JP7202783B2 - Photosensitive resin laminate, dry film, cured product, electronic component, and method for manufacturing electronic component - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photosensitive resin laminate, a dry film, a cured product, an electronic component, and a method for producing an electronic component.

Inductors, which are passive electronic components that can store electrical energy in the form of magnetism, need to be improved in inductance in order to use them as power system inductors, for example. As one of means for improving inductance, it is known to mix magnetic particles in an organic material to form a core with high magnetic permeability (for example, Patent Documents 1 and 2).

On the other hand, as electronic devices have become lighter, thinner, shorter and smaller in recent years, printed wiring boards have become more accurate and denser, and electronic components such as inductors mounted on printed wiring boards have also been required to be smaller. One of the measures to reduce the size of such electronic components is to form a laminated structure, and in recent years, instead of the laminated ceramic technology, a construction method using an organic insulating layer has been proposed (see Patent Document 3).

In recent years, there has also been a demand for miniaturization of power supply system inductors that form a high magnetic permeability core by mixing magnetic particles with an organic material as described above. Conventionally, photolithography has been widely used in the printing industry and the electronics industry as a method capable of collectively forming this fine pattern.

However, since the magnetic particles used in power supply inductors generally do not transmit light, in order to reduce the size and form a fine pattern, an organic material mixed with magnetic particles is patterned by photolithography to create a laminated structure. It was difficult to convert

JP-A-2002-121381 JP 2009-263645 A JP 2016-225611 A

Accordingly, an object of the present invention is to provide a photosensitive resin laminate that can be patterned by photolithography despite containing magnetic particles, a dry film in which the laminate is supported or protected by a film, and the laminate. It is an object of the present invention to provide a cured product of a body or a laminate of the dry film, an electronic component having the cured product, and a method for producing an electronic component using the laminate.

In view of the above, the present inventors have made intensive studies. The inventors have found that pattern exposure can be performed from the side of the photosensitive resin layer so that even the resin layer containing magnetic particles can be patterned by alkali development, leading to the completion of the present invention.

That is, the photosensitive resin laminate of the present invention comprises a resin layer (A) containing an alkali-soluble resin and magnetic particles and a photosensitive resin layer (B) containing an alkali-soluble resin and a photopolymerization initiator. It is characterized by

In the photosensitive resin laminate of the present invention, the resin layer (A) preferably further contains a thermosetting resin.

In the photosensitive resin layered product of the present invention, the magnetic particles preferably have an average particle size (D50) of 0.01 to 50 μm.

In the photosensitive resin laminate of the present invention, the resin layer (A) preferably has a relative magnetic permeability (μ′) at a frequency of 100 MHz of more than 1 to 100 or less.

The dry film of the present invention is characterized in that at least one side of the photosensitive resin laminate is supported or protected by a film.

The cured product of the present invention is characterized by being obtained by curing the photosensitive resin laminate or the photosensitive resin laminate of the dry film.

The electronic component of the present invention is characterized by having the cured product.

The electronic component of the present invention is preferably an inductor.

In the method for producing an electronic component according to the present invention, the photosensitive resin layered product is exposed from the photosensitive resin layer (B) side, and then alkali-developed to form the resin layer (A) and the photosensitive resin layer. (B) is characterized by including the step of patterning.

According to the present invention, a photosensitive resin laminate that can be patterned by photolithography despite containing magnetic particles, a dry film in which the laminate is supported or protected by a film, and the laminate Alternatively, it is possible to provide a cured product of the dry film laminate, an electronic component having the cured product, and a method for producing an electronic component using the laminate.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which shows typically one embodiment of the photosensitive resin laminated body of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which shows typically one embodiment which formed the photosensitive resin laminated body of this invention on the base material in which the electrode was formed. FIG. 3 is a schematic cross-sectional view after patterning and development processing are performed on the embodiment of the photosensitive resin structure of the present invention shown in FIG. 2 ;

The photosensitive resin laminate of the present invention is characterized by laminating a resin layer (A) containing an alkali-soluble resin and magnetic particles and a photosensitive resin layer (B) containing an alkali-soluble resin and a photopolymerization initiator. and

As shown in FIG. 1, the photosensitive resin laminate 1 of the present invention is composed of a resin layer (A) and a photosensitive resin layer (B). For example, as shown in FIG. 2, after forming the photosensitive resin laminate 1 of the present invention on the substrate 2 on which the conductor pattern 3 is formed, by photolithography, as shown in FIG. It becomes possible to pattern even the resin layer (A).

In the present invention, even if the amount of the magnetic particles contained in the resin layer (A) is large, pattern formation by photolithography is possible, so that a cured product with a high relative magnetic permeability (μ') is formed. be able to. For example, the relative magnetic permeability (μ′) at a frequency of 100 MHz is preferably more than 1 to 100 or less, more preferably more than 2 to 100 or less, more preferably more than 4 to 100 or less. can.

Components contained in the resin layer (A) and the photosensitive resin layer (B) of the photosensitive resin laminate of the present invention are described in detail below.

[Magnetic particles]
The magnetic particles are not particularly limited, but are preferably soft magnetic particles characterized by a small coercive force and a large relative magnetic permeability μ′. Specifically, iron (Fe), silicon steel (Fe—Si), permalloy (Fe—Ni), sendust (Fe—Si—Al), permendur (Fe—Co), soft ferrite (Mn ferrite, Mn -Mg-Sr ferrite, Ni-Zn-Cu ferrite, Mn-Zn ferrite, Ni-Zn ferrite, etc.), amorphous magnetic alloys (Fe-Si-B, Fe-Si-BC, Fe-Co-Si-B , Fe--Ni--Mo--B), nanocrystalline magnetic alloys (Fe--Si-- _B --Nb--Cu, Fe--Zr--B--Cu, Fe--Co--Zr--B--Cu). , Al ₂ O ₃ , TiO ₂ , ZrO ₂ , and magnetic particles coated with an insulating coating such as various resins.

Generally, magnetic particles are black, gray, or brown, and conventionally, they do not transmit light, making patterning difficult. It can be patterned favorably.

The magnetic particles are mixed at a ratio of 90 parts by weight of the magnetic particles to 10 parts by weight of the fluorine-based binder resin, and when the relative magnetic permeability (μ') at a frequency of 100 MHz is measured, the relative magnetic permeability (μ') is Those in the range of more than 1 to 2000 or less are preferably used. Relative permeability (μ') is a value measured using a vector network analyzer (manufactured by Keysight Technologies).

The average particle diameter (D50) of the magnetic particles is preferably 0.01 to 50 μm, more preferably 0.05 to 20 μm, even more preferably 0.1 to 10 μm. When the thickness is 0.01 μm or more, the handling during manufacturing is facilitated. When the thickness is 50 μm or less, the shape of the formed pattern wall surface becomes smooth, so that a good pattern shape can be obtained. The average particle diameter (D50) of the magnetic particles is the value of D50 measured using a Microtrac particle size analyzer manufactured by Microtrac Bell, and not only the primary particle diameter but also the secondary particles (aggregates). diameter is also included.

The magnetic particles may be blended after being slurried.

The magnetic particles may be used singly or in combination of two or more.

In the present invention, even if the amount of the magnetic particles contained in the resin layer (A) is large, the pattern can be formed by photolithography. However, it may be, for example, 15% by mass or more in terms of solid content, further 25% by mass or more, or even 50% by mass or more in terms of solid content.

From the viewpoint of pattern formation by photolithography, the photosensitive resin layer (B) preferably does not contain magnetic particles, but may contain magnetic particles as long as the effects of the present invention are not impaired. The amount of the magnetic particles contained in the photosensitive resin layer (B) is preferably 0 to 5% by mass, more preferably 0 to 3% by mass, even more preferably 0 to 1% by mass, in terms of solid content. % by weight is particularly preferred.

[Alkali-soluble resin]
The alkali-soluble resins contained in the resin layer (A) and the photosensitive resin layer (B) may be the same or different.

Examples of alkali-soluble resins include compounds having two or more phenolic hydroxyl groups, carboxyl group-containing resins, compounds having phenolic hydroxyl groups and carboxyl groups, and compounds having two or more thiol groups. Among them, it is preferable that the alkali-soluble resin is a carboxyl group-containing resin or a phenolic resin, because the adhesion to the substrate is improved. In particular, the alkali-soluble resin is more preferably a carboxyl group-containing resin because of its excellent developability. The alkali-soluble resin may be an alkali-soluble resin having an ethylenically unsaturated group or an alkali-soluble resin having no ethylenically unsaturated group.

Specific examples of carboxyl group-containing resins include compounds (both oligomers and polymers) listed below. In this specification, (meth)acrylate is a generic term for acrylate, methacrylate and mixtures thereof, and the same applies to other similar expressions.

(1) A carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth)acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, isobutylene, or the like.

(2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates; Carboxyl group-containing urethane resins obtained by polyaddition reaction of diol compounds such as polyols, polyester-based polyols, polyolefin-based polyols, acrylic polyols, bisphenol A-based alkylene oxide adduct diols, and compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups.

(3) Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates, polycarbonate-based polyols, polyether-based polyols, polyester-based polyols, polyolefin-based polyols, acrylic polyols, and bisphenol A-based A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with the terminal of a urethane resin obtained by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

(4) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( A carboxyl group-containing urethane resin produced by a polyaddition reaction of a meth)acrylate or its partial acid anhydride modified product, a carboxyl group-containing dialcohol compound and a diol compound.

(5) During the synthesis of the resin of (2) or (4) above, a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule such as hydroxyalkyl (meth)acrylate is added, and the terminal ( Meta) acrylated urethane resin containing carboxyl groups.

(6) During the synthesis of the resin of (2) or (4), one isocyanate group and one or more (meth)acryloyl groups in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate A carboxyl group-containing urethane resin that is terminally (meth)acrylated by adding a compound having

(7) A carboxyl group obtained by reacting a polyfunctional epoxy resin with (meth)acrylic acid and adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride to the hydroxyl group present in the side chain. Contained resin.

(8) A carboxyl group-containing resin obtained by reacting (meth)acrylic acid with a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl groups of a bifunctional epoxy resin with epichlorohydrin, and adding a dibasic acid anhydride to the resulting hydroxyl groups. .

(9) A carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group.

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

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

(12) an epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol; Maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride such as adipic acid.

(13) In addition to the carboxyl group-containing resins described in (1) to (12) above, one epoxy group and one or more ( A carboxyl group-containing resin obtained by adding a compound having a meth)acryloyl group.

Among the carboxyl group-containing resins, it is preferable to include at least one of the carboxyl group-containing resins described in (7), (8), (10), (11), and (13) above. From the viewpoint of further improving insulation reliability, it is preferable to include the carboxyl group-containing resins described in (10) and (11) above.

Examples of compounds having a phenolic hydroxyl group include compounds having a biphenyl skeleton, a phenylene skeleton, or both skeletons, phenol, ortho-cresol, para-cresol, meta-cresol, 2,3-xylenol, 2,4-xylenol, 2 ,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, catechol, resorcinol, hydroquinone, methylhydroquinone, 2,6-dimethylhydroquinone, trimethylhydroquinone, pyrogallol, phloroglucinol, etc. phenolic resins having various skeletons synthesized by

Examples of compounds having a phenolic hydroxyl group include phenol novolac resins, alkylphenol borac resins, bisphenol A novolak resins, dicyclopentadiene type phenol resins, Xylok type phenol resins, terpene-modified phenol resins, polyvinylphenols, and bisphenol F. , bisphenol S-type phenolic resins, poly-p-hydroxystyrene, condensates of naphthol and aldehydes, and condensates of dihydroxynaphthalene and aldehydes.

Commercially available phenolic resins include, for example, HF1H60 (manufactured by Meiwa Kasei Co., Ltd.), Phenolite TD-2090, Phenolite TD-2131 (manufactured by Dai Nippon Printing Co., Ltd.), Vesmol CZ-256-A (manufactured by DIC), and Siyounol. BRG-555, Shounol BRG-556 (manufactured by Showa Denko Co., Ltd.), CGR-951 (manufactured by Maruzen Oil Co., Ltd.), polyvinylphenol CST70, CST90, S-1P, S-2P (manufactured by Maruzen Oil Co., Ltd.).

で表される少なくとも一方の構造と、アルカリ可溶性官能基と、を有するアミドイミド樹脂も好適に用いることができる。シクロヘキサン環またはベンゼン環に直結したイミド結合を有する樹脂を含むことにより、強靭性および耐熱性に優れた硬化物を得ることができる。特に、（１）で表される構造を有するアミドイミド樹脂は、光の透過性に優れるため、解像性を向上させることができる。前記アミドイミド樹脂は、透明性を有することが好ましく、例えば、前記アミドイミド樹脂の乾燥塗膜２５μｍにおいて、波長３６５ｎｍの光の透過率は７０％以上であることが好ましい。 Further, as an alkali-soluble resin, the following formula (1) or (2),

An amide imide resin having at least one structure represented by and an alkali-soluble functional group can also be suitably used. By containing a resin having an imide bond directly bonded to a cyclohexane ring or a benzene ring, a cured product having excellent toughness and heat resistance can be obtained. In particular, the amide-imide resin having the structure represented by (1) is excellent in light transmittance, so that resolution can be improved. The amide-imide resin preferably has transparency. For example, a dry coating film of the amide-imide resin having a thickness of 25 μm preferably has a transmittance of 70% or more for light having a wavelength of 365 nm.

The content of the structures of formulas (1) and (2) in the amide-imide resin is preferably 10 to 70% by mass. By using such a resin, it is possible to obtain a cured product that is excellent in solvent solubility, heat resistance, physical properties such as tensile strength and elongation, and dimensional stability. It is preferably 10 to 60% by mass, more preferably 20 to 50% by mass.

（式（３Ａ）および（３Ｂ）中、それぞれ、Ｒは１価の有機基であり、Ｈ、ＣＦ_３またはＣＨ_３であることが好ましく、Ｘは直接結合または２価の有機基であり、直接結合、ＣＨ_２またはＣ（ＣＨ_３）_２等のアルキレン基であることが好ましい。）で表される構造を有する樹脂が、引張強度や伸度等の物性および寸法安定性に優れるため好ましい。溶解性や機械物性の観点から、前記アミドイミド樹脂として、式（３Ａ）および（３Ｂ）の構造を１０～１００質量％有する樹脂を好適に用いることができる。より好ましくは２０～８０質量％である。 As the amide imide resin having the structure represented by formula (1), in particular, formula (3A) or (3B)

(in formulas (3A) and (3B), respectively, R is a monovalent organic group, preferably H, _CF3 or _CH3 ; X is a direct bond or a divalent organic group; It is preferably a bond, or an alkylene group such as CH ₂ or C(CH ₃ ) ₂ .) is preferable because it has excellent physical properties such as tensile strength and elongation, and dimensional stability. From the viewpoint of solubility and mechanical properties, resins having 10 to 100% by mass of the structures of formulas (3A) and (3B) can be preferably used as the amideimide resin. More preferably, it is 20 to 80% by mass.

As the amideimide resin, an amideimide resin containing 5 to 100 mol % of the structures of formulas (3A) and (3B) can be preferably used from the viewpoint of solubility and mechanical properties. It is more preferably 5 to 98 mol %, still more preferably 10 to 98 mol %, particularly preferably 20 to 80 mol %.

（式（４Ａ）および（４Ｂ）中、それぞれ、Ｒは１価の有機基であり、Ｈ、ＣＦ_３またはＣＨ_３であることが好ましく、Ｘは直接結合または２価の有機基であり、直接結合、ＣＨ_２またはＣ（ＣＨ_３）_２などのアルキレン基であることが好ましい。）で表される構造を有する樹脂が、引張強度や伸度等の機械的物性に優れる硬化物が得られることから好ましい。溶解性や機械物性の観点から、前記アミドイミド樹脂として、式（４Ａ）および（４Ｂ）の構造を１０～１００質量％有する樹脂を好適に用いることができる。より好ましくは２０～８０質量％である。 Further, as the amide imide resin having the structure represented by formula (2), in particular, formula (4A) or (4B)

(in formulas (4A) and (4B), respectively, R is a monovalent organic group, preferably H, _CF3 or _CH3 ; X is a direct bond or a divalent organic group; A bond, an alkylene group such as CH ₂ or C(CH ₃ ) ₂ is preferable.) A cured product having excellent mechanical properties such as tensile strength and elongation can be obtained. preferred from From the viewpoint of solubility and mechanical properties, resins having 10 to 100% by mass of the structures of formulas (4A) and (4B) can be preferably used as the amideimide resin. More preferably, it is 20 to 80% by mass.

As the amideimide resin, an amideimide resin containing 2 to 95 mol % of the structures of the formulas (4A) and (4B) can also be preferably used because it exhibits good mechanical properties. More preferably 10 to 80 mol %.

The amide-imide resin can be obtained by a known method. An amideimide resin having the structure (1) can be obtained, for example, by using a diisocyanate compound having a biphenyl skeleton and a cyclohexanepolycarboxylic acid anhydride.

Diisocyanate compounds having a biphenyl skeleton include 4,4'-diisocyanate-3,3'-dimethyl-1,1'-biphenyl, 4,4'-diisocyanate-3,3'-diethyl-1,1'-biphenyl , 4,4′-diisocyanate-2,2′-dimethyl-1,1′-biphenyl, 4,4′-diisocyanate-2,2′-diethyl-1,1′-biphenyl, 4,4′-diisocyanate- 3,3'-ditrifluoromethyl-1,1'-biphenyl, 4,4'-diisocyanate-2,2'-ditrifluoromethyl-1,1'-biphenyl and the like. In addition, aromatic polyisocyanate compounds such as diphenylmethane diisocyanate may be used.

Cyclohexanepolycarboxylic anhydrides include cyclohexanetricarboxylic anhydride and cyclohexanetetracarboxylic anhydride.

Further, the amideimide resin having the structure (2) can be obtained, for example, by using the diisocyanate compound having the biphenyl skeleton and the polycarboxylic acid hydrate having two acid anhydride groups.

Examples of polycarboxylic acid waters having two acid anhydride groups include pyromellitic dianhydride, benzophenone-3,3′,4,4′-tetracarboxylic dianhydride, diphenyl ether-3,3′, 4,4'-tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, biphenyl- 2,2′,3,3′-tetracarboxylic dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 1,1 -bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,3-bis(3,4-dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)ether di Anhydrides, alkylene glycol bis-anhydrotrimellitate such as ethylene glycol bis-anhydro-trimellitate, and the like.

The amide-imide resin has an alkali-soluble functional group in addition to the structures represented by the formulas (1) and (2). By having an alkali-soluble functional group, it becomes a resin composition that can be developed with an alkali. The alkali-soluble functional group contains a carboxyl group, a phenolic hydroxyl group, a sulfo group, etc., and preferably contains a carboxyl group.

Specific examples of the amide-imide resin include Unidic V-8000 series manufactured by DIC Corporation and SOXR-U manufactured by Nippon Kodoshi Kogyo Co., Ltd.

The acid value of the alkali-soluble resin is preferably in the range of 20-200 mgKOH/g, more preferably in the range of 30-150 mgKOH/g, in terms of solid content. By setting the acid value of the alkali-soluble resin within the above range, good alkali development becomes possible, and a normal cured product pattern can be formed. Although the weight-average molecular weight of the alkali-soluble resin varies depending on the resin skeleton, it is generally preferably from 2,000 to 150,000. When the weight-average molecular weight is 2,000 or more, the tack-free property of the dried coating film, the humidity resistance of the coating film after exposure, and the resolution are good. On the other hand, when the weight average molecular weight is 150,000 or less, developability and storage stability are good. More preferably 5,000 to 100,000.

Alkali-soluble resin may be used individually by 1 type, and may be used in combination of 2 or more type. When the amideimide resin is used as the alkali-soluble resin, a dry film having good adhesion between the resin layer and the substrate is obtained, and the workability of the dry film is excellent, so other alkali-soluble resins (i.e., Alkali-soluble resins not containing the structures of formulas (1) and (2)) are preferably used in combination, and other alkali-soluble resins include carboxyl group-containing resins starting from epoxy resins, and carboxyl groups having a urethane skeleton. containing resins (also called carboxyl group-containing urethane resins), carboxyl group-containing resins having a copolymer structure of unsaturated carboxylic acids, carboxyl group-containing resins starting from phenolic compounds, and these carboxyl group-containing resins containing It is preferably at least one of carboxyl group-containing resins obtained by adding a compound having one epoxy group and one or more (meth)acryloyl groups.

The amount of the alkali-soluble resin contained in the resin layer (A) and the photosensitive resin layer (B) is 10 to 50% by mass in terms of the solid content of the resin layer (A), and the amount of the photosensitive resin layer (B) is It is 10 to 90% by mass in terms of solid content. By setting the blending amount of the alkali-soluble resin within the above range, it is possible to have a high relative magnetic permeability (μ′) and to form a good pattern by photolithography.

[Photoinitiator]
In the present invention, the photosensitive resin layer (B) contains a photopolymerization initiator. Moreover, the resin layer (A) may also contain a photopolymerization initiator. A photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type.

As the photopolymerization initiator, an oxime ester containing a structure represented by the general formula (I), an α-aminoacetophenone containing a structure represented by the general formula (II), and a general formula (III) It is preferable to contain one or more selected from the group consisting of acylphosphine oxides containing structures and titanocenes having a structure represented by general formula (IV).

In general formula (I), ^R1 represents a hydrogen atom, a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group or a benzoyl group. ^R2 represents a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group or a benzoyl group.

The phenyl group represented by R ¹ and R ² may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a phenyl group, a halogen atom and the like.

The alkyl group represented by R ¹ and R ² is preferably an alkyl group having 1 to 20 carbon atoms, and may contain one or more oxygen atoms in the alkyl chain. Moreover, it may be substituted with one or more hydroxyl groups. Cycloalkyl groups represented by R ¹ and R ² are preferably cycloalkyl groups having 5 to 8 carbon atoms. The alkanoyl group represented by R ¹ and R ² is preferably an alkanoyl group having 2 to 20 carbon atoms. The benzoyl group represented by R ¹ and R ² may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms and a phenyl group.

In general formula (II), R ³ and R ⁴ each independently represent an alkyl group or arylalkyl group having 1 to 12 carbon atoms, and R ⁵ and R ⁶ each independently represent a hydrogen atom or a It represents 1 to 6 alkyl groups, or two may combine to form a cyclic alkyl ether group.

In general formula (III), R ⁷ and R ⁸ are each independently an alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or an aryl substituted with a halogen atom, an alkyl group, or an alkoxy group. group, or a carbonyl group having 1 to 20 carbon atoms (excluding the case where both are carbonyl groups having 1 to 20 carbon atoms).

In general formula (IV), R ⁹ and R ¹⁰ each independently represent a halogen atom, an aryl group, a halogenated aryl group, or a heterocyclic ring-containing halogenated aryl group.

（一般式（Ｖ）中、Ｘは、水素原子、炭素数１～１７のアルキル基、炭素数１～８のアルコキシ基、フェニル基、フェニル基（炭素数１～１７のアルキル基、炭素数１～８のアルコキシ基、アミノ基、炭素数１～８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）、ナフチル基（炭素数１～１７のアルキル基、炭素数１～８のアルコキシ基、アミノ基、炭素数１～８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）を表し、Ｙ、Ｚはそれぞれ、水素原子、炭素数１～１７のアルキル基、炭素数１～８のアルコキシ基、ハロゲン基、フェニル基、フェニル基（炭素数１～１７のアルキル基、炭素数１～８のアルコキシ基、アミノ基、炭素数１～８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）、ナフチル基（炭素数１～１７のアルキル基、炭素数１～８のアルコキシ基、アミノ基、炭素数１～８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）、アンスリル基、ピリジル基、ベンゾフリル基、ベンゾチエニル基を表し、Ａｒは、結合か、炭素数１～１０のアルキレン、ビニレン、フェニレン、ビフェニレン、ピリジレン、ナフチレン、チオフェン、アントリレン、チエニレン、フリレン、２，５－ピロール－ジイル、４，４’－スチルベン－ジイル、４，２’－スチレン－ジイルで表し、ｎは０か１の整数である。） Specific examples of oxime ester photopolymerization initiators include 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6- (2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) and the like. Commercially available products include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by BASF Japan, N-1919 and NCI-831 manufactured by ADEKA. A photopolymerization initiator having two oxime ester groups in the molecule or a photopolymerization initiator having a carbazole structure can also be preferably used. Specific examples include oxime ester compounds represented by the following general formula (V).

(In the general formula (V), X is a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, 1 -8 alkoxy group, amino group, alkylamino group or dialkylamino group having an alkyl group with 1 to 8 carbon atoms), naphthyl group (alkyl group with 1 to 17 carbon atoms, 1 to 8 carbon atoms (substituted by an alkoxy group, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), Y and Z are each a hydrogen atom and an alkyl group having 1 to 17 carbon atoms , alkoxy group having 1 to 8 carbon atoms, halogen group, phenyl group, phenyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, amino group, alkyl group having 1 to 8 carbon atoms alkylamino group or dialkylamino group), naphthyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, amino group, alkylamino having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), anthryl group, pyridyl group, benzofuryl group, benzothienyl group, and Ar represents a bond or alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene. , thiophene, anthrylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4′-stilbene-diyl, and 4,2′-styrene-diyl, where n is an integer of 0 or 1.)

In particular, in the general formula (V), X and Y are each a methyl group or an ethyl group, Z is a methyl group or a phenyl group, n is 0, Ar is a bond, phenylene, naphthylene, thiophene or thienylene.

（一般式（ＶＩ）中、Ｒ^１は、炭素原子数１～４のアルキル基、または、ニトロ基、ハロゲン原子もしくは炭素原子数１～４のアルキル基で置換されていてもよいフェニル基を表す。Ｒ^２は、炭素原子数１～４のアルキル基、炭素原子数１～４のアルコキシ基、または、炭素原子数１～４のアルキル基もしくはアルコキシ基で置換されていてもよいフェニル基を表す。Ｒ^３は、酸素原子または硫黄原子で連結されていてもよく、フェニル基で置換されていてもよい炭素原子数１～２０のアルキル基、炭素原子数１～４のアルコキシ基で置換されていてもよいベンジル基を表す。Ｒ^４は、ニトロ基、または、Ｘ－Ｃ（＝Ｏ）－で表されるアシル基を表す。Ｘは、炭素原子数１～４のアルキル基で置換されていてもよいアリール基、チエニル基、モルホリノ基、チオフェニル基、または、下記式（ＶＩＩ）で示される構造を表す。）

Moreover, as a preferable carbazole oxime ester compound, a compound represented by the following general formula (VI) can also be mentioned.

(In general formula (VI), R ¹ represents an alkyl group having 1 to 4 carbon atoms, or a phenyl group optionally substituted with a nitro group, a halogen atom or an alkyl group having 1 to 4 carbon atoms. R ² represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group optionally substituted with an alkyl group or alkoxy group having 1 to 4 carbon atoms. R ³ is optionally linked by an oxygen atom or a sulfur atom and is substituted by an alkyl group having 1 to 20 carbon atoms optionally substituted by a phenyl group, an alkoxy group having 1 to 4 carbon atoms; R ⁴ represents a nitro group or an acyl group represented by X-C(=O)-, X is substituted with an alkyl group having 1 to 4 carbon atoms; aryl group, thienyl group, morpholino group, thiophenyl group, or a structure represented by the following formula (VII).)

Specific examples of α-aminoacetophenone-based photopolymerization initiators include (4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane (Omnirad 369, manufactured by IGM Resins), 4-(methylthiobenzoyl). -1-methyl-1-morpholinoethane (Omnirad 907, manufactured by IGM Resins), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl ) Phenyl]-1-butanone (Omnirad 379, manufactured by IGM Resins) or a commercially available compound or a solution thereof can be used.

Specific examples of acylphosphine oxide-based photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl). )-2,4,4-trimethyl-pentylphosphine oxide. Commercially available products include Omnirad TPO and Omnirad 819 manufactured by IGM Resins.

Titanocene-based photopolymerization initiators include bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl) titanium. be done. Commercially available products include Omnirad 784 manufactured by IGM Resins.

Other photopolymerization initiators include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2- Acetophenones such as diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; Anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone;2 thioxanthones such as ,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; xanthones; various peroxides such as 3,3'4,4'-tetra-(tert-butylperoxycarbonyl)benzophenone; 1,7-bis(9-acridinyl)heptane;

In addition to the above photopolymerization initiators, tertiary amines such as N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine It can be used in combination with one or more of known and commonly used photosensitizers such as Furthermore, when a deeper photocuring depth is required, a 3-substituted coumarin dye, a leuco dye, or the like can be used in combination as a curing aid, if necessary.

The amount of the photopolymerization initiator contained in the photosensitive resin layer (B) is 0.1 to 20% by mass in terms of solid content. When the amount of the photopolymerization initiator is 0.1% by mass or more, the surface curability is good. be done.

In addition, the resin layer (A) does not necessarily require a photopolymerization initiator. May be blended.

(Thermosetting resin)
In order to improve heat resistance and toughness, the resin layer (A) preferably contains a thermosetting resin. Moreover, the photosensitive resin layer (B) may also contain a thermosetting resin. Thermosetting resins may be used singly or in combination of two or more.

Examples of thermosetting resins include compounds having two or more cyclic ether groups and/or cyclic thioether groups in the molecule such as polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, polyisocyanate compounds, and blocked isocyanate compounds. Known thermal compounds such as compounds having two or more isocyanate groups or blocked isocyanate groups in one molecule, amine resins such as melamine resins and benzoguanamine resins and their derivatives, bismaleimide, oxazine, cyclocarbonate compounds, carbodiimide resins, etc. A curable resin is mentioned.

As the polyfunctional epoxy compound, a known and commonly used polyfunctional epoxy resin having at least two epoxy groups in one molecule can be used. The epoxy resin may be liquid or solid or semi-solid. As polyfunctional epoxy resins, bisphenol A type epoxy resin; brominated epoxy resin; novolac type epoxy resin; bisphenol F type epoxy resin; hydrogenated bisphenol A type epoxy resin; glycidylamine type epoxy resin; Formula epoxy resins; trihydroxyphenylmethane type epoxy resins; bixylenol type or biphenol type epoxy resins or mixtures thereof; bisphenol S type epoxy resins; bisphenol A novolac type epoxy resins; Resin; diglycidyl phthalate resin; tetraglycidyl xylenoyl ethane resin; naphthalene group-containing epoxy resin; epoxy resin having a dicyclopentadiene skeleton; glycidyl methacrylate copolymer epoxy resin; epoxy-modified polybutadiene rubber derivatives; and CTBN-modified epoxy resins, but are not limited to these. As the epoxy resin, bisphenol A type or bisphenol F type novolak type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, biphenol novolak type (biphenylaralkyl type) epoxy resin, naphthalene type epoxy resin, or a mixture thereof is preferable. .

The amount of the thermosetting resin contained in the resin layer (A) is 0.1 to 50% by mass in terms of solid content. When the amount of the thermosetting resin is within this range, the curability is improved and general properties such as solder heat resistance are improved. In addition, sufficient toughness is obtained, and storage stability is not lowered.

The photosensitive resin layer (B) does not necessarily require a thermosetting resin. There is no problem even if it is blended up to 50% by mass.

(Compound having an ethylenically unsaturated group)
The resin layer (A) and the photosensitive resin layer (B) may contain a compound having an ethylenically unsaturated group. A compound having an ethylenically unsaturated group can be photocured by irradiation with an active energy ray to make the irradiated portion of the resin layer insoluble in an alkaline aqueous solution, or can help the insolubilization. As the compound having an ethylenically unsaturated group, photopolymerizable oligomers, photopolymerizable vinyl monomers, and the like, which are known and commonly used photosensitive monomers, can be used. A photosensitive (meth)acrylate compound can be used as the compound having an ethylenically unsaturated group. A compound having an ethylenically unsaturated group may be used alone or in combination of two or more. In the specification of the present application, "a compound having an ethylenically unsaturated group" does not include an alkali-soluble resin having an ethylenically unsaturated group.

Examples of compounds having an ethylenically unsaturated group include commonly known polyester (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, carbonate (meth)acrylates, epoxy (meth)acrylates, and urethane (meth)acrylates. can be used, specifically hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; acrylamides such as N-dimethylacrylamide, N-methylolacrylamide and N,N-dimethylaminopropyl acrylamide; aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate and N,N-dimethylaminopropyl acrylate; hexanediol, Polyhydric alcohols such as trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, or polyhydric acrylates such as ethyloxide adducts, propylene oxide adducts, or ε-caprolactone adducts thereof; phenoxy acrylates; , bisphenol A diacrylate, and polyvalent acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, etc. Polyvalent acrylates of glycidyl ethers; not limited to the above, polyols such as polyether polyols, polycarbonate diols, hydroxyl group-terminated polybutadiene, polyester polyols are directly acrylated, or acrylates and melamine acrylates obtained by urethane acrylated via diisocyanate , and at least one of methacrylates corresponding to the above acrylates.

Furthermore, polyfunctional epoxy resins such as cresol novolak type epoxy resins are reacted with epoxy acrylate resins, and hydroxyl groups of the epoxy acrylate resins are further combined with hydroxy acrylates such as pentaerythritol triacrylate and diisocyanates such as isophorone diisocyanate. An epoxy urethane acrylate compound obtained by reacting a half urethane compound can be mentioned. Such an epoxy acrylate resin can improve the photocurability without deteriorating the dryness to the touch.

The resin layer (A) does not necessarily require a compound having an ethylenically unsaturated group. , and may be blended in an amount of 0 to 20% by mass.

The amount of the compound having an ethylenically unsaturated group contained in the photosensitive resin layer (B) is 0.1 to 20% by mass. Within this range, photocurability is improved, and pattern formation is facilitated by alkali development after exposure to active energy rays.

(Thermosetting catalyst)
When the resin layer (A) and the photosensitive resin layer (B) contain a thermosetting resin, they may further contain a thermosetting catalyst. One of the thermosetting catalysts may be used alone, or two or more thereof may be used in combination.

Examples of thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2 -cyanoethyl)-2-ethyl-4-methylimidazole; imidazole derivatives such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, amine compounds such as 4-methyl-N,N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. In addition to these, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl- S-triazine derivatives such as 4,6-diamino-S-triazine/isocyanuric acid adduct and 2,4-diamino-6-methacryloyloxyethyl-S-triazine/isocyanuric acid adduct can also be used.

Commercially available thermosetting catalysts include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ manufactured by Shikoku Kasei Co., Ltd. (all are trade names of imidazole compounds), and U-CAT3503N and U manufactured by San-Apro Co., Ltd. -CAT3502T (all are trade names of dimethylamine blocked isocyanate compounds), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like.

The blending amount of the thermosetting catalyst is 0.01 to 10% by mass in terms of solid content. When the amount of the thermosetting catalyst is within this range, the temperature required for the thermosetting reaction can be lowered.

(Organic solvent)
For the resin layer (A) and the photosensitive resin layer (B), an organic solvent is used for preparing the resin composition for forming them or for adjusting the viscosity for coating on the substrate or carrier film. can do. Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Ether, glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Esters such as propylene glycol butyl ether acetate; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha system solvents and the like. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

(Other optional ingredients)
Other additives known and commonly used in the field of electronic materials may be blended. Other additives include thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, anti-aging agents, antibacterial/antifungal agents, antifoaming agents, leveling agents, and thickeners. agent, adhesion imparting agent, thixotropy imparting agent, colorant, photoinitiator aid, sensitizer, thermoplastic resin, inorganic filler, organic filler, release agent, surface treatment agent, dispersant, dispersing aid, surface modifiers, stabilizers, phosphors, and the like.

In the present invention, the photosensitive resin layer (B) is laminated for the purpose of enabling pattern formation of the resin layer (A) containing magnetic particles by photolithography. Therefore, the photosensitive resin layer (B) may be peeled off after the pattern formation of the resin layer (A). When peeling the photosensitive resin layer (B), it is preferable that the photosensitive resin layer (B) does not contain a thermosetting resin. Moreover, when forming a permanent coating film of the photosensitive resin layer (B) without peeling the photosensitive resin layer (B), the photosensitive resin layer (B) preferably contains a thermosetting resin.

Moreover, the photosensitive resin layer (B) is preferably alkali developable, and preferably photocurable. In order to impart photocurability, the above-mentioned compound having an ethylenically unsaturated group should be contained, or the alkali-soluble resin should have an ethylenically unsaturated group.

In the present invention, the film thicknesses of the resin layer (A) and the photosensitive resin layer (B) are not particularly limited, but generally the film thickness after drying is appropriately selected in the range of 1 to 150 μm, preferably 5 to 60 μm. be.

The photosensitive resin laminate of the present invention is preferably of a negative type.

INDUSTRIAL APPLICABILITY The photosensitive resin laminate of the present invention can be suitably used for the production of electronic components, and is useful in electronic components used in various electronic devices such as digital equipment, AV equipment, and information communication terminals. The electronic component may be passive or active, preferably an inductor. In particular, the photosensitive resin laminate of the present invention, while containing magnetic particles, is excellent in photolithography properties, so that vias (interlayer connections) can be easily formed by photolithography. In particular, it can be suitably used for manufacturing laminated inductors. Although the size of the inductor is not particularly limited, it can be suitably used for manufacturing a small inductor with one side of 10 mm or less due to its excellent photolithographic properties.

The base material for forming the photosensitive resin laminate of the present invention is not particularly limited, but printed wiring boards and flexible printed wiring boards on which circuits are formed in advance with copper or the like, paper phenol, paper epoxy, glass cloth epoxy, and glass polyimide. , glass cloth/non-woven epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, fluororesin/polyethylene/polyphenylene ether, polyphenylene oxide/cyanate, etc. Copper-clad laminates of all grades (FR-4, etc.), metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) films, glass substrates, ferrite sheets, dielectric ceramic substrates, wafer plates, etc. be able to.

In manufacturing an electronic component, two or more photosensitive resin laminates of the present invention may be laminated, and in that case, other layers (for example, an electrode layer, an easy adhesion layer, an insulating layer) may be interposed therebetween. . Moreover, in laminating|stacking two or more, you may peel a photosensitive resin layer (B), and may laminate|stack only a resin layer (A).

In the present invention, the resin layer (A) can be formed using a resin composition (a) containing an alkali-soluble resin and magnetic particles. Moreover, the photosensitive resin layer (B) can be formed using a photosensitive resin composition (b) containing an alkali-soluble resin and a photopolymerization initiator. The components contained in the resin composition (a) and the photosensitive resin composition (b) are as described above for the resin layer (A) and the photosensitive resin layer (B).

A method for forming the resin layer (A), a method for forming the photosensitive resin layer (B), and a method for forming a pattern of the photosensitive resin laminate of the present invention by photolithography are described below.

[Step of forming resin layer (A)]
In this step, at least one resin layer (A) is formed from a resin composition (a) containing an alkali-soluble resin and magnetic particles. Methods for forming the resin layer (A) include a coating method and a lamination method.

In the case of a coating method, the resin composition is applied onto a substrate by a method such as screen printing, curtain coating, spray coating, or roll coating, and the temperature is about 50 to 130° C. for about 5 to 60 minutes. A resin layer (A) is formed by heating.

In the lamination method, first, the resin composition is diluted with an organic solvent to adjust the viscosity to an appropriate level, applied on a carrier film, and dried to form a dry film having the resin layer (A). Next, the resin layer (A) is laminated with a laminator or the like so as to be in contact with the substrate, and then the carrier film is peeled off.

[Method for forming photosensitive resin layer (B)]
In this step, at least one photosensitive resin layer (B) made of a photosensitive resin composition (b) containing an alkali-soluble resin and a photopolymerization initiator is formed on the resin layer (A). An additional layer may be interposed between the photosensitive resin layer (B) and the resin layer (A). The photosensitive resin layer (B) can be formed by the same method as the method for forming the resin layer (A).

The resin layer (A) and the photosensitive resin layer (B) may be formed by forming one laminated dry film and then laminating the laminated dry film on the substrate.

[Method of forming pattern by photolithography]
In the photosensitive resin laminate of the present invention, the exposed portion (the portion irradiated with light) is cured by exposure (light irradiation). Specifically, by a contact or non-contact method, selective exposure to active energy rays is performed through a photomask on which a pattern is formed, or direct pattern exposure is performed using a laser direct exposure machine. A pattern can be formed by photolithography by developing the unexposed portion with a dilute alkaline aqueous solution (eg, 0.3 to 3% by mass aqueous solution of sodium carbonate).

The exposure machine used for the active energy ray irradiation may be any device equipped with a high-pressure mercury lamp, ultra-high pressure mercury lamp, metal halide lamp, mercury short arc lamp, etc., and irradiating ultraviolet rays in the range of 350 to 450 nm. In addition, a direct writing device (eg, a laser direct imaging device that draws an image with a laser directly from CAD data from a computer) can also be used. A lamp light source or laser light source for a direct drawing machine may have a maximum wavelength in the range of 350 to 410 nm. The exposure dose for pattern formation varies depending on the film thickness and the like, but can generally be in the range of 10 to 1000 mJ/cm ² , preferably 20 to 800 mJ/cm ² .

Examples of the developing method include a dipping method, a shower method, a spray method, a brush method, and the like. Alkaline aqueous solutions such as ammonia and amines can be used.

[Dry film]
In the dry film of the present invention, at least one side of the photosensitive resin laminate of the present invention is supported or protected by a film. A dry film can be produced, for example, by diluting the photosensitive resin composition (b) with an organic solvent to adjust the viscosity to an appropriate value, followed by a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer coater, Coat the carrier film with a uniform thickness using a roll coater, gravure coater, spray coater, or the like. The coating layer is dried to form a photosensitive resin layer (B) on the carrier film. Similarly, the dry film of the present invention can be obtained by forming a resin layer (A) from the resin composition (a) on the photosensitive resin layer (B). In addition, you may form not only on a carrier film but on a cover film.

Drying is usually carried out at a temperature of 50 to 130° C. for 1 to 30 minutes to obtain a dried resin layer. Although there is no particular limitation on the thickness of the coating, it may generally be appropriately set in the range of 1 to 150 μm, preferably 5 to 60 μm, in terms of thickness after drying.

As the carrier film, a plastic film can be preferably used, and it is preferable to use a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film and a polystyrene film. The thickness of the carrier film is not particularly limited, but is generally selected appropriately within the range of 1 to 150 μm.

Furthermore, for the purpose of preventing dust from adhering to the surface of the coating film, a peelable cover film may be laminated on the surface of the coating film. As the peelable cover film, for example, polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper, etc. can be used. It suffices if the adhesive force between the membrane and the cover film is smaller.

Volatilization drying performed after coating the resin composition is performed by hot air circulation drying oven, IR oven, hot plate, convection oven, etc. (Equipped with a heat source of air heating method using steam). method and a method of spraying onto the support from a nozzle).

[Manufacturing method of electronic component]
In the method for producing an electronic component of the present invention, the photosensitive resin laminate of the present invention is exposed to light from the photosensitive resin layer (B) side, and then alkali-developed, whereby the resin layer (A) and the photosensitive It is characterized by including a step of patterning the resin layer (B). The pattern formation method is as described in the pattern formation method by photolithography above.

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

<Synthesis Example of Alkali-Soluble Resin 1 (Synthesis Example 1)>
An autoclave equipped with a thermometer, a nitrogen introduction device and an alkylene oxide introduction device, and a stirring device was charged with 119.4 g of a novolak cresol resin (Shownol CRG951, manufactured by Showa Denko Co., Ltd., OH equivalent: 119.4), and 1.5 g of potassium hydroxide. 19 g of toluene and 119.4 g of toluene were charged, and the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 g of propylene oxide was gradually added dropwise and reacted at 125-132° C. and 0-4.8 kg/cm ² for 16 hours. After cooling to room temperature, 1.56 g of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. A propylene oxide reaction solution of a novolak-type cresol resin was obtained. This was obtained by adding an average of 1.08 mol of alkylene oxide per equivalent of phenolic hydroxyl group.
Next, 293.0 g of the alkylene oxide reaction solution of the novolak type cresol resin obtained, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone and 252.9 g of toluene were mixed with a stirrer, a thermometer and air. The mixture was charged into a reactor equipped with a blowing tube, air was blown in at a rate of 10 ml/min, and the mixture was reacted at 110° C. for 12 hours while stirring. 12.6 g of water was distilled out as an azeotrope with toluene, which was produced by the reaction. After cooling to room temperature, the resulting reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution and then washed with water. After that, the toluene was removed by an evaporator while replacing it with 118.1 g of diethylene glycol monoethyl ether acetate to obtain a novolac type acrylate resin solution. Next, 332.5 g of the obtained novolak-type acrylate resin solution and 1.22 g of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing pipe, and air was blown at a rate of 10 ml/min. While stirring, 60.8 g of tetrahydrophthalic anhydride was gradually added and reacted at 95-101° C. for 6 hours. The thus obtained alkali-soluble resin 1 having both an ethylenically unsaturated bond and a carboxyl group had a solid acid value of 88 mgKOH/g and a solid content of 71%.

<Synthesis Example of Alkali-soluble Resin 2 (Synthesis Example 2)>
A flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser was charged with benzyl methacrylate and methacrylic acid in a molar ratio of 3:7, dipropylene glycol monomethyl ether as a solvent, and azobisisobutyl as a catalyst. Lonitrile (AIBN) was added and stirred at 80° C. for 4 hours under a nitrogen atmosphere to obtain a resin solution. This resin solution is cooled, and glycidyl methacrylate is added at 95 to 105° C. for 16 hours using methyl hydroquinone as a polymerization inhibitor and tetrabutylphosphonium bromide as a catalyst to add 50 mol % of the carboxyl groups of the resin. After cooling, it was taken out. The alkali-soluble resin 2 having both an ethylenically unsaturated bond and a carboxyl group thus obtained has a solid content acid value of 118 mgKOH/g, a carboxylic acid equivalent (solid content) of 475, a solid content of 50%, and a weight average molecular weight of about was 20,000.

<Synthesis Example of Alkali-soluble Resin 3 (Synthesis Example 3)>
A flask equipped with a stirrer, thermometer and condenser was charged with 848.8 g of GBL (γ-butyrolactone) and 57.5 g (0.23 mol) of MDI (diphenylmethane diisocyanate), DMBPDI (4,4′-diisocyanate-3,3). '-dimethyl-1,1'-biphenyl) 59.4 g (0.225 mol), TMA (trimellitic anhydride) 67.2 g (0.35 mol) and TMA-H (cyclohexane-1,3,4- 29.7 g (0.15 mol) of tricarboxylic acid-3,4-anhydride) was charged, the temperature was raised to 80°C while stirring, and the mixture was dissolved and reacted over 1 hour at this temperature, After the temperature was further raised to 160° C. over 2 hours, the reaction was carried out at this temperature for 5 hours. The reaction proceeded with the bubbling of carbon dioxide gas, and the inside of the system became a brown transparent liquid. A solution of alkali-soluble resin 3 (resin dissolved in γ-butyrolactone) having a viscosity at 25° C. of 7 Pa·s, a resin solid content of 17% and a solution acid value of 5.3 mgKOH/g was obtained. The solid content acid value of the resin was 31.2 mgKOH/g. As a result of measurement by gel permeation chromatography (GPC), the weight average molecular weight was about 34,000.

(Resin layer (A))
According to the formulation shown in Table 1 below, each component was blended, stirred, and dispersed with a three-roll roll to prepare each resin composition. In addition, the compounding quantity in Table 1 shows a mass part.
Methyl ethyl ketone was added to the resin composition obtained above to dilute it appropriately, and the mixture was stirred with a stirrer for 15 minutes to obtain a coating liquid. The coating liquid was applied onto a polyethylene terephthalate film having a thickness of 38 μm as a carrier film and dried at a temperature of 80° C. for 15 minutes to form a resin layer (A) having a thickness of 40 μm.

(Photosensitive resin layer (B))
Each component was blended according to the formulation shown in Table 2 below, stirred, and dispersed by a three-roll roll to prepare each resin composition. In addition, the compounding quantity in Table 2 shows a mass part.
Methyl ethyl ketone was added to the resin composition obtained above to dilute it appropriately, and the mixture was stirred with a stirrer for 15 minutes to obtain a coating liquid. The coating liquid was applied onto a polyethylene terephthalate film having a thickness of 38 μm as a carrier film and dried at a temperature of 80° C. for 15 minutes to form a photosensitive resin layer (B) having a thickness of 10 μm.

(Examples 1 to 14)
(Resolution)
The resin layer (A) is placed on a circuit-formed substrate using a vacuum laminator (MVLP-500 manufactured by Meiki Seisakusho Co., Ltd.), pressure: 0.8 MPa, 90° C., 1 minute, degree of vacuum: 133.3 Pa. It was heat-laminated under the conditions of Next, the photosensitive resin layer (B) is applied onto the resin layer (A) laminated on the substrate using a vacuum laminator (MVLP-500 manufactured by Meiki Seisakusho Co., Ltd.) at a pressure of 0.8 MPa and 90°C. , 1 minute, and a degree of vacuum of 133.3 Pa to form a photosensitive resin laminate in which the resin layer (A) and the photosensitive resin layer (B) are laminated in this order on the substrate. The photosensitive resin laminate formed on this substrate is subjected to pattern exposure with an optimum exposure dose using an exposure device equipped with a high-pressure mercury lamp (short arc lamp), and then a 1% by weight sodium carbonate aqueous solution at 30°C. was used, and development was performed for 240 seconds at a spray pressure of 0.2 MPa to form a pattern of the photosensitive resin laminate. The photosensitive resin laminate on this substrate was irradiated with ultraviolet rays in a UV conveyor furnace under the condition of an integrated exposure amount of 1000 mJ/cm ² , and then heated at 180° C. for 60 minutes to cure the photosensitive resin laminate. The pattern of the photosensitive resin laminate was formed in a form having an opening with an opening diameter of 100 μm on the copper forming the circuit of the evaluation substrate.
Here, the optimum exposure amount means the following exposure amount.
That is, the evaluation substrate obtained above is exposed through a step tablet (Kodak No. 2) using an exposure device equipped with a high-pressure mercury lamp (short arc lamp), and developed (30 ° C., 0.2 MPa, 1 mass % sodium carbonate aqueous solution) for 240 seconds, and the remaining step tablet pattern is 7 steps.
Evaluation of resolution was performed by observing an opening with an opening diameter of 100 μm with an SEM (scanning electron microscope) and evaluating according to the following criteria. Evaluation results are shown in Tables 3 and 4.
◯: Good shape in which the copper surface at the bottom of the opening is confirmed.
×: In the case of a defective opening shape in which the copper surface at the bottom of the opening is not confirmed.

(Relative permeability μ')
The resin layer (A) is applied to a 9 μm thick electrolytic copper foil (manufactured by Furukawa Electric Co., Ltd.) using a vacuum laminator (MVLP-500 manufactured by Meiki Seisakusho Co., Ltd.) at a pressure of 0.8 MPa, 90 ° C., Heat lamination was carried out under the conditions of 1 minute and a degree of vacuum of 133.3 Pa. Next, the photosensitive resin layer (B) is applied onto the resin layer (A) laminated to the electrolytic copper foil using a vacuum laminator (MVLP-500 manufactured by Meiki Seisakusho Co., Ltd.) with a degree of pressure of 0.8 MPa. Heat-laminated under the conditions of 90° C., 1 minute, degree of vacuum: 133.3 Pa, and a photosensitive resin laminate obtained by laminating the resin layer (A) and the photosensitive resin layer (B) in this order on the electrolytic copper foil. formed. The photosensitive resin laminate formed on the copper foil was subjected to solid exposure with an optimum exposure amount using an exposure device equipped with a high-pressure mercury lamp (short arc lamp). The photosensitive resin laminate on the copper foil was irradiated with ultraviolet rays in a UV conveyor furnace under the condition of an accumulated exposure amount of 1000 mJ/cm ² , and then heated at 180° C. for 60 minutes to cure the photosensitive resin laminate.
Next, the copper foil with the photosensitive resin laminate is etched away using an etchant containing 340 g/l of cupric chloride and 51.3 g/l of free hydrochloric acid, and the copper foil is thoroughly washed with water and dried. Then, a test piece of a cured product having a thickness of 50 μm was produced.
The test piece thus produced was measured for relative magnetic permeability μ′ at a frequency of 100 MHz using E5071C ENA vector network analyzer (manufactured by Keysight Technologies). Evaluation results are shown in Tables 3 and 4.

(Interlayer adhesion)
The resin layer (A) is placed on a circuit-formed substrate using a vacuum laminator (MVLP-500 manufactured by Meiki Seisakusho Co., Ltd.), pressure: 0.8 MPa, 90° C., 1 minute, degree of vacuum: 133.3 Pa. It was heat-laminated under the conditions of Next, the photosensitive resin layer (B) is applied onto the resin layer (A) laminated on the substrate using a vacuum laminator (MVLP-500 manufactured by Meiki Seisakusho Co., Ltd.) at a pressure of 0.8 MPa and 90. C., 1 minute, degree of vacuum: 133.3 Pa, heat lamination was performed to form a photosensitive resin laminate in which the resin layer (A) and the photosensitive resin layer (B) were laminated in this order on the substrate. . The photosensitive resin laminate formed on this substrate was subjected to solid exposure with an optimum exposure amount using an exposure device equipped with a high-pressure mercury lamp (short arc lamp). The photosensitive resin laminate on this substrate was irradiated with ultraviolet rays in a UV conveyor furnace under the condition of an accumulated exposure amount of 1000 mJ/cm ² , and then heated at 180° C. for 60 minutes to obtain a cured product of the photosensitive resin laminate. . On the cured product thus obtained, the resin layer (A) is applied using a vacuum laminator (MVLP-500 manufactured by Meiki Seisakusho Co., Ltd.) at a degree of pressure of 0.8 MPa, 90 ° C., 1 minute, degree of vacuum. : Heat lamination under the condition of 133.3 Pa. Next, the photosensitive resin layer (B) is applied onto the resin layer (A) laminated on the substrate using a vacuum laminator (MVLP-500 manufactured by Meiki Seisakusho Co., Ltd.) at a pressure of 0.8 MPa and 90°C. , 1 minute, and a degree of vacuum of 133.3 Pa to form a photosensitive resin laminate in which the resin layer (A) and the photosensitive resin layer (B) are laminated in this order on the substrate. The photosensitive resin laminate formed on this substrate was subjected to solid exposure with an optimum exposure amount using an exposure device equipped with a high-pressure mercury lamp (short arc lamp). The photosensitive resin laminate on this substrate was irradiated with ultraviolet rays in a UV conveyor furnace under the conditions of an integrated exposure amount of 1000 mJ/cm ² and then heated at 180 ° C. for 60 minutes to form a resin layer (A) on the circuit board. An evaluation substrate was obtained in which the photosensitive resin layer (B), the resin layer (A), and the photosensitive resin layer (B) were laminated in this order.
Using a cutter knife, 11 vertical and 11 horizontal cuts were made on the evaluation board so as to reach the circuit board from the side where the resin layer was laminated, and 100 grids were produced.
Next, a cellophane tape was strongly pressed against the cross-cut portion, and the edge of the tape was peeled off at once at an angle of 45°. Evaluation results are shown in Tables 3 and 4.
○: No peeling in all 100 squares ×: Peeling was confirmed in one or more places on the grid

(Comparative example 1)
In Examples 1 to 14, evaluation was performed in the same manner as in Examples 1 to 14, except that after laminating the resin layer A1 as the resin layer (A), the photosensitive resin layer (B) was not laminated. Evaluation results are shown in Tables 3 and 4.

(Comparative example 2)
In Examples 1 to 14, evaluation was performed in the same manner as in Examples 1 to 14, except that the resin layer (A) was not laminated and the resin layer B1 was laminated as the photosensitive resin layer (B). Evaluation results are shown in Tables 3 and 4.

*1: Alkali-soluble resin 1 synthesized above (PO-modified phenolic resin/acrylic acid/tetrahydrophthalic acid)
*2: Alkali-soluble resin 2 synthesized above (benzyl methacrylate + glycidyl methacrylate adduct of methacrylic acid copolymer)
*3: Alkali-soluble resin 3 synthesized above (carboxyl group-containing amideimide resin)
*4: Omnirad TPO manufactured by IGM Resins
*5: I Omnirad 784 manufactured by IGM Resins
*6: Irgacure OXE02 manufactured by BASF
*7: Dipentaerythritol hexaacrylate *8: Bisphenol A type epoxy resin *9: Dicyandiamide *10: Powdertech M001 Mn ferrite D50: 1.2 μm
*11: Powdertech E001 Mn-Mg-Sr ferrite D50: 0.2 μm
*12: AW2-08PF3FG amorphous magnetic alloy D50: 3.2 μm manufactured by Epson Atmix
*13: Methyl ethyl ketone

From the results shown in the above table, it can be seen that the resin laminates of Examples can be patterned by photolithography, although the resin layer (A) contains magnetic particles.

(A) Resin layer (A)
(B) Photosensitive resin layer (B)
1 photosensitive resin laminate structure 2 base material 3 conductor pattern

Claims (8)

A photosensitive resin laminate in which a resin layer (A) containing an alkali-soluble resin, a thermosetting resin and magnetic particles and a photosensitive resin layer (B) containing an alkali-soluble resin and a photopolymerization initiator are laminated, ,
A photosensitive resin laminate , wherein the magnetic particles are at least one selected from silicon steel, permalloy, sendust, permendur, soft ferrite, amorphous magnetic alloys, and nanocrystalline magnetic alloys . 2. The photosensitive resin laminate according to claim 1, wherein the magnetic particles have an average particle diameter (D50) of 0.01 to 50 μm. 3. The photosensitive resin laminate according to claim 1, wherein the resin layer (A) has a relative magnetic permeability (μ′) of more than 1 to 100 or less at a frequency of 100 MHz. A dry film, wherein at least one side of the photosensitive resin laminate according to any one of claims 1 to 3 is supported or protected by a film. A cured product obtained by curing the photosensitive resin laminate according to any one of claims 1 to 3 or the photosensitive resin laminate of the dry film according to claim 4. An electronic component comprising the cured product according to claim 5 . 7. The electronic component according to claim 6, which is an inductor. The photosensitive resin laminate according to any one of claims 1 to 3 is exposed from the photosensitive resin layer (B) side, and then alkali-developed to obtain the resin layer (A) and the photosensitive layer. A method for manufacturing an electronic component, comprising a step of patterning a resin layer (B).

Images