JP2898143B2 - Photosensitive liquid composition, photosensitive film and laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film of an alkali-developing photosensitive resin composition used as an etching resist or a plating resist used for processing a metal foil in a laminated plate on which a metal foil is laminated (hereinafter simply referred to as a film). Also called)
The present invention relates to a photosensitive liquid composition and a photosensitive film to be formed, and further to a metal foil laminate having a photosensitive resin composition film or a photosensitive film formed on the surface.

[0002]

2. Description of the Related Art Conventionally, in the fields of manufacturing printed wiring boards, metal working and the like, it is known to use a photosensitive resin composition as an etching resist or a plating resist. A material generally called a dry film, in which a coating of a photosensitive resin composition is laminated on a transparent film support, is widely used as an etching resist or a plating resist. In recent years, alkali-developing dry films have become popular due to the problem of environmental pollution.

In the field described above, a method of printing a photosensitive resin composition on a surface of a copper-clad laminate or a metal by a screen printing method to form a resist pattern is also widely and generally used. Usually, a screen printing method is mainly used for forming a rough resist pattern, and a dry film is mainly used for forming a high-density and fine resist pattern.

A method of forming a high-density and fine circuit of a printed wiring board will be described below with reference to FIG. First,
Hard copper-clad laminates and flexible copper-clad laminates (hereinafter
A film 26 and a transparent film support 24 are formed on a surface of a copper foil 22 laminated on a base material 20 such as a copper-clad laminate.
(See FIG. 4A). Lamination of the dry film on the substrate can be performed by thermocompression bonding the coating to the copper foil surface. afterwards,
The dry film is exposed through a photomask 28 on which a circuit pattern is formed, and the circuit pattern is printed on the film 26 (see FIG. 4B). Next, the transparent film support 24 is removed. The transparent film support 24 functions as a protective film for preventing the coating from sticking to the photomask during exposure. Thereafter, the unexposed portion of the coating 26 is removed (developed) with a dilute aqueous alkali solution (developer) such as a 0.2 to 2.0% by weight aqueous sodium carbonate solution (see FIG. 4C). The portion of the coating cured by exposure functions as a resist for an etching solution or a plating solution. Copper foil portions exposed by development of the film is etched to remove the copper foil (see (D) in FIG. 4), or to remove the copper foil portion of the required after plated on the exposed copper foil portions After the circuit is formed as described above, the film 26 is removed (see FIG. 4E).

When a dry film is laminated on a copper-clad laminate, the copper foil surface of the copper-clad laminate is mechanically polished or chemically etched by soft etching in order to improve the adhesion between the copper foil and the coating. It is necessary to polish and roughen the copper foil surface. At this time, deep scratches may be made on the copper foil due to handling of the substrate or uneven polishing of the copper foil surface. It is difficult to reliably embed a dry film film in the generated scratch. For this reason, at the time of etching the copper foil, the etchant infiltrates from the gap between the damaged copper foil and the coating, and causes a disconnection of the circuit. Or when plating copper foil,
The plating solution infiltrates from the gap between the damaged copper foil and the coating, and causes a short circuit.

Therefore, in the conventional dry film, the thickness of the coating is required to be at least 30 μm or more in order to embed the coating into the wound formed on the copper foil, though not enough. When the thickness of the film is large, the resist patterns 30 and 3 are formed as shown in a schematic sectional view of FIG.
When the distance between the two is less than 100 μm, the etching speed and the plating speed are affected by the thickness of the coating film, and are lower than in the case where the distance between the resist patterns 32 and 34 exceeds 100 μm. That is, as shown in FIG. 5, when etching a copper foil, for example, the resist pattern 30,
32 between the copper foils 22A, the resist patterns 32, 34
Is less likely to be etched than the copper foil 22B in between. FIG.
, 20 is a substrate. As a result, the state of etching and the thickness of plating change between gaps between fine circuit patterns of 100 μm or less and gaps between circuit patterns exceeding 100 μm. Since the width and interval of the conductor circuit pattern of the printed wiring board are not constant but extend from several tens μm to several cm, it is difficult to form a uniform conductor circuit.

When a photomask is directly adhered to a film during exposure of a dry film, the film adheres to the photomask and contaminates the photomask. Therefore, when a dry film is used, it is necessary to interpose a transparent film support 24 (for example, a thickness of 20 μm) made of a polyester film or the like as a protective layer on the coating at the time of exposure. As a result, the total thickness of the dry film increases, and when the dry film is exposed, light scattering causes a difference between the dimensions of the circuit pattern formed on the photomask and the dimensions of the circuit pattern formed on the coating. There is a problem that arises.

When the transparent film support as the protective layer is removed and the coating on the conventional dry film is exposed, a resist pattern with high dimensional accuracy can be formed on the coating. However, when the temperature of the film is 15 to 23 ° C. or higher, the film adheres to the photomask, and the resin of the film adheres to the photomask, thereby reducing the light transmittance of the photomask. Therefore, when the same photomask is used repeatedly, the exposure amount of the film is partially or entirely uneven, and the resist pattern is lost. As a result, disconnection or short circuit occurs in the conductor circuit after etching or plating. Therefore, such a method is not suitable for mass production of a printed wiring board. Recently, the cooling technology of the exposure apparatus has been advanced to prevent the adhesion between the coating film and the photomask.
When the photomask or the copper-clad laminate is cooled to 15 to 23 ° C, there are still many problems such as dew condensation on the photomask or the copper-clad laminate.

In view of these circumstances, when forming a high-density circuit, a photosensitive resin composition called a so-called liquid resist is applied to the copper foil surface of a copper-clad laminate, exposed, developed , and then etched. A method for forming a circuit is being studied. Description of the circuit formed using such a photosensitive resin composition, will be described below.

[0010] First, after the copper foil 22 is coated with a photosensitive resin composition on the copper foil 22 surface of the copper-clad laminate which is laminated to the substrate 20 and dried to form a coating film 40 of the photosensitive resin composition (See FIG. 6A). Next, the photomask 28 is placed on the film 40 and is exposed to ultraviolet light.
The circuit pattern formed in (1) is baked on the film to form the circuit pattern on the film (see FIG. 6B). afterwards,
The unexposed portion of the coating is dissolved and removed with a developer, leaving only the exposed portion 40A of the coating (see FIG. 6C). By etching the copper foil 22 in this state, only the copper foil covered with the exposed portion 40A of the film is left, and the exposed portion of the copper foil is dissolved and removed (see FIG. 6D). Next, the coating 40A is removed from the copper foil surface with a stripping solution (see FIG. 6E). Thereafter, the surface treatment of the printed wiring board thus obtained is performed by an ordinary method.

Next, another circuit forming method different from the above will be described. First, copper foil 22 is coated with a photosensitive resin composition on the copper foil 22 surface of the copper-clad laminate which is laminated to the substrate 20 and dried to form a coating 40 (shown in FIG. 7 (A) reference) . Next, the photomask 28 is placed on the film 40 and exposed to ultraviolet light, and the reverse pattern formed on the photomask is baked on the film to form the reverse pattern on the film (FIG. 7B).
reference). Here, the reverse pattern refers to a pattern opposite to a circuit pattern to be formed, that is, a pattern having a positive relationship when the circuit pattern is negative. Thereafter, the unexposed portion of the coating is dissolved and removed with a developing solution, and the exposed portion 4 of the coating is removed.
Only 0A is left (see FIG. 7C). In this state,
The exposed copper foil 22 is plated with a plating layer 4 on the surface of the copper foil.
2 (see FIG. 7D). After plating, the exposed portion 40A of the coating is removed from the copper foil with a stripping solution, and then the unplated portion of the copper foil is etched to dissolve and remove the copper foil (see FIG. 7E). . Thereafter, the surface treatment of the printed wiring board thus obtained is performed by an ordinary method.

Various photosensitive resin compositions which can be alkali-developed are disclosed. For example, JP-A-63-280245 discloses a reaction product of a styrene-maleic anhydride copolymer and hydroxy (meth) acrylate. A photosensitive resin composition comprising an ethylenically unsaturated compound (reactive diluent), a photoinitiator, and a monothiol or polythiol is shown. When exposing this photosensitive resin composition,
To prevent the photosensitive resin composition from contacting the photomask,
Requires a protective film consisting of a transparent polyester film.

JP-A-2-47658 discloses a reaction product of a styrene-maleic anhydride copolymer and an alcohol, an ethylenically unsaturated compound (reactive diluent), (meth) acrylic acid- (meth) acrylate. A photosensitive resin composition comprising a photopolymerization initiator containing a copolymer of methyl acrylate, hexaarylbiimidazole, and a thiol compound is disclosed. When exposing this photosensitive resin composition, a protective film made of polyvinyl alcohol is required so that the photosensitive resin composition does not come into contact with the photomask.

[0014]

The photosensitive resin composition is generally required to have the following characteristics as shown in Table 1 below .

[0015]

[Table 1] (A) Minimum width of conductor that can be formed 50 μm (B) Minimum space between conductors that can be formed 50 μm (C) Time required for developing the coating Within about 1 minute (D) After ultraviolet curing (E) Surface condition of the film before and after UV exposure No stickiness (f) Time required for removing the film from the copper foil surface Within about 1 minute (g) If necessary, Plating property

However, at present, there is almost no photosensitive resin composition that can satisfy the above-mentioned required characteristics. For example,
The minimum width of the conductor that can be formed and the minimum distance between the conductors are each about 100 μm or more, and the time required for developing the coating film is 1% by weight of an aqueous sodium carbonate solution at 30 ° C. as a developing solution. In this case, it took about 2 minutes, the pencil hardness of the cured film was H or less, and 3% by weight
When an aqueous solution of sodium hydroxide at 0 ° C. is used, it takes about 2 minutes to remove the film from the surface of the copper foil. In addition, the surface of the cured film may have adhesiveness, and at the time of exposure, the film and the photomask may adhere to each other, or blocking between the copper-clad laminates formed with the film in various processes of forming a conductive circuit. Or occur. Furthermore, since the strength of the coating after ultraviolet curing is not strong, the thickness of the coating cannot be reduced, and as a result, a narrower conductor width or a narrower distance between conductors cannot be achieved. Also, the plating resistance to gold plating, nickel plating, solder plating, and the like is poor.

Alternatively, in some cases, the following characteristics are generally required for the coating of the photosensitive resin composition. (A) A flaw generated in a copper foil having a depth of 70 μm can be embedded with a film before exposure. (B) The spread of the resist line width due to light scattering at the time of exposure is 5 μm or less. (C) The minimum thickness of the film that can withstand etching after exposure is 5 μm or less. (D) the softening temperature of the film before exposure is 25 ° C. or more;
No sticking to photomask film. (E) The hardness of the coating after exposure is HB or more in pencil hardness,
The coating is not easily scratched during handling. (F) The unexposed film is dissolved in a 0.1 to 2.0% by weight aqueous solution of a developing solution of amine, sodium carbonate and sodium metasilicate at 30 ° C., and can be developed in 30 seconds or less. (G) The difference between the dissolution rates of the unexposed film and the exposed film is 10 times or more in the developer. (H) The exposed film can be easily removed with a 1 to 4% by weight aqueous sodium hydroxide solution. (I) Plating solution resistance.

The coating according to the prior art is used not only for forming a fine circuit pattern but also as a resist for chemical etching in metal working, but none of them simultaneously satisfies workability and simplicity. It has sufficient sensitivity to actinic rays such as ultraviolet rays, does not require a protective layer, and can reliably embed scratches generated in a metal foil, a photosensitive solution or a photosensitive film comprising a photosensitive resin composition, Alternatively, a metal foil laminate such as a copper-clad laminate having a resist layer capable of forming a fine conductive circuit by chemical etching or plating is required.

The present invention has been made in view of the above problems, and has as its object to provide a photosensitive material satisfying the above-mentioned required characteristics .
It is an object of the present invention to provide a photosensitive liquid composition and a photosensitive film comprising a resin composition, and a metal foil laminate having a photosensitive resin composition film or a photosensitive film formed on the surface.

[0020]

[Means for Solving the Problems] The above object, and half-esterifying the compound represented by (A) the general formula (1),

Embedded image A photosensitive resin group developable with an aqueous alkali solution , comprising: (B) a saturated polymer having a carboxyl group ; (C) a photopolymerizable unsaturated compound; and (D) a photoinitiator.
15 to 30 ° C
At a liquid temperature of 1 × 10 ⁻¹ Pa · s to 5 × 10
A photosensitive solution composition is Pa · s, the photosensitive solution composition
When the film is formed, the adhesiveness of the surface is reduced, and the film is formed.
Improved peelability with an aqueous alkaline solution of the sensitive light liquid composition after
In order to achieve this, the saturated polymer is
Having a glass transition temperature of ゜ C, a photosensitive liquid composition was formed into a film.
In order to set the softening temperature at 25 ° C. or higher,
The solid content of the miscible unsaturated compound is the above-mentioned component (A) and
When the total solid content of the component (B) is 100 parts by weight,
10 to 30 parts by weight of the present invention
This can be achieved by a light-sensitive photosensitive composition.

Preferred embodiments of the photosensitive composition of the present invention
In addition, inorganic fillers or organic fillers
Is mixed.

The proportion of the photosensitive resin composition in the photosensitive liquid composition of the present invention is 10 to 70% by weight of the solid content of the component (A) and 70 to 30% by weight of the solid content of the component (B).
It is desirable that the component (D) be 1 to 15 parts by weight with respect to 0 parts by weight.

The component (A) is a copolymer of styrene and maleic anhydride having an average molecular weight of 500 to 50,000, and has at least one hydroxyl group and at least one (meth) acryloyl group in one molecule. It is a half-esterified compound esterified with a monomer. here,
The average molecular weight is a value measured by GPC.

The precursor of the half-esterified compound as the component (A) may have an average molecular weight of 500 to 50,0.
And a copolymer of styrene and maleic anhydride. The copolymer may be any copolymer having an average molecular weight of 500 to 50,000, which is obtained by copolymerizing styrene at a ratio of 0.1 to 10 mol with respect to 1 mol of maleic anhydride. Although it can be used, it is preferable to use a copolymer having an average molecular weight of about 1,000 to 5,000, which is obtained by copolymerizing styrene in a proportion of 1 to 3 mols with respect to 1 mol of maleic anhydride. For example, SMA Resin 1000, 2000, 3000, and the like manufactured by Arko Chemical Co., Ltd. are the most preferable.

On the other hand, in order to esterify the above copolymer, a monomer having at least one hydroxyl group and at least one (meth) acryloyl group Xr in one molecule is used. Such monomers include, for example, 2-
Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polycaprolactone mono (meth) acrylate, penta Erythritol tri (meta)
Acrylate, trimethylolpropane (meth) acrylate, neopentyl glycol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, mono (2- (meth) acryloyloxyethyl) acid phosphate, di (2- (Meth) acryloyloxyethyl) acid phosphate, glycerol di (meth) acrylate, glycerol mono (meth) acrylate, 2-hydroxydiethyl (meth) acrylate,
Polybutylene glycol mono (meth) acrylate, dipentaerythritol (meth) acrylate, di (2-
(Meth) acryloyloxy) acid phosphate,
Glycerol mono (meth) acrylate is exemplified.

The half-esterified compound as the component (A) can be obtained by subjecting the above-mentioned copolymer of styrene and maleic anhydride and the above-mentioned monomer to an esterification reaction. That is, a (meth) acryloyl group Xr can be introduced into the copolymer by subjecting the copolymer of styrene and maleic anhydride to the above-mentioned monomer to undergo an esterification reaction.

The synthesis of the half-esterified compound (A) is preferably carried out by a ring-opening addition reaction between the acid anhydride and the monomer having a hydroxyl group.
It is also possible to use a usual esterification reaction.

In the case of synthesizing the half-esterified compound as the component (A) , from 0.1 mol of the monomer having a hydroxyl group to 1 mol of the acid anhydride of the copolymer of styrene and maleic anhydride. The reaction is carried out in a range of 10 mol, preferably in a range of 0.5 to 2 mol. Most preferably, the monomer having a hydroxyl group equivalent to the acid anhydride of the copolymer of styrene and maleic anhydride is used, and the acid anhydride is completely ring-opened.

The above-mentioned ring-opening addition reaction can be carried out usually at 50 ° C. to 200 ° C., but in order to prevent formation of diester and gelation, 80 ° C. to 150 ° C.
It is preferable to carry out at a degree.

In starting the reaction, a copolymer of styrene and maleic anhydride is first converted to a cellosolve acetate such as butyl cellosolve acetate, a carbitol acetate such as methyl carbitol acetate, or an appropriate hydrophilic compound such as an ester. Dissolve in the solvent of Next, the above monomer having a hydroxyl group is reacted at the above reaction temperature for about 4 to 40 hours. The progress of the reaction can be determined by following the decrease in the absorption of infrared rays by the acid anhydride using an infrared absorption spectrum. The completion of the reaction can be determined by the disappearance of the absorption. When the monomer having a hydroxyl group is used in excess of a copolymer of styrene and maleic anhydride, the monomer can be used as a solvent, so that the reaction can be directly performed without a solvent.

As the reaction accelerator, tertiary amines such as triethylamine, triethanolamine, morpholine, pentamethyldiethylamine and pentamethyldiethylenetriamine, and quaternary ammonium salts can be used.

On the other hand, a known polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, t-butylhydroquinone, t-butylcatechol, benzoquinone, and phenothiazine is used to prevent the formation of a polymer during the reaction. Can also.

The ratio of the half-esterified compound as the component (A) to the photosensitive resin composition constituting the photosensitive liquid composition of the present invention is preferably 5% by weight or more and 95% by weight or less as a solid content. Preferably 10 as solids
% By weight or more and 80% by weight or less, more preferably 20% by weight or more and 63% by weight or less as a solid content. 5% by weight
Less than, when the coating is exposed, there is little difference in the crosslinking of the photosensitive resin composition between the exposed portion and the unexposed portion of the coating,
Developability when such a coating is developed with a developing solution composed of an alkaline aqueous solution is deteriorated. If the content exceeds 95% by weight, the adhesion of the exposed portion of the coating to the metal foil is reduced.

The Ru component (B) der in the present invention, mosquitoes Rubo <br/> have a hexyl group, a glass transition temperature of 60 ° C to 150
A polymer saturated with ΔC has a carboxyl equivalent of 100
To 2,000, preferably from 130 to 1,000, Ru polymer soluble der in a solvent and will be described later. (C)
In order to add the component , the glass transition temperature of the component (B) needs to be 60 ° C. to 150 ° C. (B)
If the glass transition temperature per minute is less than 60 ° C., adhesion between the photomask and the coating is likely to occur when the coating is exposed. On the other hand, if the glass transition temperature exceeds 150 ° C., the removability of the film by a stripping solution composed of an alkaline aqueous solution is reduced, and it takes a long time to remove the film from a metal foil such as a copper foil. When the carboxyl equivalent is less than 100, the film is eluted into the developing solution during development with a developing solution composed of an alkaline aqueous solution, so that the resist pattern forming accuracy is reduced. When the carboxyl equivalent exceeds 2,000, the removability of the film by the stripping solution composed of an alkaline aqueous solution is reduced, and it takes a long time to remove the film. Here, the removal of the film by the stripper refers to swelling or dissolution of the film by the stripper.

The carboxyl equivalent is measured by titrating a sample of unit weight with, for example, 0.1 N KOH to obtain oxidation,
The number of carboxyl groups per unit weight of the sample is determined.
The number average molecular weight of the sample is measured using GPC.
From these values, the carboxyl equivalent can be determined. The glass transition temperature is measured using a thermal mechanical analyzer.

The saturated polymer may have a hydroxyl group as a functional group.

Examples of the saturated polymer include acrylic resin, polyester resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer and the like.

The proportion of such a saturated polymer in the photosensitive resin composition constituting the photosensitive solution composition of the present invention is preferably 5% by weight or more and 70% by weight or less as a solid content, more preferably 10% by weight or more. It is 70% by weight or less, more preferably 20% by weight or more and 63% by weight or less. If it is less than 5% by weight, the adhesion of the coating to the metal foil will be reduced. 65
When the amount exceeds the weight percentage, the crosslinking of the photosensitive resin composition becomes insufficient when the coating is exposed, so that the coating is eluted into the developing solution during the development of the coating.

As the photopolymerizable unsaturated compound as the component (C) in the present invention, an acrylate or methacrylate of a polyhydric alcohol is suitable.
Triethylene glycol, tetraethylene glycol,
As acrylic acid esters or methacrylic acid esters of polyhydric alcohols such as diethylene glycol, propylene glycol, trimethylolpropane, pentaerythritol and neopentyl glycol, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol di ( (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, tri Methylolpropane tri (meth) acrylate, trimethylolpropane di (meth)
Acrylates may be mentioned as examples.

Further, amides such as methylene-bis- (meth) acrylamide and (meth) acrylamide, reaction products of diol (meth) acrylate with isocyanate or diisocyanate, triacrylformal, triallyl cyanurate, tris ( 2- (meth) acryloxyethyl) isocyanate, for example, FA-731A and FA-731M manufactured by Hitachi Chemical Co., Ltd., Aronix M-215, M-315, M-325 manufactured by Toa Gosei Chemical Co., Ltd. can be exemplified.

These photopolymerizable unsaturated compounds can be used alone or as a mixture .
The proportion of the photosensitive resin composition constituting
5% by weight or more and 60% by weight or less, more preferably 5% by weight
Not less than 50% by weight, more preferably not less than 7% by weight and 27% by weight.
% By weight or less. If the amount is less than 5% by weight, the film cannot be cured sufficiently, so that the film dissolves during development. Further, from the viewpoint of setting the softening temperature of the coating film to 25 ° C. or more, it is preferable that the content is 27% by weight or less.
If the softening temperature of the coating is less than 25 ° C., the coating may stick to the photomask during exposure.

As the photoinitiator which is the component (D) of the present invention, any initiator can be used as long as it initiates the polymerization of the unsaturated compound by irradiation with actinic rays such as ultraviolet rays. For example, benzophenones such as benzophenone and Michler's ketone; benzoin alkyl ethers such as benzoin, benzoin butyl ether, benzoin isopropyl ether and benzoin isobutyl ether;
2,2-dimethoxy-2-phenylacetophenone,
2,2-diethoxyacetophenone, 2,2-dichloro-4-phenoxyacetophenone, 2,2-cyclo-4
Acetophenones such as phenoxyacetophenone; 2
-Hydroxy-2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone; anthraquinones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone and 2-anthraquinone Thioxanthones such as diethylthioxanthone, diisopropylthioxanthone and chlorothioxanthone; other benzyl, 1-hydroxycyclohexylphenyl ketone, 2-methyl-
[4- (methylthio) phenyl] -2-morpholino-1
-Propanone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate and the like.

These photoinitiators can be used alone or as a mixture. The ratio of the photoinitiator to the photosensitive resin composition constituting the photosensitive solution composition of the present invention is 0.1% by weight or more and 20% by weight or less. More preferably, 1% by weight or more and 15% by weight or more.
% By weight or less.

In the present invention, the above components may be used depending on the purpose.
As components other than (A), (B), (C) and (D) , the following secondary components can be added in a limited range.

As a secondary component for improving the adhesiveness of the coating of the photosensitive resin composition, a polymer having no carboxyl group, for example, an acrylic resin, a polyester resin, a novolak resin, a phenoxy resin and the like can be mentioned. . Further, a thermal polymerization inhibitor for improving storage stability, fine powder of silica, talc, quartz powder, and an inorganic filler such as barium sulfate for improving fluidity can be added.

The sense of the purpose increasing the hardness of the surface of the coating of the optical resin composition or the purpose of adjusting the key structural viscosity softening temperature and screen printability, acrylic resins, polyester resins, phenolic resins, melamine resins, Epoxy resin, urethane resin, organic filler cured and ground thermosetting resin such as polyimide resin, and silica, talc,
Inorganic fillers such as silicate compounds such as mica and aluminosilicate compounds such as feldspar and kaolin, having a maximum diameter of 2 μm
The extender pigments selected from the following fine powders can be added alone or as a mixture of two or more. Maximum diameter is 2
If it exceeds μm, the critical resolution of the coating of the photosensitive resin composition exceeds 2 μm, making it difficult to form a resist suitable for forming a fine resist pattern. An appropriate amount is 5 to 50% by volume of the photosensitive resin composition. When the content is less than 5% by volume, the effect of adding a filler is not accompanied by an increase in the surface hardness and softening temperature of the coating film and the development of structural viscosity which is important for screen printability. On the other hand, if it exceeds 50% by volume, the coating becomes brittle, and becomes a coating having poor adhesion to metal foil such as copper foil.
Does not function as a resist.

Further, if necessary, a leveling agent, an antifoaming agent, a color former, a dye, a pigment and the like can be added.

Preferably used in the photosensitive composition of the present invention.
As an organic solvent or as a filler
Suitable for use as a photosensitive solution composition that is easy to apply
Solvents that dry easily and have low toxicity
Is selected. For example, methanol, ethanol,
Alcohol, isopropyl alcohol, butanol,
Isobutanol, ethyl acetate, butyl acetate, acetic acid
, Cyclohexyl acetate, methyl acetoacetate, adipine
Acid dimethyl, dimethyl glutamate, dimethyl succinate, etc.
Acetates, cyclohexanone, methylcyclohexane
Xanone, 2-butanone, methyl isobutyl ketone,
Ketones such as setone, α-terpionaire, ethylene glycol
Recall monomethyl ether acetate, ethylene glycol
Coal monoethyl ether acetate, ethylene glyco
Monobutyl ether acetate, ethylene glycol
Lumonomethyl ether, ethylene glycol monoethyl
Ether, ethylene glycol monobutyl ether, d
Tylene glycol dimethyl ether, ethylene glycol
Diethyl ether, ethylene glycol dibutyl ether
Ter, diethylene glycol monomethyl ether acete
Salt, diethylene glycol monoethyl ether acete
Salt, diethylene glycol monobutyl ether acete
, Diethylene glycol monomethyl ether, die
Tylene glycol monoethyl ether, diethylene glycol
Coal monobutyl ether, diethylene glycol dime
Tyl ether, diethylene glycol diethyl ether
Ethylene, diethylene glycol dibutyl ether, etc.
Derivatives of ethylene glycol, diethylene glycol, and
Ruen and mineral spirits are selected. These solvents
Alone or in combination to dissolve the photosensitive resin composition
It is prepared as an optical liquid composition.

Photosensitive liquid set including preferred embodiments of the present invention
In the composition, the above solvent is used, and 15 to 30 ° C.
At a liquid temperature of 1 × 10 ^{−1 to} 5 × 10 Pa · s
By adjust two, spray coating or roll coating, vinegar
Normal environment when using mesh for clean printing
Can easily form a coating. The viscosity is Tokyo
Adjust the temperature of the sample holder using an instrument EH type viscometer.
The measurement can be easily performed by performing the setting.

One example of the use of the photosensitive composition of the present invention is as follows.
This will be described below. The photosensitive solution composition of the present invention is
Coater, blade coater, immersion method, spray, electrophoresis method
Alternatively, use a screen printing method to
Exposure on metal foil of laminated board (for example, copper foil of copper clad laminate)
Apply the solution and then, usually at 30 ° C to 150 ° C
Dry for 1 to 30 minutes to form a film of the photosensitive resin composition
To achieve.

Thereafter, the coating of the photosensitive resin composition is exposed by passing active light through a negative type photomask. As a result, the pattern formed on the photomask is printed on the coating, and the exposed portions of the coating are cured.
The actinic ray source may be any as long as it effectively emits ultraviolet rays, and examples thereof include a carbon arc, a mercury vapor arc, an ultraviolet-emitting fluorescent lamp, an argon glow lamp, and a sun lamp. The light source is a high-pressure or ultra-high-pressure mercury lamp or a metal halide lamp, and an appropriate irradiation light amount is about 50 to 800 mJ / cm ² .

After exposing the coating of the photosensitive resin composition as described above, the unexposed portion of the coating is dissolved and removed with a weak alkali aqueous solution such as a 0.1 to 2% by weight aqueous sodium carbonate solution. Leave. As a result, a desired pattern is formed on the coating. Thereafter, the exposed metal foil is dissolved and removed with an etching solution such as ferric chloride, cupric chloride, persulfates, hydrogen peroxide / sulfuric acid, and alkaline etchant. The metal foil covered with the coating remains without being etched. Thereafter , the exposed portion of the coating of the photosensitive resin composition remaining on the metal foil is removed with an aqueous alkali solution such as a 1 to 4% by weight aqueous sodium hydroxide solution. As a result, a desired, for example, conductor circuit is obtained.

Further, the photosensitive solution composition of the present invention is applied on a metal foil of a metal foil laminate (for example, a copper foil of a copper-clad laminate) by the above-mentioned coating method and dried to form a film. Exposure through a positive type photomask to dissolve and remove unexposed portions of the coating, leaving exposed portions of the coating. Thus, a pattern (reverse pattern) opposite to the desired resist pattern is formed. Next, gold plating, nickel plating, solder plating, or the like is performed on the exposed portion of the metal foil to form a plating layer on the metal foil. Thereafter, the exposed portions of the coating of the photosensitive resin composition are removed from the metal foil with the above-described alkaline aqueous solution. Thereafter, the exposed portion of the unplated metal foil is dissolved and removed with an etching solution selected from the above-mentioned etching solutions so as not to attack the plating layer. As a result, a desired, for example, conductor circuit is obtained. Then, it is removed plating layer, also may be used as it is.

The structural viscosity of the photosensitive solution composition can be adjusted by adding an inorganic or organic filler to the photosensitive solution composition and dispersing and mixing with a disperser such as a roll mill, a media mill or a ball mill.

[0055] sense of roll coating a light liquid composition, a blade coater method, spray method, dipping method, electrostatic coating, applied to the metal foil surface of the metal foil laminated board using a screen printing method or the like, 30 to 150 The applied photosensitive liquid composition is dried at ゜ C for 1 to 30 minutes. Here, if the drying temperature is less than 30 ° C, not only require 30 minutes or more drying time, may not be completely dry, when exposing in a subsequent step, the photosensitive resin composition on the photomask The coating of the object may stick. On the other hand, when drying at a temperature exceeding 150 ° C., drying can be performed in a short time.
For example, there is a risk that a hard copper-clad laminate or a flexible copper-clad laminate may be thermally deformed. Drying, hot air dryer,
Various dryers for far infrared rays and infrared rays can be used.

FIG. 1 shows a schematic sectional view .
The coating 12A made of a photosensitive resin composition is
2 A laminate of the present invention in which the metal foil formed on the surface is laminated on the substrate 20 is obtained.

The thickness of the coating after drying is suitably 1 to 50 μm. When the thickness is less than 1 μm, the resistance of the coating film to an etching solution or a plating solution is insufficient. On the other hand, 50
If the thickness exceeds μm, the resolution of the film is low , and it is difficult to form a fine resist pattern. In addition, when the metal foil is etched, in a portion having a fine pattern interval of 100 μm or less, when the coating is thick, the etching rate and the plating rate become slow, and uniform etching and plating become difficult. As described above, the metal foil laminate in which the coating of the photosensitive resin composition is formed on the surface of the metal foil at a thickness of 1 to 50 μm has good characteristics with respect to the processing characteristics of etching and plating with respect to a fine pattern interval of 100 μm or less. Show.

Further, the above-mentioned object is to provide (a) a support 10 and (b) a photosensitive liquid composition containing a preferred embodiment of the present invention as schematically shown in FIG.
First coating 12 formed by coating and drying on support 10
And (c) the following (c-1), (c-2), (c-3) and
A photosensitive resin composition comprising the component (c-4);
Liquid temperature of 15 ° C to 30 ° C by mixing with solvent
At a viscosity of 1 × 10 ^-1 Pa · s to 5 × 10 Pa · s
and the softening temperature after film formation is less than 25 ° C.
A second liquid composition formed by applying a liquid composition on the first film and drying the liquid composition;
The photosensitive film is characterized by comprising a coating 14 of Here, (c-1) half esterification represented by the general formula (1)
Compound

Embedded image (C-2) having a carboxyl group and having a glass transition temperature of 6
0 ° C to 150 ° C saturated polymer (c-3) photopolymerizable unsaturated compound (c-4) photoinitiator

Component (C) in the photosensitive resin composition ,
By changing the amount of the component (c-3), a first film and a second film having different softening temperatures can be formed. By providing the second coating having a low softening temperature,
Adhesion to the metal foil and embedding of the photosensitive film into a scratch formed on the metal foil can be improved. Further, since the first coating having a high softening temperature is present, adhesion between the photomask film and the coating can be prevented.

The thickness of the first coating is 1 to 46 μm, and the thickness of the second coating is
The thickness of the film is preferably 49 to 4 μm.

If the thickness of the first coating is less than 1 μm, the coating sticks to the photomask. On the other hand, when the thickness exceeds 46 μm, the total thickness of the photosensitive film increases, and the resolution, etching characteristics and plating characteristics are impaired. On the other hand, if the thickness of the second coating is less than 4 μm, it becomes difficult to embed the coating in a scratch generated in the metal foil of the metal foil laminate, and a gap is generated between the coating and the scratch generated in the metal foil. The second coating has a thickness of 49 μm.
If it exceeds m, the total thickness of the photosensitive film becomes large.

As the support, for example, a plastic film such as polyethylene terephthalate, polypropylene, polyethylene and polyvinyl chloride is suitable. These supports must be capable of being peeled off from the first coating prior to exposure after the second coating is laminated to the metal foil laminate by thermocompression bonding. The thickness of the support is 5 to 100.
μm is appropriate from the viewpoint of workability, and particularly preferably 1 μm.
It is 0 to 30 μm. The three-layer photosensitive film is
It is possible to take up and save.

A photosensitive film comprising (a) a support and (b) a coating comprising the photosensitive composition formed on the support is prepared from a photosensitive composition comprising a preferred embodiment of the present invention. You can also. In this case, the thickness of the coating is 1
It is preferably from 50 to 50 μm.

In addition to the method of directly applying the photosensitive liquid composition to the metal foil laminate as described above, a photosensitive film of the present invention is prepared and a second coating having a low softening temperature is thermocompression-bonded to the metal foil laminate. By doing so, it is possible to obtain a metal foil laminated plate in which a photosensitive film is laminated on the surface of the metal foil as shown in a schematic sectional view in FIG. Here, as the metal foil of the metal foil laminate, various metal foils such as copper, nickel, stainless steel, iron, gold, silver, and molybdenum can be exemplified. In addition, examples of the base material of the laminated plate on which the metal foil is laminated include glass epoxy, paper phenol, polyimide resin, polyimide film, polyester film, ceramic, and a metal plate having an insulating layer. Preferably, the photosensitive film can be thermocompression-bonded more efficiently by first warming the metal foil laminate.

[0065]

The feature of the present invention resides in that a (meth) acryloyl group is introduced into a copolymer of styrene and maleic anhydride. When a methoxy group is introduced in place of the (meth) acryloyl group Xr, the strength of the coating does not appear at all, the curing sensitivity of the coating by ultraviolet irradiation is lost, and no photosensitivity is exhibited.
When no substituent is introduced and the copolymer of styrene and maleic anhydride itself is used, no film is formed in the first place.

The resin obtained by introducing a (meth) acryloyl group into a copolymer of styrene and maleic anhydride has photosensitivity per se, and has higher photosensitivity by adding a small amount of a photopolymerizable unsaturated compound. It can be a photosensitive resin composition, and the softening temperature of the photosensitive resin composition can be kept high.

A feature of the photosensitive solution composition of the present invention is that a saturated polymer having a carboxyl group and having a glass transition temperature of 60 to 150 ° C. is used. Thus, that Ki is possible to improve the adhesion to the metal coating. Further, the adhesiveness of the coating can be further reduced, and the coating can be easily removed by a stripping solution composed of an alkaline aqueous solution.

[0068]

Embodiments of the present invention will be described below.

REFERENCE EXAMPLE 1 200 g of a copolymer of styrene and maleic anhydride (SMA Resin 1000 manufactured by Arco Chemical Co., Ltd.) and 130 g of 2-hydroxyethyl methacrylate were dissolved in 300 g of butyl cellosolve acetate and reacted at 100 ° C. for 20 hours. A half-esterified compound (A-1) was obtained. The resin content was 52% by weight.

160 g of n-butyl acrylate, 540 g of methyl methacrylate, 100 g of 2-hydroxyethyl methacrylate and 200 g of acrylic acid are polymerized in 1000 g of butyl cellosolve acetate in the presence of a peroxide to obtain a saturated polymer having a carboxyl group (B -1)
A solution was obtained. The glass transition temperature was 60 ° C., the carboxyl equivalent was 360, and the resin content was 50% by weight.

These half-esterified compounds (A-1)
And based on the polymer (B-1) a saturated, shown in Table 2 below
The photosensitive solution of a photosensitive resin composition to formulation was prepared.

[0072]

Table 2 Formulation (parts by weight) Half-esterified compound (A-1) 30 Carboxyl group-containing saturated polymer (B-1) 30 Trimethylolpropane triacrylate (C-1) 3 FA-731A manufactured by Hitachi Chemical Co., Ltd. C-1 ′) 2 2-Methyl- [4- (methylthio) phenyl] -2-morpholino-1-propane (D-1) 3 leucocrystal violet (tris (4-dimethylaminophenyl) methane) 0.1 fine Powdered silica 3 butyl cellosolve acetate 28.9

The parts by weight in the above-mentioned composition are (A)
Each of the components -1) and (B-1) is the sum of the solid content and the solvent constituting each component. still,
The components (C-1), (C-1 ') and (D-1) have a solid content of 100%. Half-esterified compound [(A) component], saturated polymer [(B) component], photopolymerizable unsaturated compound [(C)) with respect to the photosensitive resin composition of the present invention .
The ratio of each of the components] and the photoinitiator [(D) component] refers to the weight percent of each component converted to the solid content based on the total solid content of these components. The same applies to the following embodiments.

A photosensitive solution was prepared according to the above formulation, and the photosensitive solution was applied on a copper foil of a copper-clad laminate using a doctor blade, and dried at 80 ° C. for 10 minutes using a hot-air dryer. As a result, a smooth film of the photosensitive resin composition having no tackiness was obtained. The thickness of the coating was 15 μm. Then, exposure was performed for 15 seconds from a distance of 50 cm using a 5 kW ultra-high pressure mercury lamp through a negative type photomask. At this time, the integrated light amount was 200 mJ / cm ² .

Next, the coating was developed by spraying a 1% by weight aqueous solution of sodium carbonate at 30 ° C. for 1 minute. The unexposed portion was dissolved, and a high-precision circuit pattern corresponding to a negative-type photomask was formed on the film. The pencil hardness of the exposed portion of the coating was 3H. The exposed portion of the copper foil that is not covered with the coating is removed by etching with a ferric chloride solution, and then the exposed portion of the coating is removed from the copper foil by spraying a 3% by weight aqueous solution of sodium hydroxide at 40 ° C. did. The time required for removal was 15 seconds. In this way, a printed wiring board having a circuit with a conductor width of 50 μm and an interval between conductors of 50 μm was formed. A printed wiring board having no break or short circuit in the conductor could be manufactured with a yield of 98% or more.

Reference Example 2 300 g of a copolymer of styrene and maleic anhydride (SMA Resin 2000 manufactured by ARKO CHEMICAL Co., Ltd.) and 116 g of 2-hydroxyethyl acrylate were added to cellosolve acetate 3.
The resultant was dissolved in 00 g and reacted at 110 ° C. for 15 hours to obtain a half-esterified compound (A-2). The resin content was 58% by weight.

After 111 g of ethylene glycol, 296 g of phthalic anhydride and 13 g of trimethylolpropane were esterified by a dehydration reaction, cellosolve acetate 353 was obtained.
g, to obtain a saturated polymer (B-2) having a carboxyl group. The carboxyl equivalent was 1175, the glass transition temperature was 75 ° C., and the resin content was 52% by weight.

These half-esterified compounds (A-2)
And based on the saturation of the polymer (B-2), shown in Table 3 below
The photosensitive solution of a photosensitive resin composition to formulation was prepared.

[0079]

Table 3 Formulation (parts by weight) Half-esterified compound (A-2) 38 Carboxyl group-containing saturated polymer (B-2) 25 Aronix M-325 (C-2) 12 Triallyl cyanurate (C-2 ') ) 10 2-Hydroxy-2-methylpropiophenone (D-2) 6 2,2-Diethoxyacetophenone (D-2 ′) 0.6 P-dimethylaminobenzoic acid ethyl ester (D-2 ′) 6 Tris (4-dimethylaminophenyl) methane 0.05 talc 2 cellosolve acetate 5.75

A photosensitive solution having the above composition was prepared and applied to a copper foil of a copper-clad laminate using a roll coater. Next, the photosensitive solution was dried at 80 ° C. for 10 minutes to obtain a 10 μm-thick film of the photosensitive resin composition. Exposure was performed for 12 seconds from a distance of 50 cm using a 5 kW ultra-high pressure mercury lamp through a negative type photomask. Next , the coating was developed by spraying a 1% by weight aqueous solution of sodium carbonate at 30 ° C. for 50 seconds to form a high-precision circuit pattern corresponding to the circuit pattern formed on the negative type photo film on the coating.

The pencil hardness of the exposed portion of the coating was 3H. After the exposed copper foil not covered with the coating was removed by etching in the same manner as in Reference Example 1 , the exposed portion of the coating was removed from the copper foil by spraying a 2% by weight aqueous solution of sodium hydroxide at 40 ° C. The removal time was 17
Seconds. In this way, a printed wiring board having a circuit with a conductor width of 50 μm and an interval between conductors of 50 μm was formed. A printed wiring board with no break or short circuit in the conductor could be manufactured with a yield of 97% or more.

[ Reference Example 3 ] 100 g of a copolymer of styrene and maleic acid (SMA resin 1000 manufactured by ARKO CHEMICAL Co., Ltd.) and 200 g of 2-hydroxypropyl methacrylate were added to cellosolve acetate 3.
The resulting mixture was dissolved in 00 g and reacted at 110 ° C. for 24 hours to obtain a half-esterified compound (A-3). 5 for resin
It was 0% by weight.

380 g of n-butyl acrylate, 420 g of methyl methacrylate, 80 g of 2-hydroxyethyl methacrylate, and 120 g of acrylic acid were polymerized in the same manner as in Reference Example 1 to obtain a saturated polymer (B-3) solution having a carboxyl group. I got The glass transition temperature was 20 ° C., the carboxyl equivalent was 600, and the resin content was 50% by weight.

These half-esterified compounds (A-3)
And based on the saturation of the polymer (B-3), shown in Table 4 below
The photosensitive solution of a photosensitive resin composition to formulation was prepared.

[0085]

Table 4 Formulation (parts by weight) Half-esterified compound (A-3) 120 Carboxyl group-containing saturated polymer (B-3) 24 Triethylene glycol diacrylate (C-3) 15 Trimethylolpropane triacrylate (C- 3 ′) 10 1-hydroxycyclohexyl phenyl ketone (D-3) 2 2,2-dimethoxy 2-phenylacetophenone (D-3 ′) 1 cellosolve acetate 20

A photosensitive solution having the above composition was prepared, and was applied by spraying onto a copper foil of a copper-clad laminate. After that, participants
The photosensitive solution was dried in the same manner as in Example 2 to form a film of the photosensitive resin composition, and after exposure, development and etching, the exposed portion of the film was removed from the copper foil. The film thickness after drying is 8 μm,
The pencil hardness of the coating was 4H. The time required to remove the exposed portion of the coating from the copper foil was 20 seconds. In this way, a printed wiring board having a circuit with a conductor width of 50 μm and an interval between conductors of 50 μm was formed.
A printed wiring board having no break or short circuit in the conductor could be manufactured with a yield of 96% or more.

Reference Example 4 The photosensitive solution obtained in Reference Example 1 was applied on a copper foil of a copper-clad laminate using a roll coater. Then, a reference example
The photosensitive solution was dried in the same manner as in Example 2 to form a film of the photosensitive resin composition, which was then exposed and developed. At the time of exposure, a positive photomask on which a pattern opposite to a circuit pattern to be formed was formed was used. The thickness of the film after drying was 11 μm. Next, the copper-clad laminate was immersed in a gold plating solution, and the exposed portion of the copper foil was subjected to gold plating. The conditions of gold plating were as follows: potassium cyanide 2 g / liter;
Using a plating solution of 0 and 40 ° C., a current of 1 A / dm ^{2 was applied} for 30 seconds. The thickness of the obtained gold plating layer is 0.6μ
m.

Next, the exposed portion of the coating was removed from the copper foil by spraying a 3% by weight aqueous solution of sodium hydroxide at 40 ° C. Thereafter, the exposed copper foil portion was removed by etching with a ferric chloride etching solution to obtain a desired conductor circuit. In this way, a printed wiring board having a circuit with a conductor width of 50 μm and an interval between conductors of 50 μm was formed. A printed wiring board having no break or short circuit in the conductor could be manufactured with a yield of 98% or more.

Reference Example 5 The photosensitive solution obtained in Reference Example 2 was applied on a copper foil of a copper-clad laminate using screen printing. Thereafter, the photosensitive liquid was dried in the same manner as in Reference Example 2 to form a film of the photosensitive resin composition, which was then exposed and developed. At the time of exposure, a positive photomask on which a pattern opposite to a circuit pattern to be formed was formed was used. The film thickness after drying is 13
μm. Next, the copper-clad laminate was immersed in a nickel plating solution, and the exposed portion of the copper foil was subjected to nickel plating. Nickel plating condition is NiSO ₄ 300mg
/ Liter, NiCl ₂ 45mg / liter, H ₃ BO
₃ 45 mg / liter, pH 4.2, using a plating solution temperature of 55 ° C, were energization of 3A / dm ² 12 min. The thickness of the obtained nickel plating was 3 μm.

Thereafter, the exposed portion of the coating was removed from the copper foil by spraying a 3% by weight aqueous solution of sodium hydroxide at 40 ° C. Next, the exposed copper foil portion was removed by etching using an ammonia complex-based alkali etching solution to obtain a desired conductor circuit. In this way, a printed wiring board having a circuit with a conductor width of 50 μm and an interval between conductors of 50 μm was formed. A printed wiring board having no break or short circuit in the conductor could be manufactured with a yield of 98% or more.

Reference Comparative Example 1 Using the material obtained in Reference Example 1 , a photosensitive solution was prepared according to the composition shown in Table 5 below.

[0092]

Table 5 Formulation (parts by weight) Half-esterified compound (A-1) 58 Carboxyl group-containing saturated polymer (B-1) 2 Trimethylolpropane triacrylate (C-1) 3 FA-731A (C-1 ') ) 2 2-Methyl- [4- (methylthio) phenyl] -2-morpholino-1-propane (D-1) 3 Leuco crystal violet 0.1 Fine powder silica 3 Butyl cellosolve acetate 28.9

In the above composition, the ratio of the saturated polymer (B-1) to the photosensitive resin composition is 2.6% by weight, which is less than 5% by weight. Therefore, the pencil strength of the coating after exposure was 3H, but the adhesion was so strong that blocking between the copper-clad laminates occurred, or the negative type photomask and the coating adhered during exposure. As a result, the printed wiring board on which a circuit having a conductor width of 50 μm and a distance between the conductors of 50 μm is formed frequently breaks and shorts, and the yield of the printed wiring board having no breaks or shorts in the conductor is 60% or less. there were.

Reference Comparative Example 2 Of the composition of the photosensitive solution obtained in Reference Example 2 , 4 parts by weight of the half esterified compound (A-2) was added, and the carboxyl group-containing saturated polymer (B-2) was added. A photosensitive solution was prepared in which the proportion of the other components was the same, except that the proportion of the component was 59 parts by weight. This photosensitive solution was applied, dried, developed, and etched in the same manner as in Reference Example 2, and then the exposed portion of the film was removed.

In the above composition, the ratio of the half-esterified compound (A-2) to the photosensitive resin composition is 5%.
Less than 3.7% by weight. Therefore, the coating was developed using a 1% by weight aqueous solution of sodium carbonate at 30 ° C. as a developing solution. However, spraying such a developing solution for 1 minute was insufficient for development, and the unexposed portion of the coating was completely removed. It took 7 minutes finally to dissolve and remove.
The time required to remove the exposed portion of the coating from the copper foil was 95 seconds. The pencil strength of the exposed film was only H. The conductor width is 50 μm, and the distance between the conductors is 50 μm.
Many breaks and shorts occurred in the printed wiring board on which the circuit of m was formed, and the yield of the printed wiring board in which no break or short occurred in the conductor was 50% or less.

[ Reference Comparative Example 3 ] The photosensitive solution obtained in Reference Comparative Example 1 was coated, dried, developed, plated and etched in the same manner as in Reference Example 4, and then the exposed portion of the film was removed from the copper foil. . The exposed portion of the coating peeled off from the copper foil surface during plating. Conductor width 50 μm,
Disconnection and short-circuit frequently occur in a printed wiring board on which a circuit with a spacing of 50 μm between conductors is formed, and the yield of the printed wiring board in which the conductor is not disconnected or short-circuited is 1
0% or less.

Next, the photosensitive composition and the photosensitive composition of the present invention will be described.
Examples related to the film are described in Examples 1 to 8,
A description will be given based on Examples 1 to 4 and Reference Examples 6 to 8 .

[0098] half ester compound of Reference Example 1 (A-
The same half-esterified compound (A'-1) as in 1) and the same half-esterified compound (A'-2) as the half-esterified compound (A-2) in Reference Example 2 were produced. Also, Reference Example 2 saturated polymer (B-2) having the same saturation as the polymer (B'-1), and a saturated Reference Example 1 polymer (B
A polymer (B'-2) having the same saturation as in -1) was prepared.

Using the half-esterified compound (A'-1) and the saturated polymer (B'-1), a photosensitive solution composition (referred to as LR1) having the composition shown in Table 6 below was prepared. Prepared. still,
The parts by weight in the formulations described below are (A'-1)
Each of the components (A'-2), (B'-1) and (B'-2) is the sum of the solid content and the solvent constituting each component. (C'-1) and (D'-1)
The components are 100% solids.

[0100]

Table 6 (photosensitive solution composition: LR1) formulation (parts by weight) half ester compound (A'-1) 80 carboxyl group-containing saturated polymer (B'-1) 80 Trimethylolpropane triacrylate (C'- 1) 20 2-Methyl- [4- (methylthio) phenyl] -2-morpholino-1-propane (D'-1) 4 (tris (4-dimethylaminophenyl) methane) 0.5 carbon tetrabromide 5 Butyl cellosolve acetate 20

Using the half-esterified compound (A'-1) and the saturated polymer (B'-1), a photosensitive solution composition (referred to as LR2) having the composition shown in Table 7 below was prepared. Prepared.

[0102]

TABLE 7 (photosensitive solution composition: LR2) formulation (parts by weight) half ester compound (A'-1) 94 carboxyl group-containing saturated polymer (B'-1) 94 Trimethylolpropane triacrylate (C'- 1) 6 2-Methyl- [4- (methylthio) phenyl] -2-morpholino-1-propane (D'-1) 4 (tris (4-dimethylaminophenyl) methane) 0.57 carbon tetrabromide 5 Butyl cellosolve acetate 2

Using the half-esterified compound (A'-1) and the saturated polymer (B'-1), a photosensitive solution composition (referred to as LR3) having the composition shown in Table 8 below was prepared. Prepared.

[0104]

TABLE 8 (photosensitive solution composition: LR3) formulation (parts by weight) half ester compound (A'-1) 70 carboxyl group-containing saturated polymer (B'-1) 70 Trimethylolpropane triacrylate (C'- 1) 30 2-Methyl- [4- (methylthio) phenyl] -2-morpholino-1-propane (D'-1) 4 (tris (4-dimethylaminophenyl) methane) 0.5 carbon tetrabromide 5 Butyl cellosolve acetate 50

Using the half-esterified compound (A'-2) and the saturated polymer (B'-2), a photosensitive solution composition (referred to as LR4) having the composition shown in Table 9 below was prepared. Prepared.

[0106]

TABLE 9 (photosensitive solution composition: LR4) formulation (parts by weight) half ester compound (A'-2) 80 carboxyl group-containing saturated polymer (B'-2) 80 Trimethylolpropane triacrylate (C'- 1) 20 2-Methyl- [4- (methylthio) phenyl] -2-morpholino-1-propane (D'-1) 4 (tris (4-dimethylaminophenyl) methane) 0.5 carbon tetrabromide 5 Butyl cellosolve acetate 20

Using the half-esterified compound (A'-2) and the saturated polymer (B'-2), the results are shown in Table 10 below.
Photosensitive composition of the be blended (a LR5) was prepared.

[0108]

TABLE 10 (photosensitive solution composition: LR5) formulation (parts by weight) half ester compound (A'-2) 130 carboxyl group-containing saturated polymer (B'-2) 30 Trimethylolpropane triacrylate (C'- 1) 20 2-Methyl- [4- (methylthio) phenyl] -2-morpholino-1-propane (D'-1) 4 (tris (4-dimethylaminophenyl) methane) 0.5 carbon tetrabromide 5 Butyl cellosolve acetate 20

Using the half-esterified compound (A'-2) and the saturated polymer (B'-2), the results are shown in Table 11 below.
Photosensitive composition of the be blended (a LR6) was prepared.

[0110]

Table 11 (Photosensitive composition: LR6) Compounding (parts by weight) Half-esterified compound (A'-2) 30 Carboxyl group-containing saturated polymer (B'-2) 130 Trimethylolpropane triacrylate (C'-) 1) 20 2-Methyl- [4- (methylthio) phenyl] -2-morpholino-1-propane (D'-1) 4 (tris (4-dimethylaminophenyl) methane) 0.5 carbon tetrabromide 5 Butyl cellosolve acetate 20

Using the half-esterified compound (A'-1) and the saturated polymer (B'-1), the results are shown in Table 12 below.
Photosensitive composition of the be blended (a LR7) was prepared.

[0112]

Table 12 (photosensitive solution composition: LR7) formulation (parts by weight) half ester compound (A'-1) 60 carboxyl group-containing saturated polymer (B'-1) 60 Trimethylolpropane triacrylate (C'- 1) 40 2-Methyl- [4- (methylthio) phenyl] -2-morpholino-1-propane (D'-1) 4 (tris (4-dimethylaminophenyl) methane) 0.5 carbon tetrabromide 5 Butyl cellosolve acetate 40

A filler composed of talc was added to the photosensitive solution of (LR7), and the mixture was uniformly dispersed and mixed by a roll mill to obtain a photosensitive solution composition containing filler (LR7-) shown in Table 13 below.
F1) was prepared.

[0114]

(Table 13) Filler-containing photosensitive solution composition: LR7-F1 Formulation (parts by weight) Photosensitive solution composition (LR7) 100 Talc 30 Butyl cellosolve acetate 30

A filler composed of talc was added to the photosensitive solution of (LR7), and the mixture was uniformly dispersed and mixed by a roll mill to obtain a photosensitive solution composition containing filler (LR7-) shown in Table 14 below.
F2) was prepared.

[0116]

[Table 14] (Photosensitive composition with filler: LR7-F2) Formulation (parts by weight) Photosensitive composition (LR7) 100 Talc 5 Butyl cellosolve acetate 5

A filler composed of talc was added to the photosensitive solution of (LR7), and the mixture was uniformly dispersed and mixed by a roll mill to obtain a photosensitive solution composition containing filler (LR7-) shown in Table 15 below.
F3) was prepared.

[0118]

(Table 15) Filler-containing photosensitive solution composition: LR7-F3 Formulation (parts by weight) Photosensitive solution composition (LR7) 100 Talc 130 Butyl cellosolve acetate 130

The photosensitive composition of (LR1) was prepared to have a thickness of 20 μm.
8 with a reverse coater
After drying at 0 ° C. for 15 minutes, a coating (first coating) of the photosensitive resin composition composed of (LR1) was obtained. Next (LR1)
Further, on the first film comprising (LR3), the photosensitive solution composition of (LR3) was further applied by a reverse coater and dried at 80 ° C. for 15 minutes to form a film of the photosensitive resin composition of (LR3) (No. 2). After drying, the thickness of the first coating consisting of (LR1) was 5 μm, and the thickness of the second coating consisting of (LR3) was 25 μm. Thus, a three-layer photosensitive film (FR1) was produced.

A photosensitive solution composition (LR7-F1) having a thickness of 2
A 0 μm polyester film was coated with a reverse coater and dried at 80 ° C. for 15 minutes to obtain a coating (first coating) of the photosensitive resin composition (LR7-F1).
R7-F1), and further (LR)
The photosensitive liquid composition of 3) was applied by a reverse coater and dried at 80 ° C. for 15 minutes to obtain a coating (second coating) of the photosensitive resin composition (LR3). After drying, (LR7-F
The thickness of the first coating consisting of 1) is 5 μm and (LR)
The thickness of the second coating consisting of 3) was 25 μm. Thus, a three-layer photosensitive film (FR2) was produced.

The photosensitive composition of (LR1) was prepared to have a thickness of 20 μm.
8 with a reverse coater
After drying at 0 ° C. for 15 minutes, a 30 μm-thick film of the photosensitive resin composition composed of (LR1) was obtained. Thus, a two-layer photosensitive film (FR3) was produced.

Hereinafter, examples in which a photosensitive layer (coating) is formed on a copper-clad laminate using the prepared and prepared photosensitive solution composition and photosensitive film will be described. In order to directly form a photosensitive layer (coating) composed of the photosensitive solution composition on a hard copper-clad laminate or a flexible copper-clad laminate, the copper foil of the copper-clad laminate was washed with a 5% aqueous sulfuric acid solution, washed with water, and dried. Thereafter, a film of the photosensitive resin composition is formed on the copper foil. A bar coater was used for applying the photosensitive liquid composition. Further, the photosensitive solution composition,
It was dried with a hot air drier at 80 ° C. for 15 minutes. To attach the photosensitive film to the copper-clad laminate, wash the copper foil of the copper-clad laminate in advance with a 5% sulfuric acid aqueous solution, rinse with water, and dry.
The copper-clad laminate was heated to 80 ° C, and the coating of the photosensitive film and the copper foil were combined and bonded at a speed of 2 m / min at a pressure of 3 kg / cm ² with a metal roll heated to 100 ° C. Next, the polyester film as the support was peeled off. Thus, a coating was formed on the copper foil of the copper-clad laminate.

Example 1 The photosensitive liquid composition (LR1) was applied on a copper foil and dried by the method described above to obtain a 20 μm-thick film of the photosensitive resin composition.

Reference Example 6 The photosensitive solution composition (LR2) was applied on a copper foil and dried by the method described above to obtain a 20 μm-thick film of the photosensitive resin composition.

[ Comparative Example 1 ] The photosensitive solution composition (LR3) was applied on a copper foil and dried by the above-mentioned method to obtain a 20 µm-thick film of the photosensitive resin composition.

Example 2 The photosensitive liquid composition (LR4) was applied on a copper foil and dried by the method described above to obtain a 20 μm-thick film of the photosensitive resin composition.

Example 3 The photosensitive solution composition (LR5) was applied on a copper foil and dried by the method described above to obtain a 20 μm-thick film of the photosensitive resin composition.

Example 4 The photosensitive solution composition (LR6) was applied on a copper foil and dried by the method described above to obtain a 20 μm-thick film of the photosensitive resin composition.

Comparative Example 2 The photosensitive liquid composition (LR7) was applied on a copper foil and dried by the method described above to obtain a 20 μm-thick film of the photosensitive resin composition.

Example 5 The photosensitive liquid composition (LR7-F1) was applied on a copper foil and dried by the method described above to obtain a 20 μm-thick film of the photosensitive resin composition.

Reference Example 7 The photosensitive liquid composition (LR7-F2) was applied on a copper foil and dried by the method described above to obtain a 20 μm-thick film of the photosensitive resin composition.

Example 6 The photosensitive liquid composition (LR7-F3) was applied on a copper foil and dried by the above-mentioned method to obtain a 20 μm film of the photosensitive resin composition.

Example 7 A photosensitive film (FR-1) was laminated on a copper foil by the method described above to obtain a two-layer coating of a photosensitive resin composition having a thickness of 25 μm.

Example 8 A photosensitive film (FR-2) was laminated on a copper foil by the method described above to obtain a two-layered film of a photosensitive resin composition having a thickness of 25 μm.

Reference Example 8 A photosensitive film (FR-3) was laminated on a copper foil in the same manner as described above to obtain a 30 μm-thick one-layer coating of a photosensitive resin composition.

Comparative Example 3 A commercially available dry film was laminated on a copper foil by the method described above to obtain a 50 μm-thick film of the photosensitive resin composition. Exposure was performed through a transparent film support (20 μm thickness) as usual.

Comparative Example 4 A commercially available dry film was laminated on a copper foil by the method described above to obtain a 50 μm film of the photosensitive resin composition. The exposure was performed by peeling the transparent film support.

[ Examples 1 to 8, Comparative Examples 1 to 4, and Reference
Examples 6 to 8 Evaluation Method] Examples 1 to 8, Comparative Examples 1 to 4, and Reference Examples
6 to Reference Example 8 were evaluated so that the difference between the above-described conventional photosensitive composition and the present invention could be confirmed. In particular, the function as an etching resist for forming a fine circuit pattern was evaluated. For evaluation, 30 μm to 200 μm
using a photomask film and ultra-high pressure mercury lamp that is depicted in μm up to 10μm increments, the exposure amount of 1 mJ / cm ² in the coating of the part to be cured by exposure is exposed in the exposure time to be irradiated.

The film was developed at a temperature of 29 to 30 ° C.
Developing was performed according to the thickness of the photosensitive layer using a spray type developing machine of an 8% by weight aqueous sodium carbonate solution. The etching of the copper foil was performed for 2 minutes by a spray type etching apparatus using an etching solution obtained by heating a 20% by weight aqueous solution of ferric chloride to 45 ° C. Plating is performed using a pyrophosphoric acid bath.
Solder plating was performed. The conditions of the solder plating were as follows: tin pyrophosphate 20 g / liter, lead nitrate 17 g / liter,
Using a tin-lead alloy plate as an anode and a sample substrate for evaluation as a cathode in an electrolytic bath containing 200 g / liter of pyrophosphoric acid, a plating solution temperature of 60 ° C. and a current density of 2 A / d
m ² , 20 minutes.

Further, the required performance was evaluated as follows. (1) Adhesion The temperature of the coating of the photosensitive resin composition at the time of exposure was maintained at 30 ° C., and the presence or absence of adhesion between the photomask film and the coating was evaluated. After exposing 10 sheets of the photosensitive resin composition coatings using the same photomask film, dirt on the photomask film due to adhesion was confirmed by the rate of decrease in the amount of transmitted ultraviolet light before and after the test.

(2) Critical resolution The line width of 100 μm drawn on the photomask film and the line width of the film of the photosensitive resin composition formed after exposure and development were measured and drawn on the photomask film. The absolute value of the increase and decrease in the line width of the line width and the line width of the actually formed photosensitive resin composition film was shown.

(3) Adhesion resistance to etching solution A copper-clad laminate having at least 10 coatings of a photosensitive resin composition having a width of 100 μm was prepared by adding 50% by weight of an aqueous ferric chloride solution.
When the copper foil is excessively etched using a spray-type etching apparatus using an etching solution heated to 50 ° C., the minimum copper foil in which a 100 μm-wide film of the photosensitive resin composition completely remains Indicated by width.

(4) Etching rate ratio A line of a film of the photosensitive resin composition is formed by exposure and development. Then, using the above-mentioned etching apparatus, the line-to-line interval is set to 200 for a line width of 100 μm.
Assuming that the copper foil etching rate of the μm portion is 1, the copper foil etching rate of the portion where the line-to-line spacing is 50 μm is shown as a ratio.

(5) Adhesion Resistance to Plating Solution The width of the plating layer which has penetrated the coating of the photosensitive resin composition having a width of 100 μm formed by exposure and development using the plating process shown above.

(6) Plating rate ratio A line of a coating of the photosensitive resin composition is formed by exposure and development. Then, using the plating process described above, the line-to-line spacing is set to 20 for a line width of 100 μm.
When the plating speed for the copper foil at the portion of 0 μm was set to 1, the plating speed for the copper foil at the portion where the interval between the lines was 50 μm was shown as a ratio.

(7) Developing time The developing time under the developing conditions described above is shown.

(8) Peeling time The coating of the photosensitive resin composition is exposed at an exposure of 100 mJ / cm ² to cure the coating. The copper-clad laminate on which the coating was formed was immersed in a 3% by weight aqueous solution of sodium hydroxide heated to 45 ° C., and the time was measured until the coating swelled and peeled off the copper foil.

(9) Embedding into wounds formed on copper foil Before forming a coating of the photosensitive resin composition on the copper foil, a knife wound having a depth of 5 to 70 μm was formed on the copper foil of the copper-clad laminate. Is formed, and a film of the photosensitive resin composition is formed on the wound. Cross-section observation of the cross section at each depth of the flaw was performed, and the maximum depth at which the photosensitive resin was sufficiently filled to the deepest part of the flaw was shown.

(10) Softening temperature Using a thermal mechanical analyzer, the formed film of the photosensitive resin composition was heated together with the copper-clad laminate, and a palpation needle was placed on the film of the photosensitive resin composition. The amount of displacement of the needle due to thermal expansion during the heating process and the amount of displacement of the needle due to softening of the coating were measured together with the sample temperature. The temperature at which penetration of the palpation needle into the coating started was defined as the temperature at which softening started.

Examples 1 to 8 and Comparative Examples 1 to Comparative Examples
Tables 16 and 17 show the results of evaluation of No. 4 and Reference Examples 6 to 8 by the method described above.

[0151]

[Table 16]

[0152]

[Table 17]

[0153]

By using the photosensitive composition of the present invention, fine processing of metal foil can be easily performed with high precision and high yield, and the time required for developing the film can be improved.
The time required for removing the coating from the copper foil can be reduced. Further, the photosensitive solution composition of the present invention has excellent resistance to a plating solution.

[0154] sensitive light liquid compositions of the present invention and the photosensitive film
By forming a photosensitive resin film based on , excellent resolution, it is possible to reliably embed the scratches on the copper foil surface of the copper-clad laminate, because there is no adhesion between the photosensitive resin composition film and the photomask film In addition, the optical path length at the time of exposure can be shortened, and light scattering can be prevented, so that a resist pattern with high accuracy and high yield can be formed. In addition, even a thin film has excellent resistance to an etching solution or a plating solution, a small difference between an etching rate and a plating rate between a fine portion and a rough portion between resist patterns, and a high accuracy and excellent uniformity, for example, a printed wiring board. Can be manufactured.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of a metal foil laminate having a coating made of a photosensitive solution composition of the present invention formed on a metal foil surface.

FIG. 2 is a schematic sectional view of the photosensitive film of the present invention.

FIG. 3 is a schematic cross-sectional view of a metal foil laminate obtained by laminating a photosensitive film of the present invention on a metal foil surface.

FIG. 4 is a view for explaining a circuit forming step using a conventional dry film.

FIG. 5 is a diagram showing a problem in circuit formation using a conventional dry film.

6 is a diagram showing an outline of a circuit formed using the photosensitive resin composition.

[Figure 7] different from the FIG 6 is a diagram showing an outline of a circuit formed using the photosensitive resin composition.

[Explanation of symbols]

 Reference Signs List 10 support 12A coating 12 first coating 14 second coating 20 base material 22 copper foil 24 transparent film support of dry film 26 coating in dry film 28 photomask 30, 32, 34 resist pattern 40, 40A Coating 42 Plating layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/033 G03F 7/033 H05K 3/06 H05K 3/06 H (72) Inventor Kunio Nishihara 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa No. Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Kazuyoshi Ono 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Toatsu Chemical Co., Ltd. (56) References JP-A-2-47657 (JP, A) JP-A-2-166452 (JP, A) JP-A-61-201237 (JP, A) JP-A-64-55550 (JP, A) JP-A-2-154264 (JP, A) JP-A-2-5061 (JP) , A) (58) Field surveyed (Int.Cl. ⁶ , DB name) G03F 7/038 C08F 2/44 C08F 299/00 G03F 7/004 G03F 7/027 G03F 7/033

Claims (5)

(57) [Claims] (A) a half-esterified compound represented by the general formula (1): (B) A saturated polymer having a carboxyl group; (C) a photopolymerizable unsaturated compound; and (D) a photoinitiator. 15 ~ 30 ~ C
At a liquid temperature of 1 × 10 ⁻¹ Pa · s to 5 × 10
A photosensitive liquid composition having a Pa · s, which reduces the adhesiveness of the surface of the photosensitive liquid composition when the film is formed, and improves the releasability of the formed photosensitive liquid composition with an aqueous alkali solution. Therefore, the saturated polymer is 60
The solid content of the photopolymerizable unsaturated compound has a glass transition temperature of た め C to 150 ° C. and a softening temperature of 25 ° C. or higher when the photosensitive composition is formed into a film.
The total solid content of the components (A) and (B) is 100
A photosensitive solution composition comprising 10 parts by weight to 30 parts by weight in terms of parts by weight. 2. The photosensitive liquid composition according to claim 1, further comprising an inorganic filler or an organic filler. (A) a support; and (b) a first coating formed by applying the photosensitive composition of claim 1 or 2 on the support and drying; and (c) A) a mixture of a photosensitive resin composition composed of the following components (c-1), (c-2), (c-3) and (c-4) and an organic solvent, at 15 ° C. The viscosity at a liquid temperature of 1 to 10 ° C. is 1 × 10 ⁻¹ Pa · s to 5 × 10 Pa · s.
s, and a photosensitive solution composition having a softening temperature after film formation of less than 25 ° C. is applied on the first film and dried.
A photosensitive film, comprising: a film of: (C-1) Half-esterified compound represented by the general formula (1) (C-2) having a carboxyl group and having a glass transition temperature of 6
0 ° C to 150 ° C saturated polymer (c-3) Photopolymerizable unsaturated compound (c-4) Photoinitiator 4. A laminate comprising a metal foil and a photosensitive film formed by applying the photosensitive liquid composition according to claim 1 on the surface of the metal foil and drying. 5. The photosensitive film according to claim 3,
A laminate having metal foil laminated thereon, wherein the second coating is laminated on the metal foil surface so as to be in contact with the metal foil surface.