JP7202282B2 - Photosensitive resin composition and dry film containing photosensitive resin composition - Google Patents

Description

The present invention provides a coating material, in particular, a photosensitive resin composition capable of forming a coating material having a matte appearance and excellent resolution, soldering heat resistance, and insulation reliability, and applying the photosensitive resin composition to a film. It relates to a dry film having a coated film.

A conductive circuit pattern of a conductor (for example, copper foil) is formed on a substrate such as a printed wiring board or a flexible printed wiring board, and an electronic component is mounted on the soldering land of the circuit pattern by soldering. Circuit portions other than the lands are covered with an insulating film (for example, a solder resist film) as a protective film. As the insulating protective film, a photocured film of a photosensitive resin composition containing a photosensitive resin and a photopolymerization initiator may be used.

A dry film may be used as a method of forming the insulating protective film on the substrate. The dry film is formed by applying a photosensitive resin composition to a resin support film such as polyethylene terephthalate to form a coating film, and drying the coating film to form a solder resist layer on the support film. It can be manufactured by laminating a cover film on the formed solder resist layer. The solder-resist layer is formed on the substrate by laminating the solder-resist layer and the substrate while peeling off the cover film of the dry film. After that, the support film is exposed to light to cure the solder resist layer, and then heat curing is performed to form an insulating protective film on the substrate.

On the other hand, a photocured film of a photosensitive resin composition is sometimes required to have a matte appearance depending on the conditions of use as a protective film, such as imparting a luxurious feel. Therefore, it has been proposed to obtain a matte appearance of a photocured film by using a support film in which a support film and an intermediate layer are integrated by coating one side of a polyethylene terephthalate film (Patent document 1). In Patent Document 1, the intermediate layer formed by the coating treatment is a roughening agent, and the effect of the intermediate layer imparts a matte appearance to the photocured film. Therefore, in Patent Document 1, the support film of the dry film is roughened.

However, in Patent Document 1, since the intermediate layer is formed on the support film, the light irradiated during the photocuring treatment may be diffusely reflected by the support film due to haze or the like caused by the intermediate layer. When the light is diffusely reflected by the support film, the light is halated and the portion of the coating film that should be removed by development is also photocured. Moreover, in Patent Document 1, since the components of the intermediate layer adhere to the photocured film and the photocured film is contaminated with foreign matter, there is room for improvement in solder heat resistance and insulation reliability.

On the other hand, a protective film having a matte appearance formed on a wiring board is required to have solder heat resistance and insulation reliability in addition to resolution.

JP 2018-116255 A

In view of the above circumstances, the present invention provides a photosensitive resin composition capable of obtaining a photocured product having excellent resolution and a matte appearance while having solder heat resistance and insulation reliability. With the goal.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７は、それぞれ、独立して、炭素数１～２０個の飽和脂肪族炭化水素基、または少なくとも１つのエチレン性不飽和基を有する炭素数２～２０個の不飽和脂肪族炭化水素基を意味する。）で表される化合物を含有する［１］乃至［６］のいずれか１つに記載の感光性樹脂組成物。
［８］前記Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７は、それぞれ、独立して、炭素数１～５個の飽和脂肪族炭化水素基である［７］に記載の感光性樹脂組成物。
［９］前記Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７は、メチル基である［７］に記載の感光性樹脂組成物。
［１０］前記（Ｂ１）融点が１３０℃以上の結晶性エポキシ化合物１００質量部に対して、前記（Ｃ）脂肪族系ウレア化合物を３０質量部以上１５０質量部以下含有する［１］乃至［９］のいずれか１つに記載の感光性樹脂組成物。
［１１］ソルダーレジスト膜の形成用である［１］乃至［１０］のいずれか１つに記載の感光性樹脂組成物。
［１２］基板にソルダーレジスト膜を形成するためのドライフィルム用である［１］乃至［１１］のいずれか１つに記載の感光性樹脂組成物。
［１３］［１］乃至［１２］のいずれか１つに記載の感光性樹脂組成物を有するドライフィルム。 The gist of the configuration of the present invention is as follows.
[1] (A) a carboxyl group-containing photosensitive resin, (B) an epoxy compound, (C) an aliphatic urea compound, (D) a reactive diluent, and (E) a photopolymerization initiator, contains,
The (B) epoxy compound contains (B1) a crystalline epoxy compound having a melting point of 130° C. or higher,
9.0 parts by mass or more of the (B1) crystalline epoxy compound having a melting point of 130° C. or higher relative to 100 parts by mass of the (A) carboxyl group-containing photosensitive resin, and 100 parts by mass of the (A) carboxyl group-containing photosensitive resin A photosensitive resin composition containing 9.0 parts by mass or more of (C) the aliphatic urea compound per part.
[2] 50 parts by mass or less of the (B1) crystalline epoxy compound having a melting point of 130° C. or higher per 100 parts by mass of the (A) carboxyl group-containing photosensitive resin; The photosensitive resin composition according to [1], which contains 50 parts by mass or less of (C) the aliphatic urea compound based on the parts by mass.
[3] The photosensitive resin composition according to [1] or [2], wherein (B1) the crystalline epoxy compound having a melting point of 130°C or higher has a melting point of 130°C or higher and 170°C or lower.
[4] The photosensitive resin composition according to any one of [1] to [3], wherein (B1) the crystalline epoxy compound having a melting point of 130°C or higher contains a trifunctional epoxy compound.
[5] The photosensitive resin composition according to any one of [1] to [4], wherein (B) the epoxy compound further contains (B2) a liquid epoxy compound that is liquid at normal temperature and atmospheric pressure. thing.
[6] The photosensitive resin composition according to any one of [1] to [5], wherein the aliphatic urea compound (C) has a melting point of 100°C or higher and 250°C or lower.
[7] The (C) aliphatic urea compound has the following general formula (1)

(wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, or at least one means an unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms and an ethylenically unsaturated group). elastic resin composition.
[8] R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a saturated aliphatic hydrocarbon group having 1 to 5 carbon atoms [7] The photosensitive resin composition according to .
[9] The photosensitive resin composition according to [7], wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are methyl groups.
[10] Contains 30 parts by mass or more and 150 parts by mass or less of the aliphatic urea compound (C) with respect to 100 parts by mass of the (B1) crystalline epoxy compound having a melting point of 130° C. or higher [1] to [9] ] The photosensitive resin composition as described in any one of .
[11] The photosensitive resin composition according to any one of [1] to [10], which is used for forming a solder resist film.
[12] The photosensitive resin composition according to any one of [1] to [11], which is used as a dry film for forming a solder resist film on a substrate.
[13] A dry film comprising the photosensitive resin composition according to any one of [1] to [12].

As used herein, the term "melting point" means the temperature at the point of change at which a decrease in the amount of heat indicating endotherm occurs, as measured by differential scanning calorimetry (DSC) at a heating rate of 10°C/min. Moreover, "normal temperature" means 25 degreeC.

According to the aspect of the photosensitive resin composition of the present invention, (B) the epoxy compound contains (B1) a crystalline epoxy compound having a melting point of 130° C. or higher, and (A) 100 parts by mass of the carboxyl group-containing photosensitive resin On the other hand, by containing (B1) 9.0 parts by mass or more of a crystalline epoxy compound having a melting point of 130 ° C. or more and (C) 9.0 parts by mass or more of an aliphatic urea compound, solder heat resistance and insulation reliability It is possible to obtain a photocured product having a matte appearance with excellent resolution.

According to the aspect of the photosensitive resin composition of the present invention, (B1) 9.0 parts by mass or more and 50 parts by mass or less of a crystalline epoxy compound having a melting point of 130° C. or higher is added to 100 parts by mass of the carboxyl group-containing photosensitive resin. , (C) By containing 9.0 parts by mass or more and 50 parts by mass or less of an aliphatic urea compound, while reliably imparting excellent insulation reliability to the photocured product, furthermore, excellent alkali developability is imparted can do.

According to the embodiment of the photosensitive resin composition of the present invention, the melting point of (B1) the crystalline epoxy compound having a melting point of 130° C. or higher is 130° C. or higher and 170° C. or lower, thereby reliably obtaining an excellent matte appearance. be able to.

According to the embodiment of the photosensitive resin composition of the present invention, (B1) the crystalline epoxy compound having a melting point of 130° C. or higher contains a trifunctional epoxy compound, thereby further improving solder heat resistance.

According to the aspect of the photosensitive resin composition of the present invention, (C) the aliphatic urea compound has a melting point of 100° C. or higher and 250° C. or lower, thereby You can improve your sexuality in a balanced manner.

According to the aspect of the photosensitive resin composition of the present invention, (C) the aliphatic urea compound is a compound represented by the above general formula (1), thereby reliably obtaining an excellent matte appearance. can be done.

According to the embodiment of the photosensitive resin composition of the present invention, (B1) 100 parts by mass of a crystalline epoxy compound having a melting point of 130° C. or higher and (C) 30 parts by mass or more and 150 parts by mass or less of an aliphatic urea compound. By containing it, it is possible to improve solder heat resistance, insulation reliability, and resolution in a well-balanced manner while having a matte appearance.

Next, the photosensitive resin composition of the present invention will be explained below. The photosensitive resin composition of the present invention comprises (A) a carboxyl group-containing photosensitive resin, (B) an epoxy compound, (C) an aliphatic urea compound, (D) a reactive diluent, and (E) and a photopolymerization initiator, wherein the (B) epoxy compound contains (B1) a crystalline epoxy compound having a melting point of 130 ° C. or higher, and the (A) carboxyl group-containing photosensitive resin per 100 parts by mass 9.0 parts by mass or more of the (B1) crystalline epoxy compound having a melting point of 130 ° C. or higher, and 9.0 parts by mass of the (C) aliphatic urea compound per 100 parts by mass of the (A) carboxyl group-containing photosensitive resin. .0 parts by mass or more.

(A) Carboxyl Group-Containing Photosensitive Resin The carboxyl group-containing photosensitive resin is not particularly limited. For example, a carboxyl group having one or more, preferably two or more, photosensitive unsaturated double bonds in one molecule. Containing resin is mentioned. As the carboxyl group-containing photosensitive resin, for example, acrylic acid or methacrylic acid (hereinafter referred to as "(meth)acrylic acid") is added to at least part of the epoxy groups of a polyfunctional epoxy resin having two or more epoxy groups in one molecule. A radically polymerizable unsaturated monocarboxylic acid such as epoxy (meth)acrylate is reacted to obtain a radically polymerizable unsaturated monocarboxylic acid epoxy resin such as epoxy (meth)acrylate, and hydroxyl groups generated in the resulting resin are , polybasic acid-modified radically polymerizable unsaturated monocarboxylic acid epoxy resins such as polybasic acid-modified epoxy (meth)acrylate obtained by reacting polybasic acid and/or polybasic acid anhydride.

The polyfunctional epoxy resin is not particularly limited as long as it is a difunctional or higher epoxy resin, and any epoxy resin can be used. Although the epoxy equivalent of the polyfunctional epoxy resin is not particularly limited, for example, the upper limit thereof is preferably 3000 g/eq, more preferably 2000 g/eq, and particularly preferably 1500 g/eq. On the other hand, the lower limit of the epoxy equivalent of the polyfunctional epoxy resin is, for example, preferably 100 g/eq, particularly preferably 200 g/eq.

Examples of polyfunctional epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenylaralkyl type epoxy resin, phenylaralkyl type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, ε-caprolactone-modified epoxy resin, phenol novolak-type epoxy resin, cresol novolak-type epoxy resin, bisphenol-modified novolac-type epoxy resin, cycloaliphatic epoxy resin, glycidyl ester-type epoxy resin, glycidylamine-type epoxy resin, heterocyclic epoxy resin, etc. can be mentioned. These polyfunctional epoxy resins may be used alone or in combination of two or more.

The radically polymerizable unsaturated monocarboxylic acid is not particularly limited, and examples thereof include (meth)acrylic acid, crotonic acid, cinnamic acid, tiglic acid, and angelic acid. Among these, (meth)acrylic acid is preferred in terms of availability. These radically polymerizable unsaturated monocarboxylic acids may be used alone or in combination of two or more. The radically polymerizable unsaturated monocarboxylic acid reacts with the epoxy group of the polyfunctional epoxy resin to introduce a photosensitive unsaturated double bond into the resin, thereby imparting photosensitivity to the resin.

The method of reacting the polyfunctional epoxy resin and the radically polymerizable unsaturated monocarboxylic acid is not particularly limited. organic solvent).

A photosensitive unsaturated double bond is introduced by reacting a polybasic acid and/or a polybasic acid anhydride with a hydroxyl group generated by the reaction of a polyfunctional epoxy resin and a radically polymerizable unsaturated monocarboxylic acid. A free carboxyl group is further introduced into the resin. By introducing a free carboxyl group into a resin into which a photosensitive unsaturated double bond has been introduced, alkali developability is imparted to the resin. Polybasic acids and polybasic anhydrides are not particularly limited, and both saturated and unsaturated can be used. Examples of polybasic acids include succinic acid, maleic acid, adipic acid, citric acid, phthalic acid, phthalic acid derivatives (e.g., tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyl Tetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, methyltetrahydro phthalic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid), trimellitic acid, pyromellitic acid and diglycolic acid. Examples of the polybasic acid anhydride include anhydrides of the above-described polybasic acids. These compounds may be used alone or in combination of two or more.

The reaction method of the radically polymerizable unsaturated monocarboxylic acid epoxy resin and the polybasic acid and/or the polybasic acid anhydride is not particularly limited. and/or heating the polybasic acid anhydride in a suitable diluent (eg, inert organic solvent).

The polybasic acid-modified radically polymerizable unsaturated monocarboxylated epoxy resin described above can also be used as the carboxyl group-containing photosensitive resin. A part of the group is further reacted with a compound having one or more radically polymerizable unsaturated groups and an epoxy group (e.g., a glycidyl compound) to further introduce a radically polymerizable unsaturated group into the side chain of the resin. By doing so, a carboxyl group-containing photosensitive resin having improved photosensitivity may be obtained.

In the carboxyl group-containing photosensitive resin with further improved photosensitivity, the radically polymerizable unsaturated group is bonded to the side chain of the polybasic acid-modified radically polymerizable unsaturated monocarboxylic oxide epoxy resin skeleton through the addition reaction of the glycidyl compound. Therefore, the photopolymerization reactivity, that is, the photocurability is further improved, and excellent photosensitivity is exhibited. Examples of glycidyl compounds include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, pentaerythritol triacrylate monoglycidyl ether, and pentaerythritol trimethacrylate monoglycidyl ether. The compound having one or more radically polymerizable unsaturated groups and an epoxy group may be used alone, or two or more of them may be used in combination.

The acid value of the carboxyl group-containing photosensitive resin is not particularly limited, but the lower limit is preferably 30 mgKOH/g, particularly preferably 40 mgKOH/g, from the viewpoint of obtaining reliable alkali developability. On the other hand, the upper limit of the acid value of the carboxyl group-containing photosensitive resin is preferably 200 mgKOH/g from the viewpoint of preventing dissolution of the exposed portion (photocured portion) by the alkaline developer, and the moisture resistance and insulation of the photocured product are 150 mgKOH/g is particularly preferable from the viewpoint of preventing deterioration in reliability.

The mass average molecular weight (Mw) of the carboxyl group-containing photosensitive resin is not particularly limited, but the lower limit is preferably 6000, more preferably 7000, more preferably 8000, from the viewpoint of toughness and dryness to the touch of the photocured product. is particularly preferred. On the other hand, the upper limit of the mass average molecular weight (Mw) of the carboxyl group-containing photosensitive resin is preferably 200,000, more preferably 100,000, and particularly preferably 50,000, from the viewpoint of reliably preventing deterioration in alkali developability.

The carboxyl group-containing photosensitive resin may be synthesized by the above reaction using each of the above starting materials, or a commercially available carboxyl group-containing photosensitive resin may be used. Examples of commercially available carboxyl group-containing photosensitive resins include "SP-4621" (Showa Denko Co., Ltd.), "KAYARAD ZAR-2000", "KAYARAD ZFR-1122", "KAYARAD FLX-2089", and "KAYARAD." ZCR-1569H” (above, Nippon Kayaku Co., Ltd.), “Cychromer P (ACA) Z-250” (Daicel Co., Ltd.), and the like. Moreover, these carboxyl group-containing photosensitive resins may be used alone or in combination of two or more.

(B) Epoxy compound The epoxy compound contains (B1) a crystalline epoxy compound having a melting point of 130°C or higher. The crystalline epoxy compound having a melting point of 130° C. or higher is contained in an amount of 9.0 parts by mass or more based on 100 parts by mass of the carboxyl group-containing photosensitive resin (solid content, hereinafter the same). By containing 9.0 parts by mass or more of a crystalline epoxy compound having a melting point of 130° C. or higher with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin together with (C) an aliphatic urea compound described later, solder heat resistance and It is possible to obtain a photocured product having insulation reliability, excellent resolution, and a matte appearance.

A crystalline epoxy compound having a melting point of 130° C. or higher is preferably sparingly soluble in a non-reactive diluent such as an organic solvent. As used herein, the term “sparingly soluble” means that a sample solution (concentration of crystalline epoxy compound: 1.0% by mass) in which a crystalline epoxy compound is added to a non-reactive diluent such as an organic solvent is dried at 80°C. Leave it in the machine for 12 hours, stir it, and then leave it in a dryer at 80°C for 12 hours. Observing the dissolution state of the crystalline epoxy compound, it means that the dissolution amount of the crystalline epoxy compound is 5% by volume or less. Although the non-reactive diluent to which the crystalline epoxy compound is added is not particularly limited, ethyl diglycol acetate, dipropylene glycol monomethyl ether, and aromatic hydrocarbons are preferred. The crystalline epoxy compound is solid at room temperature (25° C.) and has a relatively low molecular weight (for example, molecular weight of 200 to 1000).

The melting point of the crystalline epoxy compound is not particularly limited as long as it is 130° C. or higher, but the lower limit is preferably 135° C., particularly 138° C., from the viewpoint of reliably imparting an excellent matte appearance to the photocured product. preferable. On the other hand, the upper limit of the melting point of the crystalline epoxy compound is preferably 170°C, more preferably 165°C, and particularly preferably 160°C, from the viewpoint of obtaining a photocured product having mechanical strength by increasing the crosslink density.

The amount of the crystalline epoxy compound having a melting point of 130° C. or higher is not particularly limited as long as it is 9.0 parts by mass or more with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. is preferably 15 parts by mass, more preferably 20 parts by mass, and particularly preferably 25 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin, from the point of reliably improving the On the other hand, the upper limit of the amount of the crystalline epoxy compound having a melting point of 130° C. or higher is determined based on the coatability of the photosensitive resin composition and the quality of the photosensitive resin composition with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. From the viewpoint of imparting excellent alkali developability to the photocured product while obtaining dispersibility during production, 50 parts by mass is preferable, and further improves the resolution by imparting even better alkali developability to the photocured product. 40 parts by mass is more preferable, and 35 parts by mass is particularly preferable, from the viewpoint of

The functional number of the crystalline epoxy compound having a melting point of 130° C. or higher is not particularly limited. From the viewpoint of improving solder heat resistance in a well-balanced manner, it is more preferably bifunctional or more and trifunctional or less, and from the viewpoint of further improving solder heat resistance, trifunctional is particularly preferable.

Examples of crystalline epoxy compounds having a melting point of 130° C. or higher include triazine-type epoxy resins, hydroquinone-type epoxy resins, tetrakisphenolethane-type epoxy resins, and the like. These epoxy compounds may be used alone or in combination of two or more.

Moreover, as an epoxy compound, (B2) a liquid epoxy compound that is liquid at normal temperature and atmospheric pressure may be further contained. Since the liquid epoxy compound is uniformly dispersed in the photosensitive resin composition of the present invention, the crosslink density of the entire photocured product of the photosensitive resin composition is increased, and the light having sufficient mechanical strength is obtained. It contributes to obtaining a cured product. Examples of liquid epoxy compounds include epoxy resins that are liquid at normal temperature and atmospheric pressure. Examples of epoxy resins that are liquid at normal temperature and atmospheric pressure include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, biphenylaralkyl type epoxy resin, phenylaralkyl type epoxy resin, and naphthalene type epoxy resin. , phenol novolak type epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, adamantane type epoxy resin, and the like. These liquid epoxy compounds may be used alone or in combination of two or more.

The amount of the liquid epoxy compound is not particularly limited, and from the viewpoint of reliably obtaining a photocured product with sufficient mechanical strength, it is 10 parts by mass or more and 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. The following is preferable, and 15 parts by mass or more and 50 parts by mass or less is particularly preferable.

(C) Aliphatic Urea Compound 9.0 parts by mass or more of the crystalline epoxy compound having a melting point of 130° C. or higher is contained with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin, and the aliphatic urea compound is carboxyl. By containing 9.0 parts by mass or more with respect to 100 parts by mass of the group-containing photosensitive resin, a photocured product having excellent matte appearance and solder heat resistance while having resolution and insulation reliability is obtained. be able to. An aliphatic urea compound is an aliphatic urea compound that does not have an aromatic ring in its chemical structure.

The melting point of the aliphatic urea compound is not particularly limited, but is preferably 100° C. or higher and 250° C. or lower from the viewpoint of improving the matte appearance, insulation reliability, resolution and soldering heat resistance in a well-balanced manner. 120° C. or higher and 230° C. or lower are preferable, and 140° C. or higher and 210° C. or lower are particularly preferable, from the viewpoint of further improving the reactivity of the adhesive resin and the aliphatic urea compound to obtain better insulation reliability and soldering heat resistance. .

The amount of the aliphatic urea compound compounded is not particularly limited as long as it is 9.0 parts by mass or more with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. From the point of ensuring improvement, it is preferably 15 parts by mass, more preferably 20 parts by mass, and particularly preferably 25 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. On the other hand, the upper limit of the amount of the aliphatic urea compound compounded is preferably 50 parts by mass, more preferably 40 parts by mass, with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin, in order to reliably obtain excellent insulation reliability. is more preferred, and 35 parts by mass is particularly preferred.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７は、それぞれ、独立して、炭素数１～２０個の飽和脂肪族炭化水素基、または少なくとも１つのエチレン性不飽和基を有する炭素数２～２０個の不飽和脂肪族炭化水素基を意味する。）で表される化合物を挙げることができる。 Aliphatic urea compounds include aliphatic urea compounds having a cycloaliphatic structure. As an aliphatic urea compound having a cyclic aliphatic structure, the following general formula (1)

(wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, or at least one means an unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms and having an ethylenically unsaturated group.).

Among these, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently is more preferably an aliphatic urea compound represented by general formula (1), which is a saturated aliphatic hydrocarbon group having 1 to 5 carbon atoms, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , Further preferred are aliphatic urea compounds of general formula (1) in which R ⁷ is each independently a saturated aliphatic hydrocarbon group having 1 to 3 carbon atoms, and R ¹ , R ² , R ³ , R Particularly preferred is an aliphatic urea compound of general formula (1) in which ⁴ , R ⁵ , R ⁶ and R ⁷ are all methyl groups. The aliphatic urea compound of general formula (1), wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are all methyl groups, is represented by N′-[3-[[[ (dimethylamino)carbonyl]amino]methyl]-3,5,5-trimethylcyclohexyl]-N,N-dimethylurea. The melting point of N'-[3-[[[(dimethylamino)carbonyl]amino]methyl]-3,5,5-trimethylcyclohexyl]-N,N-dimethylurea is about 150°C.

The blending ratio of the aliphatic urea compound and the crystalline epoxy compound having a melting point of 130° C. or higher is not particularly limited. From the point of view of being able to It is more preferable to contain 70 parts by mass or more and 110 parts by mass or less of the aliphatic urea compound.

With the photosensitive resin composition of the present invention, as described above, a photocured product having a matte appearance, that is, a matted appearance can be obtained. For example, after coating the photosensitive resin composition of the present invention, it is dried at 110° C. for 5 minutes, irradiated with ultraviolet rays of 150 mJ/cm ² , and photocured after heat curing at 150° C. for 60 minutes. The gloss value obtained by measuring the 60-degree specular reflectance of the object surface using a gloss meter is preferably 55% or less. By reducing the gloss value to 55% or less, it is possible to obtain a photocured product having a matte appearance and a hiding power. Although the gloss value is preferably as low as possible, for example, it is more preferably 35% or less, and particularly preferably 30% or less.

(D) Reactive diluent A reactive diluent is, for example, a photopolymerizable monomer and a compound having at least one polymerizable double bond per molecule, preferably two or more polymerizable double bonds per molecule. The reactive diluent enhances the photocuring of the photosensitive resin composition and contributes to the acid resistance, heat resistance, alkali resistance, etc. of the photocured product. Examples of reactive diluents include monofunctional (meth)acrylate monomers and bifunctional or higher (meth)acrylate monomers. Specific examples include 2-hydroxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, caprolactone-modified (meth) Monofunctional (meth)acrylates such as acrylates, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, diethylene glycol di(meth)acrylate , neopentyl glycol adipate di(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, dicyclopentanyl di(meth)acrylate, ethylene oxide-modified phosphoric acid di(meth)acrylate, allylated cyclohexyl di(meth) Bifunctional (meth)acrylates such as acrylates and isocyanurate di(meth)acrylates, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, pentaerythritol tri( Trifunctional or higher such as meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, tris(acryloxyethyl)isocyanurate, propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. (meth)acrylates, urethane (meth)acrylates, and the like. By adding urethane (meth)acrylate, flexibility can be imparted to the photocured product. These may be used alone or in combination of two or more.

The content of the reactive diluent is not particularly limited. preferable.

(E) Photopolymerization Initiator The photopolymerization initiator is not particularly limited. 9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(0-acetyloxime), 2-(acetyloxyiminomethyl)thioxanthen-9-one, 1,8- Octanedione, 1,8-bis[9-ethyl-6-nitro-9H-carbazol-3-yl]-, 1,8-bis(O-acetyloxime), 1,8-octanedione, 1,8- Bis[9-(2-ethylhexyl)-6-nitro-9H-carbazol-3-yl]-, 1,8-bis(O-acetyloxime), (Z)-(9-ethyl-6-nitro-9H -carbazol-3-yl)(4-((1-methoxypropan-2-yl)oxy)-2-methylphenyl)methanone oxime ester photopolymerization initiators such as O-acetyloxime, 2-benzyl-2- dimethylamino-1-morpholinophenone)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2 α-Aminoalkylphenone-based photopolymerization such as -methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1,1-benzyl-1-(dimethylamino)propyl-4-morpholinophenyl-ketone initiators.

Other photopolymerization initiators other than oxime ester photopolymerization initiators and α-aminoalkylphenone photopolymerization initiators include, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin- Benzoin-based photopolymerization initiators such as n-butyl ether and benzoin isobutyl ether; benzophenone-based photopolymerization initiators such as benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone Anthraquinone-based photopolymerization initiators such as 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and other thioxanthone-based photopolymerization initiators, ethyl-4- (dimethylamino) benzoate, 2-n-butoxyethyl-4-(dimethylamino) benzoate, methyl-4-(dimethylamino) benzoate, isoamyl-4-(dimethylamino) benzoate, 2-(dimethylamino) ethyl benzoate, Benzoate-based photopolymerization initiators such as 2-ethylhexyl-4-(dimethylamino) benzoate and the like are included.

Among the above photopolymerization initiators, oxime ester photopolymerization initiators and α-aminoalkylphenone photopolymerization initiators are preferable from the viewpoint of excellent photosensitivity. These photopolymerization initiators may be used alone or in combination of two or more. The amount of the photopolymerization initiator is not particularly limited, but is preferably 1.0 parts by mass or more and 10 parts by mass or less, and 2.0 parts by mass or more and 8.0 parts by mass or more. 0 parts by mass or less is particularly preferable.

In addition to the components (A) to (E) described above, the photosensitive resin composition of the present invention may optionally contain other components such as extender pigments, flame retardants, curing accelerators, and additives. , coloring agents, non-reactive diluents and the like can be added as appropriate.

Examples of extender pigments include aluminum hydroxide, aluminum oxide, and barium sulfate. Examples of curing accelerators include mercaptobenzoxazale and its derivatives, dicyandiamide (DICY) and its derivatives, melamine and its derivatives, boron trifluoride-amine complex, organic acid hydrazide, diaminomaleonitrile (DAMN) and derivatives thereof, guanamine and its derivatives, amine imides (AI) and polyamines; Examples of additives include antifoaming agents such as silicone-based, hydrocarbon-based and acrylic-based agents, dispersants such as (meth)acrylic-based polymers, thixotropic agents, and antioxidants.

The coloring agent is not particularly limited, and may be a pigment, a dye, or the like, and may be a white coloring agent, a blue coloring agent, a green coloring agent, a yellow coloring agent, a purple coloring agent, a black coloring agent, an orange coloring agent, or the like. Any colorant can be used as appropriate. Examples of the coloring agent include inorganic coloring agents such as titanium oxide which is a white coloring agent, acetylene black which is a black coloring agent, and carbon black, and phthalocyanine green which is a green coloring agent and phthalocyanine blue which is a blue coloring agent. Examples include phthalocyanine-based coloring agents such as lionol blue, and organic coloring agents such as diketopyrrolopyrrole-based coloring agents such as chromophthal orange, which is an orange coloring agent.

The flame retardant is for imparting flame retardancy to the cured product of the photosensitive resin composition of the present invention. Examples of flame retardants include phosphorus-based flame retardants. Phosphorus-based flame retardants include, for example, tris(chloroethyl) phosphate, tris(2,3-dichloropropyl) phosphate, tris(2-chloropropyl) phosphate, tris(2,3-bromopropyl) phosphate, tris(bromo Halogen-containing phosphoric acid such as chloropropyl)phosphate, 2,3-dibromopropyl-2,3-chloropropylphosphate, tris(tribromophenyl)phosphate, tris(dibromophenyl)phosphate, tris(tribromoneopentyl)phosphate Esters; non-halogen aliphatic phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate; triphenyl phosphate, cresyldiphenyl phosphate, dicresylphenyl phosphate, tricresyl phosphate, trixyl Nyl phosphate, xylenyl diphenyl phosphate, tris(isopropylphenyl) phosphate, isopropylphenyl diphenyl phosphate, diisopropylphenyl phosphate, tris(trimethylphenyl) phosphate, tris(t-butylphenyl) phosphate, hydroxyphenyldiphenyl phosphate, octyldiphenyl phosphate Non-halogenated aromatic phosphates such as aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, zinc bisdiphenylphosphinate, bisdiethyl Metal salts of phosphinic acids such as titanyl phosphinate, titanium tetrakisdiethylphosphinate, titanyl bismethylethylphosphinate, titanium tetrakismethylethylphosphinate, titanyl bisdiphenylphosphinate, titanium tetrakisdiphenylphosphinate, 9,10-dihydro-9 Phosphine oxide compounds such as -oxa-10-phosphaphenanthrene-10-oxide, diphenylvinylphosphine oxide, triphenylphosphine oxide, trialkylphosphine oxide and tris(hydroxyalkyl)phosphine oxide. Among these, organic phosphate-based flame retardants are preferred. These may be used alone or in combination of two or more.

A non-reactive diluent is a component for adjusting the viscosity, coating properties and drying properties of the photosensitive resin composition. Examples of non-reactive diluents include organic solvents. Examples of organic solvents include ketones such as methyl ethyl ketone; aromatic hydrocarbons such as benzene, toluene and xylene; alcohols such as methanol, ethanol, n-propanol, isopropanol and cyclohexanol; Cyclic hydrocarbons, petroleum ether, petroleum solvents such as petroleum naphtha, cellosolves such as cellosolve and butyl cellosolve, carbitol, carbitol such as butyl carbitol, ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbi Esters such as tall acetate, butyl carbitol acetate, ethylene glycol acetate and ethyl diglycol acetate can be used. These may be used alone or in combination of two or more.

The method for producing the photosensitive resin composition of the present invention described above is not limited to a specific method. It can be produced by kneading or mixing by kneading means such as rolls, ball mills, sand mills, bead mills and kneaders, or stirring and mixing means such as super mixers, planetary mixers and trimixes. Moreover, prior to the kneading or mixing, pre-kneading or pre-mixing may be carried out, if necessary.

Next, an example of how to use the photosensitive resin composition of the present invention will be described. Here, a method of forming a solder resist film using a dry film coated with the photosensitive resin composition of the present invention on a flexible printed wiring board having a circuit pattern formed by etching a copper foil is taken as an example. explain.

The dry film includes a support film (e.g., thermoplastic film such as polyethylene terephthalate film and polyester film), a solder resist layer coated on the support film, and a cover film (e.g., polyethylene film) protecting the solder resist layer. , polypropylene film). The photosensitive resin composition of the present invention is applied onto a support film by a known method such as a roller coating method or a bar coater method to form a coating film having a predetermined thickness. A solder resist layer is formed on the support film by drying the formed coating film of the photosensitive resin composition. After that, by laminating a cover film on the formed solder resist layer, a dry film having a coating film of the photosensitive resin composition of the present invention can be produced.

The solder-resist layer is formed on the flexible printed wiring board by attaching the solder-resist layer to the flexible printed wiring board while removing the cover film from the dry film produced as described above. Note that the support film is still laminated on the solder resist layer. Thereafter, if necessary, pre-drying is performed by heating for about 1 to 10 minutes at a temperature of about 100 to 120 ° C. in order to volatilize the non-reactive diluent (organic solvent) in the photosensitive resin composition. A non-reactive diluent (organic solvent) is volatilized from the resin composition to make the surface of the solder resist layer tack-free. Thereafter, a negative film having a pattern other than the lands of the circuit pattern that is translucent is placed on the support film, and the negative film is irradiated with ultraviolet rays (for example, a wavelength range of 300 to 400 nm) to form a solder resist. Light cure the layer. Thereafter, the support film is peeled off, and the solder resist layer is developed by removing the non-exposed areas corresponding to the lands with a dilute alkaline aqueous solution. As a developing method, a spray method, a shower method, or the like is used, and examples of the dilute alkaline aqueous solution used include a 0.5 to 5% by mass sodium carbonate aqueous solution. After alkali development, the solder resist layer is heat cured for 20 to 80 minutes in a hot air circulating dryer at 130 to 170° C. to form a solder resist film on the flexible printed wiring board. can.

Examples of the present invention will now be described, but the present invention is not limited to these examples as long as the gist of the present invention is not exceeded.

Examples 1-6, Comparative Examples 1-7
Each component shown in Tables 1 and 2 below was blended in the mixing ratio shown in Tables 1 and 2 below, and mixed and dispersed at room temperature (about 25 ° C.) using a three-roll, Examples 1 to 6 and Comparative A photosensitive resin composition was prepared for use in each of Examples 1-7. Unless otherwise specified, the blending amount of each component shown in Tables 1 and 2 below is in parts by mass. In addition, blanks in the blending amounts in Tables 1 and 2 below mean that there is no blending.

The details of each component in Tables 1 and 2 below are as follows.
(A) Carboxyl group-containing photosensitive resin KAYARAD ZCR-1569H: solid content (resin content) 65% by mass, Nippon Kayaku Co., Ltd. KAYARAD ZCR-1569H has at least It is a polybasic acid-modified epoxy acrylate resin having a chemical structure prepared by partially reacting acrylic acid to obtain an epoxy acrylate and reacting the hydroxyl groups of the epoxy acrylate with a polybasic acid.

(B) Epoxy compound (B1) Crystalline epoxy compound having a melting point of 130°C or higher TEPIC-HP: melting point 150 to 156°C, trifunctional epoxy compound, Nissan Chemical Industries, Ltd. YDC-1312: melting point 138 to 145°C, Bifunctional epoxy compound, Nippon Steel Chemical Co., Ltd. (B2) Liquid epoxy compound EPICLON 850-S: DIC

(C) Aliphatic urea compound U-Cat3513N: Melting point about 150°C, N'-[3-[[[(dimethylamino)carbonyl]amino]methyl]-3,5,5-trimethylcyclohexyl]-N, N-Dimethylurea, San-Apro Co., Ltd.

(D) Reactive diluent EBECRYL8405: Daicel Cytec Co., Ltd. (E) Photopolymerization initiator OXE02: Ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl] -1-(0-Acetyloxime), BASF Irgacure 369: 1-benzyl-1-(dimethylamino)propyl-4-morpholinophenyl-ketone, BASF

Extender pigment, Hygilite H42M: Showa Denko Co., Ltd. Flame retardant, Exolit OP-935: Clariant Japan Co., Ltd. Curing accelerator Melamine: Nissan Chemical Industries, Ltd. DICY-7: Mitsubishi Chemical Co., Ltd. Additive AC-303: Dispersion Kyoeisha Chemical Co., Ltd. Colorant Denka Black: Denki Kagaku Kogyo Co., Ltd. Non-reactive diluent EDGAC: Sanyo Kaseihin Co., Ltd.

Crystalline epoxy compound with a melting point of less than 130°C TEPIC-SP: Melting point 95 to 125°C, Nissan Chemical Industries, Ltd. YX-4000: Melting point about 105°C, Mitsubishi Chemical Corporation

Dry Film Production Process Support film for dry film production: polyethylene terephthalate (PET) film (film thickness: 12 μm).
Coating method of photosensitive resin composition on support film: Bar coater method (coating so that thickness of dry film after preliminary drying is 25 μm)
Pre-drying: 110°C, 5 minutes

Test sample preparation process Evaluation substrate: flexible substrate (polyimide film, film thickness 25 μm, conductor thickness 12.5 μm)
Surface treatment of evaluation substrate: Surface treatment using 5 mass% sulfuric acid Conditions for lamination of dry film to evaluation substrate: 50 ° C., pressure 0.5 MPa, vacuum 30 s / pressure 30 s
Exposure treatment (photocuring treatment): A coating film of a photosensitive resin composition is irradiated with 150 mJ/cm ² of ultraviolet rays (wavelength: 300 to 400 nm) using a projection exposure device (light source: high-pressure mercury lamp, manufactured by USHIO Co., Ltd.). Development: 1 wt% sodium carbonate aqueous solution Temperature 30°C, spray pressure 0.2 MPa, development time 60 seconds Thermal curing treatment (post cure): 150°C, 60 minutes

Evaluation items (1) Gloss value (matte appearance)
Using a coating film surface and a gloss meter VG-2000 (Nippon Denshoku Industries Co., Ltd.), the 60-degree specular reflectance was measured. At a gloss value of 55% or less, it was evaluated that a matte appearance was obtained.

(2) Photo via resolution After the coating film of the photosensitive resin composition was exposed through a predetermined photomask (via opening diameter φ200 μm), the diameter of the photo via opened by development was measured with a metallographic microscope.

(3) Insulation reliability (insulation reliability in the thickness direction (Z-axis direction) of the cured coating film)
For the test sample prepared in the above test sample preparation process, the upper surface of the cured coating film with an electromagnetic wave shielding film (SF-PC5000 manufactured by Tatsuta Electric Wire Co., Ltd.) is used as the anode, and copper, which is the conductor of the evaluation board, is used as the cathode. , respectively. Next, 50 V was applied in a thermo-hygrostat at 60° C. and a humidity of 95%, and the resistance value was continuously measured using an ion migration tester (manufactured by IMV, "MIG-8600B/128"). The measurement start time is when 50 V is applied, and the time until the resistance value drops below 1.0E+6 (1.0×10 ⁶ ) Ω is measured. Z-axis direction) insulation reliability was evaluated.
A: Dielectric breakdown time of 1500 hours or more.
○: Dielectric breakdown time of 1000 hours or more and less than 1500 hours.
Δ: Dielectric breakdown time of 500 hours or more and less than 1000 hours.
x: Dielectric breakdown time less than 500 hours.

(4) Soldering heat resistance The cured coating film of the test sample was immersed in a solder bath at 260 ° C. for 10 seconds according to the test method of JIS C-6481, and then a peeling test with cellophane tape was performed as one cycle, and this was repeated 1 to 3 times. After the repetition, the state of the coating film was visually observed and evaluated according to the following criteria.
⊚: No change is observed in the coating film even after repeating 3 cycles.
◯: A very slight change is observed in the coating film after repeating 3 cycles.
Δ: A change is observed in the coating film after repeating 2 cycles.
x: Peeling is recognized in the coating film after 1 cycle.

Evaluation results are shown in Tables 1 and 2 below.

As shown in Table 1 above, 9.0 parts by mass or more of a crystalline epoxy compound having a melting point of 130° C. or higher and 9.0 parts by mass or more of an aliphatic urea compound are added to 100 parts by mass of the carboxyl group-containing photosensitive resin. In Examples 1 to 6, in which it was contained, the gloss value of the cured coating film was reduced to 55% or less, and a matte appearance could be obtained. Further, in Examples 1 to 6, an aperture diameter of φ180 μm or more, which is close to the aperture diameter of φ200 μm of the via of the photomask, was obtained, and the resolution was excellent. Further, Examples 1 to 6 were excellent in insulation reliability and solder heat resistance.

In particular, Examples 1 to 4 containing about 20 parts by mass or more of a crystalline epoxy compound having a melting point of 130° C. or more and about 20 parts by mass or more of an aliphatic urea compound with respect to 100 parts by mass of a carboxyl group-containing photosensitive resin. , the gloss value of the cured coating film was reduced to 30% or less, and an excellent matte appearance could be obtained. In addition, Example 1 in which the crystalline epoxy compound having a melting point of 130°C or higher is a trifunctional epoxy compound is compared with Example 3 in which the crystalline epoxy compound having a melting point of 130°C or higher is a difunctional epoxy compound. Solder heat resistance is further improved. In Example 2, in which a trifunctional epoxy compound and a bifunctional epoxy compound were used in combination as crystalline epoxy compounds having a melting point of 130° C. or higher, the solder heat resistance was evaluated as ⊚ as in Example 1. In Example 1, even if the peeling test was repeated more than in Example 2, no change in the coating film was observed.

On the other hand, as shown in Table 2 above, in Comparative Example 1 using a PET film whose surface was coated with a matting agent, the aperture diameter was φ150 μm, and the halation of ultraviolet rays during exposure was removed by development. The portion of the coating film to be coated was also photocured, and resolution was not obtained. Moreover, in Comparative Example 1, sufficient insulation reliability and solder heat resistance could not be obtained.

In addition, in Comparative Examples 2, 3, and 5 using a crystalline epoxy compound having a melting point of less than 130°C, and Comparative Example 4 using no crystalline epoxy compound, the gloss value of the cured coating film was 70%, which is matte. Couldn't get the look. Also in Comparative Examples 5 and 7, in which no aliphatic urea compound was used, the gloss value of the cured coating film was 70%, and a matte appearance could not be obtained. Even in Comparative Example 6, which contains 8 parts by mass of a crystalline epoxy compound having a melting point of 130° C. or higher and 8 parts by mass of an aliphatic urea compound with respect to 100 parts by mass of a carboxyl group-containing photosensitive resin, the gloss value of the cured coating film is At 70%, a matte appearance could not be obtained.

The photosensitive resin composition of the present invention contains 9.0 parts by mass or more of a crystalline epoxy compound having a melting point of 130° C. or higher and 9.0 parts by mass of an aliphatic urea compound per 100 parts by mass of a carboxyl group-containing photosensitive resin. By containing at least 1 part, it is possible to obtain a photocured product having a matte appearance with excellent resolution while having solder heat resistance and insulation reliability. Used in the field of protective films, particularly in the field of forming a protective film such as a solder resist on a flexible printed wiring board by applying a dry film having a coating film obtained by applying a photosensitive resin composition to the flexible printed wiring board. Good value.

Claims (13)

(A) a carboxyl group-containing photosensitive resin, (B) an epoxy compound, (C) an aliphatic urea compound (excluding an epoxy compound), (D) a reactive diluent, and (E) a photopolymerization initiator and contains
The (B) epoxy compound contains (B1) a crystalline epoxy compound having a melting point of 130° C. or higher,
9.0 parts by mass or more of the (B1) crystalline epoxy compound having a melting point of 130° C. or higher relative to 100 parts by mass of the (A) carboxyl group-containing photosensitive resin, and 100 parts by mass of the (A) carboxyl group-containing photosensitive resin 9.0 parts by mass or more of the (C) aliphatic urea compound per part ,
The photosensitive resin composition, wherein the (C) aliphatic urea compound is an aliphatic urea compound having a cycloaliphatic structure . (A) a carboxyl group-containing photosensitive resin, (B) an epoxy compound, (C) an aliphatic urea compound (excluding an epoxy compound), (D) a reactive diluent, and (E) a photopolymerization initiator and contains
The (B) epoxy compound contains (B1) a crystalline epoxy compound having a melting point of 130° C. or higher,
9.0 parts by mass or more of the (B1) crystalline epoxy compound having a melting point of 130° C. or higher relative to 100 parts by mass of the (A) carboxyl group-containing photosensitive resin, and 100 parts by mass of the (A) carboxyl group-containing photosensitive resin 9.0 parts by mass or more of the (C) aliphatic urea compound per part,
The photosensitive resin composition, wherein the aliphatic urea compound (C) has a melting point of 100° C. or higher and 250° C. or lower. ( A) a carboxyl group-containing photosensitive resin, (B) an epoxy compound, (C) an aliphatic urea compound (excluding an epoxy compound), (D) a reactive diluent, and (E) a photopolymerization initiator and contains
The (B) epoxy compound contains (B1) a crystalline epoxy compound having a melting point of 130° C. or higher,
9.0 parts by mass or more of the (B1) crystalline epoxy compound having a melting point of 130° C. or higher relative to 100 parts by mass of the (A) carboxyl group-containing photosensitive resin, and 100 parts by mass of the (A) carboxyl group-containing photosensitive resin 9.0 parts by mass or more of the (C) aliphatic urea compound per part,
The (C) aliphatic urea compound has the following general formula (1)

(wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, or at least one means an unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms and an ethylenically unsaturated group.). 50 parts by mass or less of the (B1) crystalline epoxy compound having a melting point of 130 ° C. or higher per 100 parts by mass of the (A) carboxyl group-containing photosensitive resin, and 100 parts by mass of the (A) carboxyl group-containing photosensitive resin. 4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the (C) aliphatic urea compound is contained in an amount of 50 parts by mass or less. 5. The photosensitive resin composition according to any one of claims 1 to 4 , wherein the (B1) crystalline epoxy compound having a melting point of 130°C or higher has a melting point of 130°C or higher and 170°C or lower. 6. The photosensitive resin composition according to any one of claims 1 to 5 , wherein the (B1) crystalline epoxy compound having a melting point of 130°C or higher contains a trifunctional epoxy compound. 7. The photosensitive resin composition according to any one of claims 1 to 6 , wherein the (B) epoxy compound further contains (B2) a liquid epoxy compound that is liquid at normal temperature and atmospheric pressure. The R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a saturated aliphatic hydrocarbon group having 1 to 5 carbon atoms, according to claim 3 . A photosensitive resin composition. 4. The photosensitive resin composition according to claim ³ , wherein said ^R1 , ^R2 , R3, ^R4 , ^R5 , ^R6 and ^R7 are methyl groups. 10. Any one of claims 1 to 9 , wherein 30 parts by mass or more and 150 parts by mass or less of the aliphatic urea compound (C) is contained with respect to 100 parts by mass of the (B1) crystalline epoxy compound having a melting point of 130° C. or higher. The photosensitive resin composition according to Item 1. 11. The photosensitive resin composition according to any one of claims 1 to 10 , which is used for forming a solder resist film. 12. The photosensitive resin composition according to any one of claims 1 to 11 , which is used as a dry film for forming a solder resist film on a substrate. A dry film comprising the photosensitive resin composition according to any one of claims 1 to 12 .