JPH1160683A - Radiation-sensitive resin composition and cured film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compsn. which can form an insulating layer having such a resolution as to enable the formation of photoviaholes with small-diameters at a high accuracy, capable of being developed with an aq. alkali soln., and excellent in adhesiveness and resistance to a plating liquid by incorporating an alkali-soluble resin, an epoxy compd. and a compd. having an oxetanyl or thiiranyl group in the molecule into the same. SOLUTION: This compsn. contains an alkali-soluble resin pref. a combination of polyvinylphenol with another phenol resin [e.g. poly(p-vinylphenol) and a cresol novolak resin]), an epoxy compd. [pref. an epoxy-modified particulate rubber (e.g. a compd. obtd. by reacting a particulate rubber obtd. from butadiene, methyl methacrylate. methacrylic acid and divinylbenzene with an epoxy compd.)], and a compd. having oxetanyl or thiiranyl group in the molecule e.g. 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene).

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 for 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. . However,
These methods are not preferable methods from the viewpoint of productivity because a plurality of holes cannot be formed at the same time or require many steps, and are not satisfactory methods from the viewpoint 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 conductive 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.

[0005] With respect to such a multilayer wiring board, a multilayer is formed on an insulating layer made of a photosensitive resin composition, and is then subjected to a plating treatment to form a through hole called a photo via hole for achieving electrical connection. A method of manufacturing a wiring board by a stacking method has been proposed (Japanese Unexamined Patent Publication No.
148590). 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. 5-2 / 1993).
73753).

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, An object of the present invention is to provide a radiation-sensitive resin composition having high heat resistance and heat resistance and capable of forming an insulating layer in which conductive wiring is formed with excellent adhesion.

[0009]

In order to achieve the above object, the present invention provides a radiation-sensitive resin composition containing the following components A to C. [Component A] alkali-soluble resin [Component B] epoxy compound [Component C] a compound having a group selected from the group consisting of an oxetanyl group and a thiiranyl group in the molecule. In the present invention, radiation-sensitive is curing in response to radiation. The property that can be performed. Radiation includes visible light, ultraviolet light, far ultraviolet light, X-rays, and electron beams.

[0010]

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 2,000, as measured by gel permeation chromatography (GPC).
Phenol resins other than polyvinylphenol having the above-mentioned weight and the same polystyrene-equivalent weight average molecular weight of 200 or more, preferably 2,000 or more (hereinafter referred to as a specific phenol resin) can be mentioned. The polyvinyl phenol used as the component A is obtained by polymerizing a vinyl phenol monomer by a conventional method, or by polymerizing a phenolic hydroxyl group in a state protected by a protecting group, and then removing the protecting group. Examples include those obtained by various production methods such as those obtained. Also,
Various monomers obtained by introducing various substituents into vinyl phenol monomers, for example, various types obtained from vinyl cresol, 2,4-dimethyl vinyl phenol, fluorinated vinyl phenol, chlorinated vinyl phenol, brominated vinyl phenol, etc. Substituted polyvinyl phenols can also be used.

Although the molecular weight of the polyvinyl phenol is not particularly limited, the weight average molecular weight is 2,000 or more, particularly 2,000 to 20,000, from the viewpoints 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 is obtained, for example, by subjecting a phenol compound and an aldehyde compound to addition condensation using an acid catalyst, preferably in a ratio of 0.7 to 1 mol of the aldehyde compound to 1 mol of the phenol compound. Here, specific examples of the phenol compound include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol,
p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol,
3,5-xylenol, 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. Preferred as the specific phenol resin are phenol, o-cresol, m-cresol, p
-It is obtained by reacting a phenol compound selected from cresol with an aldehyde compound selected from formaldehyde and paraformaldehyde.

The specific phenol resin used as the component A must have a weight average molecular weight of 200 or more from the viewpoints of resolution, developability, plating solution resistance, and the like of the obtained insulating layer. Those in the range of 200 to 20,000 are preferred.

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 C. 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] As the epoxy compound of the component B, for example, glycidyl acrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methacrylate, a polymer thereof, or a polymer or other polymerizable polymer may be used. Glycidyl ether type epoxy resins represented by copolymers with compounds having a bond, bisphenol type epoxy resins, novolak type epoxy resins, cresol novolak type epoxy resins, etc., glycidyl ester type epoxy resins, aromatic glycidylamine Epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, liquid rubber-modified epoxy resins, crosslinked polymers chemically modified with epoxy groups (hereinafter referred to as epoxy-modified particles Oxirane ring Goods and the like, preferably epoxy modified particulate rubber.

When this epoxy-modified particulate rubber is added, the surface of the insulating layer is sufficiently roughened in the step of roughening the insulating layer obtained from the composition of the present invention, which will be described later. The adhesion of the conductor wiring formed on the layer becomes large.

The epoxy-modified particulate rubber used as the component B is obtained by chemically modifying a particulate rubber material having a functional group that reacts with an epoxy group, for example, a carboxyl group, with an appropriate epoxy compound. Having an average particle size of 0.01 to 20 μm, preferably 0.01 to 20 μm.
It is 5.0 μm. Details of the epoxy-modified particulate rubber are described in, for example, JP-A-4-15830.

The particulate rubber material for obtaining the epoxy-modified particulate rubber of the component B is obtained, for example, by copolymerizing a monomer composition containing the following monomers (a) to (c). It consists of a crosslinked polymer having a carboxyl group. (A) a polyfunctional monomer having a plurality of polymerizable double bonds in one molecule; (b) a monomer having a carboxyl group copolymerizable with the polyfunctional monomer (a) (hereinafter referred to as “carboxyl group”). (C) The above (b) which is copolymerizable with the polyfunctional monomer (a)
Other polyfunctional monomers having a plurality of polymerizable double bonds in one molecule (a) include, for example, ethylene glycol di (meth)
Acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, propylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate,
Pentaerythritol tetra (meth) acrylate,
1,4-butanediol di (meth) acrylate, 1,
Examples thereof include 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 material. Used in If this proportion is less than 0.1 mol%, the shape of the particulate rubber is not sufficiently maintained in the composition, so that the surface of the insulating layer cannot be sufficiently roughened. Is inferior in developability. On the other hand, when this proportion exceeds 20 mol%, the surface is not completely dissolved in the surface roughening treatment, so that the surface roughening cannot be sufficiently achieved, and the obtained particulate rubber has an affinity for other components. The workability of the resulting composition is deteriorated due to a decrease in the property, the strength of the insulating layer after the photocuring treatment is significantly reduced, and the adhesion of the formed plating layer becomes insufficient.

Specific examples of the carboxyl group-containing monomer (b) include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, and tetraconic acid; dicarboxylic acids such as succinic acid and fumaric acid and an addition polymerizable group. And a half ester with an unsaturated alcohol having the formula: These carboxyl group-containing monomers (b) can be used singly or in combination of two or more depending on the specific use of the obtained composition.

The above carboxyl group-containing monomer (b)
Is from 0.1 to 30 mol%, preferably from 0.5 to 20 mol%, based on the whole monomer composition for obtaining the particulate rubber material.
Used in the ratio of When this ratio is less than 0.1 mol%, the epoxy-modified particulate rubber obtained by the epoxy-modifying treatment has a small number of surface epoxy groups, and thus the affinity of the epoxy-modified particulate rubber for the composition is low. Therefore, it is difficult to uniformly disperse the composition in the composition, and as a result, good surface roughening cannot be achieved, and the obtained insulating layer has poor toughness and resolution. If it exceeds 30 mol%, the resulting insulating layer becomes hard and brittle, and both are not preferred.

The copolymerizable monomer (c) used together with the polyfunctional monomer (a) and the carboxyl group-containing monomer (b) includes various radical polymerizable monomers depending on the purpose. Can be used.

Examples of the copolymerizable monomer include butadiene, isoprene, dimethylbutadiene, and chloroprene. Further, styrene, α-methylstyrene, vinyltoluene, acrylonitrile, vinyl chloride, vinylidene chloride, (meth) acrylamide , Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

The particulate rubber material 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. For this reason, it is preferable to use an emulsion polymerization method.

In the case of the emulsion polymerization method, the above polyfunctional monomer (a), carboxyl group-containing monomer (b),
What is necessary is just to carry out radical emulsion polymerization of the copolymerizable monomer (C), salting out, washing and drying according to a known method. 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, Japanese Unexamined Patent Publication No.
No. 15,830, which has a low ion content, specifically, sodium,
It is preferable to use particulate rubber having a content of metal ions such as 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 material obtained as described above has a carboxyl group on its surface.
This carboxyl group is epoxidized with an epoxy compound, whereby an epoxy-modified particulate rubber used as the component B of the present invention is obtained.

For the epoxy modification, for example, a particulate rubber material having a carboxyl group on the surface of the particle is heated and reacted with an epoxy compound containing a plurality of epoxy groups in one molecule, for example, an epoxy resin. A carboxyl group present on the particle surface of the particulate rubber material can be converted into an epoxy group. Specifically, for example, a particulate rubber material having a carboxyl group and an epoxy resin,
For example, the reaction may be performed in a reaction solvent at a temperature of 40 to 100 ° C. using a catalyst such as tetrabutylammonium bromide. The reaction solvent is not particularly limited as long as it does not participate in the reaction and can keep the reaction system uniform. When the epoxy compound to be used is in a liquid state, the reaction solvent is unnecessary.

In the treatment of the particulate rubber material with the epoxy compound, the particulate rubber material may be mixed with the epoxy compound and thermally reacted. The ratio of the particulate rubber material to the epoxy compound in this reaction is preferably 10 to 30% by weight and 90 to 70% by weight, respectively. When the proportion of the particulate rubber material exceeds 30% by weight, it becomes difficult to uniformly disperse the particulate rubber in the composition because the degree of epoxy modification is low. As the epoxy compound used here, an epoxy resin can be preferably used. The epoxy resin is not particularly limited, and various epoxy resins such as bisphenol type epoxy resin, (cresol) novolak type epoxy resin, and alicyclic type epoxy resin can be used. Brominated epoxy resin, urethane-modified epoxy resin And various modified epoxy resins.

Here, the use ratio of the epoxy compound is preferably 15% by weight or less based on the whole of the composition, and if it exceeds 15% by weight, the alkali developability of the obtained insulating layer is lowered, and the epoxy compound is preferably used. It is difficult to obtain a proper profile.

It is not necessary that all of the carboxyl groups present on the surface of the particulate rubber material be modified by the epoxy group, but only a part thereof is modified and other carboxyl groups remain as they are. It may be possible to obtain good developability.

B comprising the above-mentioned epoxy-modified particulate rubber
The components are present in a state of being uniformly dispersed in the composition of the present invention, and are selected by a strongly oxidizing roughening treatment solution in the step of roughening the surface of the insulating layer formed from the composition. Reacts and dissolves, whereby the surface of the insulating layer is roughened.

That is, since the particulate rubber is epoxy-modified, it has a good affinity for other components, so that it exists in a sufficiently uniformly dispersed state in the composition of the present invention. I will be. In the surface-roughening treatment, the surface-roughening treatment solution having strong oxidizing property is brought into contact with the epoxy-modified particulate rubber present on the surface of the insulating layer to form a copolymer of the epoxy-modified particulate rubber. As a result of the double bond being cut and the copolymer being dissolved in the surface-roughening treatment solution, the epoxy-modified particulate rubber disappears or is removed from the insulating layer, thereby causing minute irregularities on the surface of the insulating layer. It is formed and roughened.

On the other hand, if the particulate rubber which is not epoxy-modified is used, a uniform dispersion state cannot be obtained in the composition. It will not be uniform and will be uneven.

It should be noted that even when an epoxy compound such as an epoxy resin used for epoxy modification of the particulate rubber is used as a single component, the particulate rubber cannot be dispersed sufficiently uniformly.

Further, since the above-mentioned epoxy-modified particulate rubber is present in a uniformly dispersed state inside the insulating layer obtained from the composition of the present invention, shrinkage caused by exposure or heat treatment in the insulating layer is caused. Stress, thermal stress caused by the difference of the coefficient of thermal expansion with the substrate, etc. are alleviated,
As a result, dimensional accuracy of the multilayer wiring board and high reliability as an insulating layer can be obtained. Further, according to the composition containing the epoxy-modified 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 component B is usually 1 to 50% by weight, preferably 5 to 40% by weight, more preferably 5 to 40% by weight, based on the total amount of the components A to C.
It is 10 to 30% by weight. If this ratio is too small, sufficient surface roughening treatment cannot be achieved, and the resulting insulating layer may have insufficient toughness, heat resistance, and plating solution resistance. If the content is too large, a thin film obtained from the composition may not have sufficient developability.

[0040] [C component] The C component in the present invention is 1 minute.
A group selected from oxetanyl and thiiranyl groups
An oxetane or thiirane compound having the formula: representative
Compounds include oxetanyl groups in the molecule and
And a compound having a thiiranyl group. Oxetanyl group-containing compounds Examples of compounds having one or more oxetanyl groups in the molecule
The following equations (A), (B) and (C)
Compounds to be used can be mentioned.

[0041]

Embedded image [In each of the formulas (A), (B) and (C), R ¹
Is an alkyl group such as a methyl group, an ethyl group, and a propyl group; R ² is an alkylene group such as a methylene group, an ethylene group and a propylene group; and R ³ is a methyl group, an ethyl group, a propyl group, and a hexyl group. An alkyl group such as a phenyl group and an xylyl group; a formula:

[0042]

Embedded image (Where x is an integer of 0 to 50), a dimethylsiloxane residue represented by the same formula, an alkylene group, a phenylene group, or a phenylene group as exemplified for R ² ;
A group represented by (5),

[0043]

Embedded image (Where y is an integer from 1 to 50),

[0044]

Embedded image (Where, x is a single bond or _{-CH 2 -, - C (CH} 3)
_2- , -C (CF ₃ ) _2- or -SO _2- ).

[0045]

Embedded image n is equal to the valence of R ³ and is an integer of 1 to 4. Specific examples of the compounds represented by the formulas (A) to (C) include bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene (trade name “XDO” manufactured by Toa Gosei Co., Ltd.), [(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, and compounds represented by the following chemical formulas (D) to (H).

[0046]

Embedded image

In addition to the above, compounds having a high molecular weight polyvalent oxetane ring can also be used. Specific examples thereof include oxetane oligomers (trade name: Oligo)
-OXT "manufactured by Toagosei Co., Ltd.) and the following chemical formulas (I) to
The compound represented by (K) can be mentioned.

[0048]

Embedded image

[Wherein p, q and s are from 1 to
It is an integer of 10,000. ] Thiranyl group-containing compound Thiylanyl group-containing compound has one or more thiiranyl groups in the molecule.
Compounds. 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 20,000.
It is in the range of 0.

The compound containing a thiiranyl group is synthesized exclusively by substituting the oxygen atom of the oxirane ring in the oxirane-containing compound with a sulfur atom. The method is described in, for example, JM Charlesworth J. Polym. Sc. Polym. Phys. . 17
329 (1979), using thiocyanate, and RD Schuetz et al., J. Org.
26 3467 (1961), etc., using thiourea. The synthesis method from cyclic carbonate is 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. Among them, particularly preferred examples of the thiyanyl group-containing compound include glycidyl ether type epoxy resins represented by bisphenol type epoxy resin, novolak type epoxy resin, cresol novolak type epoxy resin and the like, glycidyl ester type epoxy resin, aromatic glycidyl Amine type epoxy resins,
Thiirane compounds in which an oxygen atom in the oxirane ring of the oxirane ring-containing compound is substituted with a sulfur atom.

In the composition of the present invention, the compounding ratio of the compound selected from the oxetanyl group-containing compound and the thiiranyl group-containing compound as the component C is usually 0.5 to 40 with respect to the total of the components A to C. % By weight, preferably 3 to
30% by weight. The component C is a component that rapidly polymerizes upon exposure to light, and has an effect on maintaining the shape of the exposed portion. In particular, it is effective in preventing the heat sagging phenomenon caused by the softening of the resin during the baking after the formation of the via hole.
Therefore, if the proportion of the C component is too small, there is no effect in preventing heat sag. The C component is also effective in lowering water absorption after curing and suppressing curing shrinkage during curing, but the resulting insulating layer does not have sufficiently low water absorption, and the resulting curing shrinkage does not occur. Is not small enough. On the other hand, if this ratio is too large, a thin film of the obtained composition may not have sufficient developability.

[Other Components] In addition to the above components A to C, 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.

Crosslinking Agent The composition of the present invention preferably contains a crosslinking agent which reacts with the alkali-soluble resin of 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. Examples of such amino resins include (poly) methylolated melamine, (poly) methylolated glycoluril, (poly)
Examples include nitrogen-containing compounds having a plurality of active methylol groups in one molecule, such as methylolated benzoguanamine and (poly) methylolated urea. 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. Further, the crosslinking agent may include an oligomer component 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 (“Symel 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, the content of the crosslinking agent is preferably in a range where a thin film of the composition is sufficiently cured by the action of a photopolymerization initiator and heat. Usually, it is 1 to 50% by weight, preferably 5 to 30% by weight, based on the total amount of the components A to C.

As a preferable compounding component of the liquid rubber , the number average molecular weight is from 1,000 to 1,000.
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 comprises an A component,
It is necessary to have a high compatibility or affinity with the B component and the C component, and if a low compatibility or affinity with these components is used, the resulting composition has a high tackiness. May be difficult to handle.

Suitable liquid rubbers include various known synthetic rubbers. Acrylic rubber (AC) can be used because it has high compatibility with the component A and the like.
M), acrylonitrile-butadiene rubber (NBR),
Acrylonitrile acrylate butadiene rubber (N
BA) is preferable, and if necessary, an epoxy group,
Those having at least one functional group selected from 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 C.

Radiation Polymerization Initiator The composition of the present invention usually contains a radiation polymerization initiator. As the radiation polymerization initiator, those generally known as a cationic photopolymerization initiator are preferable, and specifically, a diazonium salt “ADEKA ULTRASET PP-33” [manufactured by Asahi Denka Kogyo Co., Ltd.] ], Sulfonium salts "OPTOMER SP-150", "OPTO
MER SP-170 "," OPTOMER SP17 "
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 mixing ratio of the radiation polymerization initiator in the composition of the present invention is 0.01 to the total of the components A to C.
To 5% by weight, more preferably 0.1 to 5% by weight.
02 to 2% by weight. If this proportion is less than 0.01% by weight, the resulting insulating layer will have a remarkable decrease in sensitivity due to the influence of the surrounding environment such as oxygen.
If the amount is more than 10% by weight, the compatibility with other components is inferior, and the storage stability of the composition decreases.

Other Optional Ingredients The composition of the present invention may contain an adhesion aid for improving the adhesion 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)
Ethyltrimethoxysilane and the like can be mentioned, and the blending ratio is preferably 2% by weight or less based on the total amount of the components A to C.

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 silicone compound and a fluorine compound having a low surface tension. These additives are used in an amount not to impair the purpose of the present invention, and preferably in an amount of 50% by weight or less of the total of the components A to C.

[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 to be used can be changed according to the use of the composition or the method of coating used, and is not particularly limited as long as the composition can be brought into a uniform state. The amount is 5 to 60% by weight, preferably 10 to 40% by weight in the obtained liquid composition.

[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.

When a multilayer wiring board is manufactured 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 coated on the surface of a wiring board having conductive wiring formed on the surface of a substrate so that the conductive wiring is covered. A thin film is formed by applying, 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 thickness of the thin film formed in the thin film forming step after drying is, for example, 5 to 100 μm.
It is preferably from 0 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. 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.
2000 mJ / cm ² .

(3) Reaction-Promoting Heating Step In this reaction-promoting heating step, the thin film after the exposure treatment step is usually heated at a temperature of 70 to 130 ° C. for about 1 to 20 minutes, whereby 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 removed by dissolving it in a developing solution composed of an aqueous alkali 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 0.5 to 3.
A 0% by weight aqueous solution is preferred.

Examples of the developing method include a puddle method, a dipping method, a paddle method, a spray, and a shower developing method. After the development processing, for example, washing with running water is performed, 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 photocuring 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 by 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 120 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 apparatus as those used in the exposure processing step, the exposure can be performed, for example, at an exposure amount of 100 to 4000 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 establish a connection with another wiring board, that is, an 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. The processing method is 50
What is necessary is just to immerse the insulating layer in the treatment liquid heated to 90 degreeC for 5-130 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 a desired copper plating layer is formed by electrolytic copper plating using the copper plating layer as an electrode, if necessary. 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 coating layer is formed by applying a photosensitive resin composition containing no plating catalyst over the entire surface of the insulating layer supporting the catalyst, 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.

After the conductor wiring is formed on the surface of the insulating layer which is the uppermost layer of the multilayer wiring board, it is preferable to perform post-baking 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.

[0088]

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 seven types 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: phenol novolak resin [weight average molecular weight Mw
A4: Poly (p-vinylphenol) [Maruzensekika, weight average molecular weight Mw = 3000] A5: Poly (brominated p-vinylphenol) [Maruzenishika's “Marcalinker MB”, weight average molecular weight Mw = 40
A6: poly (m-vinylphenol) [weight average molecular weight Mw = 3000]

[Component B] The following three types of epoxy-modified particulate rubbers B1 to B3 were produced. Particulate Rubber B1 Butadiene, methyl methacrylate, methacrylic acid, and divinylbenzene are in a weight ratio of 70: 25: 4: 1.
By emulsion polymerization of the monomer composition obtained by mixing at a ratio of the above, a particulate rubber material M1 comprising a crosslinked polymer having a carboxyl group having an average particle size of 0.058 μm was prepared,
Epoxy resin “Epicoat 828” (manufactured by Yuka Shell Epoxy Co., Ltd.) 100 parts
Parts as a modification reaction catalyst together with 1% of triphenylphosphine based on the particulate rubber material, and added at 90 ° C. to about 2 parts.
By mixing and stirring for a time, an epoxy-modified particulate rubber B1 was obtained.

Incidentally, the particulate rubber B1 was dissolved in tetrahydrofuran, and the residual carboxyl group (carboxylic acid) was quantified by an acid-base titration method using phenolphthalein as an indicator. The rubber-like rubber B1 had all carboxyl groups on the surface converted to epoxy groups. Particulate rubber B2 butadiene, acrylonitrile, methacrylic acid,
Emulsion polymerization of a monomer composition obtained by mixing divinylbenzene with a weight ratio of 67: 30: 2: 1 results in a crosslinked polymer having a carboxyl group having an average particle size of 0.070 μm. A particulate rubber material was prepared, and an epoxy resin "EP-410" was added to 15 parts of the particulate rubber material.
0E "(manufactured by Asahi Denka Kogyo Co., Ltd.) as a modification reaction catalyst together with 1% of triphenylphosphine based on the particulate rubber material, and mixed and stirred at 90 ° C. for about 2 hours. Epoxy-modified particulate rubber B2
I got Particulate rubber B3 butadiene, acrylonitrile, methacrylic acid,
Emulsion polymerization of a monomer composition obtained by mixing divinylbenzene with a weight ratio of 77: 19: 3: 1 results in a crosslinked polymer having a carboxyl group having an average particle size of 0.062 μm. A particulate rubber material was prepared, and an epoxy resin “EP-410” was added to 10 parts of the particulate rubber material.
0E "(manufactured by Asahi Denka Kogyo Co., Ltd.) as a modification reaction catalyst together with 1% of triphenylphosphine based on the particulate rubber material, and mixed and stirred at 90 ° C. for about 2 hours. Epoxy-modified particulate rubber B3
I got

[Component C] The following two types of oxetanyl group-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) The following one kind was prepared as a thiiranyl group-containing compound. C3: 2,2 '-[(1-methylethylidene) bis (4,1-phenyleneoxymethylene)] bisthiirane

[Component D] The following two amino resins were prepared. D1: Hexamethoxymethylated melamine D2: Tetramethoxymethylated glycoluril

[Component E] The following three types of liquid rubber were prepared. E1: Butadiene-acrylonitrile-methacrylic acid copolymer [butadiene: acrylonitrile: methacrylic acid = 60: 35: 5 (molar ratio), number average molecular weight Mn = 60
E2: Butadiene-acrylonitrile-hydroxyethyl acrylate-methacrylic acid copolymer [butadiene:
Acrylonitrile: hydroxyethyl acrylate = 5
5:30:15 (molar ratio), number average molecular weight Mn = 800
E3: butadiene-acrylonitrile-hydroxyethyl acrylate-methacrylic acid copolymer [butadiene:
Acrylonitrile: hydroxyethyl acrylate: methacrylic acid = 60: 25: 10: 5 (molar ratio), number average molecular weight Mn = 4500, glass transition point Tg-30 ° C.]

[F Component] The following three photopolymerization initiators were prepared. F1: 2,4-trichloromethyl (4′-methoxyphenyl) -6-triazine F2: 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine F3: diphenyliodonium-9,10-dimethoxyanthracene sulfonate

[Solvent] The following four kinds of organic solvents were prepared. MMP: Methyl 3-methoxypropionate DAA: Diacetylacetone PGMEA: Propylene glycol monomethyl ether acetate EEP: Ethyl 3-ethoxypropionate

<Examples 1 to 10 and Comparative Examples 1 to 7 (Preparation of Composition)> According to the formulation shown in Table 1 or 2, the above components A to F and, if necessary, a solvent were blended.
Each of the obtained blends was mixed and stirred with a Henschel mixer to prepare a photosensitive resin composition of each example.

<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 is used as a test piece. On each of the surfaces, each of the compositions prepared in Examples 1 to 10 and Comparative Examples 1 to 7 was applied using a spin coater, and dried at 90 ° C. for 10 minutes in a hot air oven. A thin film having a thickness of about 50 μm 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.
Alternatively, development processing was performed by immersing and rocking for the time shown in Table 4 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.

Resolution 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. The results are shown in Tables 3 and 4. Heat drooping-roughened state Next, each test piece which an insulating layer is formed and cured by heating for 60 minutes at a temperature 0.99 ° C. in a forced air oven. At this time, the shape change of the edge of the photo via hole was observed with an electron microscope, and the presence or absence of heat sag was confirmed. Thereafter, the heat-cured test piece was heated to a temperature of 65 ° C.
10 minutes in a potassium permanganate-sodium hydroxide aqueous solution (potassium permanganate concentration 3%, sodium hydroxide concentration 2%) maintained for 10 minutes to roughen the surface of the insulating layer. Done, then 5% concentration
Of oxalic acid at room temperature for 5 minutes for neutralization treatment, and further sufficiently washed with water. For each of the test pieces, the surface state of the insulating layer was observed with a scanning electron microscope to evaluate the state of the surface roughening treatment. The results are shown in Tables 3 and 4. The evaluation method was “good” when the surface was sufficiently roughened and fine irregularities were formed, and “poor” otherwise.

Peel strength Each of the test pieces was immersed in a palladium chloride-based catalyst solution at room temperature for 6 minutes to allow the plating catalyst to be carried on the surface of the roughened insulating layer and the inner surface of the through hole. The plating catalyst was activated by immersing it 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, sulfuric acid concentration 5
(2 g / L, pH = 1.0), using an electrolytic copper plating solution with a current density of 3.0 mA / dm, to form a copper metal layer having a total thickness of about 20 μm on the surface of the insulating layer. The test piece was heat-treated at 150 ° C. for 1 hour. Cuts at 1 cm intervals were formed on the surfaces of these test pieces, and the test pieces were peeled from the end faces with a peel tester to measure the peel strength (JIS C 6481) of the copper metal layer. This peel strength is the mode value after peeling off 10 cm.
The results are shown in Tables 3 and 4.

(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 ,
A film was formed by heating at 2 ° C. for 2 hours to form a film of the composition of the present invention, and peeled from the polyethylene terephthalate film to obtain a test film. About this test film, the elastic modulus measuring device “Rheoviblon RHEO”
-1021 "(Orientec) with frequency 10H
The change in elastic modulus was measured at z, and the peak top of tan δ was determined as the value of the glass transition point. Tables 3 and 4 show the results.
Shown in

[0103]

[Table 1]

[0104]

[Table 2]

[0105]

[Table 3]

[0106]

[Table 4]

[0107]

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 Can be. In particular, since heat sagging of the insulating layer after the development processing hardly occurs, a highly accurate pattern can be obtained. Therefore, by using the composition,
A highly reliable multilayer wiring board can be manufactured efficiently.

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[Procedure amendment]

[Submission date] November 14, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction contents]

[0046]

Embedded image

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Hozumi Sato 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside Nippon Gosei Rubber Co., Ltd.

Claims (2)

[Claims] 1. A radiation-sensitive resin composition comprising the following components A to C: [Component A] Alkali-soluble resin [Component B] epoxy compound [Component C] Compound having a group selected from the group consisting of an oxetanyl group and a thiiranyl group in the molecule 2. A cured film obtained by curing the composition according to claim 1, which is insoluble in an aqueous alkali solution.