JP5493519B2 - Radiation-sensitive resin composition and use thereof, dielectric and electronic component - Google Patents

Description

  The present invention relates to a radiation-sensitive resin composition and use thereof, a dielectric obtained from the radiation-sensitive resin composition, and an electronic component having the dielectric.

In recent years, a technique has been studied in which a dielectric layer having a high dielectric constant is provided on a multilayer printed wiring board, and the dielectric layer is used as a capacitor. For example, an attempt has been made to form a dielectric layer having a high dielectric constant using inorganic powder. When Fe ₃ O ₄ or ZnO + carbon is added as an inorganic powder to polystyrene, a dielectric layer having a high dielectric constant can be obtained. It has been known.

  However, in such a system, even if the dielectric constant of the dielectric layer can be increased, the dielectric loss tangent of the dielectric layer increases, and thus the heat generation of the dielectric layer in the alternating electric field increases. For this reason, there is a problem that a defect due to thermal stress (eg, fracture of the joint portion) occurs, that is, the reliability and durability of the multilayer printed wiring board are likely to be lowered.

  As a method for obtaining a dielectric layer having a high dielectric constant, a method for forming a dielectric layer by firing high-dielectric constant inorganic powder at a high temperature is known. However, since the method requires high-temperature firing at about 1000 ° C., the method cannot be applied when the dielectric layer is provided in a state where the electronic component is mounted on the wiring board.

  With respect to the above problem, Patent Document 1 discloses that (i) 500 ° C. or lower by using a composition containing inorganic particles having a specific average particle size, an alkali-developable resin, and a photosensitive acid generating compound. (Ii) even a thin film has a high dielectric constant and a low dielectric loss tangent and can form a dielectric pattern with high dimensional accuracy.

  On the other hand, Patent Document 2 discloses a composition capable of forming an insulating film excellent in resolution, electrical insulation, and thermal shock, although the purpose is not to increase the dielectric constant of the dielectric layer. . The composition comprises (A) an alkali-soluble resin, (B) a compound having at least two alkyl etherified amino groups in the molecule, (D) an oxirane ring-containing compound, and (E) a photofunctional acid generator. Containing.

  However, recent demands for smaller, thinner and higher density electronic components have become even more stringent, so the above characteristics (eg, resolution, electrical insulation, dielectric constant, dielectric loss tangent) have been further improved. There is a need for a radiation sensitive resin composition capable of forming a dielectric by low-temperature firing.

JP 2003-287883 A JP 2003-215802 A

The present invention has been made in view of the above circumstances. That is, an object of the present invention is to provide a radiation-sensitive resin composition having the following characteristics (1) and (2).
(1) High sensitivity to radiation (exposure light) and low temperature firing is possible.
(2) It is possible to form a dielectric having a high dielectric constant and a low dielectric loss tangent and excellent in resolution and electrical insulation even if it is a thin film.

  Another object of the present invention is to provide a dielectric obtained from the radiation-sensitive resin composition and an electronic component having the dielectric.

  The present inventors have intensively studied to solve the above problems. As a result, it was found that a composition having the above characteristics (1) to (2) cannot be obtained simply by blending dielectric inorganic particles with a conventionally known radiation-sensitive resin composition. For example, when dielectric inorganic particles are blended with the composition of Patent Document 2, the resolution of the formed dielectric is greatly reduced.

  The present inventors conducted further studies based on the above findings. As a result, it has been found that the above-mentioned problems can be solved by blending a radiation-sensitive resin composition having a specific composition with an azo-based ultraviolet absorber having a pyrazole ring together with ferroelectric inorganic particles, thereby completing the present invention. It came. That is, the present invention relates to the following [1] to [12].

  [1] having (A) a polymer having a phenolic hydroxyl group, (B) a radiation-sensitive acid generator, (C) a crosslinking agent, (E) ferroelectric inorganic particles, and (F) a pyrazole ring. A radiation-sensitive resin composition containing an azo-based ultraviolet absorber.

[2] The radiation-sensitive resin composition according to [1], which contains at least a novolak resin as the component (A).
[3] The component (C) contains at least one selected from (C1) a compound having at least two alkyl etherified amino groups in the molecule and (C2) an oxiranyl group-containing compound. [1] The radiation sensitive resin composition according to [2].

[4] The radiation-sensitive resin composition according to [3], wherein the oxiranyl group-containing compound (C2) is a bisphenol A type epoxy resin.
[5] The radiation sensitive resin composition according to any one of [1] to [4], wherein the component (E) is inorganic particles made of a titanium metal oxide.

[6] The radiation-sensitive resin composition according to [5], wherein the inorganic particles made of the titanium-based metal oxide are inorganic particles made of a metal oxide having a perovskite structure.
[7] The radiation-sensitive resin composition according to any one of [1] to [6], wherein the volume average particle size of the component (E) is 0.01 to 3.0 μm.

[8] The radiation-sensitive resin composition according to any one of [1] to [7], further including (G) a phenolic low-molecular compound.
[9] The radiation-sensitive resin composition according to any one of [1] to [8], further including (I) a polymer having a structural unit derived from a carboxyl group-containing (meth) acrylate.

[10] The radiation sensitive resin composition according to any one of [1] to [9], which is a dielectric forming material.
[11] A dielectric obtained from the radiation-sensitive resin composition according to any one of [1] to [10].

  [12] An electronic component having the dielectric according to [11].

  According to the present invention, (1) a radiation-sensitive resin composition that is highly sensitive to radiation (exposure light) and that can be fired at low temperature, and (2) a high dielectric constant and low dielectric constant even for a thin film. Provided is a radiation-sensitive resin composition capable of forming a dielectric having a tangent and excellent in resolution and electrical insulation. Moreover, according to this invention, the dielectric material obtained from the said radiation sensitive resin composition and the electronic component which has this dielectric material are provided.

In particular, the dielectric according to the present invention is excellent in resolution.
Since the dielectric according to the present invention has the above characteristics, it can be suitably used as a member of an electronic component (eg, semiconductor element, (multilayer) printed wiring board, capacitor, high frequency antenna). That is, the dielectric according to the present invention can meet the recent demand for downsizing, thinning, and high density of electronic components.

FIG. 1 is a schematic diagram for explaining a base material for insulation evaluation in Examples.

  Hereinafter, the radiation-sensitive resin composition according to the present invention, its use, a dielectric obtained from the radiation-sensitive resin composition, and an electronic component having the dielectric will be described in detail including preferred embodiments.

[Radiation sensitive resin composition]
The radiation sensitive resin composition according to the present invention comprises (A) a polymer having a phenolic hydroxyl group, (B) a radiation sensitive acid generator, (C) a crosslinking agent, and (E) ferroelectric inorganic particles. And (F) an azo ultraviolet absorber having a pyrazole ring.

  Moreover, the radiation sensitive resin composition which concerns on this invention is derived from (D) solvent, (G) phenolic low molecular weight compound, (H) adhesion assistant, (I) carboxyl group containing (meth) acrylate as an arbitrary component. It may further contain a polymer having the above structural unit and other additives.

<< (A) Polymer having phenolic hydroxyl group >>
(A) The polymer having a phenolic hydroxyl group (hereinafter also referred to as “phenol resin (A)”) is not particularly limited as long as it has a property of being dissolved in an alkali developer. However, a polymer having a structural unit derived from a carboxyl group-containing (meth) acrylate is excluded.

  Examples of the phenol resin (A) include novolak resins, hydroxystyrene homo- or copolymers, phenol-xylylene glycol condensation resins, cresol-xylylene glycol condensation resins, phenol-dicyclopentadiene condensation resins, and the like.

The novolak resin can be obtained by condensing phenols and aldehydes in the presence of a catalyst (eg, oxalic acid).
Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2, 3 -Xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol , Catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol and the like.

Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, and benzaldehyde.
Preferable specific examples of the novolak resin include a phenol / formaldehyde condensed novolak resin, a cresol / formaldehyde condensed novolak resin, and a phenol-naphthol / formaldehyde condensed novolak resin.

  The radiation-sensitive resin composition according to the present invention preferably contains at least the novolac resin as the phenol resin (A), and more preferably contains the novolac resin and the hydroxystyrene homopolymer or copolymer. preferable.

  The phenol resin (A) has a polystyrene-reduced weight average molecular weight (Mw) of 2000 or more by gel permeation chromatography (GPC) from the viewpoint of resolution, thermal shock resistance, and heat resistance of the formed dielectric. Preferably, it is more preferably 2000 to 20000; the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably 1 to 10, preferably 1.5 to 5 More preferably. In addition, the average molecular weight of a phenol resin (A) is measured on the conditions as described in [Example] mentioned later.

  In the radiation sensitive resin composition according to the present invention, the phenol resin (A) is preferably contained in the range of 5 to 60% by weight, more preferably 10 to 35% by weight in terms of solid content. However, solid content conversion means that the total amount of other components excluding the solvent (D) is 100% by weight. When the content of the phenol resin (A) is in the above range, it is preferable in that the formed coating film has sufficient developability with respect to an alkaline developer.

<< (B) Radiation sensitive acid generator >>
(B) The radiation-sensitive acid generator (hereinafter also referred to as “acid generator (B)”) is a compound that generates an acid upon irradiation with radiation. Due to the catalytic action of this acid, the phenol resin (A) and the cross-linking agent (C) can react to form a negative pattern.

  The acid generator (B) is not particularly limited as long as it is a compound that generates an acid upon irradiation with radiation, and includes an onium salt compound, a halogen-containing compound, a diazoketone compound, a sulfone compound, a sulfonic acid compound, a sulfonimide compound, a diazomethane compound, and the like. Is mentioned.

  Examples of onium salt compounds include iodonium salts, sulfonium salts, thiophenium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like. Preferred examples of onium salt compounds include iodonium salts such as diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, and diphenyliodonium tetrafluoroborate; Sulfonium salts such as fluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, 4-t-butylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyl diphenylsulfonium p-toluenesulfonate ; 4,7-di-n-butoxy Thiophenium salts such borderless Le tetrahydrothiophenium tri Julio b methanesulfonate and the like.

  Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Preferable specific examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds such as 1,10-dibromo-n-decane and 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane; Haloalkyl such as (trichloromethyl) -s-triazine, 4-methoxyphenyl-bis (trichloromethyl) -s-triazine, styryl-bis (trichloromethyl) -s-triazine, naphthyl-bis (trichloromethyl) -s-triazine And haloalkyl group-containing heterocyclic compounds such as group-containing s-triazine derivatives.

  Examples of the diazo ketone compound include a 1,3-diketo-2-diazo compound, a diazobenzoquinone compound, a diazonaphthoquinone compound, and the like. Preferable specific examples of the diazoketone compound include ester compounds of phenols and 1,2-naphthoquinonediazide-4-sulfonic acid.

  Examples of the sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds, and α-diazo compounds of these compounds. Preferred specific examples of the sulfone compound include 4-trisphenacylsulfone, mesitylphenacylsulfone, and bis (phenacylsulfonyl) methane.

  Examples of the sulfonic acid compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Preferable specific examples of the sulfonic acid compound include benzoin tosylate, pyrogallol tris trifluoromethane sulfonate, o-nitrobenzyl trifluoromethane sulfonate, and o-nitrobenzyl p-toluene sulfonate.

  Preferred specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethyl). Sulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide.

  Preferable specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, and bis (phenylsulfonyl) diazomethane.

  Of these, halogen-containing compounds are preferred, haloalkyl group-containing heterocyclic compounds are more preferred, and haloalkyl group-containing s-triazine derivatives are preferred from the viewpoint of the sensitivity of the resin composition, the dielectric constant of the formed dielectric, and the dielectric loss tangent. Is more preferable. Moreover, an acid generator (B) may be used individually by 1 type, and may use 2 or more types together.

  In the radiation-sensitive resin composition according to the present invention, the acid generator (B) is 100 weights of phenol resin (A) from the viewpoint of ensuring the sensitivity of the resin composition, the resolution of the formed dielectric, the pattern shape, and the like. The amount is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 5 parts by weight with respect to parts. When the content of the acid generator (B) is less than the above range, the coating film is insufficiently cured, and the heat resistance of the formed dielectric may be reduced. When the content of the acid generator (B) exceeds the above range, the transparency of the coating film against radiation is lowered, and the pattern shape of the dielectric may be deteriorated.

<< (C) Crosslinking agent >>
The crosslinking agent (C) is not particularly limited as long as it has a property of acting as a crosslinking component (curing component) that reacts with the phenol resin (A), but (C1) an alkyl etherified amino group is at least 2 in the molecule. Compounds (hereinafter also referred to as “crosslinking agent (C1)”) and (C2) oxiranyl group-containing compounds (hereinafter also referred to as “epoxy resin (C2)”) are preferable. A crosslinking agent (C) may be used individually by 1 type, and may use 2 or more types together.

  In the radiation sensitive resin composition according to the present invention, the crosslinking agent (C) is preferably 5 to 150 parts by weight, more preferably 8 to 80 parts by weight, particularly preferably 100 parts by weight of the phenol resin (A). Is included in the range of 10 to 60 parts by weight.

<Crosslinking agent (C1)>
The crosslinking agent (C1) has at least two alkyl etherified amino groups in the molecule. The crosslinking agent (C1) acts as a crosslinking component that reacts with the phenol resin (A). The alkyl ether group in the crosslinking agent (C1) and the phenolic hydroxyl group in the phenol resin (A) react with dealcoholization to form a negative pattern.

As the crosslinking agent (C1), at least a part of the active methylol group possessed by (poly) methylolated melamine, (poly) methylolated glycoluril, (poly) methylolated benzoguanamine, (poly) methylolated urea or the like is alkyl etherified. The nitrogen-containing compound made is mentioned. Examples of the alkyl include methyl, ethyl, butyl and the like, and the alkyl contained in the crosslinking agent (C1) may be one kind or two or more kinds. The “active methylol group” means a functional group having a —CH ₂ OH substituent (oxymethyl group) on an amino group.

  Preferable specific examples of the nitrogen-containing compound include hexamethoxymethylated melamine, hexabutoxymethylated melamine, tetramethoxymethylated glycoluril, and tetrabutoxymethylated glycoluril.

A crosslinking agent (C1) may be used individually by 1 type, and may use 2 or more types together. Moreover, as the crosslinking agent (C1), an oligomer in which the nitrogen-containing compound is partially self-condensed may be used.
In the radiation sensitive resin composition according to the present invention, the crosslinking agent (C1) is preferably in the range of 1 to 100 parts by weight, more preferably 5 to 50 parts by weight with respect to 100 parts by weight of the phenol resin (A). included. When content of a crosslinking agent (C1) is less than the said range, hardening of the coating film by exposure may become inadequate. As a result, patterning may become difficult or the heat resistance of the formed dielectric may be reduced. If the content of the cross-linking agent (C1) exceeds the above range, the resolution and electrical insulation properties of the formed dielectric may be lowered.

<Epoxy resin (C2)>
Although epoxy resin (C2) is not specifically limited, For example, it is a compound which has at least two oxiranyl group (oxirane ring) in a molecule | numerator. The epoxy resin (C2) also acts as a crosslinking component that reacts with the phenol resin (A).

  As the epoxy resin (C2), phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol type epoxy resin, tetraphenol type epoxy resin, phenol-xylylene type epoxy resin Naphthol-xylylene type epoxy resin, phenol-naphthol type epoxy resin, phenol-dicyclopentadiene type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin and the like.

  Among these, bisphenol A type epoxy resins are particularly preferable from the viewpoints of the sensitivity of the resin composition, the dielectric constant of the formed dielectric, and the dielectric loss tangent. Moreover, an epoxy resin (C2) may be used individually by 1 type, and may use 2 or more types together.

  In the radiation-sensitive resin composition according to the present invention, the epoxy resin (C2) is preferably 1 to 70 parts by weight, more preferably 3 to 30 parts by weight with respect to 100 parts by weight of the phenol resin (A). included. When the content of the epoxy resin (C2) is lower than the above range, the chemical resistance of the formed dielectric may be reduced, and when it exceeds the above range, the resolution of the formed dielectric may be reduced.

  In this invention, it is preferable to use at least 1 sort (s) chosen from a crosslinking agent (C1) and an epoxy resin (C2) as a crosslinking agent (C), and uses together a crosslinking agent (C1) and an epoxy resin (C2). It is more preferable to use these cross-linking agents in a specific quantitative ratio. That is, in the radiation sensitive resin composition according to the present invention, the epoxy resin (C2) is preferably 50 to 200 parts by weight, more preferably 50 to 100 parts by weight with respect to 100 parts by weight of the crosslinking agent (C1). Particularly preferably, it is contained in the range of 50 to 70 parts by weight. It is particularly preferable to use the crosslinking agent (C1) and the epoxy resin (C2) in the above-mentioned quantitative ratios in terms of the sensitivity of the resin composition and the resolution, dielectric constant, and dielectric loss tangent of the formed dielectric.

<< (D) Solvent >>
In order to improve the handleability of the radiation sensitive resin composition according to the present invention or to adjust the viscosity and storage stability, it is preferable to use a solvent (D).

Examples of the solvent (D) include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, etc. Of propylene glycol dialkyl ethers;
Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate;
Cellosolves such as ethyl cellosolve and butyl cellosolve;
Carbitols such as butyl carbitol;
Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, Aliphatic carboxylic acid esters such as n-butyl propionate and isobutyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, Other esters such as ethyl pyruvate;
Aromatic hydrocarbons such as toluene and xylene; Ketones such as 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone; N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone And lactones such as γ-butyrolacun.

  Among these, lactic acid esters and propylene glycol monoalkyl ether acetates are preferable. Moreover, a solvent (D) may be used individually by 1 type, and may use 2 or more types together.

  In the radiation-sensitive resin composition according to the present invention, the content of the solvent (D) may be within a range in which the dielectric inorganic particles (E) can stably exist, and the film thickness of the dielectric to be formed. It may be set appropriately depending on When using a solvent (D), the content is 10-1000 weight part normally with respect to 100 weight part of ferroelectric inorganic particles (E).

<< (E) Ferroelectric inorganic particles >>
(E) The ferroelectric inorganic particles (hereinafter also referred to as “inorganic particles (E)”) are not particularly limited as long as they are inorganic particles used for the dielectric forming material. The dielectric constant is preferably 30 or more, more preferably 50 or more, and further preferably 70 or more. There is no problem with the dielectric constant of the inorganic particles (E) being high, and the upper limit is not particularly limited, but is usually about 30000.

  As the inorganic particles (E), inorganic particles made of a metal oxide are preferable, and inorganic particles made of a titanium metal oxide are more preferable. The “titanium metal oxide” refers to a compound containing a titanium element and an oxygen element as essential elements.

  Examples of the titanium-based metal oxide include (E-i) a titanium-based single metal oxide containing a single titanium element as a metal element constituting the crystal structure, and (E-ii) a metal element constituting the crystal structure. A titanium-based double oxide containing titanium element and other metal elements can be preferably used.

  (E-i) Examples of the titanium-based single metal oxide include titanium dioxide-based metal oxides. As said titanium dioxide type metal oxide, the titanium dioxide type metal oxide of an anatase structure or a rutile structure is mentioned. Among the titanium-based single metal oxides, titanium dioxide-based metal oxides having a rutile structure are preferable.

  The “titanium dioxide-based metal oxide” means a system containing only titanium dioxide or a system containing titanium dioxide and a small amount of additives, and the crystal structure of titanium dioxide as a main component is maintained. The same applies to other metal oxides.

  (E-ii) The titanium-based complex oxide includes barium titanate, lead titanate, strontium titanate, bismuth titanate, magnesium titanate, neodymium titanate, calcium titanate metals. An oxide etc. are mentioned. Among the titanium-based complex oxides, metal oxides having a perovskite structure are preferable. Specific examples include barium titanate-based, lead titanate-based, strontium titanate-based, and bismuth titanate-based metal oxides. It is done. In particular, barium titanate metal oxide and strontium titanate metal oxide are preferable.

The “titanium-based double oxide” is an oxide formed by combining a titanium-based single metal oxide and a metal oxide composed of at least one other metal element. This means that there is no acid ion. The “metal oxide having a perovskite structure” refers to a metal oxide having a crystal structure found in a double oxide represented by the chemical formula RMX ₃ .

Moreover, in order to improve the dispersibility to an aqueous medium, the particle | grains which modified | denatured the surface of the said inorganic particle with silica, an alumina, etc. can also be used suitably as an inorganic particle (E).
An inorganic particle (E) may be used individually by 1 type, and may use 2 or more types together.

  In the radiation-sensitive resin composition according to the present invention, the inorganic particles (E) are preferably 20% with respect to a total of 100% by weight of the phenol resin (A), the acid generator (B), and the inorganic particles (E). It is contained in the range of -95% by weight, more preferably 40-90% by weight, particularly preferably 60-85% by weight. When the content of the inorganic particles (E) is in the above range, it is preferable in terms of both resolution and dielectric constant.

  The volume average particle diameter of the inorganic particles (E) is usually 0.01 to 3.0 μm, preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.0 μm, still more preferably 0.02 to 0.02 μm. 0.8 μm. The ratio (Dw / Dn) of the weight average particle diameter (Dw) and the number average particle diameter (Dn) is preferably 1.05 or more, more preferably 1.1 or more, still more preferably 1.2 or more, Especially preferably, it is 1.25 or more. The upper limit of Dw / Dn is not particularly limited, but is usually about 10. When Dw / Dn is less than the above value, when the formed dielectric is a thin film, the packing of the inorganic particles (E) is deteriorated, which may increase the leakage current. The average particle size of the inorganic particles (E) is a value measured by a zeta potential measurement method, and the average particle size refers to the average primary particle size.

  The shape of the inorganic particles (E) is not particularly limited, and examples thereof include a spherical shape, a granular shape, a piece shape, a plate shape, a scale shape, a whisker shape, a rod shape, and a filament shape. Among these shapes, a spherical shape, a granular shape, a flake shape, and a flake shape are preferable.

<< (F) Azo UV absorber having a pyrazole ring >>
(F) By using an azo ultraviolet absorber having a pyrazole ring (hereinafter, also referred to as “pyrazole ring-containing ultraviolet absorber (F)”), the resolution of the formed dielectric material is greatly improved. The reason for this is presumed to be because light scattering by the inorganic particles (E) in the exposure step described later can be suppressed.

Examples of the pyrazole ring-containing ultraviolet absorber (F) include 1-phenyl-3-methyl-4- (4-methylphenylazo) -5-oxypyrazole.
In the radiation-sensitive resin composition according to the present invention, the pyrazole ring-containing ultraviolet absorber (F) is preferably 0.1 to 20 parts by weight, more preferably 0.8 parts per 100 parts by weight of the phenol resin (A). It is contained in the range of 3 to 15 parts by weight, particularly preferably 0.5 to 10 parts by weight. When the content of the pyrazole ring-containing ultraviolet absorber (F) is in the above range, it is preferable in that halation can be effectively suppressed and the resolution is improved.

<< (G) phenolic low molecular weight compound >>
The radiation-sensitive resin composition according to the present invention preferably contains (G) a phenolic low molecular compound (hereinafter also referred to as “phenol compound (G)”) different from the phenol resin (A).

  As the phenolic compound (G), 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, Tris (4-hydroxyphenyl) ethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) -1-methylethyl ] Benzene, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene, 1,1-bis (4-hydroxyphenyl) -1- [4- {1 -(4-Hydroxyphenyl) -1-methylethyl} phenyl] ethane, 1,1,2,2-tetra (4-hydroxyphenyl) Such as a single, and the like. The molecular weight of such a phenol compound (G) is usually 100 to 900.

  When the phenol compound (G) is used, in the radiation sensitive resin composition according to the present invention, the phenol compound (G) is preferably more than 0 part by weight and 40 parts by weight with respect to 100 parts by weight of the phenol resin (A). Part or less, more preferably more than 0 part by weight and 30 parts by weight or less.

<< (H) Adhesion aid >>
The radiation sensitive resin composition according to the present invention preferably contains an adhesion assistant (H). Examples of the adhesion assistant (H) include silane coupling agents, aluminum coupling agents, titanate coupling agents, zirconate coupling agents, and the like. The adhesion assistant (H) may be used alone or in combination of two or more.

  Among these, a silane coupling agent is preferable in that excellent adhesion can be obtained in a relatively small amount. A functional silane coupling agent and a silane coupling agent represented by the following general formula (1) [saturated Alkyl group-containing (alkyl) alkoxysilane. Hereinafter also referred to as “silane coupling agent (1)”. ] Is more preferable.

  The said functional silane coupling agent means the silane coupling agent which has reactive substituents, such as a carboxyl group, a vinyl group, a methacryloyl group, an isocyanate group, and an epoxy group.

  Preferred examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxy. Examples include silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane.

式（１）中、ｐは３〜２０の整数、好ましくは４〜１６の整数であり、ｍは１〜３の整数、ｎは１〜３の整数、ａは１〜３の整数である。

In the formula (1), p is an integer of 3 to 20, preferably 4 to 16, m is an integer of 1 to 3, n is an integer of 1 to 3, and a is an integer of 1 to 3.

Specific examples of the silane coupling agent (1) include n-propyldimethylmethoxysilane, n-butyldimethylmethoxysilane, n-decyldimethylmethoxysilane, n-hexadecyldimethylmethoxysilane, n-icosanedimethylmethoxysilane, and the like. Saturated alkyldimethylmethoxysilanes (a = 1, m = 1, n = 1);
Saturated alkyldiethylmethoxysilanes such as n-propyldiethylmethoxysilane, n-butyldiethylmethoxysilane, n-decyldiethylmethoxysilane, n-hexadecyldiethylmethoxysilane, n-icosanediethylmethoxysilane (a = 1, m = 1, n = 2);
Saturated alkyldipropylmethoxysilanes such as n-butyldipropylmethoxysilane, n-decyldipropylmethoxysilane, n-hexadecyldipropylmethoxysilane, n-icosanedipropylmethoxysilane (a = 1, m = 1, n = 3);
Saturated alkyldimethylethoxysilanes such as n-propyldimethylethoxysilane, n-butyldimethylethoxysilane, n-decyldimethylethoxysilane, n-hexadecyldimethylethoxysilane, n-icosanedimethylethoxysilane (a = 1, m = 2, n = 1);
Saturated alkyldiethylethoxysilanes such as n-propyldiethylethoxysilane, n-butyldiethylethoxysilane, n-decyldiethylethoxysilane, n-hexadecyldiethylethoxysilane, n-icosanediethylethoxysilane (a = 1, m = 2, n = 2);
Saturated alkyldipropylethoxysilanes (a = 1, m = 2, n-butyldipropylethoxysilane, n-decyldipropylethoxysilane, n-hexadecyldipropylethoxysilane, n-icosanedipropylethoxysilane) n = 3);
Saturated alkyldimethylpropoxysilanes such as n-propyldimethylpropoxysilane, n-butyldimethylpropoxysilane, n-decyldimethylpropoxysilane, n-hexadecyldimethylpropoxysilane, n-icosanedimethylpropoxysilane (a = 1, m = 3, n = 1);
Saturated alkyldiethylpropoxysilanes such as n-propyldiethylpropoxysilane, n-butyldiethylpropoxysilane, n-decyldiethylpropoxysilane, n-hexadecyldiethylpropoxysilane, n-icosanediethylpropoxysilane (a = 1, m = 3, n = 2);
Saturated alkyldipropylpropoxysilanes such as n-butyldipropylpropoxysilane, n-decyldipropylpropoxysilane, n-hexadecyldipropylpropoxysilane, n-icosanedipropylpropoxysilane (a = 1, m = 3, n = 3);
Saturated alkylmethyldimethoxysilanes such as n-propylmethyldimethoxysilane, n-butylmethyldimethoxysilane, n-decylmethyldimethoxysilane, n-hexadecylmethyldimethoxysilane, n-icosanemethyldimethoxysilane (a = 2, m = 1, n = 1);
Saturated alkylethyldimethoxysilanes such as n-propylethyldimethoxysilane, n-butylethyldimethoxysilane, n-decylethyldimethoxysilane, n-hexadecylethyldimethoxysilane, n-icosaneethyldimethoxysilane (a = 2, m = 1, n = 2);
Saturated alkylpropyldimethoxysilanes such as n-butylpropyldimethoxysilane, n-decylpropyldimethoxysilane, n-hexadecylpropyldimethoxysilane, n-icosanepropyldimethoxysilane (a = 2, m = 1, n = 3) ;
Saturated alkylmethyldiethoxysilanes such as n-propylmethyldiethoxysilane, n-butylmethyldiethoxysilane, n-decylmethyldiethoxysilane, n-hexadecylmethyldiethoxysilane, n-icosanemethyldiethoxysilane (A = 2, m = 2, n = 1);
Saturated alkylethyldiethoxysilanes such as n-propylethyldiethoxysilane, n-butylethyldiethoxysilane, n-decylethyldiethoxysilane, n-hexadecylethyldiethoxysilane, n-icosaneethyldiethoxysilane (A = 2, m = 2, n = 2);
Saturated alkylpropyldiethoxysilanes (a = 2, m = 2) such as n-butylpropyldiethoxysilane, n-decylpropyldiethoxysilane, n-hexadecylpropyldiethoxysilane, n-icosanepropyldiethoxysilane , N = 3);
Saturated alkylmethyldipropoxysilanes such as n-propylmethyldipropoxysilane, n-butylmethyldipropoxysilane, n-decylmethyldipropoxysilane, n-hexadecylmethyldipropoxysilane, n-icosanemethyldipropoxysilane (A = 2, m = 3, n = 1);
Saturated alkylethyldipropoxysilanes such as n-propylethyldipropoxysilane, n-butylethyldipropoxysilane, n-decylethyldipropoxysilane, n-hexadecylethyldipropoxysilane, n-icosaneethyldipropoxysilane (A = 2, m = 3, n = 2);
Saturated alkylpropyl dipropoxysilanes such as n-butylpropyldipropoxysilane, n-decylpropyldipropoxysilane, n-hexadecylpropyldipropoxysilane, n-icosanepropyldipropoxysilane (a = 2, m = 3) , N = 3);
Saturated alkyltrimethoxysilanes such as n-propyltrimethoxysilane, n-butyltrimethoxysilane, n-decyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-icosanetrimethoxysilane (a = 3, m = 1);
Saturated alkyltriethoxysilanes such as n-propyltriethoxysilane, n-butyltriethoxysilane, n-decyltriethoxysilane, n-hexadecyltriethoxysilane, n-icosanetriethoxysilane (a = 3, m = 2);
Saturated alkyltripropoxysilanes such as n-propyltripropoxysilane, n-butyltripropoxysilane, n-decyltripropoxysilane, n-hexadecyltripropoxysilane, n-icosanetripropoxysilane (a = 3, m = 3). A silane coupling agent (1) may be used individually by 1 type, and may use 2 or more types together.

  Among the silane coupling agents (1), n-butyltrimethoxysilane, n-decyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-decyldimethylmethoxysilane, n-hexadecyldimethylmethoxysilane, n- Butyltriethoxysilane, n-decyltriethoxysilane, n-hexadecyltriethoxysilane, n-decylethyldiethoxysilane, n-hexadecylethyldiethoxysilane, n-butyltripropoxysilane, n-decyltripropoxysilane N-hexadecyltripropoxysilane and the like are particularly preferable.

  When the adhesion assistant (H) is used, in the radiation-sensitive resin composition according to the present invention, the adhesion assistant (H) is preferably 0.001 to 10 weights with respect to 100 parts by weight of the phenol resin (A). Parts, more preferably 0.001 to 5 parts by weight.

<< (I) Polymer having constitutional unit derived from carboxyl group-containing (meth) acrylate >>
(I) By using a polymer having a structural unit derived from a carboxyl group-containing (meth) acrylate (hereinafter also referred to as “(meth) acrylate resin (I)”), the resolution of the formed dielectric is greatly improved. To do. The reason is presumed that the (meth) acrylate resin (I) interacts with the inorganic particles (E) and chelate coordinates.

  In addition, (meth) acrylate resin (I) is taken in into a bridge | crosslinking system, for example, when the carboxyl group in this resin reacts with the epoxy group which a bridge | crosslinking component has in the hardening process mentioned later.

  The (meth) acrylate resin (I) is not particularly limited as long as it is a polymer having a structural unit derived from a carboxyl group-containing (meth) acrylate, but from the viewpoint of resolution and electrical insulation, a monocyclic aliphatic hydrocarbon group A polymer having a structural unit derived from a carboxyl group-containing (meth) acrylate having a monocyclic aliphatic hydrocarbon group is more preferable.

  The “monocyclic aliphatic hydrocarbon group” means a hydrocarbon group having a monocyclic structure having no aromaticity and a substituted hydrocarbon group thereof. Specifically, a 3-9 membered cycloalkyl group such as a cyclohexyl group; a 3-9 membered cycloalkylene group such as a cyclohexylene group; a 3-9 membered cycloalkenyl group such as a cyclohexenyl group; A 3- to 9-membered cycloalkenylene group such as a cyclohexenylene group; a substituted cycloalkyl group or a substituted cycloalkylene in which at least one of the hydrogen atoms of these groups is substituted with an alkyl group, a hydroxyl group, a carboxyl group, or the like Group, a substituted cycloalkenyl group or a substituted cycloalkenylene group.

  The (meth) acrylate resin (I) has a carboxyl group-containing (meth) acrylate [eg: a carboxyl group-containing (meth) acrylate having no monocyclic aliphatic hydrocarbon group, a monocyclic aliphatic hydrocarbon group Carboxyl group-containing (meth) acrylate], if necessary, a monomer having a monocyclic aliphatic hydrocarbon group (excluding the carboxyl group-containing (meth) acrylate; the same shall apply hereinafter), It can be produced by polymerizing a monomer.

  In order to introduce a monocyclic aliphatic hydrocarbon group into the (meth) acrylate resin (I), (1) a carboxyl group-containing (meth) acrylate having a monocyclic aliphatic hydrocarbon group may be used. (2) A carboxyl group-containing (meth) acrylate having a monocyclic aliphatic hydrocarbon group and a monomer having a monocyclic aliphatic hydrocarbon group may be used. (3) Monocyclic aliphatic A carboxyl group-containing (meth) acrylate having no hydrocarbon group and a monomer having a monocyclic aliphatic hydrocarbon group may be used, and (4) a single amount described in (1) to (3) above In addition to the body, other monomers may be further used.

<Carboxyl group-containing (meth) acrylate>
The carboxyl group-containing (meth) acrylate is a compound having at least one, preferably one carboxyl group, and at least one, preferably one (meth) acryloyl group in the molecule.

  Examples of the carboxyl group-containing (meth) acrylate include a carboxyl group-containing (meth) acrylate having no monocyclic aliphatic hydrocarbon group and a carboxyl group-containing (meth) acrylate having a monocyclic aliphatic hydrocarbon group.

  As a carboxyl group-containing (meth) acrylate having no monocyclic aliphatic hydrocarbon group, a (meth) acrylate represented by the following general formula (2) (hereinafter referred to as “carboxyl group-containing (meth) acrylate (2)”) And a maleic ester of a polyfunctional (meth) acrylate having a hydroxyl group and no monocyclic aliphatic hydrocarbon group (eg, pentaerythritol tri (meth) acrylate).

  The carboxyl group-containing (meth) acrylate having a monocyclic aliphatic hydrocarbon group is a (meth) acrylate represented by the following general formula (3) (hereinafter also referred to as “carboxyl group-containing (meth) acrylate (3)”). Etc.).

  Moreover, you may use these oligomers of 2-20 mer.

式（２）中、Ｒは水素原子またはメチル基を示し、Ｘは二価の有機基を示す。

In formula (2), R represents a hydrogen atom or a methyl group, and X represents a divalent organic group.

The divalent organic group (X) is represented by an alkylene group, an arylene group, an alkylene arylene group,-(A ¹ -COO) _m -A ² -or -A ^2- (OCO-A ¹ ) _m-. Wherein A ¹ and A ² each independently represents an alkylene group, an arylene group or an alkylene arylene group, and when m represents an integer of 2 or more, a plurality of A ^{1 s} may be the same or different. Represents an integer of 1 or more, preferably an integer of 1 to 5.). Carbon number of the said bivalent organic group (X) is 1-50 normally, Preferably it is 1-20.

As specific examples of the carboxyl group-containing (meth) acrylate (2),
2- (meth) acryloyloxyethylmalonic acid,
2- (meth) acryloyloxyethyl succinic acid,
2- (meth) acryloyloxyethyl glutaric acid,
-2- (meth) acryloyloxyethylphthalic acid (o, m, p-form),
2- (meth) acryloyloxypropylphthalic acid (o, m, p-form),
-The carboxyl group containing (meth) acrylate represented by the following general formula (2a) is mentioned.

式（２ａ）中、Ｒは水素原子またはメチル基を示し、ｎは１〜１０の整数を示し、ｍは１〜１０の整数、好ましくは１〜５の整数を示す。なお、Ｃ_mＨ_2mは直鎖状または分岐鎖状のアルキレン基を示す。

In formula (2a), R represents a hydrogen atom or a methyl group, n represents an integer of 1 to 10, and m represents an integer of 1 to 10, preferably an integer of 1 to 5. C _m H _2m represents a linear or branched alkylene group.

  Examples of the carboxyl group-containing (meth) acrylate represented by the general formula (2a) include acrylic acid dimer and ω-carboxy-polycaprolactone mono (meth) acrylate.

式（３）中、Ｒは水素原子またはメチル基を示し、Ａ¹はシクロアルキレン基またはシクロアルケニレン基を示し、Ａ²はアルキレン基、シクロアルキレン基、シクロアルケニレン基、アリーレン基またはアルキレンアリーレン基を示す。Ａ¹およびＡ²はそれぞれ同一でも異なってもよく、またｍが２以上の整数を示す場合、複数あるＡ¹はそれぞれ同一でも異なってもよい。前記アルキレン基、シクロアルキレン基、シクロアルケニレン基、アリーレン基またはアルキレンアリーレン基の炭素数は、通常は１〜２０、好ましくは１〜１０である。ｍは１以上の整数、好ましくは１〜５の整数である。

In formula (3), R represents a hydrogen atom or a methyl group, A ¹ represents a cycloalkylene group or a cycloalkenylene group, A ² represents an alkylene group, a cycloalkylene group, a cycloalkenylene group, an arylene group or an alkylene arylene group. Show. A ¹ and A ² may be the same or different, and when m represents an integer of 2 or more, a plurality of A ¹ may be the same or different. Carbon number of the said alkylene group, cycloalkylene group, cycloalkenylene group, arylene group or alkylene arylene group is 1-20 normally, Preferably it is 1-10. m is an integer of 1 or more, preferably an integer of 1 to 5.

As specific examples of the carboxyl group-containing (meth) acrylate (3),
-2- (meth) acryloyloxyethyl tetrahydrophthalic acid,
2- (meth) acryloyloxyethyl hexahydrophthalic acid,
-2- (meth) acryloyloxypropyltetrahydrophthalic acid,
2- (meth) acryloyloxypropyl hexahydrophthalic acid,
・ These positional isomers (o, m, p-isomer)
Is mentioned.

  As a commercial item of the carboxyl group-containing (meth) acrylate, “Aronix M-5300”, “Aronix M-5400”, “Aronix M-5500”, “Aronix M-5600” manufactured by Toagosei Chemical Co., Ltd .; Shin-Nakamura “NK Ester SA” and “NK Ester A-SA” manufactured by Kagaku Co .; “Biscoat # 2000”, “Biscoat # 2100”, “Biscoat # 2150”, “Biscoat # 2180” manufactured by Osaka Organic Chemical Co., Ltd .; “HOA-MS”, “HO-MS”, “HOA-MPL”, “HO-MPL” and the like manufactured by Kagaku Co., Ltd. may be mentioned.

<Monomer having a monocyclic aliphatic hydrocarbon group>
Monomers having a monocyclic aliphatic hydrocarbon group include cycloalkyl (meth) acrylate (eg, cyclohexyl (meth) acrylate), hydroxycycloalkyl (meth) acrylate (eg, hydroxycyclohexyl (meth) acrylate), etc. Is mentioned.

<Other monomers>
Other monomers include (meth) acrylic acid esters (excluding monomers having a carboxyl group-containing (meth) acrylate and a monocyclic aliphatic hydrocarbon group); (meth) acrylic acid, croton Unsaturated monocarboxylic acids such as acids; aromatic vinyl compounds such as styrene, α-methylstyrene, vinyl benzoic acid, vinyl phthalic acid, vinyl toluene; carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate; itaconic acid, Examples thereof include unsaturated dicarboxylic acids such as maleic acid and fumaric acid. Another monomer may be used individually by 1 type and may use 2 or more types together.

  The (meth) acrylic acid ester is represented by the following general formula (4). The said (meth) acrylic acid ester may be used individually by 1 type, and may use 2 or more types together.

式（４）中、Ｒは水素原子またはメチル基を示し、Ｚは一価の有機基（但し、カルボキシル基および／または単環式脂肪族炭化水素基を有する有機基を除く。）を示す。

In formula (4), R represents a hydrogen atom or a methyl group, and Z represents a monovalent organic group (excluding an organic group having a carboxyl group and / or a monocyclic aliphatic hydrocarbon group).

  Examples of the monovalent organic group (Z) include an alkyl group having 1 to 20 carbon atoms, a group in which a hydrogen atom of the alkyl group is substituted with a hydroxyl group, a phenoxyalkyl group having 6 to 20 carbon atoms, and 2 carbon atoms. ˜20 alkoxyalkyl groups and the like.

  Examples of the (meth) acrylic acid ester represented by the general formula (4) include alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, phenoxyalkyl (meth) acrylate, and alkoxyalkyl (meth) acrylate.

  Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) ) Acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, ethylhexyl (meth) acrylate , Nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (medium) ) Acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate and the like.

  Examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl. (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. are mentioned.

  Examples of the phenoxyalkyl (meth) acrylate include phenoxyethyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate.

  Examples of the alkoxyalkyl (meth) acrylate include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, and 2-methoxybutyl. Examples include (meth) acrylate.

<Polymerization initiator>
When manufacturing (meth) acrylate resin (I), it is preferable to use a polymerization initiator. As a polymerization initiator, azo compounds such as N, N′-azobisisobutyronitrile; azide compounds such as 4-azidobenzaldehyde; benzyl, benzoin, benzophenone, camphorquinone, 2-hydroxy-2-methyl-1- Phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl- [4 ′-(methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl Carbonyl compounds such as 2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; di-t-butyl peroxide, di-t-hexyl peroxide, benzoyl peroxide, dilauroyl peroxide, t -Butyl hydroperoxide, cumene Such as peroxide compounds such as Hydro peroxide. A polymerization initiator may be used individually by 1 type, and may use 2 or more types together.

  In the (meth) acrylate resin (I), among all the structural units, a structural unit derived from a carboxyl group-containing (meth) acrylate, preferably a structure derived from a carboxyl group-containing (meth) acrylate having a monocyclic aliphatic hydrocarbon group The unit is usually contained in the range of 1 to 100% by weight, preferably 5 to 60% by weight, more preferably 10 to 50% by weight.

  When the content of the structural unit derived from the carboxyl group-containing (meth) acrylate is in the above range, it is preferable from the viewpoint of the resolution of the formed dielectric. When the content of the structural unit derived from a carboxyl group-containing (meth) acrylate having a monocyclic aliphatic hydrocarbon group is in the above range, it is preferable from the viewpoint of the resolution and electrical insulation of the dielectric formed.

  Mw of (meth) acrylate resin (I) is a polystyrene conversion value measured by GPC, preferably 1,000 to 100,000, more preferably 2,000 to 80,000, particularly preferably 3,000 to 50. , 000. When Mw is in the above range, the resolution of the formed dielectric is excellent. Mw can be controlled by appropriately selecting the polymerization temperature and the copolymerization ratio of the monomers. In addition, the average molecular weight of (meth) acrylate resin (I) is measured on the conditions described in [Example] described later.

  In the radiation-sensitive resin composition according to the present invention, the (meth) acrylate resin (I) is preferably 1 to 100 parts by weight, more preferably 5 to 80 parts by weight with respect to 100 parts by weight of the phenol resin (A). Especially preferably, it is contained in the range of 10 to 60 parts by weight. When the content of the (meth) acrylate resin (I) is within the above range, it is preferable from the viewpoint of the resolution of the formed dielectric.

"Additive"
The radiation sensitive resin composition according to the present invention comprises a plasticizer, a dispersant, a filler, a storage stabilizer, an antifoaming agent, an antioxidant, an ultraviolet absorber other than the component (F), a development accelerator, and a sensitization. You may contain additives, such as an agent and a leveling agent.

<< Method for preparing radiation-sensitive resin composition >>
The radiation-sensitive resin composition according to the present invention can be prepared by kneading the above components using a kneader (eg, roll kneader, mixer, homomixer, ball mill, bead mill). The radiation sensitive resin composition according to the present invention can be suitably used as a dielectric forming material.

[Dielectric]
The dielectric according to the present invention is obtained from the above radiation sensitive resin composition. A dielectric having the following characteristics can be produced using the above radiation sensitive resin composition, for example, according to the description of [Method of forming dielectric] described later.

  The dielectric constant of the dielectric according to the present invention is preferably 10.0 or more, more preferably 15.0 or more, and further preferably 20.0 or more. The upper limit of the dielectric constant is not particularly limited, but is usually about 200.

  The dielectric loss tangent of the dielectric according to the present invention is preferably 0.1 or less, more preferably 0.05 or less, and still more preferably 0.03 or less. The lower limit of the dielectric loss tangent is not particularly limited, but is usually about 0.001.

In addition, in this invention, a dielectric constant and a dielectric loss tangent are the values measured by the method as described in JISK6481 (frequency 1MHz), respectively, and are the values specifically measured on the conditions as described in [Example] mentioned later. .
The thickness of the dielectric according to the present invention is preferably 20 μm or less, more preferably 10 μm or less. The lower limit of the thickness of the dielectric is not particularly limited, but is usually about 1 μm.

[Method of forming dielectric]
The dielectric according to the present invention includes, for example, [1] a step of applying the radiation sensitive resin composition on a substrate to form a coating film (application step), and [2] a step of exposing the coating film (exposure). Step), [3] a step of developing the coated film after exposure to form a patterned film (developing step), and [4] a step of heating the patterned film to form a dielectric (curing step). ). Moreover, you may provide the heating process of 50-300 degreeC in the said each process for the purpose of drying or preliminary reaction.

[1] Coating process In the coating process, the radiation-sensitive resin composition is coated on a substrate using, for example, a coating machine to form a coating film. Preferable specific examples of the coating machine include a spinner, a screen printing machine, a gravure coating machine, a roll coating machine, and a bar coater. Preferable specific examples of the substrate include a silicon wafer having a metal sputtered film; a printed circuit board; and a plate-like member made of glass, alumina or the like.

  As a specific example of the coating step, the radiation sensitive resin composition is applied onto a silicon wafer having a metal sputtered film using a spinner or the like, and a film made of the radiation sensitive resin composition using a hot plate or the like. Is dried to form a coating film.

[2] Exposure process In the exposure process, the coating film is exposed. Specifically, [1] The surface of the coating film formed in the coating step is selectively irradiated (exposed) with radiation through an exposure mask, preferably followed by heat treatment (hereinafter, this heat treatment is performed). To form a latent image of the pattern on the coating film.

  Examples of the radiation include visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray, and visible light, ultraviolet light, and far ultraviolet light are preferable, and ultraviolet light is more preferable. Although the exposure pattern of the exposure mask varies depending on the purpose, for example, a dot pattern of 1 to 100 μm square is used.

  Examples of the radiation irradiation apparatus include an ultraviolet irradiation apparatus such as a high-pressure mercury lamp used in a photolithography method, an exposure apparatus used when manufacturing a semiconductor and a liquid crystal device, and the like.

  PEB is preferably carried out in order to accelerate the curing reaction (crosslinking reaction) between the phenol resin (A) and the crosslinking agent (C) caused by the acid generated by exposure. The condition is that the heating temperature is usually 70 to 150 ° C., preferably 80 to 120 ° C .; the heating time is about 1 to 60 minutes.

[3] Development step In the development step, the coated film after exposure is developed to form a patterned film. Specifically, the latent image of the pattern formed on the coating film is made visible by developing the coating film that has been exposed, preferably subsequently PEBed, in the exposure step [2]. By the development process, a pattern (pattern corresponding to the exposure mask) composed of the coating film remaining portion and the coating film removing portion is formed.

  Development process conditions include developer type / composition / concentration, development time, development temperature, development method (eg, immersion method, rocking method, shower method, spray method, paddle method), development device, etc. It can be appropriately selected depending on the case.

  As the developer, an alkali developer is preferably used. Thereby, the phenol resin (A) in a coating film can be easily dissolved and removed. In addition, since the inorganic particles (E) in the coating film are uniformly dispersed by the phenol resin (A), the inorganic particles (E) are dissolved by washing the phenol resin (A) as a binder in a developer. E) can also be removed at the same time.

  Examples of the alkaline compound that is an effective component of the alkaline developer include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, diammonium hydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, silicic acid. Inorganic alkaline compounds such as lithium, sodium silicate, potassium silicate, lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, ammonia; tetramethylammonium hydroxide, trimethylhydroxyethylammonium hydro Organic alkalinity such as oxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, ethanolamine Such compounds, and the like.

  The alkaline developer can be prepared by dissolving one or more of the above alkaline compounds in a solvent such as water. Here, the concentration of the alkaline compound in the alkaline developer is usually 0.001 to 10% by weight, preferably 0.01 to 5% by weight. The alkaline developer may contain additives such as nonionic surfactants and organic solvents.

  In addition, it is preferable to perform a water-washing process after performing the developing process with an alkaline developer. Moreover, you may provide the process of scraping off the unnecessary part which remain | survives in the patterned film side surface and board | substrate exposed part after a development process as needed.

[4] Curing process In the curing process, the patterned film is heat-treated to form a dielectric. By the curing step, the patterned film can be sufficiently cured, and a dielectric cured product having the above characteristics can be formed.

  The heat treatment is performed using, for example, an oven, an infrared lamp, a hot plate, etc .; the heating temperature is preferably 300 ° C. or less, more preferably 100 to 300 ° C., further preferably 150 to 250 ° C .; the heating time is preferably 1 It is carried out in the range of minutes to 24 hours, more preferably 10 minutes to 12 hours.

[Electronic parts]
The dielectric according to the present invention can be obtained by heat treatment at a low temperature of 300 ° C. or less as described above, and preferably has a dielectric constant of 10.0 or more and a dielectric loss tangent of 0.1 or less. Therefore, by using the dielectric, a thin film capacitor having a large capacitance can be formed.

  The electronic component according to the present invention has the dielectric. Examples of such electronic components include semiconductor packages, (multilayer) printed wiring boards, capacitors, and high frequency antennas. The electronic component according to the present invention can meet the recent demands for miniaturization, thinning, and high density.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by these Examples. In the following examples and comparative examples, “parts” and “%” are used to mean “parts by weight” and “% by weight” unless otherwise specified.

[Method of measuring weight average molecular weight (Mw) and number average molecular weight (Mn)]
The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured under the following conditions.
・ Measurement method: Gel permeation chromatography (GPC) method ・ Standard material: polystyrene ・ Device: manufactured by Tosoh Corporation, trade name: HLC-8020
Column: Tosoh Corporation guard column _{H XL -H, TSK gel G7000H XL} , TSK gel GMH XL 2 present, TSK gel G2000H those obtained by sequentially connecting the _XL-solvent: tetrahydrofuran Sample concentration: 0.7%
・ Injection volume: 70 μL
・ Flow rate: 1 mL / min
Moreover, the characteristics of the patterned film and the dielectric cured product were evaluated by the following methods.

[Evaluation 1. (Sensitivity and resolution)
The radiation-sensitive resin compositions obtained in Examples and Comparative Examples were spin-coated on a 4-inch silicon wafer and heated at 110 ° C. for 3 minutes using a hot plate to produce a uniform coating film having a thickness of 7 μm. . Then, using the aligner (MAS-200e manufactured by Suss Microtec), the coating film was exposed through an exposure mask so that the exposure amount of ultraviolet rays from a high-pressure mercury lamp at a wavelength of 350 nm was 100 to 2000 mJ / cm ² . .

  The coated film after the exposure was heated (PEB) at 110 ° C. for 3 minutes using a hot plate, and immersed and developed at 23 ° C. for 5 minutes using a 2.38% tetramethylammonium hydroxide aqueous solution.

  The obtained patterned film was observed with an optical microscope, and the minimum dimension resolved was taken as the resolution. Further, the 100 μm pattern was observed with an optical microscope, and the minimum exposure amount at which the pattern dimension was 100 μm ± 5 μm was determined as the optimum exposure amount (sensitivity).

[Evaluation 2. Dielectric constant and dielectric loss tangent)
A radiation sensitive resin composition obtained in Examples and Comparative Examples was spin-coated on a 5 cm square Suss substrate and heated at 110 ° C. for 3 minutes using a hot plate to produce a uniform coating film having a thickness of 10 μm. did. Then, the said coating film was exposed by the exposure amount made into the optimal exposure amount by the said sensitivity evaluation using the aligner (MAS-200e by Suss Microtec).

  The coated film after the exposure was heated (PEB) at 110 ° C. for 3 minutes using a hot plate, and immersion developed at 23 ° C. for 5 minutes using a 2.38% tetramethylammonium hydroxide aqueous solution.

Subsequently, heat treatment was performed in an oven at 200 ° C. for 1 hour. An electrode with a guide ring (area: 1 cm ² , thickness: 0.1 μm) was formed on the obtained dielectric cured product on the Suss substrate by an aluminum vapor deposition method. The dielectric constant and dielectric loss tangent at 1 MHz were measured at 10 points with an LCR meter (HP4248A, manufactured by Hewlett Packard) between the substrate made of Suss and the electrode, and the average value was obtained.

[Evaluation 3. Electrical insulation)
As shown in FIG. 1, the radiation sensitive resin compositions obtained in Examples and Comparative Examples are applied on a substrate 3 for insulating evaluation having a patterned copper foil 2 on a substrate 1, and a hot plate Was used for 3 minutes at 110 ° C. to prepare a substrate having a 10 μm thick coating on the copper foil 2. Then, it heated at 190 degreeC for 1 hour using the convection type oven, the said coating film was hardened, and the cured film was formed. The test substrate on which the cured film was formed was put into a migration evaluation system (model “AEI, EHS-221MD” manufactured by Tabai Espec), temperature 121 ° C., humidity 85%, pressure 1.2 atm, and applied voltage 5 V. The treatment was performed for 200 hours under the following conditions. Next, the resistance value (Ω) of this test substrate was measured, and the electrical insulation was evaluated according to the following criteria.
AA: 1 × 10 ¹¹ Ω or more BB: Less than 1 × 10 ¹¹ Ω

[Synthesis Example 1] Synthesis of cresol novolak resin (A-1) To a 3 L three-necked separable flask equipped with a stirrer, a condenser tube and a thermometer, mixed cresol (m-cresol / p-cresol = 60/40 (molar ratio) )) 840 g, 37% formaldehyde aqueous solution 600 g and oxalic acid 0.36 g were charged.

  While stirring this solution, the separable flask was immersed in an oil bath, and the temperature in the flask was kept at 100 ° C. for reaction for 3 hours. Thereafter, the oil bath temperature was raised to 180 ° C., and at the same time, the inside of the separable flask was decompressed to remove water, unreacted cresol, unreacted formaldehyde and oxalic acid.

  Subsequently, the melted cresol novolak resin was recovered by returning to room temperature to obtain a cresol novolak resin (A-1) (Mw = 6500) of m-cresol / p-cresol = 60/40 (molar ratio).

[Synthesis Example 2] Synthesis of p-hydroxystyrene homopolymer (A-2) 100 parts of pt-butoxystyrene was dissolved in 150 parts of propylene glycol monomethyl ether, and the reaction temperature was maintained at 70 ° C under a nitrogen atmosphere. Then, polymerization was carried out for 10 hours using 4 parts of N, N′-azobisisobutyronitrile.

  Thereafter, sulfuric acid was added to the reaction solution, and the reaction temperature was maintained at 90 ° C. for 10 hours, and the pt-butoxystyrene unit was deprotected and converted to the p-hydroxystyrene unit. Ethyl acetate was added to the obtained polymer, washing with water was repeated 5 times, the ethyl acetate phase was separated, the solvent was removed, and p-hydroxystyrene homopolymer (A-2) (Mw = 10000, Mw / Mn = 3.5) was obtained.

[Synthesis Example 3] Synthesis of (meth) acrylate resin (I-1) 30 g of methyl methacrylate, 40 g of lauryl methacrylate, 2-acryloyloxypropyltetrahydrophthalic acid (manufactured by Osaka Organic Chemical Co., Ltd., “Biscoat # 2180”), N, 5 g of N′-azobisisobutyronitrile was mixed and stirred with 50 g of propylene glycol monomethyl ether to obtain a uniform acrylic monomer solution.

Separately, 150 g of propylene glycol monomethyl ether was weighed in a separable flask, and this solution was bubbled with nitrogen gas for 30 minutes and then heated to 90 ° C.
The acrylic monomer solution was continuously dropped into this solution over a period of 2 hours, and then reacted at 90 ° C. for 4 hours. Then, it was made to react at 100 degreeC for 1 hour, and Mw = 15000 (meth) acrylate resin (I-1) was obtained.

[Examples 1 to 4, Comparative Example 1]
Phenol resin (A), acid generator (B), crosslinking agent (C), solvent (D), inorganic particles (E), pyrazole ring-containing ultraviolet absorber (F), phenol compound (G), adhesion aid ( H) and (meth) acrylate resin (I) were each weighed in the amounts shown in Table 1, kneaded with a bead mill, and then filtered with a stainless mesh (500 mesh) to prepare a radiation sensitive resin composition. The said evaluations 1-3 were performed using the said radiation sensitive resin composition. The evaluation results are shown in Table 2.
In addition, the component of Table 1 is as follows.

<Phenolic resin (A)>
A-1: m-cresol / p-cresol = 60/40 (molar ratio) cresol novolak resin (Mw = 6500, cresol / formaldehyde condensed novolak resin)
A-2: p-hydroxystyrene homopolymer (Mw = 10000, Mw / Mn = 3.5)
<Acid generator (B)>
B-1: Styryl-bis (trichloromethyl) -s-triazine <Crosslinking agent (C1)>
C1-1: Hexamethoxymethylated melamine (Mitsui Cytec Co., Ltd., trade name: Cymel 300)
<Epoxy resin (C2)>
C2-1: Bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name: EP-828)
<Solvent (D)>
D-1: Ethyl lactate D-2: Propylene glycol monomethyl ether acetate

<Inorganic particles (E)>
E-1: Strontium titanate (perovskite structure, dielectric constant = 330, volume average particle size = 500 nm, manufactured by Nippon Chemical Industry Co., Ltd.)
<Pyrazole ring-containing UV absorber (F)>
F-1: 1-phenyl-3-methyl-4- (4-methylphenylazo) -5-oxypyrazole <Phenol compound (G)>
G-1: 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane <Adhesion aid (H)>
H-1: γ-glycidoxypropyltrimethoxysilane (manufactured by Chisso Corporation, trade name: S-510)
<(Meth) acrylate resin (I)>
I-1: (Meth) acrylate resin synthesized in Synthesis Example 3 (Mw = 15000)

DESCRIPTION OF SYMBOLS 1 ... Board | substrate 2 ... Copper foil 3 ... Base material for insulation evaluation

Claims (10)

(A) a polymer having a phenolic hydroxyl group;
(B) a radiation sensitive acid generator;
(C) a crosslinking agent;
(E) ferroelectric inorganic particles;
(F) an azo ultraviolet absorber having a pyrazole ring ;
(I) A radiation-sensitive resin composition comprising a polymer having a structural unit derived from a carboxyl group-containing (meth) acrylate .   The radiation sensitive resin composition of Claim 1 which contains a novolak resin at least as said (A) component. As the component (C),
(C1) a compound having at least two alkyl etherified amino groups in the molecule;
(C2) The radiation sensitive resin composition of Claim 1 or 2 containing at least 1 sort (s) chosen from an oxiranyl group containing compound.   The radiation-sensitive resin composition according to claim 3, wherein the oxiranyl group-containing compound (C2) is a bisphenol A type epoxy resin.   The radiation sensitive resin composition according to any one of claims 1 to 4, wherein the component (E) is inorganic particles made of a titanium metal oxide.   The radiation-sensitive resin composition according to claim 5, wherein the inorganic particles made of the titanium-based metal oxide are inorganic particles made of a metal oxide having a perovskite structure.   The volume sensitive particle diameter of said (E) component is 0.01-3.0 micrometers, The radiation sensitive resin composition of any one of Claims 1-6. The radiation-sensitive resin composition according to any one of claims 1 to 7 , which is a dielectric forming material. The dielectric obtained from the radiation sensitive resin composition of any one of Claims 1-8 . An electronic component having the dielectric according to claim 9 .

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