KR20240096690A - Photosensitive resin composition, photosensitive element, printed wiring board, and method for producing printed wiring board - Google Patents

Abstract

It contains (A) an acid-modified vinyl group-containing resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) an inorganic filler, and (E) a thermosetting resin, and (C) component has a thioxanthone-based skeleton. A photosensitive resin composition containing a compound having a naphthalene ring, and (E) a photosensitive resin composition containing a resin having a naphthalene ring.

Description

Photosensitive resin composition, photosensitive element, printed wiring board, and method for producing printed wiring board

This disclosure relates to a photosensitive resin composition, a photosensitive element, a printed wiring board, and a method of manufacturing a printed wiring board.

In the field of printed wiring boards, forming permanent resist on printed wiring boards is practiced. In printed wiring boards, permanent resist has a role in preventing corrosion of conductor layers and maintaining electrical insulation between conductor layers, and is used as a surface protection layer or interlayer insulating layer.

In recent years, electronic devices have been miniaturizing and improving their performance, and even in multilayer printed wiring boards used in electronic devices, higher density is progressing due to an increase in the number of circuit layers and miniaturization of wiring. In particular, the density of semiconductor package substrates such as BGA (ball grid array) and CSP (chip size package) on which semiconductor chips are mounted is significantly increasing in density. In addition to the miniaturization of wiring, interlayer insulating layers have become thinner and vias for interlayer connections have been developed. There is a demand for narrowing the diameter of the hole. Additionally, as interlayer insulating layers in printed wiring boards become thinner, excellent electrical insulation reliability between layers is also required. In terms of electrical insulation reliability, particularly excellent electrical insulation reliability (HAST resistance) after a highly accelerated life test (Highly Accelerated Stress Test) is required.

A method of manufacturing a printed wiring board includes a method of manufacturing a multilayer printed wiring board using a build-up method in which an interlayer insulating layer and a conductor circuit layer are sequentially laminated (see, for example, Patent Document 1). In multilayer printed wiring boards, with the miniaturization of circuits, the semi-additive method of forming circuits by plating is becoming mainstream. In the conventional semi-additive method, for example, (1) a process of laminating a thermosetting resin film on a conductor circuit and curing the thermosetting resin film by heating to form an interlayer insulating layer, (2) interlayer A via is formed by laser processing, and a desmear treatment and roughening treatment are performed by alkaline permanganate treatment, etc.; (3) electroless copper plating is applied to the substrate, and a pattern is formed using a resist; , (4) forming a copper circuit by performing electrolytic copper plating, and (4) forming a copper circuit by peeling off the resist and performing flash etching of the electroless layer. .

As described above, laser processing has become the mainstream method for forming vias in the interlayer insulating layer formed by curing a thermosetting resin film, but there is a limit to reducing the diameter of vias by laser irradiation using a laser processing machine. In addition, when forming vias using a laser processing machine, it is necessary to form each via hole one by one, and when it is necessary to prepare numerous vias due to increased density, a large amount of time is required to form vias, and manufacturing efficiency is reduced. There is a problem with being bad.

Under such circumstances, as a method capable of forming a plurality of vias at once, a method of forming a plurality of small-diameter vias at once using a photosensitive resin composition by a photolithography method has been proposed (e.g., patent (see document 2).

Patent Document 1: Japanese Patent Publication No. 7-304931 Patent Document 2: Japanese Patent Publication No. 2017-116652

In recent years, the miniaturization of wiring, thinning of interlayer insulating layers, and narrowing of via holes for interlayer connection are further progressing, and the interlayer insulating layers are required to have better resolution and electrical insulation reliability. The photosensitive resin composition described in Patent Document 2 cannot be said to sufficiently satisfy these requirements, and there is room for further improvement.

Accordingly, the present disclosure aims to provide a photosensitive resin composition, a photosensitive element, a printed wiring board, and a method for manufacturing a printed wiring board that can obtain excellent resolution and excellent electrical insulation reliability.

One aspect of the present disclosure contains (A) an acid-modified vinyl group-containing resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) an inorganic filler, and (E) a thermosetting resin, and (C) ) It relates to a photosensitive resin composition in which the component contains a compound having a thioxanthone-based skeleton, and the component (E) contains a resin having a naphthalene ring.

In the photosensitive resin composition, the component (A) comprises at least one acid-modified vinyl group-containing epoxy resin (A1) made of bisphenol novolak-type epoxy resin (a1), the epoxy resin (a1), and may contain at least one acid-modified vinyl group-containing epoxy resin (A2) made of a different epoxy resin (a2).

In the photosensitive resin composition, the epoxy resin (a2) is at least one selected from the group consisting of novolak-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and triphenolmethane-type epoxy resin. It's okay.

In the photosensitive resin composition, the acid-modified vinyl group-containing epoxy resins (A1) and (A2) are formed by reacting the epoxy resins (a1) and (a2) with an ethylenically unsaturated group-containing organic acid (b), respectively. Resins (A1') and (A2') may be formed by reacting a polybasic acid anhydride (c) containing a saturated or unsaturated group.

In the photosensitive resin composition, the epoxy resin (a1) may have a structural unit represented by the following general formula (I), or a structural unit represented by the following general formula (II).

[Formula 1]

[In formula (I), R ¹¹ represents a hydrogen atom or a methyl group, and Y ¹ and Y ² each independently represent a hydrogen atom or a glycidyl group. A plurality of R ¹¹ may be the same or different, and at least one of Y ¹ and Y ² represents a glycidyl group.]

[Formula 2]

[In Formula (II), R ¹² represents a hydrogen atom or a methyl group, and Y ³ and Y ⁴ each independently represent a hydrogen atom or a glycidyl group. A plurality of R ¹² may be the same or different, and at least one of Y ³ and Y ⁴ represents a glycidyl group.]

In the photosensitive resin composition, the component (B) may contain a compound having three or more ethylenically unsaturated bonds in the molecule.

The photosensitive resin composition may further contain (F) pigment.

In the photosensitive resin composition, the component (E) may contain an epoxy resin having a naphthalene ring.

In the photosensitive resin composition, the acid value of the component (A) may be 30 to 150 mgKOH/g.

Another aspect of the present disclosure relates to a photosensitive element including a support film and a photosensitive layer formed using the photosensitive resin composition described above.

Another aspect of the present disclosure relates to a printed wiring board provided with a permanent resist containing a cured product of the photosensitive resin composition described above.

Another aspect of the present disclosure includes a process of forming a photosensitive layer on a substrate using the above-described photosensitive resin composition or a photosensitive element, a process of exposing and developing the photosensitive layer to form a resist pattern, and the resist pattern. It relates to a method of manufacturing a printed wiring board, comprising a step of curing to form a permanent resist.

According to the present disclosure, it is possible to provide a photosensitive resin composition, a photosensitive element, a printed wiring board, and a method for manufacturing a printed wiring board that can obtain excellent resolution and excellent electrical insulation reliability.

1 is a cross-sectional view schematically showing a photosensitive element according to this embodiment.
Fig. 2 is a schematic diagram showing the manufacturing method of the multilayer printed wiring board according to the present embodiment.

Hereinafter, the present disclosure will be described in detail. In this specification, the term “process” includes not only independent processes but also processes that cannot be clearly distinguished from other processes as long as the intended function of the process is achieved. The term "layer" includes not only the structure of the shape formed on the entire surface when observed in a plan view, but also the structure of the shape formed on a part of the surface. The numerical range indicated using “~” represents a range that includes the numerical values written before and after “~” as the minimum and maximum values, respectively. In the numerical range described in stages in this specification, the upper or lower limit of the numerical range at one level may be replaced with the upper or lower limit of the numerical range at another level. In the numerical range described in this specification, the upper or lower limit of the numerical range may be replaced with the value shown in the examples.

In this specification, when referring to the amount of each component in the composition, if there are multiple substances corresponding to each component in the composition, it means the total amount of the multiple substances present in the composition, unless otherwise specified. .

In this specification, “(meth)acrylate” means at least one of “acrylate” and the corresponding “methacrylate”, and other similar expressions such as (meth)acrylic acid, (meth)acryloyl, etc. The same is true for . In this specification, “solid content” refers to the non-volatile content from which volatile substances (water, solvent, etc.) contained in the photosensitive resin composition have been removed, and also includes liquid, starch syrup, or wax-like components at room temperature (near 25°C). .

This embodiment relates to the following photosensitive resin composition, photosensitive element, printed wiring board, and manufacturing method of the printed wiring board.

[1] Containing (A) an acid-modified vinyl group-containing resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) an inorganic filler, and (E) a thermosetting resin, wherein the component (C) is A photosensitive resin composition containing a compound having an oxanthone-based skeleton, wherein the component (E) contains a resin having a naphthalene ring.

[2] The component (A) is at least one acid-modified vinyl group-containing epoxy resin (A1) made of bisphenol novolak-type epoxy resin (a1), and an epoxy resin different from the epoxy resin (a1). The photosensitive resin composition according to [1], which contains at least one acid-modified vinyl group-containing epoxy resin (A2) made of (a2).

[3] The above [2], wherein the epoxy resin (a2) is at least one selected from the group consisting of novolak-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and triphenolmethane-type epoxy resin. The photosensitive resin composition described in ].

[4] The acid-modified vinyl group-containing epoxy resins (A1) and (A2) are resins (A1') formed by reacting the epoxy resins (a1) and (a2), respectively, with an organic acid (b) containing an ethylenically unsaturated group. The photosensitive resin composition according to [2] or [3] above, which is a resin obtained by reacting (A2') with a polybasic acid anhydride (c) containing a saturated or unsaturated group.

[5] Any of the above [2] to [4], wherein the epoxy resin (a1) has a structural unit represented by the following general formula (I), or a structural unit represented by the following general formula (II) The photosensitive resin composition described in .

[Formula 3]

[In formula (I), R ¹¹ represents a hydrogen atom or a methyl group, and Y ¹ and Y ² each independently represent a hydrogen atom or a glycidyl group. A plurality of R ¹¹ may be the same or different, and at least one of Y ¹ and Y ² represents a glycidyl group.]

[Formula 4]

[In Formula (II), R ¹² represents a hydrogen atom or a methyl group, and Y ³ and Y ⁴ each independently represent a hydrogen atom or a glycidyl group. A plurality of R ¹² may be the same or different, and at least one of Y ³ and Y ⁴ represents a glycidyl group.]

[6] The photosensitive resin composition according to any one of [1] to [5] above, wherein the component (B) contains a compound having three or more ethylenically unsaturated bonds in the molecule.

[7] (F) The photosensitive resin composition according to any one of [1] to [6] above, further containing a pigment.

[8] The photosensitive resin composition according to any one of [1] to [7] above, wherein the component (E) contains an epoxy resin having a naphthalene ring.

[9] The photosensitive resin composition according to any one of [1] to [8] above, wherein the acid value of the component (A) is 30 to 150 mgKOH/g.

[10] A photosensitive element comprising a support film and a photosensitive layer formed using the photosensitive resin composition according to any one of [1] to [9] above.

[11] A printed wiring board comprising a permanent resist containing a cured product of the photosensitive resin composition according to any one of [1] to [9] above.

[12] A process of forming a photosensitive layer on a substrate using the photosensitive resin composition according to any one of [1] to [9] above or the photosensitive element according to [10] above, and exposing and developing the photosensitive layer. A method of manufacturing a printed wiring board comprising a step of forming a resist pattern and a step of curing the resist pattern to form a permanent resist.

[Photosensitive resin composition]

The photosensitive resin composition according to the present embodiment contains (A) an acid-modified vinyl group-containing resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) an inorganic filler, and (E) a thermosetting resin, The component (C) contains a compound having a thioxanthone-based skeleton, and the component (E) contains a resin having a naphthalene ring. The photosensitive resin composition according to this embodiment may further contain one or more of (F) pigment, (G) elastomer, (H) curing agent, and (I) ion trapping agent. The photosensitive resin composition according to the present embodiment is a negative photosensitive resin composition, and the cured film of the photosensitive resin composition can be suitably used as a permanent resist such as a surface protective layer and an interlayer insulating layer. Hereinafter, each component used in the photosensitive resin composition of this embodiment is explained in more detail.

((A) component: acid-modified vinyl group-containing resin)

The photosensitive resin composition according to this embodiment contains acid-modified vinyl group-containing resin as component (A). The acid-modified vinyl group-containing resin is not particularly limited as long as it has a vinyl bond that is a photopolymerizable ethylenically unsaturated bond and an alkali-soluble acidic group.

(A) Groups having an ethylenically unsaturated bond include, for example, vinyl group, allyl group, propargyl group, butenyl group, ethyneyl group, phenyletyneyl group, maleimide group, nadimide group, and (meth)acryloyl group is mentioned. Among these, from the viewpoint of reactivity and resolution, (meth)acryloyl group is preferable. Examples of the acidic group that the component (A) has include a carboxyl group, a sulfo group, and a phenolic hydroxyl group. Among these, a carboxy group is preferable from the viewpoint of resolution.

The (A) component is (a) an epoxy resin (hereinafter sometimes referred to as “component (a)”) and (b) an organic acid containing an ethylenically unsaturated group (hereinafter sometimes referred to as “(b) component”). An acid-modified vinyl group formed by reacting a resin (A') formed by reacting (c) a saturated or unsaturated group-containing polybasic acid anhydride (hereinafter sometimes referred to as "component (c)"). It is preferable that it is an epoxy derivative.

Examples of acid-modified vinyl group-containing epoxy derivatives include acid-modified epoxy (meth)acrylate. Acid-modified epoxy (meth)acrylate is a resin obtained by acid-modifying epoxy (meth)acrylate, which is a reaction product of component (a) and component (b), with component (c). As acid-modified epoxy (meth)acrylate, for example, an addition reaction product obtained by adding a saturated or unsaturated polybasic acid anhydride to an esterified product obtained by reacting an epoxy resin with a vinyl group-containing monocarboxylic acid can be used.

As the component (A), for example, an acid-modified vinyl group-containing product made by using a bisphenol novolak-type epoxy resin (a1) (hereinafter sometimes referred to as “epoxy resin (a1)”) as the (a) component. Resin (A1) (hereinafter sometimes referred to as "component (A1)"), and epoxy resin (a2) other than epoxy resin (a1) as component (a) (hereinafter referred to as "epoxy resin (a2)"). and acid-modified vinyl group-containing resin (A2) (hereinafter sometimes referred to as “component (A2)”) made using .

Examples of the epoxy resin (a1) include an epoxy resin having a structural unit represented by the following formula (I) or (II).

[Formula 5]

In formula (I), R ¹¹ represents a hydrogen atom or a methyl group, and plural R ¹¹ may be the same or different. Y ¹ and Y ² each independently represent a hydrogen atom or a glycidyl group, but at least one of Y ¹ and Y ² is a glycidyl group. From the viewpoint of further improving resolution, R ¹¹ is preferably a hydrogen atom, and from the viewpoint of further improving insulation reliability, Y ¹ and Y ² are preferably glycidyl groups.

The number of structural units represented by formula (I) in the epoxy resin (a1) is 1 or more, and may be 10 to 100, 15 to 80, or 15 to 70. If the number of structural units is within the above range, it becomes easy to improve resolution and insulation reliability. Here, the number of structural units of the structural unit represents an integer value for a single molecule, and represents a rational number that is the average value for an aggregate of multiple types of molecules. Hereinafter, the number of structural units of each structural unit is the same.

[Formula 6]

In formula (II), R ¹² represents a hydrogen atom or a methyl group, and plural R ¹² may be the same or different. Y ³ and Y ⁴ each independently represent a hydrogen atom or a glycidyl group, but at least one of Y ³ and Y ⁴ is a glycidyl group. From the viewpoint of further improving resolution, R ¹² is preferably a hydrogen atom, and from the viewpoint of further improving insulation reliability, Y ³ and Y ⁴ are preferably glycidyl groups.

The number of structural units represented by formula (II) in the epoxy resin (a1) is 1 or more, and may be 10 to 100, 15 to 80, or 15 to 70. If the number of structural units is within the above range, it becomes easy to improve resolution and insulation reliability.

In formula (II), the epoxy resin in which R ¹² is a hydrogen atom and Y ³ and Y ⁴ are glycidyl groups is the EXA-7376 series (manufactured by DIC Corporation, brand name), where R ¹² is a methyl group and Y The epoxy resin in which ³ and Y ⁴ are glycidyl groups is commercially available as the EPON SU8 series (manufactured by Mitsubishi Chemical Corporation, brand name).

The epoxy resin (a2) is not particularly limited as long as it is an epoxy resin different from the epoxy resin (a1), but from the viewpoint of further improving resolution and insulation reliability, novolak-type epoxy resin, bisphenol A-type epoxy resin, or bisphenol F-type It is preferable that it is at least one type selected from the group consisting of epoxy resin, triphenol methane type epoxy resin, and biphenyl type epoxy resin.

Examples of the novolak-type epoxy resin include an epoxy resin having a structural unit represented by the following formula (III). Examples of the bisphenol A-type epoxy resin or bisphenol F-type epoxy resin include an epoxy resin having a structural unit represented by the following formula (IV). Examples of the triphenol methane type epoxy resin include an epoxy resin having a structural unit represented by the following formula (V). Examples of the biphenyl type epoxy resin include an epoxy resin having a structural unit represented by the following formula (VI).

As the epoxy resin (a2), a novolak-type epoxy resin having a structural unit represented by the following formula (III) is preferable. Examples of the novolak-type epoxy resin having such a structural unit include the novolak-type epoxy resin represented by the following formula (III').

[Formula 7]

In formulas (III) and (III'), R ¹³ represents a hydrogen atom or a methyl group, Y ⁵ represents a hydrogen atom or a glycidyl group, and at least one of Y ⁵ is a glycidyl group. In formula (III'), n ₁ is a number of 1 or more, and a plurality of R ¹³ and Y ⁵ may be the same or different. From the viewpoint of further improving resolution and insulation reliability, R ¹³ is preferably a hydrogen atom.

In formula (III'), the molar ratio of Y ⁵ as a hydrogen atom and Y ⁵ as a glycidyl group is 0/100 to 30/70 or 0/100 to 10/90 from the viewpoint of further improving resolution and insulation reliability. You can continue. n ₁ is 1 or more, but may be 10 to 200, 30 to 150, or 30 to 100. When n ₁ is within the above range, resolution and insulation reliability are likely to be improved.

Examples of the novolak-type epoxy resin represented by formula (III') include phenol novolak-type epoxy resin and cresol novolak-type epoxy resin. These novolak-type epoxy resins can be obtained, for example, by reacting phenol novolak resin or cresol novolak resin with epichlorohydrin by a known method.

Examples of the phenol novolak-type epoxy resin or cresol novolak-type epoxy resin represented by formula (III') include YDCN-701, YDCN-702, YDCN-703, YDCN-704, YDCN-704L, YDPN-638, YDPN-602 (above, manufactured by Nittetsu Chemical & Materials Co., Ltd., brand name), DEN-431, DEN-439 (above, manufactured by Dow Chemical Company, brand name), EOCN-120, EOCN-102S, EOCN-103S, EOCN-104S , EOCN-1012, EOCN-1025, EOCN-1027, BREN (above, manufactured by Nippon Kayaku Co., Ltd., brand name), EPN-1138, EPN-1235, EPN-1299 (above, manufactured by BASF Corporation, brand name), N-730, N-770, N-865, N-665, N-673, VH-4150, VH-4240 (manufactured by DIC Corporation, brand name), etc. are commercially available.

As the epoxy resin (a2), a bisphenol A-type epoxy resin or a bisphenol F-type epoxy resin having a structural unit represented by the following formula (IV) is preferably used. Examples of the epoxy resin having such a structural unit include bisphenol A-type epoxy resin or bisphenol F-type epoxy resin represented by the following formula (IV').

[Formula 8]

In formulas (IV) and (IV'), R ¹⁴ represents a hydrogen atom or a methyl group, multiple R ^14s may be the same or different, and Y ⁶ represents a hydrogen atom or a glycidyl group. In formula (IV'), n ₂ represents a number of 1 or more, and when n ₂ is 2 or more, plural Y ⁶ may be the same or different, and at least one Y ⁶ is a glycidyl group.

From the viewpoint of further improving resolution, R ¹⁴ is preferably a hydrogen atom, and from the viewpoint of further improving insulation reliability, Y ⁶ is preferably a glycidyl group. n ₂ represents 1 or more, but may be 10 to 100, 10 to 80, or 15 to 60. When n ₂ is within the above range, resolution and insulation reliability are likely to be improved.

The bisphenol A-type epoxy resin or bisphenol F-type epoxy resin in which Y ⁶ in formula (IV) is a glycidyl group is, for example, the bisphenol A-type epoxy resin or bisphenol F-type epoxy resin in formula (IV) in which Y ⁶ is a hydrogen atom. It can be obtained by reacting the hydroxyl group (-OY ⁶ ) of the resin with epichlorohydrin.

In order to promote the reaction between hydroxyl groups and epichlorohydrin, it is best to carry out the reaction in the presence of an alkali metal hydroxide at a reaction temperature of 50 to 120°C in a polar organic solvent such as dimethylformamide, dimethylacetamide, or dimethyl sulfoxide. desirable. If the reaction temperature is within the above range, the reaction does not slow down excessively and side reactions can be suppressed.

Examples of the bisphenol A-type epoxy resin or bisphenol F-type epoxy resin represented by formula (IV') include jER807, jER815, jER825, jER827, jER828, jER834, jER1001, jER1004, jER1007 and jER1009 (above, manufactured by Mitsubishi Chemical Corporation) , brand name), DER-330, DER-301, DER-361 (above, manufactured by Dow Chemical Company, brand name), YD-8125, YDF-170, YDF-175S, YDF-2001, YDF-2004, YDF-8170 ( The products above (manufactured by Nittetsu Chemical & Materials Co., Ltd., brand name) are commercially available.

As the epoxy resin (a2), a triphenol methane type epoxy resin having a structural unit represented by the following formula (V) is preferably used. Examples of the triphenolmethane type epoxy resin having such a structural unit include the triphenolmethane type epoxy resin represented by the following formula (V').

[Formula 9]

In formulas (V) and (V'), Y ⁷ represents a hydrogen atom or a glycidyl group, plural Y ⁷ may be the same or different, and at least one Y ⁷ is a glycidyl group. In formula (V'), n ₃ represents a number of 1 or more.

From the viewpoint of further improving resolution and insulation reliability, the molar ratio of Y ⁷ , which is a hydrogen atom in Y ⁷ , and Y ⁷ , which is a glycidyl group, may be 0/100 to 30/70. As can be seen from this molar ratio, at least one of Y ⁷ is a glycidyl group. n ₃ is 1 or more, but may be 10 to 100, 15 to 80, or 15 to 70. When n ₃ is within the above range, resolution and insulation reliability are likely to be improved.

As the triphenolmethane type epoxy resin represented by formula (V'), for example, FAE-2500, EPPN-501H, EPPN-502H (above, manufactured by Nippon Kayaku Co., Ltd., brand name), etc. are commercially available.

As the epoxy resin (a2), a biphenyl type epoxy resin having a structural unit represented by the following formula (VI) is preferably used. Examples of the biphenyl type epoxy resin having such a structural unit include the biphenyl type epoxy resin represented by the following formula (VI').

[Formula 10]

In formulas (VI) and (VI'), Y ⁸ represents a hydrogen atom or a glycidyl group, plural Y ⁸ may be the same or different, and at least one Y ⁸ is a glycidyl group. In formula (V'), n ₄ represents a number of 1 or more.

Examples of the biphenyl type epoxy resin represented by formula (VI') include NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, and CER-3000- L (above, manufactured by Nippon Kayaku Co., Ltd., brand name) and the like are commercially available.

Examples of the epoxy resin (a2) include a novolak-type epoxy resin having a structural unit represented by formula (III), a bisphenol A-type epoxy resin having a structural unit represented by formula (IV), and a structural unit represented by formula (IV). At least one type selected from the group consisting of bisphenol F-type epoxy resins is preferable, and a bisphenol F-type epoxy resin having a structural unit represented by formula (IV) is more preferable.

From the viewpoint of further improving resolution and insulation reliability, as epoxy resin (a1), component (A1) using a bisphenol novolak-type epoxy resin having a structural unit represented by formula (II), and as epoxy resin (a2), You may use a combination of component (A2) using a bisphenol A-type epoxy resin or a bisphenol F-type epoxy resin having a structural unit represented by formula (IV).

(b) Components include, for example, acrylic acid, acrylic acid dimers, methacrylic acid, β-furfuryl acrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, and acrylic acid derivatives such as α-cyanocinnamic acid; A semi-ester compound that is a reaction product of a hydroxyl group-containing acrylate and a dibasic acid anhydride; and a half-ester compound that is a reaction product of a vinyl group-containing monoglycidyl ether or a vinyl group-containing monoglycidyl ester and a dibasic acid anhydride. (b) The component may be used individually or in combination of two or more types.

A half ester compound is obtained, for example, by reacting a hydroxyl group-containing acrylate, a vinyl group-containing monoglycidyl ether, or a vinyl group-containing monoglycidyl ester with a dibasic acid anhydride.

Examples of hydroxyl group-containing acrylates, vinyl group-containing monoglycidyl ethers, and vinyl group-containing monoglycidyl esters include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxy Butyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate , and glycidyl (meth)acrylate.

Examples of dibasic acid anhydrides include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and ethyl. Hexahydrophthalic anhydride, and itaconic anhydride can be mentioned.

In the reaction of component (a) and component (b), it is preferable to react at a ratio of 0.6 to 1.05 equivalents of component (b) relative to 1 equivalent of the epoxy group of component (a), and 0.8 to 1.0 equivalents. It is more preferable to react in proportion. By reacting at this ratio, the photosensitivity increases and the linearity of the resist pattern outline tends to be excellent.

Component (a) and component (b) can be reacted by dissolving in an organic solvent. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol. Glycol ethers such as glycol monoethyl ether; Esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, and carbitol acetate; Aliphatic hydrocarbons such as octane and decane; Petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha can be mentioned. The organic solvent may be used individually or in combination of two or more types.

A catalyst may be used to promote the reaction between component (a) and component (b). Catalysts include, for example, triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, and triphenylphosphine. . The catalyst may be used individually or in combination of two or more types.

From the viewpoint of promoting the reaction of component (a) and component (b), the amount of catalyst used is 0.01 to 10 parts by mass, 0.05 to 2 parts by mass, based on a total of 100 parts by mass of component (a) and component (b). , or 0.1 to 1 mass may be given.

In the reaction between component (a) and component (b), a polymerization inhibitor may be used for the purpose of preventing polymerization during the reaction. Examples of polymerization inhibitors include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol. The polymerization inhibitor may be used individually or in combination of two or more types.

From the viewpoint of improving stability, the amount of the polymerization inhibitor used is 0.01 to 1 part by mass, 0.02 to 0.8 parts by mass, or 0.04 to 0.5 parts by mass, based on a total of 100 parts by mass of component (a) and component (b). do.

The reaction temperature of component (a) and component (b) may be 60 to 150°C, 80 to 120°C, or 90 to 110°C from the viewpoint of productivity.

Component (A'), which is formed by reacting component (a) and component (b), has a hydroxyl group formed by a ring-opening addition reaction between the epoxy group of component (a) and the carboxyl group of component (b). By reacting component (c) with component (A'), the hydroxyl group of component (A') (including the hydroxyl group originally present in component (a)) and the acid anhydride group of component (c) are semi-esterified. An acid-modified vinyl group-containing resin is obtained.

(c) Components include, for example, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and ethyl. Hexahydrophthalic anhydride, and itaconic anhydride can be mentioned. Among these, tetrahydrophthalic anhydride is preferable from the viewpoint of resolution. (c) Component may be used individually or in combination of two or more types.

In the reaction of component (A') and component (c), for example, by reacting 0.1 to 1.0 equivalents of component (c) with respect to 1 equivalent of hydroxyl group in component (A'), the acid value of component (A) is reduced. It can be adjusted.

The reaction temperature of component (A') and component (c) may be 50 to 150°C, 60 to 120°C, or 70 to 100°C from the viewpoint of productivity.

If necessary, as component (a), a portion of hydrogenated bisphenol A type epoxy resin may be used in combination, and styrene-maleic acid-based resins such as hydroxyethyl (meth)acrylate modified product of styrene-maleic anhydride copolymer You may use some of them together.

It is preferable that the (A) component contains the (A1) component from the viewpoint of further improving resolution and insulation reliability. Component (A) may contain component (A1) and component (A2).

(A) The acid value of the component is not particularly limited. The acid value of component (A) may be 30 mgKOH/g or more, 40 mgKOH/g or more, or 50 mgKOH/g or more from the viewpoint of improving the solubility of the unexposed portion in aqueous alkaline solution. The acid value of the component (A) may be 150 mgKOH/g or less, 120 mgKOH/g or less, or 100 mgKOH/g or less from the viewpoint of improving the electrical properties of the cured film.

(A) The weight average molecular weight (Mw) of component is not particularly limited. The Mw of component (A) may be 3000 or more, 4000 or more, or 5000 or more from the viewpoint of improving the adhesiveness and insulation reliability of the cured film. The Mw of component (A) may be 30,000 or less, 25,000 or less, or 18,000 or less from the viewpoint of improving the resolution of the photosensitive layer.

Mw can be measured by gel permeation chromatography (GPC). For example, Mw can be measured under the following GPC conditions, and the value converted using a standard polystyrene calibration curve can be used as Mw. To create a calibration curve, a 5-sample set (“PStQuickMP-H” and “PStQuick B”, manufactured by Tosoh Corporation) can be used as standard polystyrene.

GPC device: High-speed GPC device “HCL-8320GPC” (manufactured by Tosoh Corporation)

Detector: Differential refractometer or UV detector (manufactured by Tosoh Corporation)

Column: Column TSKgel SuperMultipore HZH (column length: 15 cm, column inner diameter: 4.6 mm) (manufactured by Tosoh Corporation)

Eluent: Tetrahydrofuran (THF)

Measurement temperature: 40℃

Flow rate: 0.35mL/min

Sample concentration: 10mg/THF 5mL

Injection volume: 20μL

The content of component (A) in the photosensitive resin composition is 20 to 70% by mass, 25 to 60% by mass, based on the total solid content of the photosensitive resin composition, from the viewpoint of improving the heat resistance, electrical properties and chemical resistance of the permanent resist. It may be mass%, or 30 to 50 mass%.

((B) Ingredient: Photopolymerizable compound)

The component (B) is not particularly limited as long as it is a photopolymerizable compound or a photocrosslinkable compound. Preferred examples include compounds having a functional group that exhibits photopolymerization. Functional groups exhibiting photopolymerizability include, for example, ethylene such as vinyl group, allyl group, propargyl group, butenyl group, ethyneyl group, phenylethyneyl group, maleimide group, nadimide group, and (meth)acryloyl group. A functional group having a sexually unsaturated bond can be mentioned.

As the component (B), from the viewpoint of photosensitivity, compounds with a molecular weight of 1000 or more are preferable, for example, hydroxyalkyl compounds such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. (meth)acrylates; mono- or di(meth)acrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, and polyethylene glycol; (meth)acrylamides such as N,N-dimethyl(meth)acrylamide and N-methylol(meth)acrylamide; Aminoalkyl (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate; Polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, and tris-hydroxyethyl isocyanurate, or their ethylene oxide or propylene oxide adducts polyvalent (meth)acrylates; (meth)acrylates of ethylene oxide or propylene oxide adducts of phenols, such as phenoxyethyl (meth)acrylate and polyethoxy di(meth)acrylate of bisphenol A; (meth)acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; Preferred examples include melamine (meth)acrylate. These (B) components can be used individually or in combination of multiple types. From the viewpoint of improving sensitivity, component (B) may contain the polyhydric alcohol or polyhydric (meth)acrylates of these ethylene oxide or propylene oxide adducts.

In addition, in order to increase the crosslinking density by photocuring and improve heat resistance and electrical insulation reliability, a compound having three or more ethylenically unsaturated bonds in the molecule can be selected as component (B). Examples of such compounds include the above-mentioned polyvalent (meth)acrylates, and dipentaerythritol tri(meth)acrylate can be selected from the viewpoint of improving sensitivity.

The content of component (B) in the photosensitive resin composition may be appropriately selected from 2 to 50 mass%, 3 to 20 mass%, or 3 to 10 mass% based on the total solid content in the photosensitive resin composition. When the content of component (B) is 2% by mass or more, photosensitivity improves and the exposed portion tends to be difficult to elute during development, and when the content of component (B) is 50% by mass or less, heat resistance tends to improve.

((C) component: photopolymerization initiator)

The photopolymerization initiator that is component (C) is capable of polymerizing component (A) and component (B). The photosensitive resin composition according to the present embodiment contains a compound having a thioxanthone-based skeleton as the (C) component. (C) Component may be used individually or in combination of two or more types. When the component (C) contains a compound having a thioxanthone-based skeleton, the photosensitive resin composition can obtain excellent resolution. Therefore, when an interlayer insulating layer or a surface protective layer is produced using a photosensitive resin composition, via holes of a smaller diameter can be formed in these layers.

Compounds having a thioxanthone-based skeleton include, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone. and thioxanthone compounds. Among these, from the viewpoint of obtaining better resolution, the compound having a thioxanthone-based skeleton may contain 2,4-diethylthioxanthone.

(C) Component may contain a photopolymerization initiator other than the compound having a thioxanthone-based skeleton. Other photopolymerization initiators are not particularly limited, and examples include benzoin compounds such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2 -Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propane Acetophenone compounds such as , N,N-dimethylaminoacetophenone; Anthraquinone compounds such as 2-methyl anthraquinone, 2-ethy anthraquinone, 2-tert-buty anthraquinone, 1-chloro anthraquinone, 2-amy anthraquinone, and 2-amino anthraquinone; Ketal compounds such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenone, such as benzophenone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis(diethylamino)benzophenone, Michler's ketone, and 4-benzoyl-4'-methyldiphenyl sulfide. compound; 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-( o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di(p-methoxyphenyl)-5-phenylimidazole dimer, 2-(2,4-dimethoxyphenyl)-4, Imidazole compounds such as 5-diphenylimidazole dimer; Acridine compounds such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; Acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 1,2-Octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carba oxime ester compounds such as zol-3-yl]ethanone 1-(O-acetyloxime) and 1-phenyl-1,2-propanedione-2-[O-(ethoxycarbonyl)oxime]; and tertiary amine compounds such as N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine. there is.

The content of the compound having a thioxanthone-based skeleton in the photosensitive resin composition may be 0.01 to 15% by mass, 0.03 to 5% by mass, or 0.05 to 0.5% by mass, based on the total solid content of the photosensitive resin composition. When this content is 0.01% by mass or more, better resolution tends to be obtained.

The content of the compound having a thioxanthone-based skeleton in component (C) may be 5 to 100% by mass, 6 to 100% by mass, or 7 to 100% by mass, based on the total solid content of component (C). . When this content is 5% by mass or more, better resolution tends to be obtained.

The content of component (C) in the photosensitive resin composition may be 0.2 to 15% by mass, 0.5 to 10% by mass, 0.5 to 5% by mass, or 0.5 to 1% by mass, based on the total solid content of the photosensitive resin composition. do.

((D) Ingredient: Inorganic filler)

The photosensitive resin composition according to this embodiment contains an inorganic filler as (D) component. By containing component (D), the adhesive strength and hardness of the permanent resist can be improved. (D) Component may be used individually or in combination of two or more types.

Inorganic fillers include, for example, silica, alumina, titania, tantalum oxide, zirconia, silicon nitride, barium titanate, barium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, lead titanate, lead zirconate titanate, and titanium. Lanthanum acid zirconate Lead, gallium oxide, spinel, mullite, cordierite, talc, aluminum titanate, yttria-containing zirconia, barium silicate, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, zinc oxide, titanium acid. Examples include magnesium, hydrotalcite, mica, calcined kaolin, and carbon.

The component (D) may contain silica from the viewpoint of improving the heat resistance of the permanent resist, may contain barium sulfate from the viewpoint of improving the heat resistance and adhesive strength of the permanent resist, or may contain silica and barium sulfate. . From the viewpoint of improving the dispersibility of the inorganic filler, an inorganic filler whose surface has been previously treated with an alumina or an organic silane compound may be used.

The average particle size of the inorganic filler may be 0.01 to 5.0 μm, 0.05 to 3.0 μm, 0.1 to 2.0 μm, or 0.15 to 1.0 μm from the viewpoint of resolution.

The average particle diameter of component (D) is the average particle diameter of the inorganic filler in a dispersed state in the photosensitive resin composition, and is taken as a value obtained by measuring as follows. First, the photosensitive resin composition was diluted 1000 times with methyl ethyl ketone, and then, using a submicron particle analyzer (Beckman Coulter Co., Ltd., product name: N5), in accordance with the international standard ISO13321, the refractive index was 1.38 in the solvent. The dispersed particles are measured, and the particle size at 50% of the integrated value (volume basis) in the particle size distribution is taken as the average particle size.

The content of component (D) may be 5 to 70 mass%, 6 to 60 mass%, or 10 to 50 mass% based on the total solid content of the photosensitive resin composition. If the content of component (D) is within the above range, the low thermal expansion coefficient, heat resistance, and film strength can be further improved.

(D) When using silica as the component, the content of silica may be 5 to 60 mass%, 10 to 55 mass%, or 15 to 50 mass% based on the total solid content of the photosensitive resin composition. (D) When using barium sulfate as the component, the content of barium sulfate may be 5 to 30% by mass, 5 to 25% by mass, or 10 to 20% by mass, based on the total solid content of the photosensitive resin composition. When the content of silica and barium sulfate is within the above range, low thermal expansion coefficient, solder heat resistance, and adhesive strength tend to be excellent.

((E) Ingredient: Thermosetting resin)

The photosensitive resin composition according to this embodiment contains a thermosetting resin as the (E) component, and contains a resin having a naphthalene ring as the (E) component. When the photosensitive resin composition contains a resin having a naphthalene ring as the (E) component, the insulation reliability, heat resistance, adhesiveness, and chemical resistance of the cured film (permanent resist) formed from the photosensitive resin composition can be improved. (E) Component may be used individually or in combination of two or more types.

Examples of the thermosetting resin having a naphthalene ring include epoxy resins having a naphthalene ring, such as naphthalene-type epoxy resin, naphthol novolac-type epoxy resin, naphthol-type epoxy resin, naphthol aralkyl-type epoxy resin, and naphthylene ether-type epoxy resin. .

(E) Component may contain a thermosetting resin other than a thermosetting resin having a naphthalene ring (i.e., a thermosetting resin not having a naphthalene ring). Other thermosetting resins are not particularly limited and include, for example, epoxy resin, phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, and unsaturated polyester. Resins, allyl resins, dicyclopentadiene resins, silicone resins, triazine resins, and melamine resins can be mentioned.

Examples of epoxy resins include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, hydrogenated bisphenol A-type epoxy resin, brominated bisphenol A-type epoxy resin, bisphenol S-type epoxy resin, novolac-type epoxy resin, and biphenyl. type epoxy resin, dicyclopentadiene type epoxy resin, hydantoin type epoxy resin, triglycidyl isocyanurate, and bixylenol type epoxy resin.

The content of the thermosetting resin having a naphthalene ring in the photosensitive resin composition may be 1 to 20% by mass, 1.5 to 10% by mass, or 2 to 8% by mass, based on the total solid content of the photosensitive resin composition. If this content is 1% by mass or more, better insulation reliability tends to be obtained, and if this content is 20% by mass or less, better resolution tends to be obtained.

The content of the thermosetting resin having a naphthalene ring in the component (E) may be 5 to 100% by mass, 8 to 80% by mass, or 10 to 50% by mass, based on the total solid content of the component (E). When this content is 5% by mass or more, better insulation reliability tends to be obtained.

The content of component (E) in the photosensitive resin composition may be 2 to 30 mass%, 5 to 25 mass%, or 8 to 20 mass% based on the total solid content of the photosensitive resin composition. When the content of component (E) is within the above range, the insulation reliability and heat resistance of the formed cured film can be further improved while maintaining good developability.

The photosensitive resin composition according to the present embodiment is used in combination with a compound having a thioxanthone skeleton as component (C) and a resin having a naphthalene ring as component (E), thereby forming a permanent resist such as a surface protective layer and an interlayer insulating layer. It can show the excellent effect of being able to achieve both the required excellent resolution and excellent electrical insulation reliability at a high level.

((F) Ingredient: Pigment)

The photosensitive resin composition according to this embodiment may further contain a pigment as the (F) component from the viewpoint of improving the identification or appearance of the manufacturing device. As the (F) component, a colorant that develops a desired color can be used, such as when concealing wiring (conductor patterns). (F) Component may be used individually or in combination of two or more types.

Examples of the component (F) include phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black.

The content of component (F) is 0.01 to 5.0% by mass, 0.03 to 3.0% by mass, or 0.05 to 0.05% by mass, based on the total amount of solid content in the photosensitive resin composition, from the viewpoint of making the manufacturing device easier to identify and hiding the wiring more. It may be 2.0% by mass.

((G) Ingredient: Elastomer)

The photosensitive resin composition according to this embodiment may further contain an elastomer as the (G) component. By containing component (G), it is possible to suppress a decrease in flexibility and adhesive strength caused by strain (internal stress) inside the resin due to curing shrinkage of component (A).

Examples of the (G) component include styrene-based elastomer, olefin-based elastomer, urethane-based elastomer, polyester-based elastomer, polyamide-based elastomer, acrylic elastomer, and silicone-based elastomer. These elastomers are composed of a hard segment component that contributes to heat resistance and strength, and a soft segment component that contributes to flexibility and toughness. Among these, olefin-based elastomers and polyester-based elastomers are preferable.

As styrene-based elastomers, for example, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, and styrene block copolymer. and lene-ethylene-propylene-styrene block copolymer. As a component constituting the styrene-based elastomer, in addition to styrene, styrene derivatives such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene can be used.

As olefin-based elastomers, for example, ethylene-propylene copolymer, ethylene-α-olefin copolymer, ethylene-α-olefin-nonconjugated diene copolymer, propylene-α-olefin copolymer, butene-α-olefin copolymer. Non-conjugated die such as polymer, ethylene-propylene-diene copolymer, dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenorbornene, ethylidenenorbornene, butadiene, isoprene, etc. Examples include copolymers of ene and α-olefin, epoxy-modified polybutadiene, and carboxylic acid-modified butadiene-acrylonitrile copolymer.

The epoxy-modified polybutadiene preferably has hydroxyl groups at the molecule ends, more preferably has hydroxyl groups at both ends of the molecule, and more preferably has hydroxyl groups only at both ends of the molecule. The number of hydroxyl groups in the epoxy-modified polybutadiene may be 1 or more, preferably 1 to 5, more preferably 1 or 2, and still more preferably 2.

As a urethane-based elastomer, a compound composed of a hard segment made of low-molecular-weight (short-chain) diol and diisocyanate and a soft segment made of high-molecular-weight (long-chain) diol and diisocyanate can be used.

Examples of short-chain diols include ethylene glycol, propylene glycol, 1,4-butanediol, and bisphenol A. The number average molecular weight of the short-chain diol is preferably 48 to 500.

Examples of long-chain diols include polypropylene glycol, polytetramethylene oxide, poly(1,4-butylene adipate), poly(ethylene-1,4-butylene adipate), polycaprolactone, Examples include poly(1,6-hexylene carbonate), and poly(1,6-hexylene-neopentylene adipate). The number average molecular weight of the long-chain diol is preferably 500 to 10,000.

As the polyester-based elastomer, a compound obtained by polycondensation of dicarboxylic acid or a derivative thereof and a diol compound or a derivative thereof can be used.

Examples of dicarboxylic acids include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid; Aliphatic dicarboxylic acids having 2 to 20 carbon atoms, such as adipic acid, sebacic acid, and dodecanedicarboxylic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. Dicarboxylic acid can be used individually or in combination of two or more types.

Examples of diol compounds include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, etc. aliphatic diol; Alicyclic diols such as 1,4-cyclohexanediol; and aromatic diols such as bisphenol A, bis-(4-hydroxyphenyl)methane, bis-(4-hydroxy-3-methylphenyl)propane, and resorcin.

A polyester-based elastomer, a multi-block aerial containing aromatic polyester (e.g., polybutylene terephthalate) as a hard segment component and aliphatic polyester (e.g., polytetramethylene glycol) as a soft segment component. Combination can be used. There are various grades of polyester-based elastomers depending on the type, ratio, and molecular weight of the hard and soft segments.

Polyamide-based elastomers are roughly divided into two types: polyether block amide type and polyether ester block amide type, which use polyamide in the hard segment and polyether or polyester in the soft segment. Examples of polyamide include polyamide-6, polyamide-11, and polyamide-12. Examples of polyethers include polyoxyethylene glycol, polyoxypropylene glycol, and polytetramethylene glycol.

The acrylic elastomer can be a compound containing a structural unit based on (meth)acrylic acid ester as a main component. Examples of (meth)acrylic acid ester include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, methoxyethyl (meth)acrylate, and ethoxyethyl (meth)acrylate. can be mentioned. The acrylic elastomer may be a compound obtained by copolymerizing (meth)acrylic acid ester and acrylonitrile, or may be a compound obtained by further copolymerizing a monomer having a functional group that serves as a crosslinking point. Examples of monomers having a functional group include glycidyl methacrylate and allyl glycidyl ether.

Examples of acrylic elastomers include acrylonitrile-butylacrylate copolymer, acrylonitrile-butylacrylate-ethyl acrylate copolymer, methyl methacrylate-butyl acrylate-methacrylic acid copolymer, and Acrylonitrile-butylacrylate-glycidyl methacrylate copolymer can be mentioned. As the acrylic elastomer, acrylonitrile-butylacrylate-glycidyl methacrylate copolymer or methyl methacrylate-butyl acrylate-methacrylic acid copolymer is preferable, and methyl methacrylate-butyl acrylate-methacrylate is preferred. Crylic acid copolymers are more preferred.

Silicone-based elastomer is a compound containing organopolysiloxane as a main component. Examples of organopolysiloxane include polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane. The silicone-based elastomer may be a compound obtained by modifying part of organopolysiloxane with vinyl groups, alkoxy groups, etc.

From the viewpoint of improving the adhesion of the cured film, the component (G) may contain a carboxylic acid-modified butadiene-acrylonitrile copolymer or a polyester-based elastomer having a hydroxyl group.

The content of component (G) may be 2 to 40 parts by mass, 4 to 30 parts by mass, 6 to 20 parts by mass, or 10 to 15 parts by mass with respect to 100 parts by mass of component (A). When the content of component (G) is within the above range, the elastic modulus in the high temperature region of the cured film decreases, and the unexposed portion becomes more likely to be eluted into the developing solution.

((H) Hardener)

The photosensitive resin composition of this embodiment may further contain a hardening|curing agent as (H) component. Examples of the component (H) include compounds that are themselves cured by heat, ultraviolet rays, etc., or compounds that are cured by reacting with the carboxyl group or hydroxyl group of the acid-modified vinyl group-containing resin (A) by heat, ultraviolet rays, etc. . By using component (H), insulation reliability, heat resistance, adhesive strength, chemical resistance, etc. can be further improved. (H) Component may be used individually or in combination of two or more types.

Examples of the (H) component include thermosetting compounds such as melamine compounds, urea compounds, oxazoline compounds, and block-type isocyanates. Examples of melamine compounds include triaminotriazine, hexamethoxymelamine, and hexabutoxylated melamine. Examples of the urea compound include dimethylolurea.

Examples of block-type isocyanate include addition reaction products of polyisocyanate compounds and isocyanate blocking agents. Examples of this polyisocyanate compound include tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, naphthylene diisocyanate, and bis(isocyanate). Nate methyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, etc. Isocyanate compounds, their adduct forms, biuret compounds, and isocyanurate compounds can be mentioned.

The content of component (H) may be 0.01 to 20 mass%, 0.1 to 10 mass%, or 0.1 to 3 mass% based on the total solid content of the photosensitive resin composition. By keeping the content of component (H) within the above range, the insulation reliability and heat resistance of the formed cured film can be further improved while maintaining good developability.

((I) Ingredient: Ion trapping agent)

The photosensitive resin composition according to this embodiment may further contain an ion trapping agent as the (I) component from the viewpoint of improving the resist shape, adhesiveness, fluidity, and reliability. (I) The component is not particularly limited as long as it can capture ions in the ion trapping agent and has the function of capturing at least one of cations and anions.

The ions captured in this embodiment are, for example, sodium ions (Na ⁺ ) and chloride ions (Cl ^- ) mixed in a composition whose solubility in a solvent changes by reacting with irradiation of light, electron beam, etc. , bromine ion (Br ^- ), copper ion (Cu ⁺ , Cu ²⁺ ), etc. By capturing these ions, electrical insulation, electrical corrosion resistance, etc. are improved.

(I) It is preferable that the component is an ion trapping agent having at least one type selected from the group consisting of Zr (zirconium), Bi (bismuth), Mg (magnesium), and Al (aluminum). (I) Component may be used individually or in combination of two or more types.

(I) Components include a cation trapping agent that captures cations, an anion trapping agent that captures anions, and a zwitterionic trapping agent that captures cations and anions.

As a cation trapping agent, for example, zirconium phosphate, zirconium tungstate, zirconium molybdate, zirconium tungstate, zirconium antimonate, zirconium selenate, zirconium tellurate, zirconium silicate, zirconium phosphosilicate, zirconium polyphosphate, etc. Examples include inorganic ion exchangers of metal oxides.

Examples of the anion trapping agent include inorganic ion exchangers such as bismuth oxide hydrate and hydrotalcite.

Examples of the zwitterionic ion trapping agent include inorganic ion exchangers such as metal hydrous oxides such as aluminum oxide hydrate and zirconium oxide hydrate. As a zwitterionic trapping agent, IXE-1320 (Mg, Al-containing compound), IXE-600 (Bi-containing compound), IXE-633 (Bi-containing compound), IXE-680 (Bi-containing compound), and IXE manufactured by Toagosei Co., Ltd. -6107 (compound containing Zr, Bi), IXE-6136 (compound containing Zr, Bi), IXEPLAS-A1 (compound containing Zr, Mg, Al), IXEPLAS-A2 (compound containing Zr, Mg, Al), IXEPLAS-B1 (Compounds containing Zr and Bi) are commercially available.

The (I) component can be used in a granular form, and from the viewpoint of improving insulation, the average particle diameter of the (I) component may be 5 μm or less, 3 μm or less, or 2 μm or less, and may be 0.1 μm or more. The average particle diameter of component (I) is the particle diameter of the particles in a dispersed state in the photosensitive resin composition, and can be measured by the same method as the method for measuring the average particle diameter of component (D).

When the photosensitive resin composition of the present embodiment contains component (I), the content is not particularly limited, but is 0.05 to 0.05 based on the total solid content of the photosensitive resin composition from the viewpoint of improving electrical insulation and corrosion resistance. It may be 10% by mass, 0.1 to 5% by mass, or 0.2 to 1% by mass.

(Other ingredients)

The photosensitive resin composition according to this embodiment may further contain various additives as needed. Examples of additives include polymerization inhibitors such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol; Thickeners such as bentone and montmorillonite; Silicone-based, fluorine-based, and vinyl resin-based antifoaming agents; Silane coupling agent; and flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphate compounds, aromatic condensed phosphoric acid esters, and halogen-containing condensed phosphoric acid esters.

(solvent)

The photosensitive resin composition according to the present embodiment contains a solvent to dissolve and disperse each component, thereby facilitating application on a substrate and forming a coating film of uniform thickness.

Examples of solvents include ketones such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol. Glycol ethers such as glycol monoethyl ether; Esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, and carbitol acetate; Aliphatic hydrocarbons such as octane and decane; and petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. The solvent may be used individually or in combination of two or more types.

The compounding quantity of the solvent is not particularly limited, but the ratio of the solvent in the photosensitive resin composition may be 10 to 50 mass%, 20 to 40 mass%, or 25 to 35 mass%.

The photosensitive resin composition of this embodiment can be prepared by uniformly mixing each of the components described above using a roll mill, bead mill, or the like.

[Photosensitive element]

The photosensitive element according to the present embodiment includes a support film and a photosensitive layer containing the photosensitive resin composition described above. 1 is a cross-sectional view schematically showing a photosensitive element according to this embodiment. As shown in FIG. 1, the photosensitive element 1 includes a support film 10 and a photosensitive layer 20 formed on the support film 10.

The photosensitive element 1 is formed by applying the photosensitive resin composition according to the present embodiment to the support film 10 by a known method such as reverse roll coat, gravure roll coat, comma coat, or curtain coat, and then drying the coated film. It can be manufactured by forming the photosensitive layer 20.

Examples of the support film include polyester films such as polyethylene terephthalate and polybutylene terephthalate, and polyolefin films such as polypropylene and polyethylene. The thickness of the support film may be, for example, 5 to 100 μm. The thickness of the photosensitive layer may be, for example, 5 to 50 μm, 5 to 40 μm, or 10 to 30 μm. The surface roughness of the support film is not particularly limited, but the arithmetic mean roughness (Ra) may be 1000 nm or less, 500 nm or less, or 250 nm or less.

The coating film can be dried using hot air drying, far infrared rays, or near infrared rays. The drying temperature may be 60 to 120°C, 70 to 110°C, or 80 to 100°C. Drying time may be 1 to 60 minutes, 2 to 30 minutes, or 5 to 20 minutes.

A protective film 30 covering the photosensitive layer 20 may be further provided on the photosensitive layer 20 . The photosensitive element 1 may have a protective film 30 laminated on the side of the photosensitive layer 20 opposite to the side in contact with the support film 10 . As the protective film 30, for example, a polymer film such as polyethylene or polypropylene may be used.

[Printed wiring board]

The printed wiring board according to this embodiment is provided with a permanent resist containing a cured product of the photosensitive resin composition according to this embodiment.

The method for manufacturing a printed wiring board according to this embodiment includes the steps of forming a photosensitive layer on a substrate using the photosensitive resin composition or photosensitive element described above, exposing and developing the photosensitive layer to form a resist pattern, A process of curing the resist pattern to form a permanent resist is provided. Below, an example of each process will be described.

First, a substrate such as a copper-clad laminate is prepared, and a photosensitive layer is formed on the substrate. The photosensitive layer may be formed by applying a photosensitive resin composition on a substrate and drying it. Examples of methods for applying the photosensitive resin composition include screen printing, spraying, roll coating, curtain coating, and electrostatic coating. The drying temperature may be 60 to 120°C, 70 to 110°C, or 80 to 100°C. The drying time may be 1 to 7 minutes, 1 to 6 minutes, or 2 to 5 minutes.

The photosensitive layer may be formed on the substrate by peeling the protective film from the photosensitive element and laminating the photosensitive layer. Examples of a method of laminating the photosensitive layer include heat laminating using a laminator.

Next, the negative film is brought into contact with the photosensitive layer directly or through a support film, and exposed by irradiating actinic light. Examples of actinic rays include electron beams, ultraviolet rays, and X-rays, with ultraviolet rays being preferred. As a light source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a halogen lamp, etc. can be used. The exposure amount may be 10 to 2000 mJ/cm ² , 100 to 1500 mJ/cm ² , or 300 to 1000 mJ/cm ² .

After exposure, a resist pattern is formed by removing the unexposed portion with a developer. Examples of the development method include the dipping method and the spray method. As a developer, for example, an aqueous alkaline solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, or tetramethylammonium hydroxide can be used.

A pattern cured film (permanent resist) can be formed by subjecting the resist pattern to at least one of post-exposure and post-heating. The exposure amount of post-exposure may be 100 to 5000 mJ/cm ² , 500 to 2000 mJ/cm ² , or 700 to 1500 J/cm ² . The heating temperature of post-heating may be 100 to 200°C, 120 to 180°C, or 135 to 165°C. The heating time for post-heating may be 5 minutes to 12 hours, 10 minutes to 6 hours, or 30 minutes to 2 hours.

Next, a method for manufacturing a multilayer printed wiring board provided with the cured product of the photosensitive resin composition according to the present embodiment as an interlayer insulating layer and/or a surface protective layer is explained.

FIG. 2 is a schematic diagram showing one aspect of a method for manufacturing a multilayer printed wiring board comprising the cured product of the photosensitive resin composition of the present embodiment as at least one of a surface protective layer and an interlayer insulating layer. The multilayer printed wiring board 100A shown in FIG. 2(f) has a wiring pattern on the surface and inside. In the multilayer printed wiring board 100A, a plurality of wiring patterns are provided in layers, an interlayer insulating layer is provided between each layer, and a surface protection layer is provided on the surface. At least one of the surface protective layer and the interlayer insulating layer is formed using the photosensitive resin composition of this embodiment or the photosensitive element of this embodiment. The multilayer printed wiring board 100A is obtained by laminating a copper clad laminate, an interlayer insulating layer, metal foil, etc., and appropriately forming a wiring pattern by an etching method or a semi-additive method. Hereinafter, based on FIG. 2, a manufacturing method of the multilayer printed wiring board 100A will be described. In the following description, the case where both the surface protective layer and the interlayer insulating layer are formed using the photosensitive resin composition of this embodiment or the photosensitive element of this embodiment is explained.

First, an interlayer insulating layer 103 is formed on both sides of a substrate (such as a copper-clad laminate) 101 having a wiring pattern 102 on the surface (see Figure 2 (a)). The interlayer insulating layer 103 is photosensitive by the method described in the above-described method of manufacturing a printed wiring board, that is, by applying the photosensitive resin composition of the present embodiment or by heat laminating the photosensitive element of the present embodiment using a laminator. It is formed by forming a layer, using a negative film on the photosensitive layer, exposing and curing areas other than those where electrical connection to the outside (conductor pattern of another layer) is required, and further removing unexposed areas ( (see Figure 2(b)). This interlayer insulating layer 103 is made of a film having an opening 104. Here, the smear (residue) existing around the opening 104 can be removed by desmear treatment.

Next, the seed layer 105 is formed by electroless plating (see (c) of FIG. 2). On the seed layer 105, a photosensitive layer containing a photosensitive resin composition (photosensitive resin composition for semi-additive use) is formed, and predetermined locations are exposed and developed to form a resin pattern 106 (FIG. 2) (see (d) of).

Subsequently, the wiring pattern 107 is formed in the portion of the seed layer 105 where the resin pattern 106 is not formed by the electrolytic plating method, and the resin pattern 106 is removed using a stripper, and then the seed layer is removed. The portion where the wiring pattern 107 of (105) is not formed is removed by etching (see Figure 2(e)).

A multilayer printed wiring board 100A can be produced by repeating the above operation and forming a surface protective layer 108 containing a cured product of the photosensitive resin composition described above on the outermost surface (see Fig. 2(f)). In the multilayer printed wiring board 100A obtained in this way, semiconductor elements are mounted at corresponding locations, and electrical connection can be secured.

Since the multilayer printed wiring board according to the present embodiment has a surface protective layer and/or an interlayer insulating layer formed using the photosensitive resin composition or a photosensitive element of the present embodiment, the surface protective layer and/or the interlayer insulating layer have high resolution. and excellent electrical insulation reliability. Therefore, not only can the interlayer insulating layer be made thinner, but the diameter of the opening (via hole) for interlayer connection can also be made smaller.

According to the photosensitive resin composition according to the present embodiment, it is possible to form a permanent resist such as an interlayer insulating layer or surface protective layer of a semiconductor device that is excellent in resolution and electrical insulation reliability, and the interlayer insulating layer or surface protective layer, etc. A semiconductor element provided and an electronic device including the semiconductor element can be provided. The semiconductor element may be, for example, a memory, a package, etc. having a multi-layer wiring structure, a redistribution structure, etc. Examples of electronic devices include mobile phones, smartphones, tablet-type terminals, computers, and hard disk suspensions. By providing a pattern cured film formed from the photosensitive resin composition according to the present embodiment, it is possible to provide compact and high-performance semiconductor elements and electronic devices with excellent electrical insulation reliability.

Example

Hereinafter, the present disclosure will be described in more detail by way of examples, but the present disclosure is not limited to these examples.

(Synthesis Example 1)

Bisphenol F novolac type epoxy resin (manufactured by DIC Corporation, brand name "EXA-7376", a bisphenol F novolak containing a structural unit in formula (II) wherein Y ³ and Y ⁴ are glycidyl groups and R ¹² is a hydrogen atom. Rockfish-type epoxy resin, epoxy equivalent weight: 186) 350 parts by mass, 70 parts by mass of acrylic acid, 0.5 parts by mass of methylhydroquinone, and 120 parts by mass of carbitol acetate were mixed with stirring at 90°C. The mixed solution was cooled to 60°C, 2 parts by mass of triphenylphosphine was added, and it was allowed to react at 100°C until the acid value of the solution became 1 mgKOH/g or less. 98 parts by mass of tetrahydrophthalic anhydride (THPAC) and 85 parts by mass of carbitol acetate were added to the reaction solution, and the reaction was performed at 80°C for 6 hours. Thereafter, the reaction liquid was cooled to room temperature, and (A) a solution (solid content concentration: 73% by mass) of THPAC-modified bisphenol F novolak-type epoxy acrylate (A-1) as an acid-modified vinyl group-containing resin was obtained.

As components (B) to (F) and (H), the following materials were prepared.

(B) Photopolymerizable compound

DPHA: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)

(C) Photopolymerization initiator

Omnirad DETX: 2,4-diethylthioxanthone (manufactured by IGM Resins B.V.)

Omnirad 907: 2-methyl-[4-(methylthio)phenyl]morpholino-1-propanone (manufactured by IGM Resins B.V.)

Omnirad 819: Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (manufactured by IGM Resins B.V.)

(D) Inorganic filler

SC2050: Silica filler (manufactured by Admatex Co., Ltd., average particle size 0.5 μm)

(E) Thermosetting resin

NC-7000L: Naphthol aralkylcresol copolymerized epoxy resin (manufactured by Nippon Kayaku Co., Ltd.)

HP-4032D: 1,6-bis(2,3-epoxypropan-1-yloxy)naphthalene (manufactured by DIC Corporation)

YX-4000: Biphenyl type epoxy resin (manufactured by Mitsubishi Chemical)

(F) Pigment

Phthalocyanine pigment: manufactured by Sanyo Shikiso Co., Ltd.

(H) Hardener

Melamine: manufactured by Nissan Kagaku Kogyo Co., Ltd.

[Examples 1 to 8 and Comparative Examples 1 to 3]

<Production of photosensitive resin composition>

Each component was mixed in the mixing amount (mass parts, solid content equivalent) shown in Table 1, and kneaded with a 3-roll mill. After that, carbitol acetate was added so that the solid content concentration was 60% by mass, and a photosensitive resin composition was prepared.

<Production of photosensitive elements>

A 16-μm-thick polyethylene terephthalate film (manufactured by Toyobo Film Solutions Co., Ltd., brand name "G2-16") was prepared as a support film. On the support film, the photosensitive resin composition of Examples and Comparative Examples was uniformly applied so that the film thickness after drying was 25 μm, and dried at 75° C. for 30 minutes using a hot air convection dryer to form a photosensitive layer. Subsequently, a polyethylene film (manufactured by Tama Poly Co., Ltd., brand name "NF-15") was laminated as a protective film on the surface of the photosensitive layer opposite to the side in contact with the support film, and a photosensitive element was produced. .

(Evaluation of resolution)

A copper-clad laminate board with a thickness of 1.0 mm (manufactured by Showa Denko Materials Co., Ltd., brand name "MCL-E-67") was prepared. While peeling and removing the protective film from the photosensitive element, a press-type vacuum laminator (made by Meiki Seisakusho Co., Ltd., product name "MVLP-500") was applied to the copper-clad laminate board at a press pressure of 0.4 MPa and a press plate temperature of 80. The photosensitive layer was laminated under conditions of ℃, vacuum evacuation time of 40 seconds, laminate press time of 20 seconds, and atmospheric pressure of 4 kPa or less to obtain a laminate. Next, an i-line exposure apparatus (Ushio) is applied through a negative mask having a via pattern of a predetermined size (opening diameter size: 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 150, 200 μmϕ). Exposure was performed using Co., Ltd., product name "UX-2240SM-XJ-01", while changing the exposure amount in increments of 50 mJ/cm ² in the range of 100 to 500 mJ/cm ² . The evaluation of resolution below was performed using a test piece exposed to an exposure amount that was capable of forming an opening of the smallest size among the exposure amounts within the above range. Afterwards, using a 1% by mass aqueous solution of sodium carbonate, spray development was carried out at a pressure of ^1.765 Then, the unexposed portion was dissolved and developed. Next, using an ultraviolet exposure device (manufactured by Oak Seisakusho Co., Ltd., product name "OKM-2317"), the developed photosensitive layer was exposed to an exposure dose of 2000 mJ/cm ² and heated at 170°C for 1 hour to form a copper coating layer. A test piece having a cured product of the photosensitive layer on which a via pattern (opening portion) of a predetermined size was formed was produced on a substrate. The test piece was observed using a metallurgical microscope, and resolution was evaluated based on the following standards. The evaluation results are shown in Table 1.

A: The minimum diameter of the opening was 30μm or less.

B: The minimum diameter of the opening exceeded 30 μm and was 100 μm or less.

C: The minimum diameter of the opening exceeded 100 μm.

(Evaluation of insulation reliability)

A copper-clad laminate board with a thickness of 1.0 mm (manufactured by Showa Denko Materials Co., Ltd., brand name "MCL-E-67") was prepared. While peeling and removing the protective film from the photosensitive element, a press-type vacuum laminator (made by Meiki Seisakusho Co., Ltd., product name "MVLP-500") was applied to the copper-clad laminate board at a press pressure of 0.4 MPa and a press plate temperature of 80. The photosensitive layer was laminated under conditions of ℃, vacuum evacuation time of 25 seconds, laminate press time of 25 seconds, and atmospheric pressure of 4 kPa or less to obtain a laminate. The obtained laminate was exposed to the entire surface at an exposure dose of 500 mJ/cm ² using a parallel light exposure machine (manufactured by Oak Seisakusho Co., Ltd., brand name “EXM-1201”) using an ultra-high pressure mercury lamp as a light source. Next, exposure was performed at an exposure dose of 2,000 mJ/cm ² using an ultraviolet exposure device (manufactured by Oak Seisakusho Co., Ltd., product name “OKM-2317”) and heated at 170°C for 1 hour to form a photosensitive layer on the copper-clad laminate. formed a cured product.

Next, in order to chemically condition the surface of the cured product, an aqueous solution containing diethylene glycol monobutyl ether: 200 ml/L and sodium hydroxide: 5 g/L was prepared as a swelling liquid. This swelling liquid was heated to 70°C, and the cured product was immersed for 10 minutes. Next, as a roughening solution, an aqueous solution containing 60 g/L of potassium permanganate and 40 g/L of sodium hydroxide was prepared. This roughening liquid was heated to 70°C, and the cured product was immersed for 15 minutes. Next, an aqueous solution containing tin chloride (SnCl ₂ ): 30 g/L and hydrogen chloride: 300 ml/L was prepared as a neutralizing liquid. This neutralization liquid was heated to 40°C, the cured product was immersed for 5 minutes, and potassium permanganate was reduced.

Next, the surface of the chemically conditioned cured product was degreased and cleaned with an alkaline cleaner at 60°C (manufactured by Atotech Japan Co., Ltd., brand name “Cleaner Securigant 902”) for 5 minutes. After washing, the chemically conditioned cured product was treated with a 23°C predip solution (manufactured by Atotech Japan Co., Ltd., brand name “Predip Neogant B”) for 1 minute. Thereafter, the cured product was treated with an activator solution at 35°C (manufactured by Atotech Japan Co., Ltd., brand name "Activator Neogant 834") for 5 minutes, and then with a reducing solution at 30°C (manufactured by Atotech Japan Co., Ltd., brand name " The cured product was treated with Reducer Neogant WA") for 5 minutes.

The laminate thus obtained was placed in a chemical copper solution (manufactured by Atotech Japan Co., Ltd., product names "Basic Printgant MSK-DK", "Copper Printgant MSK", "Stabilizer Printgant MSK"), and electroless plating was applied. This was carried out until the pressure reached about 0.5 μm. After the electroless plating, annealing was performed at a temperature of 120°C for 30 minutes to remove remaining hydrogen gas. After that, copper sulfate electroplating was performed, and annealing treatment was performed at 180°C for 60 minutes to form a conductor layer with a thickness of 38 μm.

The formed conductor layer was etched to form a circular electrode of ϕ6 mm. Subsequently, a photosensitive solder resist film (manufactured by Showa Denko Materials Co., Ltd., product name "FZ-2700GA") was applied on the electrode and the cured material so that the layer thickness was 25 μm, using a press-type vacuum laminator (manufactured by Meiki Seisakusho Co., Ltd.). , product name "MVLP-500"), lamination was performed under conditions of compression pressure of 0.4 MPa, press plate temperature of 80°C, vacuum evacuation time of 25 seconds, laminate press time of 40 seconds, and atmospheric pressure of 4 kPa or less, and lamination was performed for evaluation. got a sieve

The obtained laminate for evaluation was exposed to the entire surface at an exposure dose of 500 mJ/cm ² using a parallel light exposure machine (manufactured by Oak Seisakusho Co., Ltd., brand name “EXM-1201”) using an ultra-high pressure mercury lamp as a light source. Next, it was exposed to an exposure dose of 2,000 mJ/cm ² using an ultraviolet ray exposure device and heated at 160°C for 1 hour to form a cured film of a photosensitive solder resist film.

Subsequently, wiring is performed so that the circular electrode is a positive electrode and the copper foil on the side where the circular electrode of the copper-clad laminate board is formed is a monopole, and the pressure cooker (model name "Unsaturated ultra-accelerated life test device PC-422RP", Hirayama Seiji Co., Ltd. (Sakusho Co., Ltd.) and exposed for 200 hours under the conditions of 135°C, 85%RH, and 5.5V. After that, the resistance value between the electrodes was measured, and the insulation reliability was evaluated according to the following evaluation criteria. The results are shown in Table 1.

A: The resistance value after 200 hours was 10×10 ⁷ Ω or more.

B: The resistance value after 200 hours was less than 10×10 ⁷ Ω and more than 10×10 ⁶ Ω.

C: The resistance value after 200 hours was less than 10×10 ⁶ Ω.

[Table 1]

One… photosensitive element
10… support film
20… photosensitive layer
30… protective film
100A… Multilayer printed wiring board
101… write
102, 107… wiring pattern
103… Interlayer insulation layer
104… opening
105… seed layer
106… resin pattern
108… surface protective layer

Claims (13)

Contains (A) an acid-modified vinyl group-containing resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) an inorganic filler, and (E) a thermosetting resin,
The component (C) includes a compound having a thioxanthone skeleton,
A photosensitive resin composition in which the component (E) contains a resin having a naphthalene ring. In claim 1,
The component (A) is at least one acid-modified vinyl group-containing epoxy resin (A1) made of bisphenol novolak-type epoxy resin (a1), and an epoxy resin (a2) different from the epoxy resin (a1). A photosensitive resin composition containing at least one acid-modified vinyl group-containing epoxy resin (A2) made using. In claim 2,
The photosensitive resin composition wherein the epoxy resin (a2) is at least one selected from the group consisting of novolak-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and triphenolmethane-type epoxy resin. In claim 2,
The acid-modified vinyl group-containing epoxy resins (A1) and (A2) are resins (A1') and ( A photosensitive resin composition, which is a resin obtained by reacting A2') with a polybasic acid anhydride (c) containing a saturated or unsaturated group. In claim 2,
A photosensitive resin composition in which the epoxy resin (a1) has a structural unit represented by the following general formula (I), or a structural unit represented by the following general formula (II).
[Formula 1]

[In formula (I), R ¹¹ represents a hydrogen atom or a methyl group, and Y ¹ and Y ² each independently represent a hydrogen atom or a glycidyl group. A plurality of R ¹¹ may be the same or different, and at least one of Y ¹ and Y ² represents a glycidyl group.]
[Formula 2]

[In formula (II), R ¹² represents a hydrogen atom or a methyl group, and Y ³ and Y ⁴ each independently represent a hydrogen atom or a glycidyl group. A plurality of R ¹² may be the same or different, and at least one of Y ³ and Y ⁴ represents a glycidyl group.] In claim 1,
A photosensitive resin composition in which the component (B) contains a compound having three or more ethylenically unsaturated bonds in the molecule. In claim 1,
(F) A photosensitive resin composition further containing a pigment. In claim 1,
A photosensitive resin composition in which the component (E) contains an epoxy resin having a naphthalene ring. In claim 1,
A photosensitive resin composition wherein the acid value of the component (A) is 30 to 150 mgKOH/g. A photosensitive element comprising a support film and a photosensitive layer formed using the photosensitive resin composition according to any one of claims 1 to 9. A printed wiring board comprising a permanent resist containing a cured product of the photosensitive resin composition according to any one of claims 1 to 9. A step of forming a photosensitive layer on a substrate using the photosensitive resin composition according to any one of claims 1 to 9,
A process of forming a resist pattern by exposing and developing the photosensitive layer;
A method of manufacturing a printed wiring board, comprising a step of curing the resist pattern to form a permanent resist. A process of forming a photosensitive layer on a substrate using the photosensitive element according to claim 10,
A process of forming a resist pattern by exposing and developing the photosensitive layer;
A method of manufacturing a printed wiring board, comprising a step of curing the resist pattern to form a permanent resist.