JPH1160896A - Radiation-sensitive resin composition and cured film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a radiation-sensitive curable compsn. which forms an insulating layer which has excellent resolving properties, can be developed with an aq. alkali soln., and has high resistances to plating and heat and a low water absorption by compounding an alkali-soluble resin with a crosslinker, a compd. having at least one thiiranyl group in the molecule and a radiation polymn. initiator. SOLUTION: This compsn. comprises 30-95 wt.% alkali-soluble resin (A), 1-60 wt.% amino resin (B) having a plurality of active methylol groups in the molecule as the crosslinker, 1-50 wt.% compd. (C) having at least one thiiranyl group in the molecule and prepd. by substituting the oxygen atom of the oxirane ring of an oxirane-contg. compd. with a sulfur atom, and 0.01-5 wt.% radiation polymn. initiator (D), the sum of all the above ingredients being 100 wt.%. If necessary, a liq. rubber, a particulate rubber or the like is incorporated into the compsn. Polyvinylphenol having a wt. average mol.wt. of 200 or higher and/or another phenol resin is used as ingredient A.

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. And a radiation-sensitive resin composition.

[0002]

2. Description of the Related Art Recently, there is a demand for higher density printed wiring boards, and a demand for a multilayer wiring board in which a plurality of conductive wiring layers are stacked via an insulating layer is increasing. 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. By doing so, a through-hole called a through-hole penetrating the whole of the laminated body is formed by a drill or the like on the multilayer laminated body, and the inner wall surface of the through-hole is subjected to a plating process, and 2. Description of the Related Art There is known a method of manufacturing by forming a plating layer for conducting two superposed conductive wires (hereinafter, also referred to as a 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 a wiring misalignment occurs due to shrinkage of the base material of the wiring board. There are problems that it is difficult to reduce the diameter of the corresponding through hole and 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. When a multilayer wiring board is manufactured by this stacking method, in order to conduct the two conductor wirings stacked through the insulating layer, a through hole is formed and plating is performed in the same manner as in the case of the lamination press method. In addition to the application method, 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 of forming a through hole or a via hole in an 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 known. Have been. However, these methods are not preferable methods in terms of productivity such that a plurality of holes cannot be formed at the same time or require many steps, and are not satisfactory methods in terms of processing accuracy. .

As a means for overcoming such inconvenience, a method has been proposed in which a photosensitive resin composition is used as a material for forming an insulating layer interposed between conductor wiring layers, and a through hole is formed in the insulating layer by photolithography. ing.
According to this method, a plurality of through-holes can be formed at the same time, so that high production efficiency can be obtained in the production of a multilayer wiring board, and moreover, the through-holes can be formed with higher precision than the conventional method. This is advantageous in manufacturing a multilayer wiring board having a fine wiring pattern. Regarding such a multilayer wiring board, a multilayer wiring board which is formed on an insulating layer made of a photosensitive resin composition and which is later subjected to a plating treatment to form a through hole called a photo via hole for achieving electrical connection is provided. A method of manufacturing by a stacking method has been proposed (see JP-A-4-148590). An application example using a photosensitive epoxy resin as a photosensitive resin composition for forming such an insulating layer has also been proposed (see Japanese Patent Application Laid-Open No. Hei 5-273753).

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 a 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 a substance used for forming the conductor wiring, for example, an electroless copper plating solution. (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 the insulating layer having the roughened surface has an anchor effect. Thereby, the adhesion of the conductor wiring to the insulating layer becomes large. (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]

To achieve the above object, the present invention provides a radiation-sensitive resin composition containing the following components A to D and a cured film obtained by curing the composition. provide. [Component A] alkali-soluble resin [Component B] cross-linking agent [Component C] a compound containing at least one thiyanyl group in one molecule [Component D] radiation polymerization initiator In the present invention, radiation-sensitive is radiation-sensitive. It refers to the property that can be cured. Radiation includes visible light, ultraviolet light, far ultraviolet light, X-rays, and electron beams.

The radiation-sensitive resin composition containing the above components A to D of the present invention has compatibility or high affinity with components A, B and C in order to further enhance the adhesion. It is practically more preferable to mix rubbers. In particular, liquid rubber having a number average molecular weight in the range of 1,000 to 100,000 and a glass transition point Tg of -20 ° C. or less is very suitably used.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the radiation-sensitive resin composition of the present invention will be described in detail. [Component A] Typical examples of the alkali-soluble resin of the component A include polystyrene-equivalent weight average molecular weight of 200 or more, preferably 2000, measured by gel permeation chromatography (GPC).
Phenol resins other than polyvinylphenol having a weight average molecular weight of 200 or more, preferably 2,000 or more in terms of polystyrene as described above (hereinafter, referred to as a specific phenol resin) can be exemplified.

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. Although the molecular weight of the polyvinyl phenol is not particularly limited, the weight average molecular weight is 200 or more, particularly in the range of 200 to 20,000, from the viewpoint of resolution, developability, plating solution resistance, and the like in the obtained insulating layer. Are preferred.

A typical example of the specific phenol resin used as the component A is a novolak resin. The novolak resin includes, for example, a phenol compound and an aldehyde compound, preferably a phenol compound 1
It is obtained by addition condensation using an acid catalyst in a ratio of 0.7 to 1 mol of the aldehyde compound to the mol. Here, specific examples of the phenol compound include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol and p-cresol.
-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,
Examples include pyrogallol, phlorogrisinol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol and the like.

Specific examples of the aldehyde compound include formaldehyde, paraformaldehyde, furfural,
Benzaldehyde, nitrobenzaldehyde, acetaldehyde and the like can be mentioned. As the acid catalyst,
For example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid and the like are used. Further, a preferred specific phenol resin is obtained by reacting a phenol compound selected from phenol, o-cresol, m-cresol and p-cresol with an aldehyde compound selected from formaldehyde and paraformaldehyde. 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 phenol or the specific phenol resin may be used alone, or two or more of them may be used in combination. It is preferable to use polyvinyl phenol and a specific phenol resin in combination. In the composition of the present invention, the component A is used in such a content that the obtained insulating layer has sufficient alkali solubility. The content ratio is usually in the range of 30 to 95% by weight based on the total amount of the components A to D. If the content is too low, the resulting thin film of the composition will not have sufficient developability with an aqueous alkaline solution, while
If it is too large, the proportion of other components is relatively limited,
The resulting insulating layer is inconvenient because the toughness, heat resistance and plating solution resistance are insufficient. The preferred content is 40 to 9
0% by weight, and particularly preferably 50 to 85% by weight for practical use.

[Component B] The crosslinking agent of the component B acts as a curing agent component which reacts with the alkali-soluble resin of the component A to form a crosslinked structure. A typical example of the crosslinking agent is an amino resin having a plurality of active methylol groups in one molecule. As such an amino resin, for example,
Nitrogen-containing compounds having a plurality of active methylol groups in one molecule, such as (poly) methylolated melamine, (poly) methylolated glycoluril, (poly) methylolated benzoguanamine, (poly) methylolated urea, and the like. it can. The methylol group may be a compound in which a hydrogen atom of a hydroxyl group is substituted by an alkyl group such as a methyl group or a butyl group, or may be a mixture of a plurality of such substituted compounds. Also, B
The components may include oligomer components formed by partially condensing these compounds.

Specific examples of the amino resin include hexamethoxymethylated melamine (“Cymel 300” manufactured by Mitsui Cyanamid Co., Ltd.) and tetrabutoxymethylated glycoluril (“Cymel 1” manufactured by Mitsui Cyanamid Co., Ltd.)
170 "), a product of the my coat series, a product of the UFR series, and the like. These amino resins can be used alone or in combination of two or more. A particularly preferred B component is hexamethoxymethylated melamine.

In the composition of the present invention, it is necessary that the proportion of the component B is in such a range that a thin film of the composition can be sufficiently cured by the action of a photopolymerization initiator and heat. , And 1 to 60% by weight based on the total amount of the components A to D. If the content is too small, the resulting insulating layer may have insufficient toughness, heat resistance and plating solution resistance, while if the content is too large, the thin film formed by the resulting composition may not be sufficiently developed. It may not have the property. The content of the component B is preferably 3 to 50% by weight, and particularly preferably 5 to 30% by weight.

[Component C] The compound containing a thiiranyl group used as the component C in the present invention is a compound having one or more thiiranyl groups in the molecule. The compound may have a functional group other than a thiiranyl group in the molecule. The molecular weight is not particularly limited, but is usually 70 to
It is in the range of 20,000. Thiiranyl group-containing compounds are synthesized exclusively by replacing the oxygen atom of the oxirane ring in the oxirane-containing compound with a sulfur atom,
The method is described in, for example, JMCharlesworth J. Polym. S
c. Using thiocyanate according to the method shown in Polym. Phys. 17 329 (1979), and RD Schuetz et al.
l., J. Org. Chem. 26 3467 (1961), etc., using thiourea. Also,
Synthetic methods from cyclic carbonates are also described in S. Seales et al.
J. Org. Chem., 27 2832 (1962).

Examples of the thiirane compound used in the present invention include Tabl in M. Sander, Chem. Rev. 66 297 (1966).
thiirane compounds shown in eI and, for example, glycidyl acrylate, glycidyl methacrylate,
3,4-epoxycyclohexyl acrylate, 3,4
-Epoxycyclohexyl methacrylate, and glycidyl ether type epoxy resins represented by these polymers or other compounds having a polymerizable two bond and copolymer, bisphenol type epoxy resin, novolak type epoxy resin, cresol novolak type epoxy resin, etc. Kind,
The oxygen atom in the oxirane ring of the oxirane ring-containing compound such as glycidyl ester type epoxy resin, aromatic glycidylamine type epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, liquid rubber modified epoxy resin, etc. Thiirane compounds substituted with a sulfur atom can be mentioned. In order to obtain a good crosslinked structure, of these thiirane compounds, a compound having two or more thiylanyl groups in a molecule is preferably used.

The content of the compound containing a tyranyl group is usually 1 to 50% by weight based on the total amount of the components A to D. If this ratio is too low, the resulting insulating layer will not have a sufficiently low water absorption and the degree of shrinkage upon curing will not be sufficiently small. On the other hand, if this ratio is too large, a thin film of the obtained composition may not have sufficient developability. The preferred content of the compound containing a tyranyl group is 5 to 40% by weight, and particularly preferably 10 to 30% by weight.

[D Component] As the radiation polymerization initiator, which is the D component of the composition of the present invention, those generally known as cationic photopolymerization initiators are preferable. For example, a diazonium salt such as "ADEKA ULTRASET" PP-33 "
[Asahi Denka Kogyo Co., Ltd.], a sulfonium salt “OP
TOMER SP-150 "," OPTOMER SP
-170 "," OPTOMER SP-171 "(manufactured by Asahi Denka Kogyo Co., Ltd.), and a metallocene compound" IRGA
CURE261 "(manufactured by Ciba Geigy), triazine compounds" triazine B "," triazine PMS ",
"Triazine PP" [manufactured by Nihon SiberHegner Co., Ltd.]
Are commercially available.

The mixing ratio of the photopolymerization initiator in the composition of the present invention is usually 0.01 to 5 relative to the total of components A to D.
% By weight, more preferably 0.02% by weight.
~ 2% by weight. If the proportion is too small, the obtained insulating layer will have a remarkable decrease in sensitivity due to the influence of the surrounding environment such as oxygen, while if it is too large, the compatibility with other components will be poor, and the storage stability of the composition will decrease. I do.

[Other Components] In addition to the above-mentioned components A to D, various optional components can be added to the composition of the present invention, if necessary. Any of the components is blended within a range that does not impair the purpose of the present invention. As a preferable compounding component of the liquid rubber , the number average molecular weight is 1,000 to
100,000, preferably 1,000 to 60,00
0. By containing the liquid rubber, the composition of the present invention has good adhesion to the insulating layer of the conductor wiring formed by the plating treatment, and particularly, sufficiently high adhesion can be obtained even at a high temperature.

The liquid rubber must have a high compatibility or affinity with the A component, the B component, the C component and the D component, and a rubber having a low compatibility or affinity with these components is used. In such a case, the resulting composition may have high tackiness and may be difficult to handle. Examples of suitable liquid rubbers include various known synthetic rubbers. Since high compatibility with the component A and the like can be obtained, 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 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, and the polymerization method is also Any of a batch system, a batch system, and a continuous system may be used. 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. According to the method disclosed in Japanese Patent No. 74908, a liquid rubber having a low content ratio of an ionic component can be obtained. The proportion of the liquid rubber in the composition of the present invention is usually 1 to 40% by weight, preferably 5 to 25% by weight based on the total amount of the components A to D.

Particulate Rubber As a component for improving the adhesion of the insulating layer obtained from the composition of the present invention to the conductor wiring, a particulate rubber comprising a crosslinked polymer having a functional group on the particle surface can be mentioned. The functional group of the particulate rubber is particularly preferably a carboxyl group and / or an epoxy group. The average particle size of the particulate rubber is in the range of 0.01 to 20 μm, preferably 0.01 to 5.0 μm. For details of the particulate rubber, reference can be made, for example, to JP-A-4-15830. When this particulate rubber is added, the surface of the insulating layer becomes sufficiently roughened in the step of roughening the insulating layer obtained from the composition of the present invention described later, and is formed on the insulating layer. The adhesion of the conductor wiring becomes large.

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.

Specific examples of the monomer having a carboxyl group among the functional group-containing monomers (b) 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. As the particulate rubber of the composition for forming the interlayer insulating layer of the electronic component, for example, a particulate rubber having a low ion content, obtained by the method disclosed in JP-A-4-15830, specifically It is preferable to use a particulate rubber having a content of metal ions such as sodium and potassium of 200 ppm or less, whereby an insulating layer having good electric insulation can 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 particulate rubber, since the particulate rubber is present 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 proportion 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. 50 parts by weight are added. The preferred amount is 3-4
0 parts by weight. If this ratio is excessive, the resulting thin film of the composition may not have sufficient developability.

Other Optional Ingredients The composition of the present invention may contain an adhesion aid for improving the adhesiveness to a 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)
Ethyltrimethoxysilane and the like can be mentioned, and the mixing ratio is preferably 2 parts by weight or less per 100 parts by weight of the total amount of the components A to D.

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 moisture-resistant pigments such as alumina white, clay, barium carbonate, and barium sulfate; inorganic materials such as zinc white, lead white, graphite, lead red, ultramarine blue, navy blue, titanium oxide, zinc chromate, red iron oxide, and carbon black 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. These additives are used in an amount not to impair the object of the present invention, and preferably in an amount of 50% by weight or less of the total of the components A to D.

[Preparation of Composition] In order to prepare the composition of the present invention, when no filler or pigment is added, it is only necessary to mix and stir the respective components by a usual method. When adding a dissolver, a homogenizer,
What is necessary is just to disperse and mix using a disperser, such as 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.

[Use of Composition] The method of applying the composition of the present invention to a substrate is not particularly limited, and a general method of applying a photosensitive material can be used. Specific examples include a screen printing method, a roll coating method, a bar coating method, a dip coating method, a curtain coating method, and a spin coating method. Also,
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. After the composition of the present invention is applied to a substrate by the above method, it is dried, irradiated with ultraviolet rays, and further heated to form a cured film. Here, the drying conditions, ultraviolet irradiation conditions, and heating conditions are the same as those described in (1) a thin film forming step, (2) an exposure processing step, and (3) a heating step for promoting a reaction, respectively. The cured film of the present invention is insoluble in an aqueous alkaline solution. Here, the term “insoluble in an aqueous alkali solution” means that 180% aqueous solution of tetramethylammonium hydroxide at 20 ° C.
It means that the residual film ratio after dipping for ~ 300 seconds is 90% or more.

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 this thin film forming step, for example, the composition of the present invention is applied onto the surface of a wiring board having conductive wiring formed on the surface of a substrate so as to cover the conductive wiring, A thin film is formed by drying 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-reinforced phenol resin, ceramic, glass, and silicon wafer. As a coating method, for example, a spin coating method, a roll coating method, a curtain coating method, a screen printing method, an applicator method, or the like can be adopted. 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, a translucent 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 contained in the composition of the present invention.
It takes about 0 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 100.
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. On the other hand, if the film thickness is too large, the resolution will decrease.

(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. Then, the light irradiation area (exposure area) of the thin film is light-cured. As an exposure processing apparatus, a 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 of each component in the composition constituting the thin film, the mixing ratio, the film thickness, and the like.
3000 mJ / cm2.

(3) Heating step for accelerating the reaction In the heating step for accelerating the reaction, the thin film after the exposure 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 the 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. Dimethanol / ethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4 .3.0] -5-nonane. 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.
An aqueous solution having a concentration of 0.1 to 6.0% by weight, particularly 0.2 to 3.0% by weight.
A 0% by weight aqueous solution is preferred.

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.
The drying is carried out for about one minute, and dried 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 photo-curing 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 numerical control type drill when a through hole is required to insert a component or to connect to another wiring board, that is, to achieve 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. Examples of the surface roughening treatment liquid include alkaline treatment liquids such as an aqueous solution of potassium permanganate, a mixed aqueous solution of potassium permanganate and sodium hydroxide, a mixed acid of chromic anhydride and sulfuric acid, and other substances having strong oxidizing properties. Is used. Among these, a mixed aqueous solution of potassium permanganate and sodium hydroxide is particularly preferred. As a treatment method, the insulating layer may be immersed in a treatment solution heated to room temperature to 90 ° C. for 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 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 are reduced to, for example, 0.0%.
It becomes a rough surface state having an uneven shape of 1 to 10 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,
In the composition of the present invention, a plating catalyst can be contained, 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, an electroless copper plating process 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, by performing 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. Thus, a new conductor wiring is formed on the surface of the insulating layer, and 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 carrying 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. Also, the thickness of the coating layer is the same as the thickness of the copper metal layer by copper plating,
It is preferable that it is slightly larger. According to this method,
The formed second conductor wiring is formed in the portion where the coating layer is removed, and the insulating film of the remaining coating layer remains on the insulating layer, and the thickness of the remaining coating layer and the copper metal layer is reduced. Since the values are 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 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.

[0062]

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 kinds of alkali-soluble resins 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: Poly (p-vinylphenol) [manufactured by Maruzen Kakka, weight average molecular weight Mw = 3000] A4: Poly (brominated p-vinylphenol) [manufactured by Maruzen Kakka, trade name “Marcalinker MB”, weight average molecular weight] M
w = 4000]

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

[Component C] The following two compounds were prepared as the thiyanyl group-containing compound. C1: 100 g (1.029 mol) of potassium thiocyanate was dissolved in 400 mL of methanol in a 1 L flask, and dissolved at 40 ° C.
Kept. Glycidyl ester type epoxy resin: Epicoat 191P (made by Yuka Shell Epoxy)
A solution of 100 g (epoxy equivalent: 0.588 mol) dissolved in 400 mL of methanol was added dropwise over 30 minutes, and 20 g of potassium thiocyanate / 100 mL of methanol was further added to continue the reaction. The reaction liquid became emulsified about 2 and a half hours after the start of the addition of the epoxy resin,
After a lapse of time, the reaction was stopped because a precipitate (gel) was confirmed. The reaction solution was poured into 500 mL of water,
The organic layer was extracted with mL of methylene chloride, filtered, dried over magnesium sulfate, and then methylene chloride was removed to obtain 98 g of a product. This product is designated as C1.

C2: 50 g of 49 g (0.5 mol) of sulfuric acid
Add 0 mL of distilled water and add 79 g (1 mol) of thiourea
Was dissolved at 50 ° C. in a 1 L flask. To this, 828154 g (0.8 mol of epoxy equivalent) of Epicoat was added over 1 hour, and the reaction was further continued at 50 ° C. for 5 hours. During the reaction, the thyuronium salt precipitated as a white solid in the reaction solution. After the precipitate was separated by filtration, the precipitate was further washed with 1 L of water to remove excess acid. Sodium carbonate aqueous solution (Na2CO3 1mol / 750mL) after ventilation drying of thyuronium salt
The mixture was reacted at 60 ° C. for 6 hours, and the precipitated white solid was collected by filtration. The white solid was washed with methanol and dried to obtain 155 g of a product. This is C2.

[D Component] The following three photopolymerization initiators were prepared. D1: 2,4-trichloromethyl (4′-methoxyphenyl) -6-triazine D2: 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine D3: diphenyliodonium-9,10-dimethoxyanthracene sulfonate

[Additive 1] As the E component, the following three kinds of liquid rubbers were prepared. E1: Butadiene-acrylonitrile-methacrylic acid copolymer [butadiene: acrylonitrile: methacrylic acid = 87: 6: 7 (molar ratio), number average molecular weight Mn = 600
E2: 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.] E3: 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]

[Additive 2] As the F component, the following additive 4
Seeds 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 four 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 and 2 (Preparation of Composition)> According to the formulation shown in Table 1 below, the components A to
D component and, if necessary, additives and a solvent,
Each of the obtained blends was mixed and stirred with a Henschel mixer to prepare a photosensitive resin composition.

[0072]

[Table 1]

<Evaluation of Composition Performance and Production of Multilayer Wiring Board> (1) Preparation and Evaluation of Photosensitive Property Evaluation Test Board A plate made of glass epoxy resin having a copper metal layer formed on one surface was used as a test piece. , On one surface thereof, using the compositions prepared in Examples 1 and 2 and Comparative Examples 1 to 6 as samples, applying each of them using a spin coater,
By drying in a hot air oven at 90 ° C. for 10 minutes, 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. The exposure process is H
Using MW321B type exposure equipment, 1000
The exposure was performed at an exposure amount of mJ / cm ² . The test piece after the exposure treatment was heat-treated at 120 ° C. for 5 minutes, and then placed in a 0.75% tetramethylammonium hydroxide aqueous solution.
The developing process was performed by immersing and oscillating for 0 to 300 seconds 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.

Each of the test pieces obtained here was evaluated for resolution. 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 has been formed is cured by heating in a hot air oven at a temperature of 150 ° C. for 60 minutes, and thereafter, the thermally cured test piece is 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.

Next, each of the test pieces was immersed in a palladium chloride-based catalyst solution at room temperature for 6 minutes to carry the plating catalyst on the surface of the roughened insulating layer and the inner surface of the through hole. The plating catalyst was activated by immersion in a catalyst 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), an electrolytic copper plating treatment is performed at a current density of 3.0 mA / dm, and a copper metal layer having a total thickness of about 20 μm is insulated. , And then the test piece was heated at 150 ° C. for 1 hour.

The test pieces were cut at intervals of 1 cm on the surface and peeled off from the end faces with a peel tester to obtain the peel strength (JIS C) of the copper metal layer.
6481) was measured. Table 2 shows the results. This peel strength is the mode value after peeling off 10 cm.

(2) Measurement of glass transition point A release agent was applied to one surface of a polyethylene terephthalate film, and a thin film having a thickness of 50 μm was formed on one surface 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 at 2 ° C. for 2 hours to form a film of each of the sample compositions, 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 0 Hz, and the peak top of tan δ was determined as the value of the glass transition point. Table 2 shows the results.

(3) Warp Test of Substrate Each of the sample compositions 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 Coefficient Each of the sample compositions was applied to a 4-inch diameter silicon wafer whose weight w0 was measured 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 is formed, and then the entire surface is exposed with a contact aligner at an exposure amount of 1000 mJ / cm 2, and the test substrate after this exposure treatment is heated at 150 ° C. for 4 hours. The weight w1 of the 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.
Was measured for weight w2. Then, the water absorption (%) was determined according to the following equation. Table 2 shows the results. Water absorption = [(w1−w0) ÷ (w2−w0)] × 1
00

[0082]

[Table 2]

[0083]

The radiation-sensitive resin composition according to the present invention comprises:
Forming an insulating layer with excellent resolution that can form small-diameter photo via holes with high precision, that can be developed with an alkaline aqueous solution, and that has excellent plating solution resistance and adhesion of conductor wiring In addition, the composition film has low water absorption and a small degree of curing shrinkage. Therefore, by using the composition, a highly reliable multilayer wiring board can be efficiently manufactured.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI H05K 3/46 H05K 3/46 T (72) Inventor Hozumi Sato 2-11-24 Tsukiji, Chuo-ku, Tokyo Nippon Gosei Rubber Stocks In company

Claims (2)

[Claims] 1. A radiation-sensitive resin composition comprising the following components A to D: [Component A] alkali-soluble resin [Component B] cross-linking agent [Component C] a compound containing at least one thiylanyl group in one molecule [Component D] radiation polymerization initiator 2. A cured film obtained by curing the composition according to claim 1, which is insoluble in an aqueous alkali solution.