JPH1165116A - Radiation sensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation sensitive resin compsn. having superior resolution, developable with an aq. alkali soln., having high plating soln. and heat resistances, low in water absorption and in degree of shrinkage by curing and capable of forming an insulating layer excellent in adhesion of a conductor circuit by incorporating an alkali-soluble resin, a crosslinking agent, a compd. having a specified oxetane structure, rubber and a radiation polymn. initiator. SOLUTION: The radiation sensitive resin compsn. contains an alkali-soluble resin, a crosslinking agent, a compd. having an oxetane structure represented by the formula in its molecule, rubber and a radiation polymn. initiator. The alkali-soluble resin is preferably polyvinyl phenol and/or a phenolic resin other than polyvinyl phenol having a wt. average mol.wt. of >=2,000. The crosslinking agent is preferably an amino resin having plural active methylol groups in its molecule. The rubber is preferably liq. rubber having a number average mol.wt. of 1,000-100,000 and <=-20 deg.C glass transition temp.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation-sensitive resin composition, and more particularly, to a radiation-sensitive resin composition suitable as an insulating layer forming material for forming an insulating layer interposed between two conductor wirings arranged in a stack. The present invention relates to a radiation-sensitive resin composition used in the present invention.

[0002]

2. Description of the Related Art Recently, a multilayer wiring board having a structure in which a plurality of conductor wirings are stacked via an insulating layer has been increasingly important due to a demand for higher density in a printed wiring board. As a method of manufacturing this multilayer wiring board, a plurality of wiring boards each having conductor wiring formed on a base material are stacked, for example, via a thermosetting resin impregnated sheet called a prepreg, and press-formed in that state. In this way, a multi-layered structure is formed, a through-hole called a through-hole penetrating the whole of the multi-layered structure is formed in the multi-layered structure by a drill or the like, and an inner wall surface of the through-hole is subjected to a plating process, thereby stacking. 2. Description of the Related Art There is known a method of manufacturing by forming a plating layer for conducting two arranged conductor wirings (hereinafter, also referred to as “lamination press method”). However, in this lamination press method, it is difficult to align a plurality of wiring boards as the wiring pattern becomes finer, and the wiring shifts due to shrinkage of the wiring board base material. There is a problem that it is difficult to reduce the diameter of the through hole in accordance with a simple pattern and a problem that the manufacturing process becomes complicated.

On the other hand, an insulating layer is formed on a wiring board on which a conductive wiring is formed, and another conductive wiring conductive to the conductive wiring is formed on the insulating layer. A method of manufacturing a plate (hereinafter, also referred to as a “stacking method”) has been proposed. In the case of manufacturing a multilayer wiring board by this stacking method, in order to make the two conductor wirings stacked through the insulating layer conductive, a through hole is formed and plating is performed in the same manner as in the case of the lamination press method. In addition, there is a method in which a hole called a via hole penetrating only a part of the insulating layer is formed by a drill, and plating is performed in the hole.

As a method for forming a through hole or a via hole in the insulating layer, a method using an excimer laser, a method of forming a predetermined pattern using a processing resist, and etching the insulating layer with an appropriate solvent are used. Are known. However, these methods
It is not a preferable method from the viewpoint of productivity, such that a plurality of holes cannot be formed at the same time or many steps are required. Further, the above methods are not satisfactory from the viewpoint of processing accuracy.

Therefore, there has been proposed a method in which a photosensitive resin composition is used as a material for forming an insulating layer interposed between conductor wirings, and a through hole is formed in the insulating layer by photolithography. According to this method, since a plurality of through holes can be formed at the same time, high production efficiency can be obtained in the production of a multilayer wiring board, and moreover, the through holes can be formed with higher accuracy than the conventional method. So you can
This is advantageous in manufacturing a multilayer wiring board having a fine wiring pattern. Here, a through-hole formed in an insulating layer made of a photosensitive resin composition and subsequently subjected to a plating process to achieve electrical connection is called a photo-via hole, and is a multilayer wiring board in which the photo-via hole is formed. Have been proposed by using a stacking method (Japanese Unexamined Patent Publication No. 4-14 / 1994).
No. 8590). Further, as a photosensitive resin composition for forming such an insulating layer, an application example using a photosensitive epoxy resin has been proposed (Japanese Patent Laid-Open No. Hei 5-273).
No. 753).

As described above, according to the method of manufacturing a multilayer wiring board by a stacking method using a photosensitive resin composition for forming an insulating layer, a multilayer laminated structure can be obtained without performing a press treatment. Since a photo via hole having a sufficiently small diameter can be formed with high precision by photolithography, a multilayer wiring board having a fine wiring pattern can be suitably manufactured.

However, the photosensitive resin composition used for forming the insulating layer when the multilayer wiring board is manufactured by the stacking method is required to have the following performance. (1) The obtained insulating layer has excellent resolution. Thus, a small-diameter photo via hole corresponding to a fine pattern can be formed with high accuracy. (2) The obtained insulating layer has sufficiently high resistance (plating solution resistance) to, for example, an electroless copper plating solution used for forming conductor wiring. (3) The obtained insulating layer should be capable of forming conductive wiring on its surface with sufficient adhesion by, for example, electroless copper plating. Here, in order to improve the adhesion of the conductor wiring by copper plating, it is effective that the surface of the insulating layer is roughened, and according to the insulating layer having the roughened surface, Due to the anchor effect, the adhesion of the conductor wiring to the insulating layer is increased. (4) An alkaline aqueous solution can be used as a developer for forming photo via holes. If an alkaline aqueous solution can be used as a developer, adverse effects on the human body and the environment can be suppressed. (5) The obtained insulating layer has a sufficient electrical insulating property, has high reliability, and has high heat resistance. Thus, the present invention can be advantageously applied to the manufacture of electronic devices that are being reduced in size and weight.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide, for example, an excellent resolution which can form a small-diameter photo via hole with high precision, which can be developed with an alkaline aqueous solution, Provided is a radiation-sensitive resin composition having high heat resistance and heat resistance, low water absorption, low degree of curing shrinkage, and capable of forming an insulating layer in which conductor wiring is formed with excellent adhesion. It is in.

[0009]

In order to achieve the above object, the radiation-sensitive resin composition of the present invention is characterized by containing the following components A to E. [Component A] alkali-soluble resin [Component B] cross-linking agent [Component C] a compound having an oxetane structure represented by the formula (1) in the molecule

[0010]

Embedded image [D component] rubber [E component] radiation polymerization initiator Specifically, the A component, the B component and the D component constituting the radiation-sensitive resin composition of the present invention are preferably as follows: Thus, the effect of the present invention can be sufficiently and reliably obtained. [A component] An alkali-soluble resin comprising one or both of polyvinylphenol and a phenol resin other than polyvinylphenol having a weight average molecular weight of 2000 or more [B component] An amino resin having a plurality of active methylol groups in one molecule [D component] Liquid rubber having a number average molecular weight of 1,000 to 100,000 and a glass transition point of -20 ° C or less

In the following, "light" for all the phrases containing the word "light" means radiation such as visible light, ultraviolet light, far ultraviolet light, X-rays, and electron beams, unless clearly different. It shall be.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the radiation-sensitive resin composition of the present invention will be described in detail. [A component] This A component is an alkali-soluble resin,
Preferably, it is an alkali-soluble resin composed of one or both of polyvinyl phenol and a phenol resin other than polyvinyl phenol having a weight average molecular weight of 2,000 or more (hereinafter referred to as “specific phenol resin”).

The polyvinyl phenol used as the component A is obtained by polymerizing a vinyl phenol monomer by a conventional method, or after polymerizing a phenolic hydroxyl group protected by a protecting group, and then removing the protecting group. And those obtained by various production methods, such as those obtained by the above method. Further, a monomer in which various substituents are introduced into a vinylphenol monomer,
For example, various substituted polyvinyl phenols obtained from vinyl cresol, 2,4-dimethyl vinyl phenol, fluorinated vinyl phenol, chlorinated vinyl phenol, brominated vinyl phenol and the like can also be used. The molecular weight of this polyvinyl phenol is not particularly limited, but from the viewpoint of resolution, developability, plating solution resistance, and the like in the obtained insulating layer, the weight average molecular weight is 2,000 or more, particularly in the range of 2,000 to 20,000. Preferably, there is.

A typical example of the specific phenol resin used as the component A is a novolak resin. The novolak resin is, for example, an aromatic compound having a phenolic hydroxyl group (hereinafter, referred to as "phenols") and an aldehyde, preferably a phenol 1
It is obtained by addition-condensation using an acid catalyst at a ratio of 0.7 to 1 mol of aldehyde to mol. Here, specific examples of phenols include phenol and 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, 3,6-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol,
p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol,
Examples include phlorogrisinol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol and the like.

Specific examples of aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde and the like. As the acid catalyst, for example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid and the like are used. The specific phenolic resin used as the component A is
From the viewpoint of the resolution, developability, plating solution resistance, and the like of the obtained insulating layer, the weight average molecular weight needs to be 2000 or more, and particularly preferably in the range of 2000 to 20,000.

In the present invention, as the alkali-soluble resin as the component A, one of the above-mentioned polyvinyl phenols or specific phenol resins can be used alone or in combination of two or more. It is preferable to use a phenol resin in combination.
In the composition of the present invention, the ratio of the component A is a ratio at which the obtained insulating layer shows sufficient alkali solubility.
30 to 75% by weight of the total composition, preferably 40 to 70%
% By weight. If this ratio is too small, the resulting thin film of the composition will not have sufficient developability with an aqueous alkaline solution, while if this ratio is too large,
As a result of the relatively limited proportion of other components, the resulting insulating layer may be insufficient in toughness, heat resistance and plating solution resistance.

[Component B] The component B is a crosslinking agent,
Preferably, it is an amino resin having a plurality of active methylol groups in one molecule, reacting with the alkali-soluble resin of the component A to form a crosslinked structure, and acting as a curing agent component. Examples of the amino resin used as the component B include (poly) methylolated melamine, (poly)
Nitrogen-containing compounds having a plurality of active methylol groups in one molecule, such as methylolated glycoluril, (poly) methylolated benzoguanamine, (poly) methylolated urea, and the like, and a hydrogen atom of a hydroxyl group of the methylol group May be a compound substituted by an alkyl group such as a methyl group or a butyl group, or a mixture of a plurality of such substituted compounds. The component B may include an oligomer component obtained by partially condensing these compounds.

Examples of the amino resin as the component B include hexamethoxymethylated melamine (“Cymel 300” manufactured by Mitsui Cyanamid Co., Ltd.) and tetrabutoxymethylated glycoluril (“Cymel 1170” manufactured by Mitsui Cyanamid Co., Ltd.). A product of the Cymel series, a product of the Mycoat series, a product of the UFR series, and others can be used, and hexamethoxymethylated melamine is particularly preferred. These amino resins can be used alone or in combination of two or more.

In the composition of the present invention, the proportion of the component B must be within a range in which a thin film of the composition can be sufficiently cured by the action of a photopolymerization initiator and heat. It is 10 to 25% by weight, preferably 10 to 20% by weight of the whole product. If the proportion is too small, the resulting insulating layer may have insufficient toughness, heat resistance and plating solution resistance, while if the proportion is too large, the resulting composition may cause insufficient development of the thin film. It may not have the property.

[C component] This C component is represented by the above formula (1)
Is a compound having at least one oxetane structure represented by the following formula, and examples thereof include compounds represented by the following formulas (A), (B) and (C).

[0021]

Embedded image [In each of the above formulas (A), Formula (B) and formula (C), Z is ^{-R 2 -, - R 2 O} -, - OR 2 -, or -
R ² OR ² - represents a group represented by, R ¹ is an alkyl group such as a methyl group, an ethyl group, a propyl group, R ² is a methylene group, an ethylene group, alkylene groups such as propylene radical, R ³ is a methyl group, an ethyl group, a propyl group, hexyl, or similar alkyl groups; aryl groups such as phenyl and xylyl groups; dimethylsiloxane residue represented by the following formula (2), the same alkylene as exemplified with respect to R ² A phenylene group or a group represented by the following formulas (3) to (7), wherein n is equal to the valence of R ³ and is an integer of 1 to 4. “·” Means n bonds. The formulas (2) to (7) are shown below.

[0022]

Embedded image

[0023]

Embedded image (Wherein, X represents a single bond _{or, -CH 2 -, - C (} CH
_{3) 2 -, - C (} CF 3) 2 -, - SO 2 -, - O -, - C
O-, or -CH (CH ₃₎ - is a divalent group represented by. )

[0024]

Embedded image

Specific examples of the compounds represented by formulas (A) to (C) include bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene (also known as xylylenedioxetane, trade name "XDO") Manufactured by Gosei Co., Ltd.), bis [(3-ethyl-3-oxetanylmethoxy) methyl-
Phenyl] methane, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl-
Phenyl] propane, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] sulfone, bis [(3-ethyl-3-oxetanylmethoxy) methyl-
Phenyl] ketone, bis [(3-ethyl-3-oxetanylmethoxy) methyl-phenyl] hexafluoropropane, tri [(3-ethyl-3-oxetanylmethoxy)
Methyl] benzene, tetra [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-ethyl-3-oxetanylmethoxy) oligodimethylsiloxane represented by the following formula (D), and represented by the following formula (E) α, ω
-(3-ethyl-3-oxetanylmethoxy) oligodimethylsiloxane, 2,3-di [(3-ethyl-3-oxetanylmethoxy) methyl] represented by the following formula (F)
Examples thereof include -1,4-di (3-ethyl-3-oxetanylmethoxy) butane and compounds represented by the following chemical formulas (G) to (K). Hereinafter, formulas (D) to
(K) is shown.

[0026]

Embedded image

[0027]

Embedded image

[0028]

Embedded image

As the C component, in addition to the compounds represented by the formulas (A), (B) and (C), compounds having a high-molecular-weight polyvalent oxetane ring can be used. For example, an oxetane oligomer (trade name “O
Ligo-OXT "manufactured by Toagosei Co., Ltd.) and the compounds represented by the following chemical formulas (L) to (N).

[0030]

Embedded image In these formulas, p, q and s are integers of 1 to 10,000.

Since these oxetane structure-containing compounds do not generate hydroxyl groups in the curing reaction, a cured film formed from the composition of the present invention containing the compound has the following properties:
It has good water resistance due to low water absorption, and is applied to a substrate because the degree of curing shrinkage is small,
It has the feature of excellent dimensional accuracy when cured. On the other hand, when an epoxy compound is used, a hydroxyl group is generated in the curing reaction, so that the cured film becomes water-absorbing, so that excellent water resistance cannot be obtained. The proportion of the oxetane structure-containing compound is usually 5 to 3 of the total composition.
0% by weight, preferably 5 to 25% by weight. If this ratio is too small, the resulting insulating layer will not have sufficiently low water absorption and the degree of cure shrinkage will not be sufficiently small. On the other hand, if the ratio is too large, the resulting thin film of the composition may not have sufficient developability.

[D Component] The D component is a rubber, preferably a liquid rubber having a number average molecular weight of 1,000 to 100,000 and a glass transition point Tg of -20 ° C. or less. By doing so, the composition of the present invention has good adhesion of the conductor wiring formed by the plating treatment to the insulating layer, and particularly, sufficiently high adhesion can be obtained even at a high temperature. However, according to the composition obtained using a liquid rubber having a number average molecular weight of less than 1,000, the resulting insulating layer has insufficient plating solution resistance, while the number average molecular weight is based on a liquid rubber having a number average molecular weight of more than 100,000. In such a case, high resolution cannot be obtained in the insulating layer. Further, the glass transition point Tg of the liquid rubber used is-
When the temperature is higher than 20 ° C., the obtained insulating layer has poor adhesion of the conductor wiring, and particularly has low adhesion under high temperature and high humidity.

The liquid rubber used as the component D must have high compatibility or affinity with the component A, component B, component C or component E, and have a high compatibility or affinity with these components. If a lower one is used, the resulting composition will have a higher tackiness and cause handling problems.
Examples of the liquid rubber include various known synthetic rubbers. However, acrylic rubber (ACM), acrylonitrile-butadiene rubber (NBR), acrylonitrile acrylate, Butadiene rubber (NBA) is preferable, and if necessary, a rubber having at least one functional group selected from an epoxy group, a hydroxyl group, a carboxyl group, and an amino group can also be used. Actually, those having an epoxy group, a carboxyl group or a hydroxyl group are preferable, and a liquid rubber made of a butadiene copolymer having a carboxyl group or a hydroxyl group is particularly preferable.

The liquid rubber of the component D may be produced by any method, and various methods such as emulsion polymerization, solution polymerization, bulk polymerization and suspension polymerization can be used for the production. The polymerization system may be any of a batch system, a batch system, and a continuous system. The liquid rubber preferably has a low proportion of the ionic component contained therein, whereby the resulting insulating layer has a sufficient insulating property. When the diene monomer is contained in the monomer composition for obtaining the liquid rubber, the polymerization of the composition can be easily carried out by an emulsion polymerization method. 74908
According to the method disclosed in Japanese Patent Application Laid-Open No. H10-115, a liquid rubber having a low content ratio of an ionic component can be obtained.

In the composition of the present invention, the proportion of the D component is in a range where the metal layer formed by the plating treatment has sufficient adhesion to the insulating layer of the composition. Is usually 5 to 20% by weight, preferably 5 to 15% by weight of the whole composition. If this ratio is too small, the resulting insulating layer will have insufficient adhesion of the metal layer formed by the plating process, while if this ratio is too large, the resulting thin film of the composition will be insufficient. It may not be cured.

[Component E] The component E is a radiation polymerization initiator (photopolymerization initiator). As the photopolymerization initiator used as the component E of the present invention, those generally known as a cationic photopolymerization initiator are preferable, and specifically, a diazonium salt “ADEKA ULTRASET PP” is preferable.
-33 "[made by Asahi Denka Kogyo Co., Ltd.]," OPTOMER SP-150 "which is a sulfonium salt," OPTOME
R SP-170 "," OPTOMER SP-17 "
1 "(manufactured by Asahi Denka Kogyo KK), a metallocene compound" IRGACURE 261 "(manufactured by Ciba Geigy), and a triazine compound" triazine B "," triazine PMS "," triazine PP "[manufactured by Nihon Siber Hegner Co., Ltd.] And the like.

The proportion of the photopolymerization initiator in the composition of the present invention is usually preferably from 0.1 to 15% by weight, more preferably from 0.2 to 5% by weight, based on the whole composition. is there. If this proportion is less than 0.1% by weight, the resulting insulating layer will have a remarkable decrease in sensitivity due to the influence of the surrounding environment such as oxygen, whereas if it exceeds 15% by weight, the compatibility with other components will increase. Poor solubility, resulting in reduced storage stability of the composition.

In the composition of the present invention, the mixing ratio of each of the components A to E is particularly suitable when used as a material for forming an interlayer insulating layer of an electronic component. Although it depends on the degree of adhesion of the plating layer, etc., usually 30 to 75% by weight, preferably 40 to 70 parts by weight, and 10 to 25% by weight, preferably 10 to 20% by weight, of the B component in the whole composition. , C component 5 to 30% by weight, preferably 5 to 25% by weight, D component 5 to 20% by weight, preferably 5 to 15% by weight, E component 0.1 to 15% by weight, preferably 0.2 to 5% % By weight.

The composition of the present invention can contain an adhesion aid for improving the adhesiveness to the substrate to which the composition is applied. As this adhesion aid, a functional silane coupling agent is effective. Here, the functional silane coupling agent means a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, or an epoxy group, and examples thereof include trimethoxysilylbenzoic acid, γ -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane and the like can be mentioned, and the blending ratio is preferably 2 parts by weight or less per 100 parts by weight of the composition.

The composition of the present invention can contain a filler, a coloring agent, a viscosity modifier, a leveling agent, an antifoaming agent, and other additives as necessary. Examples of the filler include silica, alumina, talc, calcium carbonate, bentonite, zirconium silicate, and powdered glass. Coloring agents include extenders such as alumina white, clay, barium carbonate, and barium sulfate; inorganic materials such as zinc white, lead white, graphite, lead red, ultramarine, navy blue, titanium oxide, zinc chromate, red iron, carbon black, etc. Pigment: Brilliant Carmine 6B, Permanent Red 6
B, permanent red R, organic pigments such as benzidine yellow, phthalocyanine blue, and phthalocyanine green; basic dyes such as magenta and rhodamine; direct dyes such as direct scarlet and direct orange; Can be mentioned. Examples of the viscosity modifier include bentonite, silica gel, and aluminum powder. Examples of the leveling agent include various silicone compounds and polyalkylene oxide compounds. Examples of the antifoaming agent include a silicon compound and a fluorine compound having a low surface tension. The proportion of these additives is within a range that does not impair the essential properties of the composition, preferably 50% in the whole composition.
% By weight or less.

[Specific additive] The additive effective in the composition of the present invention is a particulate rubber composed of a crosslinked polymer having a functional group on the surface of the particle, particularly one having a carboxyl group or an epoxy group. The average particle diameter is preferably 0.01 to 20 μm, and more preferably 0.01 to 20 μm.
It is 5.0 μm. For more information about this particulate rubber,
For example, JP-A-4-15830 can be referred to. According to the composition of the present invention to which the particulate rubber is added, the surface of the formed insulating layer is sufficiently roughened, and the adhesion of the conductor wiring formed on the insulating layer is reduced. It will be big.

Preferred particulate rubbers include, for example, the following (A)
It can be produced by copolymerizing a monomer composition containing the monomers (c) to (c). (A) a polyfunctional monomer having a plurality of polymerizable double bonds such as vinyl groups in one molecule; (b) a monomer having a carboxyl group or an epoxy group copolymerizable with the polyfunctional monomer (a). (Hereinafter referred to as “functional group-containing monomer”) (c) A copolymerizable monomer other than the functional group-containing monomer (b), which is copolymerizable with the polyfunctional monomer (a)

Examples of the polyfunctional monomer (a) having a plurality of polymerizable double bonds in one molecule include ethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, and trimethylolpropane tri ( (Meth) acrylate, propylene glycol di (meth) acrylate, pentaerythritol tri (meth)
Examples thereof include acrylate, pentaerythritol tetra (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, divinylbenzene, and trivinylbenzene. One of these polyfunctional polymerizable monomers can be used alone, or two or more can be used in combination.

The polyfunctional monomer (a) is used in an amount of 0.1 to 20 mol%, preferably 0.5 to 10 mol%, based on the whole monomer composition for obtaining the particulate rubber. Used. When this ratio is 0.1 mol% or more, sufficiently good developability of the insulating layer can be obtained. On the other hand, when this proportion exceeds 20 mol%, the affinity of the obtained particulate rubber for other components is lowered, the workability of the obtained composition is deteriorated, and the strength of the insulating layer after photocuring treatment is reduced. , And the adhesion of the formed plating layer becomes insufficient.

Among the functional group-containing monomers (b), specific examples of the monomer having a carboxyl group include acrylic acid,
Examples include methacrylic acid, maleic acid, fumaric acid, itaconic acid, and tetraconic acid; half esters of a dicarboxylic acid such as succinic acid and fumaric acid with an unsaturated alcohol having an addition-polymerizable group. Specific examples of the monomer having an epoxy group include glycidyl (meth) acrylate, cyclohexenoxide (meth) acrylate, allyl glycidyl ether, and vinyl glycidyl ether. These functional group-containing monomers (b)
Depending on the specific application of the obtained composition, one or more arbitrary ones can be selected and used.

The functional group-containing monomer (b) is used in an amount of 0.1 to 3 based on the whole monomer composition for obtaining the particulate rubber.
It is used in a proportion of 0 mol%, preferably 0.5 to 20 mol%. When this ratio is 0.1 mol% or more, it is ensured that the obtained insulating layer has sufficient toughness and resolution. On the other hand, when this ratio exceeds 30 mol%, the obtained insulating layer has The layers can be hard and brittle.

The copolymerizable monomer (c) used together with the polyfunctional monomer (a) and the functional group-containing monomer (b)
Various radically polymerizable monomers can be used depending on the purpose. Examples of the copolymerizable monomer include butadiene, isoprene, dimethylbutadiene, and chloroprene.
-Methylstyrene, vinyltoluene, acrylonitrile, vinyl chloride, vinylidene chloride, (meth) acrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. be able to.

The particulate rubber can be directly produced as a particulate copolymer by an emulsion polymerization method or a suspension polymerization method using a radical initiator, but the particle size and its uniformity are high. It is preferable to use an emulsion polymerization method. In the case of the emulsion polymerization method, the above polyfunctional monomer (a), the functional group-containing monomer (b), and the copolymerizable monomer (c) are subjected to radical emulsion polymerization, and a known method is used. , Washing and drying. In this case, the polymerization agents such as each monomer and radical initiator may be added all at once at the start of the reaction, or may be arbitrarily divided and added sequentially. The polymerization reaction is carried out at a temperature of 0 to 80 ° C. in a reactor from which oxygen has been removed, and operating conditions such as temperature and stirring can be arbitrarily changed during the reaction. The polymerization system may be either a continuous system or a batch system. However, as a particulate rubber of a composition for forming an interlayer insulating layer of an electronic component, for example, a particulate rubber having a low ion content, which is obtained by a method disclosed in JP-A-2-206656, is used. It is preferable that an insulating layer having good electric insulation be formed.

In the above-mentioned emulsion polymerization method, examples of the radical initiator include organic peroxides such as benzoyl peroxide, cumene hydroperoxide, paramenthane hydroperoxide and lauroyl peroxide; diazo compounds represented by azobisisobutyronitrile; An inorganic compound represented by potassium persulfate, a redox catalyst represented by a combination of an organic compound and iron sulfate, and the like are used.

The particulate rubber obtained as described above is
A step of subjecting the surface of the insulating layer formed from the composition to a surface roughening treatment in which a carboxyl group or an epoxy group is present on the surface, so that the carboxyl group or the epoxy group is present in the composition of the present invention; In the above, the reaction is selectively reacted and dissolved by the strongly oxidizing roughening treatment liquid, whereby the surface of the insulating layer is roughened. That is, the particulate rubber has a carboxyl group or an epoxy group on its surface, so that it has a good affinity for other components, and thus is sufficiently uniformly dispersed in the composition of the present invention. To be present in. Then, in the surface roughening treatment, the double bond of the copolymer constituting the particle rubber is formed by contact of the surface roughening treatment liquid having strong oxidizing property with the particle rubber present on the surface of the insulating layer. As a result of the cutting and dissolution of the copolymer in the surface-roughening treatment liquid, the particulate rubber disappears or is removed from the insulating layer, thereby forming fine irregularities on the surface of the insulating layer and roughening the surface. Is done.

Further, in the insulating layer obtained from the composition containing the above-mentioned particulate rubber, since the particulate rubber exists in a state of being uniformly dispersed, the insulating layer is exposed to light or heat-treated. The resulting shrinkage stress, the thermal stress caused by the difference in the coefficient of thermal expansion with the base material, and the like are alleviated, and as a result, the dimensional accuracy of the multilayer wiring board and the high reliability of the insulating layer can be obtained. Further, according to the composition containing the particulate rubber, the toughness of the obtained insulating layer is improved, and the occurrence of cracks can be prevented.

In the composition of the present invention, the ratio of the particulate rubber is in a range sufficient to form sufficient fine irregularities in the surface roughening treatment, specifically 1 to 100 parts by weight of the component A. It is 50 parts by weight, preferably 5 to 40 parts by weight. If this ratio is excessively high, a thin film obtained from the composition may not have sufficient developability.

In order to prepare the composition of the present invention, if no filler or pigment is added, it is only necessary to mix and stir each component in a usual manner. What is necessary is just to disperse and mix using a disperser, such as a dissolver, a homogenizer, and a three-roll mill. If necessary, filtration can be performed using a mesh, a membrane filter, or the like.

The composition of the present invention contains N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methyl Pyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol,
1-nonanol, benzyl alcohol, benzyl acetate,
Ethyl benzoate, ethyl lactate, diethyl oxalate, diethyl maleate, γ-butyrolactone, cyclohexanone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, methoxymethyl propionate, ethoxyethyl propionate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether And a high boiling point solvent such as triethylene glycol dimethyl ether and triethylene glycol methyl ethyl ether. The amount of these solvents used is
The composition can be changed depending on the use of the composition or the method of application to be used, and is not particularly limited as long as the composition can be brought into a uniform state. Preferably, the amount is 10 to 40% by weight.

The method for applying the composition of the present invention to a substrate is not particularly limited, and a general method for applying a photosensitive material can be used. In particular,
Screen printing, roll coating, bar coating, dip coating, curtain coating, spin coating and the like can be mentioned. Further, after the composition of the present invention is formed into a film, the composition can be used in close contact with a substrate using a laminator.

In the case of manufacturing a multilayer wiring board using the composition of the present invention, a thin film made of the composition of the present invention is formed on the surface of the wiring board on which the conductor wiring is formed, and this thin film is formed. Is subjected to an exposure treatment and a development treatment, for example, a through hole is formed to reach the conductor wiring, thereby forming an insulating layer in a state where the conductor wiring is exposed, and the conductor wiring is formed on the surface of the insulating layer. A series of steps of forming a new conductor wiring that conducts with the semiconductor device may be repeated once or a plurality of times. That is, an insulating layer made of the composition of the present invention is formed on the wiring board having the n-th conductive wiring formed on the surface, and the surface of the insulating layer is electrically connected to the n-th conductive wiring (n + 1).
Forming a third conductive wiring by plating or the like. Here, n is an integer of 1 or more. According to the composition of the present invention, a highly reliable, high-density, high-precision heat-resistant multilayer wiring board can be manufactured with high efficiency by such a method.

Hereinafter, a method for producing a multilayer wiring board using the composition of the present invention will be specifically described in the order of steps. (1) Thin film forming step In the thin film forming step, for example, the composition of the present invention is applied on the surface of a wiring board having conductive wiring formed on the surface of a substrate so that the conductive wiring is covered, and dried. A thin film is formed by treating and removing the solvent in the composition by heating.

Here, the material of the substrate on which the conductor wiring is formed is not particularly limited, and examples thereof include glass epoxy resin, paper phenol resin, ceramic, glass, and silicon wafer. As the application method,
For example, a spin coating method, a roll coating method, a curtain coating method, a screen printing method, an applicator method, and the like can be employed. Alternatively, the composition of the present invention may be formed on a base film and dried to form a so-called dry film, which may be laminated to a substrate by a laminator or the like to form a thin film. As the substrate film, as a film having a light transmitting property, a polyester film such as polyethylene terephthalate or polybutylene terephthalate, or a polyolefin film such as stretched polypropylene or polystyrene can be used. Here, when the base film has a light transmitting property, the thin film can be photo-cured by irradiating light through the base film.

The conditions for drying after coating vary depending on the type, blending ratio, film thickness and the like of each component in the composition of the present invention.
It takes about 40 minutes. If the drying is insufficient, the remaining solvent will cause the surface of the thin film to become sticky and reduce the adhesion of the insulating layer to the substrate. On the other hand, if drying is excessive, thermal fogging causes a reduction in resolution.
The drying of the thin film is performed using a usual device such as an oven or a hot plate. The dried film thickness of the thin film formed in the thin film forming step is, for example, 10 to 10
0 μm, and preferably 30 to 70 μm.
If the film thickness is too small, an insulating layer having a sufficient insulating property cannot be formed, while if the film thickness is too large, the resolution is lowered.

(2) Exposure Processing Step In this exposure processing step, the thin film formed on the wiring board in the thin film forming step is irradiated with ultraviolet light or visible light having a wavelength of 200 to 500 nm through a mask having a predetermined pattern. Thereby, the light irradiation area (exposure area) of the thin film is light-cured. As an exposure processing apparatus, fusion,
A contact aligner, a stepper, a mirror projector, or the like can be used. Examples of the light source used for the exposure treatment include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon gas laser, an X-ray generator, and an electron beam generator. The amount of exposure to the thin film varies depending on the type, blending ratio, film thickness, and the like of each component in the composition constituting the thin film.
It is 00 to 3000 mJ / cm ² .

(3) Heating step for accelerating the reaction In the heating step for accelerating the reaction, the thin film after the exposure treatment step is usually heated at a temperature of 70 to 140 ° C. for about 1 to 40 minutes, thereby In addition to curing by a light reaction in the processing step, the curing of the thin film by a thermal reaction is promoted. If the heating is excessive, thermal fogging causes a reduction in resolution. This heating is performed using a usual device such as an oven or a hot plate. However, since the composition of the present invention has a high photocuring rate and excellent curability, this step can be omitted.

(4) Developing Step In this developing step, the composition in the non-exposed area is dissolved and removed in a developing solution composed of an alkaline aqueous solution, and only the composition in the exposed area is left. Perform formation. Here, examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, and methyldiethylamine. Dimethylethyl alcoholamine, triethyl alcoholamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4, An aqueous solution of an alkali compound such as [3,0] -5-nonane can be used. Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methyl alcohol or ethyl alcohol or a surfactant to the aqueous solution of the above alkalis, or various organic solvents that dissolve the composition of the present invention is used as a developer. Can be. Preferred developers include sodium hydroxide, potassium hydroxide, sodium carbonate, tetramethylammonium hydroxide, and the like.
The concentration is 0.1 to 6.0% by weight, particularly preferably 0.2 to 6.0% by weight.
It is a 3.0% by weight aqueous solution. Examples of the developing method include a puddle method, a dipping method, a paddle method, and a spray developing method. After the development processing, for example, washing with running water is performed for 0.1 to 20 minutes, and drying is performed using an air gun or the like or in an oven. In the development process, a part of the thin film is removed to form, for example, a through hole, and a part of the conductor wiring on the substrate surface is exposed. As a result, an insulating layer having a photo via hole is formed.

(5) Thermosetting / Post-exposure Step The composition of the present invention has both photocurable and thermosetting properties. By performing the exposure process,
Curing of the insulating layer having photovia holes is further promoted. Therefore, this thermal curing / post-exposure step is unnecessary when the insulating layer is in a sufficiently cured state. The heat curing treatment is performed using a hot plate, an oven, an infrared oven, or the like, at a temperature condition under which the insulating layer does not undergo thermal deterioration, preferably at 150 to 180 ° C. for an appropriate time of about 30 minutes to 5 hours. Will be Also, the post-exposure processing
Using the same light source and device as those used in the exposure processing step, the exposure can be performed, for example, at an exposure amount of 100 to 3000 mJ / cm ² .

(6) Flattening Step This flattening step is an optional step for flattening, for example, by polishing an insulating layer formed on a non-flat substrate. Thereby, the accuracy of circuit processing in the case of forming conductor wiring on the surface of the insulating layer can be improved. Here, as the polishing means, for example, a polishing means such as a baffle, a nylon brush, a belt sander or the like can be used.

(7) Step of Forming Through Hole This step of forming a through hole is performed by a numerically controlled drill when a through hole is required to achieve insertion of a component or connection with another wiring board, ie, interlayer connection. This is a step of mechanically punching using a machine or the like. According to the manufacturing method using the composition of the present invention, interlayer connection can be performed by a photo via hole,
This through hole forming step is an optional step performed only when necessary.

(8) Surface Roughening Step In this surface roughening step, the surface of the insulating layer is roughened in order to improve the adhesion of the conductor wiring formed on the surface of the insulating layer. The surface is roughened by the processing liquid. As the surface roughening treatment solution, an alkaline treatment solution such as an aqueous solution of potassium permanganate, an aqueous solution of potassium permanganate and sodium hydroxide, a mixed acid of chromic anhydride and sulfuric acid,
Other materials having strong oxidizing properties are used. Among these, an aqueous solution of potassium permanganate and sodium hydroxide is particularly preferred. The treatment method is from room temperature to 90 ° C.
The insulating layer may be immersed in the processing solution heated to a temperature of 5 to 120 minutes. After the surface-roughening treatment, it is necessary to neutralize with a weak acid aqueous solution such as oxalic acid if necessary, and then sufficiently wash with running water. By the surface roughening process, the surface of the insulating layer, the side wall surface of the photo via hole, and the side wall surface of the through hole become, for example, 0.01 to 10
It becomes a rough surface having irregularities of μm, and a strong adhesion to the copper plating layer constituting the conductor wiring is exerted by the anchor effect.

(9) Catalyst Treatment Step This catalyst treatment step is a step in which a plating catalyst serving as a deposition nucleus when performing electroless copper plating in the next step is carried on the surface of the insulating layer and the inner wall surface of the hole. . Here, as the plating catalyst, for example, a metal colloid such as palladium can be used. By immersing the insulating layer in various known treatment liquids in which the metal colloid is dispersed in a medium, the catalyst is supported. Is achieved. In addition,
A plating catalyst can be contained in the composition of the present invention, and in this case, this step can be omitted.

(10) Step of Forming New Conductor Wiring In the step of forming a new conductor wiring, for example, electroless copper plating is performed to form a new conductor wiring on the substrate surface via photo via holes and through holes. New conductive wiring (second conductive wiring) on the surface of the insulating layer while realizing electrical connection with the conductive wiring (first conductive wiring)
Is a step of forming As a method for forming a new conductor wiring, for example, the following methods can be mentioned.

Method A copper plating layer is formed by performing electroless copper plating on the entire surface of the insulating layer on which the catalyst is supported, and if necessary, a desired copper plating is performed by electrolytic copper plating using the copper plating layer as an electrode. A copper metal layer having a thickness is formed, a resist pattern is formed on the copper metal layer, and then the copper metal layer is etched to form a conductor pattern. Here, in addition to the region where the second conductor wiring is formed, the resist pattern is located at the position of the interlayer connection photovia hole where the interlayer connection conductor between the first conductor wiring and the second conductor wiring is formed. That is, it is also formed in a region where a conductor land is to be formed. It is preferable that the diameter of the conductor land is larger than the diameter of the photo via hole in consideration of a displacement error. The resist pattern is usually formed by photolithography using a photoresist. The etching of the copper metal layer is performed using an ammonium persulfate aqueous solution or an ammonia complex-based etchant. After the copper metal layer is etched, the resist pattern is stripped and removed by a predetermined method. The photoresist only needs to have the required resolution and resistance to the etchant, and can be removed later. In this way, the second conductor wiring that is electrically connected to the first conductor wiring on the surface of the substrate is formed on the insulating layer.

Method: After forming a resist pattern in a region other than a region where a new conductor wiring is to be formed on the surface of the insulating layer carrying the catalyst, electroless copper plating and, if necessary, electrolytic copper plating are performed. As a result, a new conductor wiring is formed on the surface of the insulating layer, a copper plating layer is formed on the inner wall surface of the photo via hole, and the resist pattern is peeled off. Also in this method, it is preferable that the width of the conductor wiring is larger than the diameter of the photo via hole.

Method A photosensitive resin composition containing no plating catalyst is applied to the entire surface of the insulating layer supporting the catalyst to form a coating layer, and the coating layer is exposed to light through a pattern mask and developed. As a result, a photovia hole is formed in the coating layer, and the coating layer portion that is to be the second conductor wiring following the photovia hole is removed, and only electroless copper plating is performed thereon. Also in this method, it is preferable that the width of the conductor wiring is larger than the diameter of the photo via hole. The thickness of the coating layer is preferably the same as or slightly larger than the thickness of the copper metal layer formed by copper plating. According to this method, the second conductor wiring to be formed is formed in the portion where the covering layer is removed, and the insulating film of the remaining covering layer remains on the insulating layer. Since the thickness of the layer is generally similar, the outer surface can have excellent flatness. The composition of the present invention can be used as a photosensitive resin composition for forming the above-mentioned coating layer.

By repeating the above steps (1) to (10), a further multilayer can be obtained. In this case, when the step (10) of forming a new conductor wiring is performed, a multilayer can be formed by combining the methods. Note that it is preferable to perform post-baking after forming the conductor wiring on the surface of the insulating layer that is the uppermost layer of the multilayer wiring board, from the viewpoint of improving the adhesion between the insulating layer and the conductor wiring. Since the insulating layer other than the uppermost layer and the conductor wiring related thereto are heated in the subsequent heating step of forming the insulating layer, it is not particularly necessary to perform post-baking as a single step.

[0073]

EXAMPLES Examples of the present invention will be specifically described below, but the present invention is not limited to these examples. Also,
Unless otherwise specified, "parts" refers to "parts by weight"
“%” Indicates “% by weight”.

[Component A] The following five components were prepared. A1: Cresol novolak resin [m-cresol: p
-Cresol = 6: 4 (molar ratio), weight average molecular weight Mw
= 11000] A2: Cresol xylenol novolak resin [m-cresol: p-cresol: 3,5-xylenol =
6: 3: 4 (molar ratio), weight average molecular weight Mw = 800
0] A3: Cresol novolak resin [m-cresol: p
-Cresol = 6: 4 (molar ratio), weight average molecular weight Mw
= 1400] A4: Poly (p-vinylphenol) [manufactured by Maruzen Kakka, weight average molecular weight Mw = 3000] A5: Poly (brominated p-vinylphenol) [Marukalinker MB manufactured by Maruzen Kabushiki, weight average molecular weight Mw = 40
00] Among them, A3 has a weight average molecular weight Mw of 2000
Less than the phenolic resin, which does not satisfy the conditions of the present invention.

[Component B] The following two amino resins were prepared. B1: Hexamethoxymethylated melamine B2: Tetramethoxymethylated glycoluril

[Component C] The following two oxetane structure-containing compounds were prepared. C1: 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene C2: Anion copolymer of 3-methyl-3-glycidyloxymethyloxetane and 3-phenyl-3-glycidyloxymethyloxetane ( Number average molecular weight Mn = 100
00)

[D Component] The following four types of liquid rubber were prepared. D1: Butadiene-acrylonitrile-methacrylic acid copolymer [butadiene: acrylonitrile: methacrylic acid = 87: 6: 7 (molar ratio), number average molecular weight Mn = 600
0, glass transition point Tg-55 ° C.] D2: butadiene-acrylonitrile-hydroxyethyl acrylate copolymer [butadiene: acrylonitrile: hydroxyethyl acrylate = 61: 27: 12
(Molar ratio), number average molecular weight Mn = 8000, glass transition point Tg-80 ° C.] D3: butadiene-acrylonitrile-methacrylic acid copolymer [butadiene: acrylonitrile: methacrylic acid = 87: 6: 7 (molar ratio), number Average molecular weight Mn = 70
0, glass transition point Tg-100 ° C. or lower] D4: Butadiene-acrylonitrile-methacrylic acid copolymer [butadiene: acrylonitrile: methacrylic acid = 87: 6: 7 (molar ratio), number average molecular weight Mn = 120
Among them, D3 does not satisfy the conditions of the present invention because its number average molecular weight Mn is as small as 700, and D4 has a number average molecular weight Mn of 120,000. Is too large to satisfy the conditions of the present invention.

[Component E] The following three photopolymerization initiators were prepared. E1: 2,4-trichloromethyl (4′-methoxyphenyl) -6-triazine E2: 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine E3: diphenyliodonium-9,10-dimethoxyanthracene sulfonate

[Additive F] The following four additives were prepared. F1: Silica particles “TS100” (manufactured by Degussa) F2: Calcium carbonate “Softon 2200” (manufactured by Bihoku Powder Co., Ltd.) F3: Particulate rubber (butadiene-acrylonitrile-methacrylic acid-divinylbenzene cross-linked copolymer [butadiene: acrylonitrile : Methacrylic acid: divinylbenzene = 76: 20: 2: 3 (weight ratio)] F4: Epoxy resin "Epicoat 828" (manufactured by Yuka Shell Epoxy)

[Solvent] The following three kinds of organic solvents were prepared. MMP: methyl 3-methoxypropionate PGMEA: propylene glycol monomethyl ether acetate EEP: ethyl 3-ethoxypropionate

<Examples 1 to 7 and Comparative Examples 1 to 6 (Preparation of Composition)> According to the formulation shown in Table 1 below, the components A to
E component and blend additives and solvents as needed,
Each of the obtained blends was mixed and stirred with a Henschel mixer to prepare a photosensitive resin composition.

[0082]

[Table 1]

<Evaluation of Composition Performance and Production of Multilayer Wiring Board> (1) Preparation and Evaluation of Photosensitive Characteristic Evaluation Test Board A plate made of glass epoxy resin having a copper metal layer formed on one surface is used as a test piece. The composition prepared in each of Examples 1 to 7 and Comparative Examples 1 to 6 was applied as a sample on the one surface thereof using a spin coater, and dried at 90 ° C. for 10 minutes in a hot air oven. Then, a thin film having a thickness of about 50 μm after drying was formed.

Each of the test pieces obtained here had a diameter of 25 μm and 50 μm, respectively, with respect to the thin film.
m, 75 μm, 100 μm, 150 μm and 200 μ
Exposure was performed through a test film mask on which a perforated pattern of m was formed. Exposure process, using an exposure apparatus (manufactured by Oak Seisakusho "HMW-321B") was performed with an exposure amount of 1000 mJ / cm ² in contact. After the test piece after the exposure processing is heated at 120 ° C. for 5 minutes,
Developing treatment was carried out for 180 to 600 seconds by showering with a 0% aqueous sodium hydroxide solution (shower pressure: 2 kg · cm ⁻² ) to form an insulating layer having a through hole reaching the copper metal layer, that is, a photo via hole. Thereafter, each of the test pieces on which the insulating layer was formed was washed with water and dried.

The resolution of each of the test pieces obtained here was evaluated. For the evaluation of resolution, photolithography was performed so that photovia holes of various sizes were formed, and as a result, the smallest of the photovia holes in which it was confirmed that the copper metal layer was exposed was confirmed. The measurement was performed by measuring the diameter of the object (this is referred to as “the minimum diameter of the through hole”). The smaller the value of the minimum diameter of the through hole, the better the resolution. Table 2 shows the results.

Next, each of the test pieces on which the insulating layer was formed was cured by heating in a hot air oven at a temperature of 150 ° C. for 60 minutes. Thereafter, the thermally cured test pieces were maintained at a temperature of 65 ° C. The surface of the insulating layer is roughened by immersing it in a potassium permanganate-sodium hydroxide aqueous solution (potassium permanganate concentration 3%, sodium hydroxide concentration 2%) for 10 minutes. For 5 minutes at room temperature in a 5% oxalic acid aqueous solution for neutralization treatment, and further sufficiently washed with water.

Further, each of the test pieces was immersed in a palladium chloride-based catalyst solution at room temperature for 6 minutes so that the plating catalyst was supported on the surface of the roughened insulating layer and the inner surfaces of the through holes. The plating catalyst was activated by immersion in an activating solution at room temperature for 8 minutes. Thereafter, each of the test pieces was washed with water, and then subjected to electroless copper plating at room temperature for 20 minutes. In this treatment, "OPC Process M Series" (manufactured by Okuno Pharmaceutical Co., Ltd.) was used as a catalyst solution, a catalyst activation solution and an electroless copper plating solution.
Next, a copper sulfate-sulfuric acid aqueous solution (copper sulfate concentration 210 g / L,
Using an electrolytic copper plating solution having a sulfuric acid concentration of 52 g / L and a pH of 1.0), electrolytic copper plating is performed at a current density of 1.0 mA / dm ² to insulate a copper metal layer having a total thickness of about 20 μm. The test piece was formed over the entire surface of the layer and then heat treated at 150 ° C. for 2 hours.

Cuts are formed at 1 cm intervals on the surface of these test pieces, and peeled off from the end faces with a peel tester, so that the peel strength of the copper metal layer (JIS C
6481) was measured. The results are shown in FIG. This peel strength is the mode value after peeling off 10 cm.

(2) Measurement of glass transition point A release agent is applied to one surface of a polyethylene terephthalate film, and a 50 μm-thick thin film is formed on one surface of the polyethylene terephthalate film by the same method as in the above (1). 1 for
After exposure at an exposure of 000 mJ / cm ² ,
The film was formed by heating each of the sample compositions by heating at 4 ° C. for 4 hours, and peeled from the polyethylene terephthalate film to obtain a test film. About this test film, the elastic modulus measurement device "Rheo Vibron RHE
O-1021 "(Orientec)
The change in elastic modulus was measured at Hz, and the peak top of tan δ was determined as the value of the glass transition point. Table 2 shows the results.

(3) Substrate Warp Test Each sample composition was dried on an upper surface of a rectangular glass epoxy substrate having a length of 1 cm, a width of 5 cm and a thickness of 0.1 mm using an applicator to a thickness of 50 μm. In this state, the substrate is placed on a horizontal table, and one end of the long side of the substrate is fixed to the table. In this state, the sample composition is measured for the glass transition point in the above (2). Curing is performed under the same conditions as in the case of above, and the degree of warpage generated on the substrate due to the curing shrinkage of the sample composition generated at this time is determined by the distance (gap distance) at which the other end on the long side of the substrate separates from the upper surface of the table. It was measured. The larger the value of the gap distance is, the larger the warpage of the substrate is, and thus the more the material has a large curing shrinkage. Table 2 shows the results.

(4) Measurement of Water Absorption Rate Each of the sample compositions was applied to a 4-inch diameter silicon wafer having a measured weight w ₀ by spin coating, dried in a hot air oven at 90 ° C. for 10 minutes, and dried. A thin film having a thickness of about 50 μm was formed, and then the entire surface was exposed with a contact aligner at an exposure amount of 1000 mJ / cm ² , and the test substrate after this exposure treatment was heated at 150 ° C. for 4 hours. The weight w ₁ of the substrate (sample before immersion) was measured. Subsequently, the test substrate is immersed in ultrapure water at room temperature for 24 hours, and then the test substrate (sample after immersion) is sufficiently wiped off with a filter paper.
The weight w ₂ was measured. Then, the water absorption (%) was determined according to the following equation. Table 2 shows the results. Water absorption = (w ₁ −w ₀ ) ÷ (w ₂ −w ₀ ) × 100

[0092]

[Table 2]

[0093]

The radiation-sensitive resin composition according to the present invention comprises:
By containing an oxetane structure-containing compound having an oxetane structure in the molecule and a specific liquid rubber as essential components together with a specific alkali-soluble resin and an amino resin, it is possible to form a small diameter photo via hole with high accuracy. It has a resolution, can be developed with an alkaline aqueous solution, and can form an insulating layer excellent in plating solution resistance and adhesion of conductor wiring,
The film of the composition has low water absorption and a small degree of curing shrinkage, and therefore, by using the composition,
A highly reliable multilayer wiring board can be manufactured efficiently.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI G03F 7/004 501 G03F 7/004 501 // H05K 3/46 H05K 3/46 TE (72) Inventor Hozumi Sato Central Tokyo 2-11-24 Tsukiji, Ward Inside JSR Co., Ltd.

Claims (1)

[Claims] 1. A radiation-sensitive resin composition comprising the following components A to E: [Component A] alkali-soluble resin [Component B] cross-linking agent [Component C] a compound having an oxetane structure represented by the formula (1) in the molecule: [D component] rubber [E component] radiation polymerization initiator