JP2023062784A - Photosensitive resin composition, laminate and cured product of the same, and transparent material having the cured product - Google Patents

Abstract

To provide a photosensitive resin composition which enables formation of a cured product that is useful as a transparent material, especially, a material for a transparent antenna of a smart phone or a car navigation employing 5G, and has good resolution, good plating resistance, appropriate transmittance, a suppressed haze value and water vapor transmittance.SOLUTION: There are provided a photosensitive resin composition that contains (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, (C) a compound having an unsaturated double bond, (D) a thermosetting resin, and (E) a filler having an average particle size of 120 nm or less, wherein a value of a ratio of total light transmittance at a wavelength of 550 nm to total light transmittance at a wavelength of 430 nm in film thickness of 20 μm of a cured product obtained from the photosensitive resin composition is within a range of 0.90 or more and less than 1.15, and a haze value at a wavelength of 550 nm of the cured product is within a range of more than 0.0% and less than 2.0%; and a cured product of the same.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a photosensitive resin composition, a laminate and a cured product thereof, and a transparent material having the cured product, for example, a transparent protective material for transparent antennas of car navigation systems, smartphones, and the like.

In recent years, from the viewpoint of high-speed and large-capacity data communication, 5G (5th generation mobile communication system) is gaining attention.
5G has the advantage of significantly improved communication speed and capacity compared to 4G, but on the other hand, due to the complexity of the circuits that adopt 5G, products such as smartphones or car navigation systems When it is used in the antenna of the third party, it may affect the appearance of the product, that is, the design property, and reduce the value of the product.
Therefore, in order to alleviate such a situation, as an example, the antenna itself, including the protective material, is configured with ultra-fine wiring and transparent materials to increase the transparency of the entire antenna, thereby maintaining the design of the product. Ideas can also arise.
In this respect, various candidates can be cited as such transparent materials. For example, Patent Document 1 discloses a curable resin composition containing an amideimide resin, and a cured product obtained from the composition having excellent transparency. is stated.

Japanese Patent No. 5839149

However, when targeting transparent antennas for smartphones or car navigation products that use 5G, in addition to the characteristics that materials for electronic circuits should originally have, protective materials for such antennas are used for transparent antennas and various other purposes. From the point of view of protecting electronic circuits from gases, high transparency and high gas barrier properties are also required. More specifically, such materials are desired to combine good resolution, good plating resistance, adequate transmittance, controlled haze and water vapor transmission.

Regarding this point, the resin composition according to the technology described in Patent Document 1 is only described as being useful as a solder resist material for printed wiring boards or semiconductor package substrates, and is premised on the adoption of 5G. It does not specifically propose a material for a transparent antenna for such products and a resin composition capable of imparting properties sufficient for the material.

Therefore, the present invention provides good resolution, good plating resistance, appropriate transmittance, suppressed haze value and water vapor, which are useful as transparent materials, especially materials for transparent antennas of smartphones or car navigation systems that employ 5G. An object of the present invention is to provide a photosensitive resin composition capable of forming a cured product having both transmittance.

As a result of intensive studies by the inventors, the above problems are
(A) a carboxyl group-containing resin;
(B) a photoinitiator;
(C) a compound having an unsaturated double bond;
(D) a thermosetting resin;
(E) a photosensitive resin composition comprising a filler having an average particle size of 120 nm or less,
The ratio of the total light transmittance at a wavelength of 550 nm to the total light transmittance at a wavelength of 430 nm at a film thickness of 20 μm of the cured product obtained from the photosensitive resin composition is in the range of 0.90 or more and less than 1.15,
It was found that the haze value of the cured product at a wavelength of 550 nm is in the range of more than 0.0% and less than 2.0%.
Among these, a preferred embodiment of the present invention relates to a photosensitive resin composition, wherein (A) the carboxyl group-containing resin is a resin having a carboxyl group obtained by addition reaction of an acid anhydride.
In another preferred embodiment of the present invention, (A) the carboxyl group-containing resin is obtained by reacting an isocyanurate-type polyisocyanate synthesized from an isocyanate having an aliphatic structure with a tricarboxylic acid anhydride having an aliphatic structure. The present invention relates to a photosensitive resin composition comprising an amide-imide resin obtained by
Still another aspect of the present invention relates to a photosensitive resin composition, wherein (D) the thermosetting resin is an epoxy resin having a Gardner color number of 5 or less.
Furthermore, a more preferred embodiment of the present invention relates to a photosensitive resin composition further comprising (F) a thermosetting catalyst that is liquid at 20°C or higher and lower than 70°C.
Yet another aspect of the present invention relates to a photosensitive resin laminate characterized by having a resin layer obtained by coating and drying the above photosensitive resin composition on a film.
Still another aspect of the present invention is a cured product obtained by curing the resin layer of the photosensitive resin composition or the photosensitive resin laminate, and a cured product comprising the cured product It also relates to a transparent antenna, characterized in that:
A more preferred embodiment of the present invention relates to a photosensitive resin composition characterized by having a water vapor transmission rate of less than 10 g/m ² /day at a film thickness of 100 μm of the cured product.

The cured product obtained from the photosensitive resin composition of the present invention not only exhibits good resolution and good plating resistance, but also has an appropriate transmittance ratio, a suppressed haze value and a water vapor transmission rate. . Therefore, it is particularly useful as a transparent material for electronic circuits, especially as a transparent protective material for transparent antennas of products such as smartphones and car navigation systems compatible with 5G.

As described above, the photosensitive resin composition of the present invention is based on the assumption that the obtained cured product is used as a transparent material for transparent antennas of products compatible with 5G. Therefore, the component composition of the photosensitive resin composition of the present invention is determined so that the transparency of the cured product satisfies a certain level.
Specifically, the transparency of such a cured product according to the present invention is the value of the ratio of the total light transmittance at a wavelength of 550 nm and the total light transmittance at a wavelength of 430 nm at a film thickness of 20 μm of the cured product (wavelength 550 nm The total light transmittance of /total light transmittance at a wavelength of 430 nm; is a level such that the haze value of is in the range of more than 0.0% and less than 2.0%.
By defining the total light transmittance ratio within the above numerical range, the yellowness of the cured product can be suppressed. Further, by specifying the haze value within the above numerical range, the haze of the cured product can be suppressed.
Such total light transmittance can be measured, for example, according to ISO13468 using an integrating sphere device.
Also, the haze value can be measured, for example, according to ISO14782 using an integrating sphere apparatus.

Furthermore, the photosensitive resin composition according to the present invention is formulated so that the cured product thereof achieves high gas barrier properties from the viewpoint of line protection. In other words, the photosensitive resin composition according to the present invention is preferably formulated so that the cured product thereof has a more suppressed water vapor transmission rate. More specifically, the cured product preferably has a water vapor transmission rate of less than 10 g/m ² /day at a film thickness of 100 μm.
Such water vapor transmission rate can be measured, for example, according to the JIS Z0208 method.

The constituent components of such a photosensitive resin composition of the present invention are described below.

[(A) Carboxyl Group-Containing Resin]
The photosensitive resin composition of the present invention employs a resin component into which a carboxyl group has been introduced in order to form a circuit pattern using exposure and alkali development. Furthermore, from the viewpoint of the purpose and application of the present invention, one having a structure with high transparency and excellent gas barrier properties must be selected.
As an example of such a carboxyl group-containing resin (A), in the present invention, a resin having a carboxyl group obtained by addition reaction of an acid anhydride is preferable. Furthermore, among these, amide-imide resins are preferably used because they are particularly excellent in transparency. Such a more preferable carboxyl group-containing resin (A) is an amideimide resin obtained by reacting an isocyanurate-type polyisocyanate synthesized from an isocyanate having an aliphatic structure with a tricarboxylic acid anhydride having an aliphatic structure. including.

[Isocyanurate-type polyisocyanate synthesized from isocyanate having an aliphatic structure]
Isocyanurate-type polyisocyanates synthesized from isocyanates having an aliphatic structure include isocyanurate-type polyisocyanates synthesized from isocyanates having a linear aliphatic structure, and isocyanurate-type polyisocyanates synthesized from isocyanates having an alicyclic structure. polyisocyanate, and the like.

Examples of isocyanurate-type polyisocyanates synthesized from isocyanates having a linear aliphatic structure include HDI3N (isocyanurate-type triisocyanate synthesized from hexamethylene diisocyanate), HTMDI3N (isocyanurate synthesized from trimethylhexamethylene diisocyanate type triisocyanate) and the like. These may be used together or singly.

Examples of isocyanurate-type polyisocyanates synthesized from isocyanates having an alicyclic structure include IPDI3N (isocyanurate-type triisocyanate synthesized from isophorone diisocyanate), HTDI3N (isocyanurate-type polyisocyanate synthesized from hydrogenated tolylene diisocyanate triisocyanate), HXDI3N (isocyanurate-type triisocyanate synthesized from hydrogenated xylene diisocyanate), NBDI3N (isocyanurate-type triisocyanate synthesized from norbornane diisocyanate), HMDI3N (isocyanurate-type triisocyanate synthesized from hydrogenated diphenylmethane diisocyanate isocyanate) and the like.

As the isocyanurate-type polyisocyanate synthesized from the isocyanate having an aliphatic structure used in the present invention, a cured film (cured product) having a particularly high Tg and excellent thermal properties is obtained, so it has an alicyclic structure. Isocyanurate-type polyisocyanates synthesized from isocyanates are preferred, and isocyanurate-type triisocyanates synthesized from isophorone diisocyanate are particularly preferred.

The content of the isocyanurate-type polyisocyanate synthesized from the isocyanate having an alicyclic structure in the isocyanurate-type polyisocyanate synthesized from the isocyanate having an aliphatic structure is the isocyanurate synthesized from the isocyanate having an aliphatic structure. Based on the mass of the type polyisocyanate, 50 to 80% by mass is preferable because a cured film (cured product) having a high Tg and excellent thermal properties is obtained, 80 to 100% by mass is more preferable, and 100% by mass is most preferable. preferable.

In addition, adducts obtained by urethanization reaction between the isocyanate compound and various polyols can also be used as long as the solvent solubility of the carboxyl group-containing resin (A) is not impaired.

[Tricarboxylic anhydride having an aliphatic structure]
The carboxyl group-containing resin (A) used in the present invention is obtained by directly forming an imide bond from the above isocyanurate-type polyisocyanate and tricarboxylic acid anhydride, thereby making the material more stable than synthesis via a polyamic acid intermediate. It is possible to synthesize an amide-imide resin which has good properties, reproducibility and solubility, and which is excellent in transparency. In the present invention, a tricarboxylic acid having an aliphatic structure in the molecule is preferably used in order to suppress browning of the carboxyl group-containing resin (A) and improve transparency.

Examples of the tricarboxylic anhydride having an aliphatic structure include tricarboxylic anhydrides having a linear aliphatic structure and tricarboxylic anhydrides having an alicyclic structure. Examples of the tricarboxylic anhydride having a linear aliphatic structure include propanetricarboxylic anhydride. Examples of tricarboxylic anhydrides having an alicyclic structure include cyclohexanetricarboxylic anhydride, methylcyclohexanetricarboxylic anhydride, cyclohexenetricarboxylic anhydride, and methylcyclohexenetricarboxylic anhydride.

Among the tricarboxylic acid anhydrides having an aliphatic structure, tricarboxylic acid anhydrides having an alicyclic structure are preferable, since a cured film (cured product) having high Tg and excellent thermal properties can be obtained in addition to transparency. Further preferably, the isocyanurate-type polyisocyanate compound is an isocyanurate-type polyisocyanate synthesized from an isocyanate having an alicyclic structure, and the tricarboxylic anhydride is a tricarboxylic anhydride having an alicyclic structure. .
Examples of tricarboxylic acid anhydrides having an alicyclic structure include cyclohexanetricarboxylic acid anhydrides. It is possible to use 1 type(s) or 2 or more types of these. In some cases, bifunctional dicarboxylic acid compounds such as adipic acid, sebacic acid, phthalic acid, fumaric acid, maleic acid and their acid anhydrides can be used in combination.

Examples of the cyclohexanetricarboxylic acid anhydride include cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid-3,5-anhydride, cyclohexane-1 , 2,3-tricarboxylic acid-2,3-anhydride and the like. Among them, cyclohexane-1,3,4-tricarboxylic acid-3,4-because it becomes an amideimide resin that has excellent solvent solubility in addition to transparency, and a cured film (cured product) having a high Tg and excellent thermal properties can be obtained. Anhydrides are preferred.

When the carboxylic acid component of the tricarboxylic anhydride reacts with the isocyanate component in the polyisocyanate, an imide and an amide are formed, resulting in an amide-imide resin. Further, when the polyisocyanate and the tricarboxylic anhydride are reacted in such a proportion that the carboxylic acid component of the tricarboxylic anhydride is left, the resulting polyamideimide resin is a carboxyl have a group. This carboxy group reacts with a polymerizable group such as an epoxy group of an epoxy resin (D) as a thermosetting resin contained in the photosensitive resin composition of the present invention, which will be described later, to form a crosslinked structure of the cured product. . Incidentally, since the reaction rate is high for imidization, even in the reaction between tricarboxylic acid and triisocyanate, the tricarboxylic acid selectively forms an imide at the anhydride.

An isocyanurate-type polyisocyanate synthesized from an isocyanate having an aliphatic structure and a tricarboxylic acid anhydride having an aliphatic structure are the number of moles of isocyanate groups in the isocyanurate-type polyisocyanate synthesized from the isocyanate having an aliphatic structure. The ratio of (N) to the total number of moles of the number of moles of the carboxy group (M1) and the number of moles of the acid anhydride group (M2) of the tricarboxylic anhydride having an aliphatic structure [(M1) + (M2)) / (N)] is 1.1 to 3, the polarity in the reaction system increases and the reaction proceeds smoothly, no isocyanate groups remain, and the stability of the resulting polyimide resin is improved. It is preferable for the following reasons: good, low remaining amount of tricarboxylic acid anhydride, and little problem of separation such as recrystallization. Among them, 1.2 to 2 are more preferable. In the present invention, the acid anhydride group refers to a --CO--O--CO-- group obtained by intramolecular dehydration condensation of two carboxylic acid molecules.

The imidization reaction is preferably carried out by mixing one or more isocyanates having an aliphatic structure and one or more tricarboxylic acid anhydrides in a solvent or in the absence of a solvent, and heating the mixture while stirring. . The reaction temperature is preferably 50°C to 250°C, particularly preferably 70°C to 180°C. By setting the reaction temperature to such a value, the reaction rate is increased, and side reactions, decomposition, etc. are less likely to occur. The reaction, accompanied by decarboxylation, forms an imide group between an anhydride group and an isocyanate group. The progress of the reaction can be tracked by analytical means such as infrared spectrum, acid value, and isocyanate group quantification. In the infrared spectrum, the characteristic absorption of the isocyanate group at 2270 cm ^-1 decreases with the reaction, and the acid anhydride group having characteristic absorptions at 1860 cm ^-1 and 850 cm ^-1 also decreases. On the other hand, the absorption of the imide group increases at 1780 cm ⁻¹ and 1720 cm ⁻¹ . The reaction may be terminated by lowering the temperature while confirming the target acid value, viscosity, molecular weight and the like. However, from the standpoint of stability over time, etc., it is more preferable to continue the reaction until the isocyanate group disappears. In addition, during or after the reaction, catalysts, antioxidants, surfactants, other solvents, etc. may be added to the extent that the physical properties of the resin to be synthesized are not impaired.

The acid value of such a carboxyl group-containing resin (A) is preferably 70 to 210 KOHmg/g, particularly preferably 90 to 190 KOHmg/g. If it is 70 to 210 KOHmg/g, it exhibits excellent performance as a cured physical property.
Also, (A) the carboxyl group-containing resin is preferably an amide imide resin that dissolves in a polar solvent containing neither nitrogen atoms nor sulfur atoms. Examples of such amideimide resins include branched amideimide resins having a branched structure and having an acid value of 60 mg KOH/g or more.

(A) The number average molecular weight of the carboxyl group-containing resin is preferably a small number average molecular weight, for example, a number average molecular weight of 500 to 1000, and a number of 700 to 900, from the viewpoint of improving compatibility with other resin components. Average molecular weight is more preferred.
Further, the content of (A) the carboxyl group-containing resin in the photosensitive resin composition of the present invention is preferably 25 to 65% by mass, preferably 35 to 55% by mass, based on the total solid content of the photosensitive resin composition. is more preferred.

[(B) Photoinitiator]
As the (B) photopolymerization initiator of the photosensitive resin composition of the present invention, any photopolymerization initiator known as a photopolymerization initiator or a photoradical generator can be used.
For example, bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-propyl phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4, Bisacylphosphine oxides such as 4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide and bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinate methyl ester, 2-methylbenzoyldiphenylphosphine oxide, isopropyl pivaloylphenylphosphinate esters, monoacylphosphine oxides such as 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, 2 -hydroxyacetophenones such as hydroxy-2-methyl-1-phenylpropan-1-one; benzoin 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-hydroxycyclohexylphenylketone, 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-dimethylaminoacetophenone and other acetophenones; Thioxanthones such as chlorothioxanthone and 2,4-diisopropylthioxanthone; anthraquinones such as; acetophenone dimethyl ketal, benzyl dimethyl ketal and other ketals; ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethyl benzoate, p-dimethylbenzoic acid ethyl ester and other benzoic acid esters; 2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl] -1-(O-acetyloxime) and other oxime esters; bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl) Titanocenes such as phenyl)titanium, bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1-pyr-1-yl)ethyl)phenyl]titanium; phenyl disulfide 2-nitrofluorene , butyroin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, and the like. A photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type.

(B) The content of the photopolymerization initiator is preferably 1 to 10% by mass with respect to the total solid content of the photosensitive resin composition. (B) If the content of the photopolymerization initiator is within the above range with respect to the total solid content of the photosensitive resin composition, the obtained cured product has both good surface curability and good resolution. be able to.

[(C) a compound having an unsaturated double bond]
(C) The compound having an unsaturated double bond can be photocured by irradiation with active energy rays to insolubilize the photosensitive resin composition of the present invention in an alkaline aqueous solution, or to help insolubilization. As such compounds, commonly known polyester (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, carbonate (meth)acrylates, epoxy (meth)acrylates, and urethane (meth)acrylates can be used. Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; N,N-dimethylacrylamide , N-methylol acrylamide, 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, and tris-hydroxyethyl isocyanurate, or polyhydric acrylates such as ethyloxide adducts, propylene oxide adducts, or ε-caprolactone adducts thereof, such as 1,6- Bifunctional acrylates such as hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tris(2-hydroxyethyl) isocyanurate triacrylate , ethylene oxide-modified trimethylol triacrylate, ethylene oxide-modified trimethylolpropane triacrylate, propylene oxide-modified trimethylolpropane triacrylate, ε-caprolactone-modified tris-(2-acryloxyethyl) isocyanurate and other trifunctional acrylates, ditri Tetrafunctional acrylates such as methylolpropane tetraacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, pentafunctional acrylates such as pentaacrylate of dipentaerythritol, hexafunctional acrylates such as dipentaerythritol hexaacrylate, phenoxy acrylate, bisphenol A Polyvalent acrylates such as diacrylates and ethylene oxide adducts or propylene oxide adducts of these phenols; glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate polyvalent acrylates; acrylates having a dicyclopentadiene skeleton such as dicyclopentadiene diacrylate; not limited to the above, polyether polyols, polycarbonate diols, hydroxyl group-terminated polybutadiene, polyester polyols such as polyols are directly acrylated, or Examples include at least one of acrylates and melamine acrylates urethane-acrylated via diisocyanate, and methacrylates corresponding to the above acrylates.

Furthermore, polyfunctional epoxy resins such as cresol novolak type epoxy resins are reacted with epoxy acrylate resins, and hydroxyl groups of the epoxy acrylate resins are further combined with hydroxy acrylates such as pentaerythritol triacrylate and diisocyanates such as isophorone diisocyanate. An epoxy urethane acrylate compound obtained by reacting a half urethane compound can be mentioned. Such an epoxy acrylate resin can improve the photocurability without deteriorating the dryness to the touch. The above compounds having an ethylenic double bond in the molecule may be used singly or in combination of two or more.

In addition, the content of (C) a compound having an unsaturated double bond is about 1 to about 1 to the total solid content of the photosensitive resin composition, from the viewpoint of the properties and sensitivity of the cured film (cured product) to be formed. A range of 30% by weight is preferred, and a range of 5 to 15% by weight is more preferred.

[(D) Thermosetting resin]
In principle, the photosensitive resin composition of the present invention may contain (D) a thermosetting resin in order to further improve heat resistance.
(D) Thermosetting resins include, for example, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, etc. having two or more cyclic ether groups and/or cyclic thioether groups in the molecule, polyisocyanate compounds, blocked isocyanate compounds, etc. Compounds having two or more isocyanate groups or blocked isocyanate groups in one molecule, amine resins such as melamine resins and benzoguanamine resins and their derivatives, bismaleimide, oxazine, cyclocarbonate compounds, known thermosetting compounds such as carbodiimide resins and flexible resins.

Among these, polyfunctional epoxy resins include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, heterocyclic epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alkylphenol novolac type epoxy resin, Resins, biphenyl-type epoxy resins, aralkyl-type epoxy resins, biphenylaralkyl-type epoxy resins, dicyclopentadiene skeleton-containing epoxy resins, epoxidized products of condensates of phenols and aromatic aldehydes having phenolic hydroxyl groups, naphthalene-type epoxy resins , fluorene-type epoxy resins, xanthene-type epoxy resins, and other epoxy resins mixed with their curing agents. Any one of these epoxy resins may be used, or two or more thereof may be used in combination. Moreover, from the viewpoint of reactivity, such an epoxy resin preferably has an epoxy equivalent weight in the range of 95 to 1,000.

Here, as described above, in the present invention, the cured product obtained from the photosensitive resin composition requires high transparency. Therefore, in order to prevent the color of the cured product from darkening, (D) the thermosetting resin is preferably selected from epoxy resins having a Gardner color number of 5 or less. By suppressing the Gardner color number of the epoxy resin to 5 or less, a cured product suitable as a transparent material, especially a protective material for transparent antennas for smartphones or car navigation systems, can be obtained, and resolution is also improved.
The Gardner color number can be measured according to JIS K6901.

Examples of epoxy resins having a Gardner color number of 5 or less include JER828 (epoxy equivalent: 190: manufactured by Mitsubishi Chemical Corporation), JER834 (epoxy equivalent: 250: manufactured by Mitsubishi Chemical Corporation), and JER1001 (epoxy equivalent: 475: manufactured by Mitsubishi Chemical Corporation). (manufactured by Mitsubishi Chemical Corporation), JER806 (epoxy equivalent 165: manufactured by Mitsubishi Chemical Corporation), JER152 (epoxy equivalent 175: manufactured by Mitsubishi Chemical Corporation), JER154 (epoxy equivalent 178: manufactured by Mitsubishi Chemical Corporation), EPICLON840 ( Epoxy equivalent 185: manufactured by DIC Corporation), EPICLON850 (epoxy equivalent 189: manufactured by DIC Corporation), EPICLON1050 (epoxy equivalent 475: manufactured by DIC Corporation), EPICLON830 (epoxy equivalent 173: manufactured by DIC Corporation), EPICLON N-660 (epoxy equivalent weight 208: manufactured by DIC Corporation), EPICLON N-695 (epoxy equivalent weight 215: manufactured by DIC Corporation), EPICLON N-730A (epoxy equivalent weight 176: manufactured by DIC Corporation), EPICLON N -770 (epoxy equivalent 188: manufactured by DIC Corporation), EOCN-1020 (epoxy equivalent 199: manufactured by Nippon Kayaku Co., Ltd.), EOCN-104S (epoxy equivalent 218: manufactured by Nippon Kayaku Co., Ltd.), EPPN- 201 (epoxy equivalent 190: manufactured by Nippon Kayaku Co., Ltd.).

The above (D) thermosetting resin, from the viewpoint of good hardness, heat resistance, electrical insulation and developability of the cured product, 5 to 45% by mass based on the total solid content of the photosensitive resin composition It is preferably used in proportions, more preferably 15 to 35% by mass.

[(E) Filler having an average particle size of 120 nm or less]
Since the photosensitive resin composition of the present invention contains (E) a filler, the resulting cured product has enhanced gas barrier properties. On the other hand, the transparency of the cured product must also be maintained at a high level. That is, from the viewpoint that both gas barrier properties and transparency must be achieved, the (E) filler used in the present invention preferably has an average particle size of 120 nm or less. (E) By using a filler having an average particle size of 120 nm or less, it is possible to suppress the haze value of the cured product while also suppressing the water vapor transmission rate, thereby achieving both gas barrier properties and transparency of the cured product. can be made

(E) Specific examples of the filler having an average particle size of 120 nm or less include silica, barium sulfate, calcium carbonate, silicon nitride, aluminum nitride, boron nitride, alumina, magnesium oxide, aluminum hydroxide, magnesium hydroxide, Examples include nonmetallic fillers such as titanium oxide, mica, talc, Neuburg silica, and organic bentonite, and metal fillers such as copper, gold, silver, palladium, and silicon.
In the photosensitive resin composition of the present invention, these fillers may be used alone or in combination of two or more.

Among these, silica with low volume expansion and excellent printability, and calcium carbonate with low volume expansion and excellent polishability are suitable.
Silica may be amorphous, crystalline, or a mixture thereof. Amorphous (fused) silica is particularly preferred. Calcium carbonate may be either natural heavy calcium carbonate or synthetic precipitated calcium carbonate.

The shape of such inorganic particles may be spherical, needle-like, plate-like, scaly, hollow, irregular, hexagonal, cubic, flaky, etc. From the viewpoint of high filler filling, a spherical shape is preferable. .

As described above, the (E) filler preferably has an average particle size of 120 nm or less, more preferably 100 nm or less, more preferably 50 nm or less, and most preferably 50 nm or less. It is preferably 15 nm or less. From the viewpoint of the transparency of the cured product, in principle, the smaller the particle size, the better, but practically, from the viewpoint of production efficiency, the lower limit of the average particle size is preferably 1 nm or more. Further, when the average particle diameter is 1 nm or more, the specific surface area is small and the particles are dispersed satisfactorily due to the effect of cohesion of the filler particles, making it easy to increase the filler filling amount.
In addition, an average particle diameter means an average primary particle diameter. The average particle size (D50) can be measured with a laser diffraction/scattering particle size distribution analyzer and a dynamic light scattering particle size distribution analyzer. Examples of the laser diffraction/scattering particle size distribution analyzer include Microtrac MT3300EXII manufactured by Microtrac Bell, and examples of the dynamic light scattering particle size distribution analyzer include Nanotrac Wave II UT151 manufactured by Microtrac Bell.

(E) The filler having an average particle size of 120 nm or less is more preferably a surface-treated inorganic filler. As the surface treatment, a surface treatment with a coupling agent, or a surface treatment that does not introduce an organic group, such as alumina treatment, may be performed. Such a surface treatment method is not particularly limited, and a known and commonly used method may be used, and the surface of the machine filler is treated with a surface treatment agent having a curable reactive group, such as a coupling agent having a curable reactive group. do it.

The surface treatment is preferably surface treatment with a coupling agent. As the coupling agent, silane-based, titanate-based, aluminate-based, and zirco-aluminate-based coupling agents can be used. Among them, silane coupling agents are preferred. Examples of such silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, N-(2-aminomethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-amino propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-anilinopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxy cyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and the like, and these may be used alone or in combination. can be used These silane-based coupling agents are preferably immobilized in advance on the surface of the inorganic filler by adsorption or reaction. Here, the treatment amount of the coupling agent with respect to the (E) filler is, for example, 0.1 to 10% by mass, preferably 0.5 to 10% by mass.

A thermosetting reactive group is preferred as the curable reactive group. Thermosetting reactive groups include hydroxyl group, carboxyl group, isocyanate group, amino group, imino group, epoxy group, oxetanyl group, mercapto group, methoxymethyl group, methoxyethyl group, ethoxymethyl group, ethoxyethyl group, oxazoline group, etc. is mentioned. Among them, at least one of an amino group and an epoxy group is preferable. The surface-treated inorganic filler may have a photocurable reactive group in addition to the thermosetting reactive group.

In addition, the surface-treated filler may be contained in the resin layer from the photosensitive resin composition in a surface-treated state, and the filler and the surface treatment agent are added to the photosensitive resin composition forming the resin layer. may be separately blended to surface-treat the filler in the composition, but it is preferable to blend a previously surface-treated filler. By blending a filler that has been surface-treated in advance, it is possible to prevent deterioration in crack resistance and the like due to the surface-treating agent that has not been consumed in the surface treatment, which may remain in the case of blending separately. In the case of surface treatment in advance, it is preferable to blend a preliminary dispersion obtained by pre-dispersing an inorganic filler in a solvent or a curable resin. Alternatively, when pre-dispersing the untreated filler in a solvent, it is more preferable to sufficiently surface-treat the filler and then blend the pre-dispersed liquid into the composition.

(E) The filler having an average particle size of 120 nm or less is preferably used in the form of a slurry mixed with a solvent or dispersant from the viewpoint of handling.
Such a slurry can be obtained, for example, by mixing and stirring a filler, optionally a coupling agent and a solvent, and performing dispersion treatment using a bead mill.

(E) The content of the filler having an average particle diameter of 120 nm or less is preferably 5 to 35% by mass, more preferably 10 to 35% by mass, based on the total mass of solids in the photosensitive resin composition of the present invention. 30% by mass. If it is 10 to 30% by mass, the transparency of the resulting cured product can be ensured, and the photosensitive resin composition can be easily converted into a liquid paste, and good printability can be obtained. It exhibits sufficiently low volume expansion and also exhibits good polishability.

[(F) Thermosetting catalyst liquid at 20°C or higher and lower than 70°C]
The photosensitive resin composition of the present invention contains (D) a thermosetting catalyst to accelerate the curing of the thermosetting resin, but from the viewpoint of not impairing the transparency of the resulting cured product, preferably ( F) It preferably contains a thermosetting catalyst that is liquid at 20°C or higher and lower than 70°C. This is because, unlike the powder form, there are very few factors that adversely affect the haze value in the cured product.

As the thermosetting catalyst, those that are liquid at 20° C. or higher and lower than 70° C. are preferably selected from those listed below.
For example imidazole, 2-methylimidazole, 2-ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-benzyl-2-methylimidazole, 1 -imidazole derivatives such as benzyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4-(dimethylamino) -N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine and other amine compounds; adipic acid dihydrazide, sebacate dihydrazide and other hydrazine compounds; Phosphorus compounds such as phenylphosphine and triphenylphosphite, and organic tin compounds such as tin octylate can be used.
In addition, commercially available products include, for example, 2MZ-H, 1,2DMZ, 2MZ-A, 2MA-OK, 2PHZ, and 2P4MHZ manufactured by Shikoku Kasei Co., Ltd. (all are trade names of imidazole compounds), San-Apro Co., Ltd. Company-made U-CAT 3502T, U-CAT 3503N (both trade names of dimethylamine compounds), U-CAT 5003 (trade names of quaternary phosphonium bromide compounds), U-CAT 5003 (quaternary phosphonium bromide compound), DBU, DBN, U-CAT SA 1, U-CAT SA 102, U-CAT SA 506, U-CAT 5002 (both bicyclic amidine compounds and salts thereof), POLYCAT 8 ( N,N-dimethylcyclohexylamine), JP-360, JP-3CP, and JP-3CP manufactured by Johoku Chemical Industry Co., Ltd. (all of which are trade names of phosphite compounds), KCS-405T (octylic acid product name of stannous) and the like.

Among the above compounds, (F) thermosetting catalysts that are liquid at 20°C or higher and lower than 70°C are more preferred, for example, U-CAT SA 1, U-CAT SA 102, U-CAT SA 506 (bicyclic amidine compounds and salts thereof; manufactured by San-Apro), POLYCAT 8 (N,N-dimethylcyclohexylamine; manufactured by San-Apro), 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole , 1-benzyl-2-phenylimidazole, JP-360 manufactured by Johoku Chemical Industry Co., Ltd. (triphenyl phosphite; manufactured by Johoku Chemical Industry Co., Ltd.), JP-3CP (tricresyl phosphite; manufactured by Johoku Chemical Industry Co., Ltd.), JP -3CP (tricresyl phosphite; manufactured by Johoku Chemical Industry Co., Ltd.) and KCS-405T (stannous octylate; manufactured by Johoku Chemical Industry Co., Ltd.).

The thermosetting catalyst (F) which is liquid at 20° C. or higher and lower than 70° C. as described above may be used alone or in combination of two or more.
In addition, the content of (F) a thermosetting catalyst that is liquid at 20 ° C. or higher and lower than 70 ° C. is used to ensure the transparency of the resulting cured product, as well as the storage stability of the photosensitive resin composition and the heat resistance of the cured product. Also from the viewpoint of properties, it is preferably 0.01 to 10.0% by mass, more preferably 0.1 to 5.0% by mass, based on the total mass of solids in the photosensitive resin composition of the present invention.

[solvent]
In the present invention, it is of course possible to use a solvent in order to make the photosensitive resin composition have a viscosity suitable for coating on a substrate or carrier film. Organic solvents are mainly used as such solvents, and specific examples thereof include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, A petroleum solvent etc. can be mentioned. More specifically, 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, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Esters such as propylene glycol butyl ether acetate; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha system solvents and the like. Such organic solvents may be used singly or in combination of two or more.

[Other ingredients]
Of course, the photosensitive resin composition of the present invention may contain other components in addition to the components described above, depending on the required properties.
Examples of such components include antifoaming agents, leveling agents, thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, foaming agents, flame retardants, antistatic agents, anti-aging agents, antibacterial/antifungal agents. agents and the like.

[Photosensitive resin laminate]
The photosensitive resin composition of the present invention can be used in the form of a photosensitive resin laminate.
For example, the photosensitive resin laminate of the present invention has a resin layer obtained by coating and drying the photosensitive resin composition of the present invention on a carrier film.
More specifically, when forming the photosensitive resin laminate of the present invention, first, the photosensitive resin composition of the present invention is diluted with the above-mentioned organic solvent to adjust the viscosity to an appropriate level, and then a comma is added. Coat the carrier film to a uniform thickness using a coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, spray coater, or the like. After that, the applied composition is usually dried at a temperature of 50 to 130° C. for 1 to 30 minutes to form a resin layer.
The film thickness of the carrier film is not particularly limited, but is generally selected appropriately so that the film thickness after drying is in the range of 10 to 150 μm, preferably 20 to 60 μm.

As the carrier film to be used, a plastic film is used, and 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. The thickness of the carrier film is not particularly limited, but is generally selected appropriately within the range of 10 to 150 μm.

After the resin layer is formed on the carrier film, a peelable cover film is further laminated on the surface of the resin layer for the purpose of preventing dust from adhering to the surface of the resin layer. A laminate can be obtained.
As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, surface-treated paper, or the like can be used. Any cover film may be used as long as the adhesive force is smaller than the adhesive force between the resin layer and the carrier film when the cover film is peeled off.

In the present invention, the photosensitive resin composition of the present invention is coated on the cover film and dried to form a resin layer, and a carrier film is laminated on the surface thereof to form a photosensitive resin laminate. It may be something to do.
That is, in the present invention, either a carrier film or a cover film may be used as the film to which the photosensitive resin composition is applied when producing the photosensitive resin laminate.

[Cured product]
The present invention also relates to a cured film (cured product) obtained by curing the resin layer of the photosensitive resin composition or photosensitive resin laminate. The cured film (cured product) of the present invention can be formed, for example, as follows.
First, a photosensitive resin composition is applied on a substrate, and the resin layer obtained after the solvent is volatilized and dried is exposed (light irradiation) to cure the exposed portion (light irradiated portion). Specifically, by a contact or non-contact method, the active energy ray is selectively exposed through a patterned photomask, or the pattern is directly exposed by a laser direct exposure machine. After that, a resist pattern is formed by developing the unexposed area with an alkaline aqueous solution (for example, a 0.3 to 3% by mass aqueous solution of sodium carbonate). Furthermore, by heating to a temperature of about 100 to 180 ° C and thermal curing (post curing), it cures as a cured film excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion and electrical properties. can form objects.

Here, the curable resin composition of the present invention, for example, using an organic solvent to adjust the viscosity suitable for the coating method, on the substrate, dip coating method, flow coating method, roll coating method, bar coater method, After coating by a method such as screen printing or curtain coating, the organic solvent contained in the composition is volatilized and dried (temporary drying) at a temperature of about 60 to 100° C. to form a tack-free resin layer. can also

As a substrate, in addition to printed wiring boards and flexible printed wiring boards on which circuits are formed in advance with copper, etc., paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/non-fabric epoxy, glass cloth/paper epoxy, synthetic Materials such as copper-clad laminates for high-frequency circuits using fiber epoxy, fluororesin, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate, etc. Copper-clad laminates of all grades (FR-4, etc.), In addition, metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates and the like can be used.

Volatilization drying or heat curing is, for example, a hot air circulation drying oven, an IR oven, a hot plate, a convection oven, etc. (a method equipped with a heat source of air heating method using steam, and a method in which the hot air in the dryer is brought into contact with countercurrent flow and method of spraying onto the support from a nozzle).

The dried photosensitive resin composition or photosensitive resin laminate can be exposed to active energy rays through a patterned photomask in a contact or non-contact manner.
In addition, the exposed portion can be photocured by direct pattern exposure of the photosensitive resin composition or the photosensitive resin laminate using a laser direct exposure machine.

The exposure device used for active energy ray irradiation may be any device equipped with a high-pressure mercury lamp, an extra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, or the like, and irradiating ultraviolet rays in the range of 350 to 450 nm. A direct writing device (eg, a laser direct imaging device that writes an image with a laser directly from CAD data from a computer) can also be used. A lamp light source or laser light source for a 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 can generally be in the range of 20-1000 mJ/cm ² , preferably in the range of 20-800 mJ/cm ² .

As a developing method, a dipping method, a shower method, a spray method, a brush method, or the like can be used. , amines, etc. can be used.

[Electronic parts]
By using the photosensitive resin composition of the present invention as described above, electronic parts having high quality, durability and reliability, such as parts used in electronic circuits, such as printed wiring boards, transistors, light emitting diodes, and laser diodes, can be produced. In addition to active components such as resistors, capacitors, inductors, connectors, etc., passive components are also provided. In particular, the photosensitive resin composition of the present invention is suitable as a material for permanent insulating films such as coverlays for printed wiring boards, solder resists, interlayer insulating materials, and insulating materials for forming rewiring layers.

[Transparent Antenna]
The present invention also relates in particular to a transparent antenna comprising the cured product described above. That is, the cured product obtained from the photosensitive resin composition of the present invention not only has excellent resolution and resistance to electroless gold plating, but also has properties of suppressed haze value and water vapor transmission rate. Therefore, it is particularly suitable as a transparent antenna material for smartphones and car navigation systems, or as a protective material for such antennas.

The method for producing the transparent antenna of the present invention is basically the same as the method for forming a circuit on a printed wiring board.
As an example, an electrolytic copper foil is adhered onto a substrate, and after chemical conversion treatment if necessary, a photosensitive resin laminate is copper foil-laminated. An antenna pattern is formed by subjecting the photosensitive resin laminate to pattern exposure and development. Next, a transparent antenna having a copper antenna pattern formed thereon is obtained by removing the copper foil from the pattern-free portion by etching and peeling off the photosensitive resin laminate.

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples.
Unless otherwise specified, "parts" and "%" are based on mass.

<Synthesis Example 1>
A flask equipped with a stirrer, thermometer and condenser was charged with 5184 g of EDGA (diethylene glycol monoethyl ether acetate), 2070 g (3 mol) of IPDI3N (isocyanurate type triisocyanate synthesized from isophorone diisocyanate: NCO%=18.2) and cyclohexane- 1782 g (9 mol) of 1,3,4-tricarboxylic acid-3,4-anhydride was added and the temperature was raised to 140°C. The reaction proceeded with foaming. The reaction was carried out at this temperature for 8 hours. The inside of the system became a pale yellow liquid, and as a result of measuring the characteristic absorption in the infrared spectrum, the characteristic absorption of the isocyanate group at 2270 cm ^-1 completely disappeared, and the absorption of the imide group at 1780 cm ^-1 and 1720 cm ^-1 . confirmed. The acid value was 140 mgKOH/g in terms of solid content, and the molecular weight was 800 in terms of polystyrene. Moreover, the concentration of the resin component was 40% by weight.
Thus, a resin solution of carboxyl group-containing resin A to which an acid anhydride was added was obtained. This resin solution is referred to as resin solution A.

<Synthesis Example 2>
A flask equipped with a stirrer, thermometer and condenser was charged with 5184 g of EDGA (diethylene glycol monoethyl ether acetate), 2070 g (3 mol) of IPDI3N (isocyanurate type triisocyanate synthesized from isophorone diisocyanate: NCO%=18.2) and cyclohexane- 1782 g (9 mol) of 1,3,4-tricarboxylic acid-3,4-anhydride was added and the temperature was raised to 140°C. The reaction proceeded with foaming. The reaction was carried out at this temperature for 8 hours. The inside of the system became a pale yellow liquid, and as a result of measuring the characteristic absorption in the infrared spectrum, the characteristic absorption of the isocyanate group at 2270 cm ^-1 completely disappeared, and the absorption of the imide group at 1780 cm ^-1 and 1720 cm ^-1 . confirmed. Furthermore, 142.0 g (1 mol) of glycidyl methacrylate was added to the obtained reaction solution, and the reaction was carried out at 115° C. for 4 hours. As a result of measuring the characteristic absorption in the infrared spectrum, 910 cm ⁻¹ which is the characteristic absorption of the epoxy group has completely disappeared. This resin solution had an acid value of 117 mgKOH/g in terms of solid content, and a number average molecular weight of 850 in terms of polystyrene. Moreover, the concentration of the resin component was 40% by weight.
Thus, a resin solution of carboxyl group-containing resin B to which an acid anhydride was added was obtained. This resin solution is referred to as resin solution B.

<Synthesis Example 3>
To 600 g of EDGA (diethylene glycol monoethyl ether acetate) was added 1070 g of an ortho-cresol novolak type epoxy resin [DIC EPICLON N-695, softening point 95°C, epoxy equivalent weight 214, average functional group number 7.6] (number of glycidyl groups (total number of aromatic rings)). : 5.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were charged, heated to 100°C with stirring, and uniformly dissolved. Then, 4.3 g of triphenylphosphine was charged, heated to 110° C. and reacted for 2 hours, then heated to 120° C. and reacted for further 12 hours. 415 g of aromatic hydrocarbon (Solvesso 150) and 534 g (3.0 mol) of methyl-5-norbornene-2,3-dicarboxylic anhydride were added to the resulting reaction solution, reacted at 110° C. for 4 hours, and cooled. After that, I took it out. The resulting cresol novolak-type carboxyl group-containing resin had a solid content acid value of 89 mgKOH/g and a resin content concentration of 65%.
Thus, a resin solution of carboxyl group-containing resin C to which an acid anhydride was added was obtained. This resin solution is referred to as resin solution C.

<Synthesis Example 4>
A flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser was charged with methyl methacrylate, ethyl methacrylate and methacrylic acid in a molar ratio of 1:1:2. Azobisisobutyronitrile (AIBN) was added as a solution and stirred at 80° C. for 4 hours under a nitrogen atmosphere to obtain a resin solution. This resin solution is cooled, and 20 mol % of glycidyl methacrylate is added to the carboxyl groups of the resin using methyl hydroquinone as a polymerization inhibitor and tetrabutylphosphonium bromide as a catalyst at 95 to 105° C. for 16 hours. was removed after cooling. The resulting carboxyl group-containing photosensitive resin having both an ethylenically unsaturated bond and a carboxyl group had a solid content acid value of 120 mgKOH/g and a resin content concentration of 70%.
Thus, a resin solution of a carboxyl group-containing resin to which no acid anhydride was added was obtained. This resin solution is referred to as resin solution D.

<Preparation Example 1: Preparation of inorganic filler slurry A>
30 g of spherical silica particles (Admanano YA050C manufactured by Admatechs, average particle size: 50 nm), 68 g of PMA (propylene glycol monomethyl ether acetate) as a solvent, and a silane coupling agent having a methacrylic group (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd. ) was blended and stirred, and dispersion treatment was performed with a bead mill (K-8 manufactured by BUHLER) at a rotation speed of 900 rpm, a pump output of 20%, and a temperature during dispersion of 40 to 50 ° C. to obtain a PMA dispersion of silica particles. rice field. The resulting dispersion is designated as inorganic filler slurry A.
The average particle size (D50) of the obtained inorganic filler slurry is a value obtained by measuring using NANOTRAC FLEX manufactured by Microtrack Bell, and is shown in Table 1 below. The average particle sizes of other inorganic filler slurries used in Examples and Comparative Examples were also measured in the same manner.

<Preparation Example 2: Preparation of inorganic filler slurry B>
30 g of spherical silica particles (Admanano YA100C manufactured by Admatechs, average particle diameter: 100 nm), 68 g of PMA (propylene glycol monomethyl ether acetate) as a solvent, and a silane coupling agent having a methacrylic group (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd. ) was blended and stirred, and dispersion treatment was performed with a bead mill (K-8 manufactured by BUHLER) at a rotation speed of 900 rpm, a pump output of 20%, and a temperature during dispersion of 40 to 50 ° C. to obtain a PMA dispersion of silica particles. rice field. Let the obtained dispersion be the inorganic filler slurry B.

<Preparation Example 3: Preparation of inorganic filler slurry C>
30 g of spherical silica particles (Admanano YA010C manufactured by Admatechs, average particle diameter: 10 nm), 68 g of PMA (propylene glycol monomethyl ether acetate) as a solvent, and a silane coupling agent having a methacrylic group (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd. ) was blended and stirred, and dispersion treatment was performed with a bead mill (K-8 manufactured by BUHLER) at a rotation speed of 900 rpm, a pump output of 20%, and a temperature during dispersion of 40 to 50 ° C. to obtain a PMA dispersion of silica particles. rice field. Let the obtained dispersion be the inorganic filler slurry C.

<Preparation Example 4: Preparation of inorganic filler slurry D>
Titanium oxide particles (STR-100N manufactured by Sakai Chemical Industry Co., Ltd., average particle size: 15 nm) 30 g, PMA (propylene glycol monomethyl ether acetate) 68 g as a solvent, and a silane coupling agent having a methacrylic group (KBM manufactured by Shin-Etsu Chemical Co., Ltd. -503) 2 g was blended and stirred, and dispersion treatment was performed with a bead mill (K-8 manufactured by BUHLER) at a rotation speed of 900 rpm, a pump output of 20%, and a temperature during dispersion of 40 to 50 ° C. to obtain a PMA dispersion of silica particles. got The resulting dispersion is designated as an inorganic filler slurry D.

<Preparation Example 5: Preparation of inorganic filler slurry E>
30 g of spherical silica particles (Admafine SO-C1 manufactured by Admatechs, average particle diameter: 250 nm), 68 g of PMA (propylene glycol monomethyl ether acetate) as a solvent, and a silane coupling agent having a methacrylic group (manufactured by Shin-Etsu Chemical Co., Ltd.) 2 g of KBM-503) was blended and stirred, and dispersion treatment was performed with a bead mill (K-8 manufactured by BUHLER) at a rotation speed of 900 rpm, a pump output of 20%, and a temperature of 40 to 50 ° C. during dispersion to disperse the silica particles in PMA. got a body An inorganic filler slurry E is obtained from the obtained dispersion.

<Examples 1 to 10 and Comparative Examples 1 to 7>
Based on the component compositions shown in Tables 1 and 2 below, each component was blended, premixed with a stirrer, and then kneaded and dispersed with a three-roll mill. A photosensitive resin composition was prepared.

Each component in Tables 1 and 2 is as follows.
^*1 Synthesis example 1
^*2 Synthesis example 2
^*3 Synthesis example 3
^*4 Synthesis example 4
^*5 2,4,6-trimethylbenzoyldiphenylphosphine oxide
^*6 Irgacure OXE02 (manufactured by BASF)
^*7 Dipentaerythritol hexaacrylate
^*8 Ethylene oxide-modified trimethylolpropane triacrylate
^*9 Bisphenol A type epoxy resin: JER834 (manufactured by Mitsubishi Chemical Corporation) (Gardner color number ≤ 5)
^{* 10} Naphthalene type epoxy resin: NC-7000L (manufactured by Nippon Kayaku Co., Ltd.) (Gardner color number > 5)
^*11 2-ethyl-4-methylimidazole (melting point: about 40°C)
^*12 U-CAT SA102 (melting point: about 40°C) (manufactured by San-Apro Co., Ltd.)
^*13 Dicyandiamide (melting point: about 208°C)
^*14 Preparation example 1
^*15 Preparation example 2
^*16 Preparation example 3
^*17 Preparation example 4
^*18 Preparation example 5
^*19 Propylene glycol monomethyl ether acetate

<Optimal Exposure>
A photosensitive resin composition prepared as described in Tables 1 and 2 above was applied onto a carrier film. This was dried by heating in a hot air dryer at 80° C. for 30 minutes to form a resin layer of a photosensitive resin composition having a thickness of 20 μm. Furthermore, a cover film was laminated on the resin layer to obtain a photosensitive resin laminate. After that, the cover film is peeled off at the time of use, the resin layer side is attached to the copper-clad laminate substrate, thermal lamination is performed, and the carrier film is peeled off. was mounted using a projection exposure apparatus (manufactured by Ushio Inc.). After peeling off the carrier film, development was carried out for 200 seconds with a 1% Na ₂ CO ₃ aqueous solution at 30° C. at a spray pressure of 0.2 MPa, and the number of steps of the remaining coating film was visually determined. The exposure amount at which the number of stages of the remaining coating film became 8 stages was defined as the proper exposure amount.

<Transmittance ratio>
A photosensitive resin composition prepared as described in Tables 1 and 2 above was applied onto a carrier film. This was dried by heating in a hot air dryer at 80° C. for 30 minutes to form a resin layer of a photosensitive resin composition having a thickness of 20 μm. Furthermore, a cover film was laminated on the resin layer to obtain a photosensitive resin laminate. After that, the cover film is peeled off at the time of use, and the resin layer side is adhered to a glass substrate (soda lime glass, plate thickness 1.0 mm) and thermally laminated. Solid exposure was performed with the optimum exposure amount. After peeling off the carrier film, development was carried out for 200 seconds using a 1% Na ₂ CO ₃ aqueous solution at 30° C. under conditions of a spray pressure of 0.2 MPa. This substrate was irradiated with ultraviolet rays in a UV conveyor furnace under the conditions of an integrated exposure amount of 1000 mJ/cm ² and then heated at 120°C for 60 minutes for thermal curing to form a cured film (cured product) having a thickness of 20 µm. got the substrate.
The total light transmittance of the resulting cured film (cured product) was measured under the following conditions.
Apparatus: UV-visible spectrophotometer (Ubest-V-570DS manufactured by JASCO Corporation) connected to an integrating sphere device (ISN-470 manufactured by JASCO Corporation)
Measurement method: Measurement was performed according to ISO 13468. First, the white plates attached to the device were set on the reference side and the sample side of the integrating sphere device, and the glass substrates (hereinafter, referred to as A glass substrate R) was set, and baseline measurement was performed. Next, the glass substrate on which the cured film (cured product) prepared by the above method is formed is set on the sample side of the ultraviolet-visible spectrophotometer, and the glass substrate R is set on the reference side of the ultraviolet-visible spectrophotometer. Total light transmittance was measured.
The transmittance ratio of the obtained cured film (cured product) was calculated by the following formula. The results are set forth in Tables 1 and 2 above.

Transmittance ratio = total light transmittance of the obtained cured film (cured product) at a wavelength of 550 nm/total light transmittance of the obtained cured film (cured product) at a wavelength of 430 nm

Evaluation methods are as follows.
A: Transmittance ratio is 0.90 or more and less than 1.10. O: Transmittance ratio is 1.10 or more and less than 1.15. 20 or more

<Haze value>
A photosensitive resin composition prepared as described in Tables 1 and 2 above was applied onto a carrier film. This was dried by heating in a hot air dryer at 80° C. for 30 minutes to form a resin layer of a photosensitive resin composition having a thickness of 20 μm. Furthermore, a cover film was laminated on the resin layer to obtain a photosensitive resin laminate. After that, the cover film is peeled off at the time of use, the resin layer side is attached to a glass substrate (soda lime glass, plate thickness 1.0 mm), thermal lamination is performed, and the carrier film is peeled off. (manufactured by Ushio Inc.) was used for solid exposure at an optimum exposure amount. After peeling off the carrier film, development was carried out for 200 seconds using a 1% Na ₂ CO ₃ aqueous solution at 30° C. under conditions of a spray pressure of 0.2 MPa. This substrate was irradiated with ultraviolet rays in a UV conveyor furnace under the conditions of an integrated exposure amount of 1000 mJ/cm ² and then heated at 120°C for 60 minutes for thermal curing to form a cured film (cured product) having a thickness of 20 µm. got the substrate.
The haze value of the resulting cured film (cured product) was measured under the following conditions. Results are listed in Tables 1 and 2.
Apparatus: UV-visible spectrophotometer (Ubest-V-570DS manufactured by JASCO Corporation) connected to an integrating sphere device (ISN-470 manufactured by JASCO Corporation)
Measurement method: Measurement was performed according to ISO 14782. First, the white plates attached to the device were set on the reference side and the sample side of the integrating sphere device, and the glass substrates (hereinafter, referred to as A glass substrate R) was set, and baseline measurement was performed. After removing the white plate on the sample side of the integrating sphere device, set the glass substrate on which the cured film (cured product) prepared by the above method was formed on the sample side of the UV-VIS spectrophotometer, and use it as a reference for the UV-VIS spectrophotometer. A glass substrate R was set on the side, and the haze value was measured. The results are set forth in Tables 1 and 2 above.
Evaluation methods are as follows.
◎: Haze value is more than 0.0% and less than 1.0% ○: Haze value is 1.0% or more and less than 2.0% △: Haze value is 2.0% or more and less than 4.0% ×: Haze value is 4.0% or more

<Water vapor transmission rate>
A photosensitive resin composition prepared as described in Tables 1 and 2 above was applied onto a carrier film. This was dried by heating in a hot air dryer at 80° C. for 30 minutes to form a resin layer of a photosensitive resin composition having a thickness of 20 μm, and a cover film was laminated on the resin layer to obtain a photosensitive resin laminate. . After that, the cover film is peeled off at the time of use, and the resin layer side is adhered to a 9 μm-thick electrolytic copper foil (manufactured by Furukawa Electric Co., Ltd.) for heat lamination. Solid exposure was performed with the optimum exposure amount. After peeling off the carrier film, development was carried out for 200 seconds using a 1% Na ₂ CO ₃ aqueous solution at 30° C. under conditions of a spray pressure of 0.2 MPa. This substrate was irradiated with ultraviolet rays in a UV conveyor furnace under the condition of an integrated exposure amount of 1000 mJ/cm ² . On the resin layer of the photosensitive resin composition irradiated with ultraviolet rays, a new photosensitive resin laminate was thermally laminated in the same manner as described above, and solidly exposed with an optimum exposure amount. After peeling off the carrier film, development was carried out for 200 seconds using a 1% Na ₂ CO ₃ aqueous solution at 30° C. under conditions of a spray pressure of 0.2 MPa. This substrate was irradiated with ultraviolet rays in a UV conveyor furnace under the condition of an integrated exposure amount of 1000 mJ/cm ² . After repeating this operation five times in total, the resin layer of the photosensitive resin composition was thermally cured by heating at 120° C. for 60 minutes.
Thus, a cured film (cured product) having a thickness of 100 μm was formed on the electrolytic copper foil. Next, the electrolytic copper foil with the cured film (cured product) is etched away using an etchant having a composition of cupric chloride of 340 g/l and free hydrochloric acid concentration of 51.3 g/l. After washing with water and drying, a test piece consisting of a cured film (cured product) having a thickness of 100 μm was produced.

The water vapor transmission rate was evaluated according to the JIS Z0208 method. First, calcium chloride (anhydrous) was placed as a moisture absorbent in a moisture permeable cup having an inner diameter of 60 mm. A cured film (cured product) having a thickness of 100 μm obtained by the above method was placed on the moisture-permeable cup to have a diameter of 70 mm, covered with a guide, and then a ring was set. A heat-melted wax sealing agent was poured into the grooves around the moisture permeable cup, and the temperature of the sealing agent returned to room temperature and solidified, thereby sealing the periphery of the cured film (cured product). After measuring the initial mass of the specimen obtained in this way, it is placed in a constant temperature and high humidity chamber of 40 ° C. × 90% RH, and weighed at intervals of 24 hours. The mass increase was obtained, and the value when it became constant within 5% was used for evaluation as follows.
○: Less than 10 g/m ² /day △: 10 g/m ² /day or more and less than 100 g/m ² /day ×: 100 g/m ² /day or more

<Resolution>
A photosensitive resin composition prepared as described in Tables 1 and 2 above was applied onto a carrier film. This was dried by heating in a hot air dryer at 80° C. for 30 minutes to form a resin layer of a photosensitive resin composition having a thickness of 20 μm, and a cover film was laminated on the resin layer to obtain a photosensitive resin laminate. . After that, the cover film was peeled off at the time of use, the resin layer side was adhered to the copper-clad laminated substrate, and pattern exposure was performed with an optimum exposure amount using a projection type exposure apparatus (manufactured by Ushio Inc.) equipped with a high-pressure mercury lamp. After peeling off the carrier film, a via pattern was formed by developing for 200 seconds using a 1% Na ₂ CO ₃ aqueous solution at 30° C. under conditions of a spray pressure of 0.2 MPa. This substrate 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 120° C. for 60 minutes to be thermally cured.
The resolution of the substrate thus produced was observed using an electron microscope. The via opening size was confirmed and evaluated as follows. Results are listed in Tables 1 and 2.
◎: A via pattern with a diameter of less than 50 μm can be formed. ○: A via pattern with a diameter of 50 μm or more and less than 100 μm can be formed. △: A via pattern with a diameter of 100 μm or more can be formed. ×: An opening shape cannot be formed.

<Electroless gold plating>
A photosensitive resin composition prepared as described in Tables 1 and 2 above was applied onto a carrier film. This was dried by heating in a hot air dryer at 80° C. for 30 minutes to form a resin layer of a photosensitive resin composition having a thickness of 20 μm, and a cover film was laminated on the resin layer to obtain a photosensitive resin laminate. . After that, at the time of use, the cover film is peeled off, the resin layer side is attached to the copper laminated substrate, the resin layer and carrier film are thermally laminated, and optimal exposure is performed using a projection type exposure device (manufactured by Ushio Inc.) equipped with a high-pressure mercury lamp. A pattern exposure was performed with a After peeling off the carrier film, a pattern of the photosensitive resin composition was formed by developing for 200 seconds using a 1% Na ₂ CO ₃ aqueous solution at 30° C. under conditions of a spray pressure of 0.2 MPa. This substrate 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 120° C. for 60 minutes to be thermally cured.
The hardened film (hardened product) forming surface of the substrate thus prepared is subjected to a predetermined pretreatment (acid degreasing + soft etching + sulfuric acid treatment), and an electroless nickel plating bath and an electroless gold plating bath are used to form nickel 3 μm, gold Gold plating was performed under the condition of 0.03 μm, and the presence or absence of peeling of the cured film (cured product) and the presence or absence of permeation of the plating solution were evaluated. Results are listed in Tables 1 and 2.
◯: No peeling or seepage.
Δ: There is slight peeling and penetration.
x: Peeling and permeation are observed.

<Production of transparent antenna>
An electrolytic copper foil with a thickness of 18 μm was adhered to a transparent polyethylene terephthalate film with a thickness of 100 μm with a transparent adhesive. After subjecting the electrolytic copper foil to chemical conversion treatment (low-reflection treatment), a photosensitive resin laminate type etching resist was laminated on the copper foil. The etching resist was subjected to pattern exposure and development to form an antenna pattern on the etching resist. A polyethylene terephthalate film having a copper antenna pattern formed thereon was obtained by removing the copper foil from the portion where the etching resist pattern was not formed by etching, and then peeling off the etching resist. This antenna pattern was a square mesh pattern with a line width of 20 μm and a line-to-line pitch of 300 μm. Thus, a transparent antenna substrate was produced.

<Visual evaluation>
A photosensitive resin composition prepared as described in Tables 1 and 2 above was applied onto a carrier film. This was dried by heating in a hot air dryer at 80° C. for 30 minutes to form a resin layer of a photosensitive resin composition having a thickness of 20 μm, and a cover film was laminated on the resin layer to obtain a photosensitive resin laminate. . After that, the cover film is peeled off at the time of use, and the resulting photosensitive resin laminate is heat-laminated on the side of the transparent antenna substrate on which the copper antenna pattern is formed. Co., Ltd.) was used for pattern exposure at the optimum exposure dose. After peeling off the carrier film, a pattern of the photosensitive resin composition was formed by developing for 200 seconds using a 1% Na ₂ CO ₃ aqueous solution at 30° C. under conditions of a spray pressure of 0.2 MPa. This substrate 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 120° C. for 60 minutes to be thermally cured.
The transparent antenna thus prepared was placed in a room with an illuminance of 500 lux with a normal fluorescent lamp lit, and a black "cross" (10.0 mm long, 10.0 mm wide, and 1.0 mm thick). was placed on white paper printed with , and 10 people evaluated how the character "cross" looked visually from a distance of 30 cm from the character "cross". The results are listed in Table 2.
◯: 10 out of 10 people can clearly see the character "ten" on the paper.
Δ: 5 out of 10 can clearly see the character “ten” on the paper.
x: 10 out of 10 people have difficulty seeing the character "cross" on the paper.

<Glass pasting evaluation>
A photosensitive resin composition prepared as described in Tables 1 and 2 above was applied onto a carrier film. This was dried by heating in a hot air dryer at 80° C. for 30 minutes to form a resin layer of a photosensitive resin composition having a thickness of 20 μm, and a cover film was laminated on the resin layer to obtain a photosensitive resin laminate. . After that, the cover film is peeled off at the time of use, and the resulting photosensitive resin laminate is heat-laminated on the side of the transparent antenna substrate on which the copper antenna pattern is formed. Co., Ltd.) was used for pattern exposure at the optimum exposure dose. After peeling off the carrier film, a pattern of the photosensitive resin composition was formed by developing for 200 seconds using a 1% Na ₂ CO ₃ aqueous solution at 30° C. under conditions of a spray pressure of 0.2 MPa. This substrate 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 120° C. for 60 minutes to be thermally cured.
The transparent antenna thus prepared is attached to a window glass that separates two rooms with different illuminance using a transparent double-sided adhesive film HJ-3160W manufactured by Nitto Denko, and one room is illuminated by a normal fluorescent lamp. The illuminance was 300 lux, and in the other room, the illuminance was 3000 lux, which is the brightness of a normal fluorescent lamp. Results are listed in Tables 1 and 2.
◎: 10 out of 10 people see no difference in cloudiness or color when viewed from one room side or the other room side 〇: 8 to 9 out of 10 people see from one room side or the other Even when viewed from the room side, there is no difference in cloudiness or color.
Δ: 3 to 7 out of 10 people do not perceive difference in cloudiness or color when viewed from one side of the room or from the other side of the room.
x: Not more than 2 out of 10 people do not perceive difference in cloudiness or color when viewed from one side of the room or from the other side of the room.

Claims (9)

(A) a carboxyl group-containing resin;
(B) a photoinitiator;
(C) a compound having an unsaturated double bond;
(D) a thermosetting resin;
(E) a photosensitive resin composition comprising a filler having an average particle size of 120 nm or less,
The ratio of the total light transmittance at a wavelength of 550 nm to the total light transmittance at a wavelength of 430 nm at a film thickness of 20 μm of the cured product obtained from the photosensitive resin composition is in the range of 0.90 or more and less than 1.15,
The photosensitive resin composition having a haze value of the cured product at a wavelength of 550 nm in a range of more than 0.0% and less than 2.0%. 2. The photosensitive resin composition according to claim 1, wherein the (A) carboxyl group-containing resin is a resin having a carboxyl group obtained by addition reaction of an acid anhydride. The carboxyl group-containing resin (A) contains an amideimide resin obtained by reacting an isocyanurate-type polyisocyanate synthesized from an isocyanate having an aliphatic structure with a tricarboxylic acid anhydride having an aliphatic structure. 2. The photosensitive resin composition of claim 1, characterized by: 4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the thermosetting resin (D) is an epoxy resin having a Gardner color number of 5 or less. 5. The photosensitive resin composition according to any one of claims 1 to 4, further comprising (F) a thermosetting catalyst that is liquid at 20°C or higher and lower than 70°C. A photosensitive resin laminate comprising a resin layer obtained by applying the photosensitive resin composition according to any one of claims 1 to 5 on a film and drying the composition. A cured product obtained by curing the resin layer of the photosensitive resin composition according to any one of claims 1 to 5 or the photosensitive resin laminate according to claim 6. 6. The photosensitive resin composition according to any one of claims 1 to 5, wherein the cured product according to claim 7 has a water vapor transmission rate of less than 10 g/m ² /day at a film thickness of 100 μm. A transparent antenna comprising the cured product according to claim 7 .