution B.

<Measurement of refractive index>
The refractive indexes of the carboxyl group-containing resin solutions A and B were measured according to JIS K 7105. Based on the measurement result of the obtained carboxyl group-containing resin solution, a value converted to a solid content of 100% was calculated as each refractive index of A and B.

(Examples 1-8 and Comparative Examples 1-3)
According to the formulation shown in Table 1 below, each component was kneaded with a three-roll mill to obtain resin compositions of Examples 1 to 8 and Comparative Examples 1 to 3.

  Using the compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 3, dry films and printed wiring boards were produced by the following operations.

<Production of dry film>
After appropriately diluting the compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 3, respectively, with methyl ethyl ketone, using an applicator, a PET film (manufactured by Toray Industries, Inc.) so that the film thickness after drying becomes 20 μm. FB-50: thickness 16 μm) and dried at 80 ° C. for 30 minutes to obtain a dry film.

<Production of evaluation substrate>
After buffing the surface of the substrate on which the circuit was formed, the dry film was pressed using a vacuum laminator (MVLP (registered trademark) -500 manufactured by Meiki Seisakusho Co., Ltd.) at a pressure of 0.8 MPa, 70 ° C. for 1 minute, The laminate was heated and laminated under the condition of vacuum degree: 133.3 Pa to obtain an evaluation substrate having a resin layer (dry film) of the unexposed photosensitive resin composition.

  Using this exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), this substrate was subjected to pattern exposure with an optimum exposure amount, and the PET film was peeled off. Thereafter, development was performed for 60 seconds using a 1 mass% sodium carbonate aqueous solution at 30 ° C. under a spray pressure of 0.2 MPa to obtain a resist pattern.

This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes. The resist pattern of the photosensitive resin composition was formed in a form having an opening of 200 μm on copper forming the circuit of the evaluation substrate.

Here, the optimum exposure amount means the following exposure amount.
That is, the evaluation substrate obtained above was exposed through a step tablet (Kodak No. 2) using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and developed (30 ° C., 0.2 MPa, 1 mass). % Sodium carbonate aqueous solution) in 60 seconds means the exposure amount when the pattern of the step tablet remaining is 7 steps.

  About the obtained evaluation board | substrate, the characteristic was evaluated as follows.

<Resolution>
An opening having an opening diameter of 200 μm was observed with an SEM (scanning electron microscope) and evaluated according to the following criteria.
○: When the copper surface at the bottom of the opening is a good shape.
X: In the case of an opening shape defect in which the copper surface at the bottom of the opening is not confirmed.

<Pencil hardness>
The cured coating film of the evaluation substrate was tested according to the test method of JIS K 5600, and the highest hardness at which the coating film was not damaged was measured.

<Evaluation of dielectric constant>
The above-mentioned dry film is applied on a 9 μm-thick electrolytic copper foil (Furukawa Electric Co., Ltd.) using a vacuum laminator (MVLP (registered trademark) -500 manufactured by Meiki Seisakusho Co., Ltd.). Heat lamination was performed for 1 minute under the condition of a degree of vacuum of 133.3 Pa. The dry film laminated on the copper foil was solid-exposed with an optimum exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and the PET film was peeled off.

The dry film was heat laminated again on the exposed dry film, and then solid exposure was performed with an optimum exposure amount. Lamination and exposure were repeated 20 times to form a dry film layer having a thickness of 400 μm on the copper foil. The copper foil thus formed with the dry film layer was irradiated with ultraviolet rays in a UV conveyor furnace under the condition of an integrated exposure amount of 1000 mJ / cm ² and then heated at 150 ° C. for 60 minutes to cure the dry film layer.

  Next, the copper foil is removed from the copper foil with a dry film layer using an etching solution having a composition of cupric chloride of 340 g / l and free hydrochloric acid concentration of 51.3 g / l, sufficiently washed with water and dried. A test piece made of a cured product having a thickness of 400 μm was prepared.

About the test piece produced in this way, the dielectric constant at 1 GHz was measured (capacitance method) using an RF impedance / material analyzer (Agilent E4991A manufactured by Agilent Technologies) and evaluated according to the following criteria.
○: When the dielectric constant is 5 or more.
X: When dielectric constant is less than 5.

<HAST resistance>
After chemically polishing a printed wiring board on which comb-shaped electrodes (line / space = 20 μm / 20 μm) are formed, the dry film is pressurized using a vacuum laminator (MVLP (registered trademark) -500 manufactured by Meiki Seisakusho) The laminate was heated and laminated under the conditions of a degree of 0.8 MPa, 70 ° C., 1 minute, and a degree of vacuum of 133.3 Pa to obtain a printed wiring board having an unexposed solder resist layer (dry film). This substrate was exposed with an appropriate exposure amount through a negative mask having an opening of 2 mm □ using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and the PET film was peeled off. Thereafter, development was performed for 60 seconds using a 1% by mass aqueous sodium carbonate solution at 30 ° C. under a spray pressure of 0.2 MPa to obtain a resist pattern. This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes. After the substrate was prepared, it was placed in a high-temperature and high-humidity tank under an atmosphere of 130 ° C. and humidity 85%, a voltage of 5.5 V was applied, and an in-chamber HAST test was performed. The insulation resistance value in the tank when a predetermined time elapsed was measured, and HAST resistance was evaluated. The judgment criteria are as follows.
A: When the insulation resistance value in the tank is less than 10 ⁶ Ω or a short circuit occurs after 400 hours or more.
○: When the insulation resistance value in the tank is less than 10 ⁶ Ω or a short circuit occurs for 200 hours or more and less than 400 hours.
X: When the insulation resistance value in the tank is less than 10 ⁶ Ω or a short circuit occurs in less than 200 hours.

  These evaluation results are also shown in Table 1 below.

＊１）カルボキシル基含有樹脂溶液Ａ（合成例１）：ＰＯ変性フェノール樹脂／アクリル酸／テトラヒドロフタル酸 固形分酸価：８８ｍｇＫＯＨ／ｇ（カルボン酸当量：６３７．５）屈折率：１．５６、配合量は不揮発分（固形分）の値
＊２）カルボキシル基含有樹脂溶液Ｂ（合成例２）：メタクリル酸メチル−アクリル酸共重合樹脂／グリシジルメタクリレート 固形分酸価：１２０ｍｇＫＯＨ／ｇ（カルボン酸当量：４６７．５）屈折率：１．５１、配合量は不揮発分（固形分）の値
＊３）光重合開始剤：２，４，６−トリメチルベンゾイル−ジフェニル−フォスフィンオキサイド
＊４）アクリレートモノマー：トリシクロデカンジメタノールジアクリレート
＊５）エポキシ樹脂：ビスフェノールＡ型エポキシ樹脂 エポキシ当量：１９０
＊６）硬化触媒：ジシアンジアミド
＊７）チタン酸バリウム：堺化学工業株式会社製 ＢＴ−０３ 屈折率：２．４０ 平均粒径：０．３μｍ
＊８）チタン酸カルシウム：堺化学工業株式会社製 ＣＴ−０３ 屈折率：２．３５ 平均粒径：０．３μｍ
＊９）チタン酸ストロンチウム：堺化学工業株式会社製 ＳＴ−０３ 屈折率：２．４９
平均粒径：０．３μｍ
＊１０）ジルコン酸カルシウム：堺化学工業株式会社製 ＣＺ−０３ 屈折率：２．１４
平均粒径：０．３μｍ
＊１１）ジルコン酸ストロンチウム：堺化学工業株式会社製 ＳＺ−０３ 屈折率：２．０８ 平均粒径：０．３μｍ
＊１２）ハイドロタルサイト：協和化学工業株式会社製 ＤＨＴ−４Ａ
＊１３）二酸化チタン：石原産業株式会社製 ＣＲ−５８ 屈折率：２．７１（ルチル型） 平均粒径：０．２８μｍ
＊１４）硫酸バリウム：堺化学工業株式会社製 Ｂ−３０ 屈折率：１．６４ 平均粒径：０．３μｍ
＊１５）溶剤：プロピレングリコールモノメチルエーテルアセテート
＊１６）当量比（エポキシ／カルボン酸）は、以下の計算式により算出した。
当量比（エポキシ／カルボン酸）＝（エポキシ樹脂の配合量／エポキシ樹脂のエポキシ当量）／（カルボキシル基含有樹脂（固形分）の配合量／カルボキシル基含有樹脂のカルボン酸当量（固形分））
＊１７）屈折率差の絶対値とは、カルボキシル基含有樹脂の屈折率と、チタン酸バリウム以外のペロブスカイト化合物の屈折率との差の絶対値を示す。

* 1) Carboxyl group-containing resin solution A (Synthesis Example 1): PO-modified phenol resin / acrylic acid / tetrahydrophthalic acid Solid content acid value: 88 mgKOH / g (carboxylic acid equivalent: 637.5) Refractive index: 1.56, Compounding amount is value of non-volatile content (solid content) * 2) Carboxyl group-containing resin solution B (Synthesis example 2): Methyl methacrylate-acrylic acid copolymer resin / glycidyl methacrylate Solid content acid value: 120 mgKOH / g (carboxylic acid equivalent) : 467.5) Refractive index: 1.51, blending amount is a non-volatile content (solid content) * 3) Photopolymerization initiator: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide * 4) Acrylate monomer : Tricyclodecane dimethanol diacrylate * 5) Epoxy resin: Bisphenol A type epoxy resin Epoxy equivalent: 190
* 6) Curing catalyst: Dicyandiamide * 7) Barium titanate: Sakai Chemical Industry Co., Ltd. BT-03 Refractive index: 2.40 Average particle size: 0.3 μm
* 8) Calcium titanate: Sakai Chemical Industry Co., Ltd. CT-03 Refractive index: 2.35 Average particle size: 0.3 μm
* 9) Strontium titanate: manufactured by Sakai Chemical Industry Co., Ltd. ST-03 Refractive index: 2.49
Average particle size: 0.3 μm
* 10) Calcium zirconate: Sakai Chemical Industry Co., Ltd. CZ-03 Refractive index: 2.14
Average particle size: 0.3 μm
* 11) Strontium zirconate: SZ-03 manufactured by Sakai Chemical Industry Co., Ltd. Refractive index: 2.08 Average particle size: 0.3 μm
* 12) Hydrotalcite: DHT-4A manufactured by Kyowa Chemical Industry Co., Ltd.
* 13) Titanium dioxide: CR-58 manufactured by Ishihara Sangyo Co., Ltd. Refractive index: 2.71 (rutile type) Average particle size: 0.28 μm
* 14) Barium sulfate: manufactured by Sakai Chemical Industry Co., Ltd. B-30 Refractive index: 1.64 Average particle size: 0.3 μm
* 15) Solvent: Propylene glycol monomethyl ether acetate * 16) The equivalent ratio (epoxy / carboxylic acid) was calculated by the following formula.
Equivalent ratio (epoxy / carboxylic acid) = (epoxy resin compounding amount / epoxy resin epoxy equivalent) / (carboxyl group-containing resin (solid content) compounding amount / carboxyl group-containing resin carboxylic acid equivalent (solid content))
* 17) The absolute value of the refractive index difference indicates the absolute value of the difference between the refractive index of the carboxyl group-containing resin and the refractive index of the perovskite compound other than barium titanate.

  As is clear from the results shown in Table 1, it was confirmed that according to this example, a resin composition having a high dielectric constant and high resolution can be obtained.

Claims (5)

A photosensitive resin composition containing a carboxyl group-containing resin, a photopolymerization initiator, and at least two perovskite compounds,
One type of the perovskite type compound is barium titanate, A photosensitive resin composition characterized by things.   The photosensitive resin composition according to claim 1, wherein an absolute value of a difference between a refractive index of the carboxyl group-containing resin and a refractive index of a perovskite compound other than the barium titanate is 0.4 to 1.0.   3. A dry film comprising the resin layer obtained by applying and drying the photosensitive resin composition according to claim 1 or 2 on a 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 a cured film obtained by curing the photosensitive resin composition according to claim 1 or 2 or the dry film according to claim 3.