DE102007038183A1 - Resist pattern formation on semiconductor chip or circuit board, uses first and second photohardenable resist films sensitive to light in different wavelength regions to reduce illumination time - Google Patents

Abstract

Production of a resist pattern involves applying first then second photohardenable resist films (F1, F2), sensitive to light in first and second wavelength regions (WL1, WL2) respectively, to a semiconductor chip or a circuit board, where film F2 blocks light of WLR1. Laser light in WL2 is applied through a screen onto part of F2 followed by applying a developer solution, to form a mask pattern. F1 is illuminated with light in WL1 through a membrane mask, and finally F1 is developed.

Description

The The invention relates to a method for producing a resist pattern.

at The production of printed circuit boards becomes a photosensitive Material as etch resist pattern for Circuit design or a solder resist pattern for circuit protection used.

At the To run a pattern exposure, it was common Procedure, the resist material with ultraviolet radiation through a mask made of glass or a film through, in or at the a negative-negative pattern is formed (such Mask can be referred to below as a photo plate) to expose and develop the exposed material.

at However, a pattern exposure using a photographic plate must Money and time are spent on a large number of photo plates, which fit to different patterns, thereby providing for many Types a low productivity revealed, which led to difficulties.

Out JP-B-2,679,454 For example, a method is known in which a resist material is directly exposed to laser light without the light being modified by a photographic plate. Thus, according to this method, the resist material is exposed directly using a laser, whereby many pattern types can be formed on the same substrate without providing many types of photographic plates.

however has a Lotresistmuster in general on a negative pattern, and at direct. Exposure is the most patterned Sections exposed sections, while only a few unexposed Sections are present. So needed a direct exposure using a laser takes a lot of time.

The direct exposure of a resist material with laser light requires the use of a resist material with a sensitivity many times higher than the conventional one Materials is. Accordingly exist for the usable resist material limitations. If, for example a printed circuit board with a resist film or textured thereon to assemble a semiconductor chip with another element is, an element must be in a part of the circuit board to be connected via adhesion to resin or metal. In this case, there are only a few resist materials that have both adhesion and sensitivity to laser light, and the degree of freedom when selecting of resist materials is very low. If a resist film from a Resist material for a plating solution It is necessary that he has chemical resistance and high photosensitivity, whereby it is difficult to increase the sensitivity while the chemical resistance preserved. As a result, the degree of freedom is also here Choose a resist material low.

Of the Invention is based on the object, a method for manufacturing of a resist pattern, by which the exposure time for a resist material is reducible, and even then the formation of a resist pattern made possible by laser exposure, if a resist material with low sensitivity to laser light selected becomes.

These The object is achieved by the method according to the appended claim 1 solved. Advantageous embodiments and developments are the subject dependent Claims.

By the method according to the invention Either the exposure time in forming a resist pattern, for example, a solder resist pattern before a soldering process formed on a printed circuit board, be shortened, thereby reducing productivity elevated or it can be a relatively short exposure time even then be achieved if a conventional Resist material is used, so that the degree of freedom in selecting a Resist material increased is. There is also no positional shift of a resist pattern.

At the Method according to the invention becomes a second light-curable Resist film exposed with laser light at a wavelength that no Exposure of a first light-curable Resistfilms leads, d. H. a wavelength in a second sensitivity wavelength range, and the second Light-curable Resistfilm is developed with a development solution that is the first Light-curable Resist film not developed. This approach will do that Mask pattern for the first light-curable Resist film formed without this would be affected and without the unexposed Sections of the same would be exposed. Accordingly, the Structuring the first light-curable Resistfilms be executed in a short time.

Further the exposure is done using laser light also for the second Light-curable resist film. So can as material for the first light-curable Resist film a first resist material with low sensitivity selected on laser light become. That is, the first photo-curable resist film of its kind so selected that he can be for its essential use is suitable, without thereby limiting the Degree of freedom in the selection of materials would be. in the As a result, a resist pattern with laser exposure can be performed.

By the method according to the appended claim 2, a mask pattern can be easily removed by that Cover film is made, the removal of which is also the Mask pattern is removed.

At the Method according to the appended claim 3 can not only make the mask pattern by removing a cover film easily removed, but this also applies to the unexposed sections the first light-curable Resist films, d. H. uncured Sections of the same.

At the Method according to the claim 4 may be the first light-curable Resist film thereby easily on a semiconductor chip or a printed circuit board be attached, that a lamination process using a foil-shaped first light-curable Resistfilms is formed. It also becomes a first photocurable Resist film used with an already existing cover film is provided, whereby the burden of a separate production a cover film can be eliminated.

At the Method according to the claim 5, a laser scan is performed to expose the mask pattern a correction based on a measured deformation of a Printed circuit board executed becomes. By this measure Any mask pattern with high accuracy in a deformation-free Condition on many different semiconductor chips or printed circuit boards with different deformations on which different conductor patterns are formed, are formed.

At the Method according to the claim 6, visible laser light is used. This can be the second Light-curable Resistfilm for be exposed without the first light-curable resist film would be illuminated, which is sensitive to ultraviolet radiation.

At the Method according to the claim 7 may be the second light-curable Resist film easily with the functions of blanking out light with one wavelength in the first sensitivity wavelength range, water solubility and sensitivity to visible light.

At the Method according to the claim 8 can be educated with the method according to claim 7 Realize effects even better.

At the Method according to the claim 9 may be the second light-curable Resist film can be easily developed using water, without being the first light-curable Resist film impaired would.

At the Method according to the claim 10, a solder resist pattern can be easily patterned within a short time become.

At the Method according to the claim 11, a plating resist pattern can be easily patterned within a short time become.

At the Method according to the claim 12 may be an etch resist pattern be easily structured within a short time.

The Invention will now be illustrated by figures embodiments explained in more detail.

1 Fig. 12 is a schematic sectional view illustrating a solder resist pattern produced by using an embodiment of a method of forming a resist pattern according to the present invention.

2a to 2h FIG. 12 are schematic sectional views illustrating the flow of an embodiment of a method of forming a resist pattern according to the present invention.

3 shows transmission spectra of fine titanium oxide particles.

4 FIG. 12 is a schematic sectional view illustrating another example of the embodiment shown in FIG 2 illustrated step of removing unexposed portions of a solder resist film.

5 FIG. 12 is a schematic sectional view illustrating a method of removing a mask pattern according to FIG 2 through a cured resist film when no cover film is used.

6a to 6i are schematic sectional views for illustrating the flow of an example 1 of a method according to the invention for producing a membrane body.

7a . 7b and 7c are plan views of a printed circuit board in the 6d . 6f respectively. 6i with sectional views along lines A-A ', BB' and CC 'in this.

8a to 8c FIG. 15 are schematic sectional views for illustrating the flow of a method for producing a resist pattern in a comparative example 1.

9a to 9c FIG. 15 are schematic sectional views for illustrating the flow of a method for producing a resist pattern in a comparative example 2.

When in the 1 Illustrated example of a solder resist pattern produced using an embodiment of a method according to the invention for producing a resist pattern is in a printed circuit board 3 a trace pattern 2 of an electrically conductive material, such as copper, on a flexible substrate 1 made of a reinforced with epoxy resin or poly imide resin glass fabric available. On the printed circuit board 3 is a lotresist pattern 5 with openings 4 in sections of the trace pattern 2 Available to connect to other elements. With the in the sections of the openings 4 Uncovered trace metal connections of other elements are soldered.

The method according to the invention for producing a resist pattern can be used in the production of the solder resist pattern, as represented by the 2a to 2h is illustrated. This method makes it possible to carry out the exposure of a solder resist material in a short time, while also making it possible to perform laser light exposure using the same solder resist material as in the conventional case.

In the present embodiment, a solder resist film becomes 7 used as the first photo-curable resist film, and a resist film 8th is used as the second photo-curable resist film for forming the solder resist pattern 5 on the printed circuit board 3 used. The flow of the method of manufacturing a resist pattern in the present embodiment will now be described on the basis of FIG 2a to 2h explained.

On the printed circuit board 3 that the conductor pattern 2 of an electrically conductive material, such as copper, on the flexible substrate 1 wears a resin or the like, as in the 2a is shown, the solder resist film 7 (the first photo-curable resist film) in the form of a cover film 6 covered dry film by a lamination process, as indicated by the 2 B is illustrated. The cover film used in the present embodiment 6 It consists essentially of a resin such as PET, it transmits visible light and ultraviolet radiation, it is not sensitive to light, it is insoluble in water, and it has very low permeability to air (or permeability to oxygen).

As Lotresistfilm 7 For example, a material suitable for bonding to other elements as in the conventional approach may be used, and it need not be a material that would be suitable for irradiation with laser light. In the present embodiment, as the material for the solder resist film 7 one which is curable by ultraviolet radiation, insoluble in water but developed by a weakly alkaline developing solution (this material will be hereinafter referred to partly as "Material I").

Examples of material I are those containing at least the following: Polymers and / or oligomers (these are partially below as component (I-A)), monomers and / or organic solvents (these are sometimes referred to below as component (I-B)) and reaction starters (these are hereinafter partly as a component (I-C).

in the Material I with the polymers and oligomers as component (I-A) and the monomers as component (I-B), at least one of these components has a photosensitive group. So the material I has hardenability by ultraviolet radiation. Examples of such photosensitive Group are photosensitive groups with an unsaturated group Bond, an oxirane bond, etc. Examples of photosensitive Group with an unsaturated one Binding is an acryloyl group, a methacryloyl group (this are hereinafter referred to as partial "(meth) -acryloyl"), a vinyl group, a Allyl group and a cinnamoyl group. Examples of a photosensitive Group with Oxiranbindung heard an epoxy group. Of these photosensitive groups, one can or more. Alternatively, two or more of the species within the component (I-A) and component (I-B) with a or more photosensitive groups.

At the Material I from the polymers and oligomers as component (I-A) and the monomers as component (I-B) at least one of the components has a acid group. So the material I is alkaline developable. Examples Such an acidic group is a carboxylic acid group and a sulfonic acid group. It can be one or more acidic groups, or there may be two or more of the species in component (I-A) and the component (I-B) with one or more acidic groups.

in the Material I is the preferred component (I-A) is one with a average molecular weight of 2000 to 30,000 (especially 5000 up to 20,000). Examples of component (I-A) are those with both photosensitive group as well as an acidic group, such as a Product obtained by treating an acid anhydride with an unsaturated one Carboxylsäureaddukt an epoxy resin is reacted (such a product is hereinafter partially referred to as "component (I-A-i) ").

at of the component (I-A-i), examples of the epoxy resin are epoxy compounds novolak type (phenolic novolak type epoxy resins, epoxy resins of Cresol novolak type, etc.), bisphenol type epoxy compounds as well Triphenylmethane type epoxy resins. Of these, one or more species be included.

at of the component (I-A-i) are examples of the unsaturated carboxylic acid acrylic acid, methacrylic acid, crotonic acid, ciamic acid or Half saturated or unsaturated Anhydrides of dibasic acids (for example "anhydrides of a dibasic Acid "in the component (I-A-i), with (meth) acrylates or unsaturated monoglycidyl compounds with a hydroxyl group in one molecule.

at of component (I-A-i), examples of the acid acrylate are anhydrides dibasic acid (Maleic anhydride, succinic anhydride, anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic endomethylenetetrahydrophthalic, Methylendomethylenetetrahydrophthalic anhydride, chlorendinic anhydride, methyltetrahydrophthalic etc.), an anhydride of an aromatic polycarboxylic acid (trimellitic anhydride, pyromellitic anhydride, Benzophenone tetracarboxylic dianhydride, etc.) and polycarboxylic anhydride derivatives (5- (2,5-Dioxotetrahydrophuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride etc.). Of these, one can or more species.

The Preferred component (I-A-i) is one prepared thereby becomes that 0.15 mol or more of the acid anhydride on each hydroxyl group is reacted as it is the adduct of the unsaturated carboxylic acid to the epoxy resin (i.e., the reaction product derived from the Epoxy resin and the unsaturated one carboxylic acid is obtained). Is more preferable the acid value the component (I-A-i) 45 to 160 mg KOH / g, in particular 50 to 140 mg KOH / g. If the acidity value too low, the solubility in an alkaline agent bad. If the acidity value is too high, be on the other hand, the properties of the resulting resist film, like the alkali resistance and the electrical properties of the cured film. Accordingly, both too low as well as too high an acid value is not preferred.

At the Material I are examples of another component (I-A) polymers, the addition-reacting, unsaturated monoglycidyl compounds with some of the carboxyl groups, as in copolymers of unsaturated carboxylic acids (For example, "unsaturated carboxylic acid, etc." in the component (I-A-i)) to unsaturated dibasic acid anhydrides (for example, "dibasic Acid anhydrides, etc. "in the component (I-A-i)).

In the component (IB) of the material I, examples of the monomers are water-soluble monomers (2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, N-vinylpyrrolidone, acryloylmorpholine, methoxytetraethylene glycol acrylate, methoxypolyethylene glycol acrylate, polyethylene glycol diacrylate, N, N-dimethylacrylamide, N-methylolacrylamide, N, N-dimethylaminopropylacrylamide, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate or methacrylate monomers (diethylene glycol diacrylate, triethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, phenoxyl acrylate, tetrahydrofuryl acrylate, cyclohexyl acrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, Glycerindiglycidyletherdiacrylat, glycerin triglycidyl ether triacrylate, Glycerintriglycidylethertriacrylat, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate or methacrylates corresponding to the above acrylates, and mono-, di-, tri- or higher polyesters polybasiger acids with hydroxyalkyl (meth ) acrylates). Of these, one or more species may be included.

Concerning the component (I-B) of the material I are examples of the organic solvent Ketones (methyl ethyl ketone, cyclohexanone, etc.), aromatic hydrocarbons (Toluene, xylene, etc.), cellosolve substances (cellosolve, butylcellosolve etc.), carbitols (carbitol, butyl carbitol, etc.) and acid esters (Ethyl acetate, butyl acetate, cellosolve acetate, butylcellosolve acetate, Carbitol acetate, butyl carbitol acetate, etc.). Of these, one can or more species.

At the Material I are examples of component (I-C) those which have a Start photopolymerization when irradiated with ultraviolet radiation (more precisely, light with a wavelength of 200 to 400 nm). As such Components (I-C) are exemplified by the following: 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1-1 ("IRGACURE 907", Ciba Specialty Chemicals K.K.), benzoin and its alkyl ethers (benzoin, benzoin methyl ether, Benzoin ethyl ether, benzoin isopropyl ether, etc.) acetophenones (acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, etc.), Antrachinones (2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylantraquinone, 1-chloroantraquinone, 2-amylanthraquinone, etc.), thioxanthones (2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone etc.), ketals (acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.), benzophenones and xanthones. Of it can be one or more species included.

in the Material I can one or more other materials may be included as additives like fillers, Sensitizers, coloring pigments, Adhesion promoters, polymerization inhibitors, epoxy compounds, epoxy hardeners, Reaction accelerator (those based on benzoic acid and such based on a tertiary Amine), solvent (Ethers, esters, ketones, etc.), anti-foaming agents (silicone oil, etc.), Leveling and anti-tampering agent.

at The additives in material I are examples of the fillers Barium sulfate, silica, talc, clay and calcium carbonate. From that can be one or more species included. Examples of Sensitizers are esters of dimethylaminobenzoic acid such as pentyl-4-dimethylaminobenzoate and aliphatic amines. Of these, one or more species be included. Examples of the coloring pigments include phthalocyanine blue, phthalocyanine and titanium oxide black. Of it can be one or more species included. Examples of the adhesion promoter are unsaturated Phosphate compounds and polyester-type diacrylates. Of these, one can or more species.

Examples the polymerization inhibitor are hydroquinone, hydroquinone monomethyl ether, Pyrogallol, tertiary Butyl catechol and phenothiazine. Of these, one or more species be included. Examples of the epoxy compounds are those which contain two or more epoxy groups in one molecule, such as epoxy resins bisphenol A type, bisphenol F type epoxy resins, epoxy resins of bisphenol S type, phenol novolak type epoxy resins, epoxy resins of the cresol novolak type, N-glycidyl type epoxy resins or alicyclic ones Epoxy resins. Of it can be one or more species included. Examples of epoxy hardeners are amine compounds, imidazole compounds, carboxylic acids, phenols, quaternary Ammonium salts and compounds containing a methylol group. Of it can be one or more species included.

at the composition of the material I, it is preferred that the proportion the component (I-B) 30 to 300 (especially 50 to 200) parts by weight is, and the proportion of component (I-C) 0.2 to 30 (especially 2 to 20) parts by weight per 100 parts by weight of component (I-A).

Then, as is done by the 2c is illustrated by lamination on the cover film 6 a resist film 8th which may be aqueous developed and has barrier properties to ultraviolet radiation as well as visible light curability (ie, a second photocurable resist film).

The resist film 8th is subjected to an exposure and development to form a pattern as a mask for the lower Lotresistfilm 7 serves. So it is necessary that the resist film 8th has ultraviolet ray barrier properties such that the ultraviolet-curable solder resist film underlying it 7 during the exposure of the resist film 8th does not experience photosensitization.

Examples of a material used as a resist film 8th which is aqueous-developable and has barrier properties to ultraviolet radiation and visible light curability (the material is hereinafter sometimes referred to as "Material II") are those which contain at least: polymers and / or oligomers (hereinafter partially as component ( II-A), monomers (hereinafter partially referred to as component (II-B)), reaction initiators (hereinafter referred to as component (II-C)), and ultraviolet-barrier materials (hereinafter referred to as component (II-D)).

At the Material II becomes a water-soluble Resin referred to as component (II-A). Such a component (II-A) is, for example, a resin having a hydrophilic group and / or a hydrophilic chemical structure in a repeated Polymer unit. Examples of the hydrophilic group are a hydroxyl group, a Methylol group, an acid group (Carboxyl group, sulfone group or the like) and the corresponding salt (Carboxylate, sulfonate or the like) and a basic group (For example, amino group) and the associated salt (for example, ammonium). Of it can be one or more hydrophilic groups. Examples of a hydrophilic chemical structure are an ether bond (oxyalkylene etc.), an ester bond, an amide bond, an acid amide bond, a hydantoin skeleton and a pyrrolidone skeleton. Of these, one can or more species.

More accurate said, the following are synthetic resins, natural Polymers and semisynthetic resins exemplified as a component (II-A): Examples of the synthetic resins as a component (II-A) are polyvinyl alcohol (PVA), polymethyl vinyl ether, polyvinyl pyrrolidone, Polyvinyl butyral, polyethylene oxide, water-soluble phenolic resins, water-soluble melamine resins, water-soluble Polyester resins and water-soluble Polyamide resins. Preference is given to water-soluble polyester resins and water-soluble polyamide resins. From that can be one or more species included.

PVA, an example of a synthetic resin as component (II-A) is, is preferably one with, for example, a degree of polymerization from 100 to 5000 (especially 500 to 2500). Too low degree of polymerization can lead to a deterioration of the film-forming properties. One On the other hand, too high a degree of polymerization can lead to it fails to achieve sufficient developability. It also has the PVA preferably over a saponification degree of 60 mol% or higher (especially 70 mol% or higher). A degree of saponification that is too low can lead to a failure to achieve sufficient developability.

polymethyl, an example of a synthetic resin as component (II-A) is, is preferably one having, for example, a molecular weight from 20,000 to 5,000,000 (especially 100,000 to 1,000,000). One too low molecular weight can lead to failure sufficient strength for the hardened To achieve film. On the other hand, too high a molecular weight may do so to lead, that it fails to achieve sufficient developability.

polyvinylpyrrolidone, an example of a synthetic resin as component (II-A) is, is preferably one having, for example, a molecular weight from 5,000 to 5,000,000 (especially 500,000 to 1,500,000). One too low molecular weight can lead to failure to achieve sufficient strength of the cured film. One On the other hand, too high a molecular weight can lead to it fails to achieve sufficient developability.

polyvinyl butyral, an example of a synthetic resin as component (II-A) is, is preferably one with, for example, a degree of butylation from 5 to 40 (especially 10 to 20) mol%. Too low degree of butylation can the developmental stability reduce. On the other hand, too high a degree of butylation can cause the Reduce developability. A preferred average degree of polymerization is 100 to 3000 (especially 6 to 2000). Too low a middle one Degree of polymerization can lead to reduced development resistance to lead. On the other hand, an excessively high degree of polymerization can be too lead to reduced developability.

Polyethylene oxide, which is an example of a synthetic resin as component (II-A), is preferably one having, for example, a molecular weight of 20,000 to 5,000,000 (especially 100,000 to 1,000,000). Too low a molecular weight may fail to achieve sufficient strength of the cured film. On the other hand, too high a molecular weight may do so lead to failure to achieve sufficient developability.

When water-soluble Phenol resin, which is an example of a synthetic resin as a component (II-A), a phenolic resin of the resol type is exemplified. Examples of a water-soluble Melamine resin as a synthetic resin are high methylol melamines (Hexamethylolmelamine, pentamethylolmelamine, etc.).

When water-soluble Polyester resin, which is an example of a synthetic resin as a component (II-A) is exemplified as one which consists of a dibasic acid and a glycol. Examples of a dibasic acid are maleic acid, phthalic acid and Itaconic acid. Examples of the glycol are glycol itself and ethylene glycol. More accurate said, can as water-soluble Polyester resin commercially available Products used, such as Aron Melt PES-1000 and Aron Melt PES-2000 (both manufactured by Toagosei Co., Ltd.).

When water-soluble Polyamide resin, which is an example of a synthetic resin as a component (II-A), a polyamide resin is exemplified by Ethylene oxide and the like is modified. More precisely, as water-soluble Polyamide resins commercially available Products such as AQNylonA-90 and AQNylonP-70 (both manufactured by Toray Industries, Inc.).

When Component (II-A) are examples of the natural resin starch, dextrin and protein (gelatin, leather glue, casein, etc.). Under natural Polymers are starch and dextrin which are preferred, those having a molecular weight from 10,000 to 500,000 (especially 20,000 to 200,000). preferably, has that Protein over a molecular weight of 5000 to 50,000 (especially 10,000 to 20,000). Too low a molecular weight can be reduced Lead film forming properties. On the other hand, too high a molecular weight can be reduced Developability lead.

Concerning the component (II-A) are examples of a semisynthetic resin modified celluloses (methylcellulose, hydroxyethylcellulose etc.). The preferred hydroxyethyl cellulose has a degree of polymerization from 50 to 1000 (especially 200 to 700). Too low degree of polymerization can lead to insufficient coating strength. Too high degree of polymerization On the other hand, it can lead to reduced developability.

When Component (II-A) may be a water-soluble resin having a photosensitive Group (hereinafter sometimes referred to as "photosensitive, water-soluble Resin "). The use of a photosensitive, water-soluble resin shows the effect an improvement in the development resistance.

When Photosensitive groups are named as exemplified in connection with the material I mentioned above. For example, as a photosensitive, water-soluble resin, which is an example of the component (II-A), called the following: Resins containing a (meth) acryloyl group, resins containing a Containing epoxy group, and resins containing a vinyl group. In connection with the photosensitive, water-soluble Resin becomes a water-soluble resin as a (meth) acryloyl group-containing resin Called resin, which is unsaturated with an unsaturated fatty acid Reaction was brought. The water-soluble resin is, for example a polyol resin (PVA, polyvinyl butyral, etc.) or a polyester resin. Examples of an unsaturated fatty acid are α, β-unsaturated fatty acids (acrylic acid, methacrylic acid, etc.), itaconic and cinnamic acid. Of it can be one or more species included.

More accurate are said to be a photosensitive, water-soluble resin, examples of a (meth) acrylic group-containing resin such with α, β-unsaturated fatty acids, which were subjected to an addition reaction with PVA. The α, β-unsaturated fatty acid can in a proportion of, for example, 5 to 40 mol% (in particular 10 to 30 mol%) with respect to the hydrophilic groups contained in the PVA be added. When the added amount of unsaturated fatty acids too is small, the effect of improving the development resistance be low. On the other hand, when the addition amount is large, the Developability be reduced. The degree of polymerization can be 100 to 5000 (especially 500 to 2500) amount.

Other Examples of a (meth) acryloyl group-containing resin those with α, β-unsaturated fatty acids, which were subjected to an addition reaction with hydroxycellulose. When the amount of oxidized unsaturated fatty acid is too small is, the effect of improving the development resistance be low. If the oxidized amount is too large, on the other hand, the Developability be reduced. The degree of polymerization can be 20 to 1000 (especially 50 to 500) amount.

When an epoxy group-containing resin which is an example of a photosensitive resin water-soluble resin is a product called manufactured by that an epoxy compound is reacted with a water-soluble resin becomes. Examples of a water-soluble Resin is PVA and a polyester resin. Of these, one or more species be included. As the epoxy compound, epichlorohydrin is exemplified called.

More accurate said, is called epichlorohydrin, that of an addition reaction was subjected to PVA. The epichlorohydrin can with a proportion from, for example, 5 to 40 mol% (especially 10 to 30 mol%) in Regarding the hydroxyl groups of PVA can be added. If the Addition amount of epichlorohydrin is too small, the effect of a Improvement of the development resistance to be low. If the additional amount is too large, On the other hand, the developability can be reduced. The degree of polymerization may be 100 to 5000 (especially 500 to 2500).

Other, epoxy resin-containing resins are, for example, 1,3-diglycidylhydantoin and 1-glycidylhydantoin. Of it can be one or more species included.

When a vinyl group-containing resin which is an example of a photosensitive, water-soluble resin is called vinyl chloride, which is an addition reaction with Hydroxyethylcellulose was subjected. The vinyl chloride can with a proportion of, for example, 5 to 30 mol% (especially 10 to 20 mol%) based on the hydroxyl groups of the hydroxycellulose added become. If the added amount of vinyl chloride is too small, can the effect of improving the development resistance be low. If the additional amount is too large, on the other hand, the Developability be reduced. The degree of polymerization can 5 to 1000 (especially 200 to 700) amount.

(chemische Formel 1) In the material II, examples of the component (II-B) are those having a photosensitive group. As the photosensitive group, those exemplified in connection with the above-mentioned material I are mentioned. Examples of component (II-B) are monofunctional (meth) acrylates (ie monofunctional acrylates and / or monofunctional methacrylates) as well as polyfunctional (meth) acrylates. Of these, one or more species may be included. Examples of the monofunctional (meth) acrylates as the component (II-B) are those represented by the following formula (Chemical Formula 1):

(chemical formula 1)

As R ₁ , an alkyl group having 1 to 12 carbon atoms is called. Examples of an alicyclic hydrocarbon group are mono- or polycycloalkyl groups or mono- or polycycloalkenyl groups. The alkyl group or the alicyclic hydrocarbon group may have a substituent (hydroxyl group, alkoxy group, carboxyl group or the like).

More accurate These are examples of monofunctional (meth) acrylates as a component (II-B) Hydroxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate and isobornyl (meth) acrylate. Of these, one or more species be included.

Examples Polyfunctional (meth) acrylates as component (II-B) are partial esterification products or perester products formed between polyol and (meth) acrylate acid become. Examples of the polyol are glycols (ethylene glycol, diethylene glycol etc.), glycerols (glycerol as such, etc.), other triols (trimethylolpropane etc.), tetraols (pentaerythritol, etc.), pentaols (sorbitol, mannitol etc.) and hexaols (dipentaerythritol, etc.). Of these, one can or more species.

More accurate These are examples of polyfunctional (meth) acrylates as a component (II-B) Ethylene glycol, di (meth) acrylate, glycerol (meth) acrylate, trimethylolpropane tri (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Of these, one or more species be included.

(chemische Formel 2)

(chemische Formel 3)

(chemische Formel 4)

(chemische Formel 5)

(chemische Formel 6) Other concrete examples of the component (II-B) are of the alicyclic type. As such of the alicyclic type, those based on cyclohexene oxide are mentioned. More specifically, those represented by the following formulas (Chemical Formula 2 to Chemical Formula 6) are named. Those of the formula (Chemical Formula 6) are preferably those in which M is an integer of 2 to 50 (especially 2 to 30) is.

(chemical formula 2)

(chemical formula 3)

(chemical formula 4)

(chemical formula 5)

(chemical formula 6)

(chemische Formel 7)

(chemische Formel 8) Still other concrete examples of the component (II-B) are those represented by the following formulas (Chemical Formula 7 and Chemical Formula 8).

(chemical formula 7)

(chemical formula 8)

From The substances represented by the above chemical formulas may have a or more species.

Yet other concrete examples of the component (II-B) are water-soluble monomers (those exemplified in connection with component (I-B) are indicated).

When Component (II-B) are in terms of development resistance those preferred over two or more (especially 3 to 6) photosensitive groups feature. Further, from the viewpoint of the coating properties those which are liquid at normal temperatures, especially those that act as solvents for the Component (II-A) serve. More specifically, as component (II-B) those preferred over Have 3 to 6 photosensitive groups, in particular dipentaerythritol (meth) acrylate etc.

in the Material II is called as component (II-C) a component, a photoradical polymerization on irradiation with visible Light (i.e., light with a wavelength of 400 to 800 nm) starts. Such a component (II-C) is, for example, one with high absorption in the visible light range. Examples of it are trichloromethyl-s-triazines such as 2- [2- (5-methyl-furan-2-yl) -ethynyl] -4,6-bis (trichiomethyl) -s-triazine (TME triazine from Sanwa Chemical Co., Ltd.), benzyl compounds such as Benzyl, α-naphthyl, Acenaphthane, 4,4'-dimethoxybenzyl and 4,4'-dicyclobenzyl, Quinone compounds such as camphorquinone, thioxanthone compounds such as 2-chlorothioxanthone, 2,4-diethoxy thioxanthone and methylthioxanthone, Acylphosphine oxide based compounds such as trimethylbenzoyldiphenylphosphine oxide and titanocene compounds. As preferred is a combination of 2,4,6-tris (trichloromethyl) -s-triazine and 3,3'-carbonylbis (7-diethylamino) coumarin (Sensitizing dye).

in the Material II, component (II-D) is preferably one such lets through the visible light and ultraviolet radiation blocks. More precisely, examples are the component (II-D) titanium oxide, calcium carbonate and zinc oxide, and it can one or more of them may be included. As titanium oxide can a such as rutile type or anatase type. Calcium carbonate is ultraviolet radiation barrier properties slight worse than titanium oxide, however, it has excellent permeability for visible Light. Preferred examples are titanium oxide and zinc oxide. The light barrier materials are preferably in the form of fine particles (particle size 0.0001 microns to 0.5 microns, especially 0.01 microns to 0.05 microns).

The 3 shows transmission spectra of fine particles of titanium oxide when a paint coating was used as the dispersion medium. In the drawing, the curve a shows the results of a measurement of fine particles having an average particle size of 0.2 μm, the curve b shows the measurement results for fine particles having an average particle size of 0.03 to 0.05 μm and the curve c shows the measurement results for fine particles having an average particle size of 0.01 to 0.003 microns. These results show that the larger the particle size, the more the visible light is transmitted, the smaller the particle size, the more visible light (light with a wavelength of about 400 nm or more) tends to be blocked, tending to block more ultraviolet radiation (light having a wavelength less than about 350 nm). On the basis of these experimental results, it was found that the fine particles should have an average particle size of 0.5 μm or less, particularly 0.05 μm or less, in order to be transparent to both visible light and to block ultraviolet radiation.

in the Material II can one or more additives may be included as exemplified for the Material I, such as fillers, sensitizers, Coloring pigments, Adhesion promoters, polymerization inhibitors, epoxy compounds, epoxy hardeners, Reaction accelerator (those based on benzoic acid and such based on a tertiary Amine), solvent (Ethers, esters, ketones, etc.), anti-foaming agents (silicone oil, etc.), Leveling and anti-tampering agent.

As the sensitizer among the additives for the material II, those which activate the photopolymerization when used in combination with the component (II-C) in comparison with the use of the component (II-C) alone are preferable. Examples thereof are amine-based compounds such as dimethylaminoethyl methacrylate, isoamyl-4-dimethylaminobenzoate, n-butylamine and triethylamine, phosphines such as triethyl-n-butylphosphine, thioxanthene-based compounds, xanthene-based compounds, ketone-based compounds, thiopyrylium-based compounds, compounds Base of a basic styryl, merocyanine-based compounds, 3-substituted coumarin-based compounds, 3,4-substituted coumarin-based compounds, cyanine-based compounds, compounds acridine-based compounds, thiazine-based compounds, phenothiazine-based compounds, anthracene-based compounds, coronone-based compounds, benzanthracene-based compounds, perylene-based compounds, ketocumarin-based compounds, fumarin-based compounds, and borate-based compounds. Of these, one or more species may be included.

at the composition of the material II, it is preferred that covered to 100 parts by weight of component (II-A) the proportions of the other Components 50 to 300 (especially 80 to 150) parts by weight of Component (II-B), 1 to 20 (especially 6 to 10) parts by weight Component (II-C) and 40 to 100 (especially 50 to 80) Make up parts by weight of component (II-D).

The Material II prepared in the manner indicated above generally has one transmissivity for visible Light of 60% or more and transmissivity for ultraviolet radiation less than 40%.

Then, the resist film becomes 8th made a resist pattern with the material II described above. In the method for producing a resist pattern of the present invention, exposure to laser light for forming a mask pattern is performed. Thus, with this method, high-accuracy exposure can be performed while the position of irradiation with laser light is in accordance with deformation of each flexible substrate 1 he follows.

Conventionally, in performing patterning by a glass or a film on which a light-blocking negative pattern was formed, it was difficult to adjust the exposure position to a positional shift of the wiring pattern 2 due to the deformation of a substrate. Also, it was not possible to change the aspect ratio of the wiring pattern 2 and to absorb changes in the angle between the x and y axes due to deformation of the substrate.

According to the invention becomes, as described below with reference to an embodiment, a resist pattern when the irradiation position of the laser light is set produced, whereby the above-mentioned problems in the conventional Structuring solved can be and exposure of high accuracy can be performed.

In the present embodiment, the irradiation position of laser light becomes in accordance with the actual position of the respective flexible substrate 1 is set, and an exposure operation is performed. For this purpose, the deformation is measured before the exposure. The value of the deformation can be determined by the coordinates of reference points 9 measured in advance, and that deviations from the reference positions are determined.

The obtained deformation value is input to a laser light exposure control device and is reflected in laser light irradiation reference control data. Based on the new data, the irradiation position of the laser light is adjusted, and laser light exposure is performed as indicated by the laser light 2d is illustrated.

Exposing the visible light curable resist film 8th done using visible laser light 10 , It is under the resist film 8th lying solder resist film 7 an ultraviolet-sensitive material that is substantially insensitive to visible light. In the present embodiment, as the visible light, use is made of 400 to 800 nm, for example, g-ray or visible light from a laser such as an argon laser (488 nm) or a FD-Nd / YAG laser (532 nm).

The exposed resist 8th is developed using water. More specifically, the development is carried out by spraying water of 10 to 80 ° C, preferably 10 to 30 ° C, for 10 to 300 seconds, preferably 10 to 60 seconds. In the 2e a state is shown in which the resist film 8th was developed with water. The Lotresistfilm 7 has developability in an alkaline medium, so that the water used here as a developer, the Lotresistfilm 7 unaffected.

After the formation of a resist pattern 11 By developing with water, the entire surface of the printed circuit board becomes 3 with ultraviolet radiation 12 irradiated as it is through the 2f is illustrated. The resist pattern is used here 11 with barrier properties against ultraviolet radiation as mask pattern for the solder resist film 7 , So are the sections of the solder resist film 7 under the resist pattern 11 to unexposed sections (uncured sections) 13 whereas other sections of the solder resist film 7 ge be hardened. By this measure, a Lotresistmuster 5 be formed.

It will be for the Lotresistfilm 7 selected suitable conditions, such as the light source for the ultraviolet radiation and the amount of ultraviolet radiation. More specifically, in the present embodiment, as the ultraviolet ray, light having a wavelength of 200 to 400 nm is used, for example, ultraviolet ray from a low, medium or (ultra) high pressure mercury vapor lamp, a xenon lamp, a metal halide lamp or a laser.

After irradiation with ultraviolet radiation 12 becomes the non-photosensitive cover film 6 peeled off the resist material 11 to remove it as by the 2g is illustrated. Then the solder resist film 7 using an alkaline developing solution designed around the unexposed sections 13 to remove, causing the Lotresistmuster 5 can be trained, as it is in the 2h is shown. As the alkaline developing solution, an aqueous solution of 0.5 to 3% of sodium carbonate is exemplified.

According to the above procedure, the solder resist film becomes 7 which avoids the need to make an exposure mask plate or an exposure mask sheet for each exposure pattern. As a result, an improvement in the exposure accuracy and a shortening of the exposure time for the solder resist film can be achieved, and positional shift of the resist pattern can be prevented. As yet, materials used heretofore can be used as solder resist materials as it is, and even with a laser sensitive low-sensitivity solder resist material can be used to form a resist pattern by laser exposure. That is, the first photo-curable resist film is selected according to a manner suitable for conventional applications without a reduction in the degree of freedom in selecting the material for use as the first photo-curable resist film, thereby forming a resist pattern can be formed by laser exposure.

For the type of printed circuit board 3 , the first photo-curable resist film, the second photo-curable resist film, and the film, etc., and also the materials, structures, and mounting method thereof are not limited to the examples given in the present embodiment.

For example, the printed circuit board used in the present embodiment is 3 a flexible substrate carrying a wiring pattern made of an electrically conductive material such as copper. However, the printed circuit board can 3 consist of a rigid substrate, and the electrically conductive material may be aluminum or gold. Furthermore, the printed circuit board 3 a printed circuit board printed on one side or both, or it may be one printed on a single layer or a multi-layer.

at the present embodiment is about it as an illustrative example, a patterning process described in which the solder resist film is the first light-curable Resist film is used with a flip-chip blanks using a lot or the like can be performed. Furthermore can the inventive method for producing a resist pattern for producing other resist patterns which serve other processes (etch resist pattern, plating resist pattern, Glass mask, etc.). The inventive method for manufacturing However, a resist pattern is particularly advantageous when the proportion of exposed areas much bigger than of unexposed areas is like exposing a solder resist film.

Also is in the present embodiment the first photocurable Resist film used as a solder resist film in the form of a dry film, which is developed by a weakly alkaline developing solution. however may be the first light-curable Resistfilm such a for be acidic development, or it can be attached by that a resist in liquid or Solform applied, printed or sprayed on. If a first light-curable Resist film of the type for acidic development is used for the second light-curable Resistfilm a material selected which is not developed by such a developer.

Like the first photo-curable resist film, the second photo-curable resist film may be prepared by coating, printing or spray-coating a liquid or sol material, or may be prepared using a material which is developed by an acid. When an acid-developable material is used for the second photo-curable resist film, a material which is not developed by an acid is used for the first photo-curable resist film is acid resistant. That is, it is essential that the first and second photo-curable resist films use materials developed by various developing solutions.

following a sour developable material is described in detail, which is usable as first or second resist material.

Examples an acid developable material are resin compositions, the at least polymers and / or oligomers and monomers and / or organic solvents in particular, only the following component (i) or the Component (ii), or both of them.

The Component (i) consists of polymers and / or oligomers with basic Structure, and component (ii) consists of polymers, oligomers and monomers, at least one of which contains a basic group.

Concerning the component (i) are examples of the polymers and oligomeric resins melamine-based (melamine resin, melamine alkyd resin, melamine benzoguanamine resin, Melamine-formaldehyde resin, melamine-phenolic resin, melamine-urea resin etc.) as well as aniline resins. Of it can be one or more species included.

Concerning the component (ii) are examples of the basic group primary, secondary and tertiary amino groups as well as a quaternary Ammonium group. Of these can be one or more basic groups. The preferred ones Basic groups are secondary and tertiary Amino groups.

Concerning component (ii) are examples of polymers, oligomers and monomers the component (I-A) having an acidic group in which these by the above basic group he sets are; Monomers as a component (I-B) with an acidic group, now the same by the above basic group is replaced; a component (II-A) with basic Group, a component (I-B) without acidic group; and the monomers component (II-B), where the above basic group is added. Of these, one or several species are included.

The acid-developable material may contain one or more of the additives contained, by way of example, in conjunction with the above Materials I and II are indicated.

Examples an acid developable material caused by ultraviolet radiation curable are resin compositions which are at least those mentioned above Polymers and / or oligomers and monomers and / or organic solvents wherein the polymer, oligomer and monomer are at least a further contains a photosensitive group (for example, those which are mentioned in connection with the material I), wherein the resin composition further containing component (I-C).

Examples acid-developable material that blocks ultraviolet radiation and curable with visible light are the resin compositions which are at least those mentioned above Polymers and / or oligomers and monomers and / or organic solvents wherein the resin composition further comprises the component (II-C) and component (II-D).

When acidic developers exemplify organic acids (maleic acid, etc.) and inorganic acids (Phosphoric acid etc.).

at of the invention the second light-curable Resist film said material blocking light with one wavelength, at the first light-curable Resist film is sensitive. That is, a material used in the wavelength is sensitive to the exposure of the first light-curable Resistfilms used, not for the second light-curable Resist film can be used. Also, no light can be same Wavelength, as used for exposing the first photo-curable resist film becomes the second light-curable Illuminate resist film. Accordingly, for the first Light-curable Resistfilm a material of a kind to be selected, as it is for this Resist film is required, and this resist film can be made using Light of a wavelength be illuminated for this material is suitable. In addition, for the second Light-curable Resistfilm a material selected where light of one wavelength can be used, that of the one used for exposing the first photo-curable resist film wavelength is different and that the second light-curable resist film does not block, and this can be exposed using light of this wavelength become.

In view of these facts, the above embodiment is not limitative, but it is at For example, the following embodiment conceivable as an alternative to the described embodiment. For example, for the first photo-curable resist film (the solder resist film 7 ) uses a material which is developable with water, blocks ultraviolet radiation and is curable with visible light (material II or the like). For the second light-curable resist film (the resist film 8th ) uses a material that blocks visible light, is curable by ultraviolet radiation, is insoluble in water, and is developed by a weakly alkaline developer. Using these materials, the respective resist films are produced. Visible light is used to expose the first photocurable resist film, whereas ultraviolet radiation is used to expose the second photocurable resist film.

When Method that makes a material visible for locking properties Light as well as hardenability by Ultraviolet radiation gives as an example the inclusion a coloring pigment (especially soot) in a photosensitive material.

Of the in the above embodiment said cover film is one with permeability for visible Light as well as ultraviolet radiation, but it can be one the light passes through only in a sensitivity wavelength range, in the first light-curable Resist film hardened can be (for example ultraviolet radiation). In the above embodiment is about it In addition, the cover film is used as such in advance the first light-curable Resistfilm (the solder resist film) is attached. However, it is permissible to have one first light-curable Resist film not covered by a cover film is to laminate a cover film on it. alternative is it permissible to laminate a cover film thereon, on which the second photo-curable resist film is trained. It is also legal the first light-curable Resist film and the cover film to install separately, for example by Applying, printing or spray coating of a material in liquid or solform for the cover film on the first photo-curable resist film. In this Case, the cover film can be removed by peeling, such as it in the present embodiment and he can also using a chemical or the like can be removed. One to remove the cover film usable chemical is one that contains a material that the resist film, the trace, the substrate, etc. are not eroded.

In the above embodiment, the unexposed portions of the first photo-curable resist film which has been exposed for patterning are removed by development. As it is in the 4 can, however, when the cover film 6 is subtracted, some or all unexposed sections 13 of the solder resist film (the first photo-curable resist film) adhere to it and removed together with it.

In addition, the cover film can be omitted. If no cover film is used, the resist pattern may be 11 be removed simultaneously with the development of the first light-curable resist film, as in the 5 is shown.

At the Attaching the cover film separately from the resist film or when Omitting the cover film, it is necessary to take a measure against an impairment the quality of the resist film to seep through the atmosphere.

Examples

The invention is illustrated by the following examples with reference to FIGS 6a to 6i as well as the 7a to 7c described in more detail.

example 1

First, a composition having a uniformly dispersed resin represented by Formula 1 below using a polyester mesh of 150 mesh on a 100 μm thick PE film 14 printed and dried for 15 minutes at 18 ° C to thereby on the PE film 14 a second photocurable resist film 8th train. Then, a 25 μm thick cover film was formed on the surface thereof 6 made of PET. In this way, a three-layered body was made of the PE film 14 , the second photo-curable resist film 8th and the cover film 6 made of PET (see the 6a ).

Separately, a substance for an alkaline developable type solder resist film having the formula 2 given below was screen printed on a printed circuit board 3 with a conductor pattern formed thereon 2 applied to thereby on the circuit board a first light-curable Re sistfilm 7 to train (see 6b ).

Then the above three-layered body became over the cover film 6 made of PET on the printed circuit board 3 applied first light-curable resist film 7 laminated. The top layer of this in the 6b represented laminate lying PE film 14 was stripped to the second photocurable resist film 8th to expose to the outside (see the 6d and 7a ). The resulting composite was laser light 10 of 432 nm at laser irradiation positions 15 (see the 7a ) to draw a predetermined pattern (see 6e ). The drawing time was 20 seconds. Then, development was performed for a few seconds using flowing water to form a second light-cured resist pattern 11 to train (see the 7b ).

Then ultraviolet radiation became 12 from the top to the entire surface of the composite to the printed circuit board 3 out (see the 6f ) using a high-pressure mercury vapor lamp, resulting in unexposed sections 13 of the first light-curable resist film remained only those under the resist pattern 11 while the other sections were hardened (see the 6g ). The duration of irradiation with the ultraviolet radiation 12 was 30 seconds. Then, the second light-curable resist pattern became 11 along with the cover film 6 deducted from PET (see the 6h ). Then the unexposed sections 13 of the first photocurable resist film was removed by developing using an aqueous solution containing 1% sodium carbonate at 30 ° C.

In this way became a printed circuit board 3 Get that with the first light-curable resist pattern 5 covered in a manner opposite to the second photohardened resist pattern 11 was structured (see the 6i and 7c ).

In Example 1, the drawing time using the laser light 10 the short duration of 20 seconds, and the irradiation with the ultraviolet radiation 12 through the high pressure mercury vapor lamp could be carried out using a different plant. So the productivity was very high. It also enabled drawing by the laser light 10 to perform a correction based on a measurement. As a result, the resist pattern became 5 formed at (and applied to) precise positions on the plate, so that excellent positional accuracy resulted. In the present embodiment, materials having the formulas 1 and 2 were used for the respective photo-cured resist films, but the same results were obtained even when other components were obtained as suitable for photocurable resist films according to the invention and as described above were specified.

formula 1

100 Parts by weight of an acrylate ester oligomer (ZAA-178 from Nippon Kayaku Co., Ltd.), 25 parts by weight of dipentaerythritol hexaacrylate (monomer), 10 parts by weight of trimethylolpropane triacrylate (monomer), 2.5 parts by weight a triazine-based reaction initiator (TME triazines from Sanwa Chemical Co., Ltd.), 0.15 parts by weight of bisketocumarin (sensitizing dye, KCD from Yamamoto Chemicals Inc.), 20 parts by weight ultrafine titanium oxide particles (UV blocking agent, average particle size 0.03 μm, TTO-55 from Ishihara Sangyo Kaisha, Ltd.), 0.5 parts by weight of polydimethylsiloxane (antifoaming agent, KS-66 from Shin-Etsu Silicone).

Formula 2

150 Parts by weight of a triphenylmethane type epoxyacrylate oligomer, modified with tetrahydrophthalic anhydride (TCR-1041 from Nippon Kayaku Co., Ltd.), 25 parts by weight of dipentaerythritol hexaacrylate (monomer), 20 parts by weight of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-1 (IRGACURE 907 from Ciba Specialty Chemicals K.K.), 30 parts by weight Triglycidyl isocyanurate (TEPIC from Nissan Chemical Industries, Ltd.), 4 parts by weight of melamine (manufactured by Nissan Chemical Industries Ltd.) Melamine), 150 parts by weight of barium sulfate (BARIFINE 100 from Sakai Chemical Industry Co., Ltd.), 0.5 parts by weight of polydimethylsiloxane (Anti-foaming agent, KS-66 of Shin-Etsu Silicone), 0.05 part by weight of a green pigment.

Comparative Example 1

Now, a comparative example 1 will be described with reference to FIGS 8a to 8c described.

A substance for an alkali-type solder resist film having the above formula 2 was screen-printed on a printed wiring board 3 , on a track 2 was trained, upset, to thereby form a first photohardenable resist film 7 train.

Then an ultraviolet laser became 16 of 365 nm for a drawing operation (irradiation) on the first photo-curable resist film 7 in the same pattern range as that of the first photohardenable resist pattern 5 used in Example 1. The drawing time was 2 minutes and 30 seconds.

Then unexposed sections 13 of the first photo-curable resist film left unhardened since they were not irradiated with the laser light by developing by using an aqueous solution of 1% sodium carbonate at 30 ° C. This procedure became a printed circuit board 3 Get that with the first light-curable resist pattern 5 was coated (see the 8c ).

In this Comparative Example 1, the positional accuracy was excellent because the laser 16 was used for the drawing process. However, the drawing time had the long value of 2 minutes and 30 seconds, which means poor productivity.

Comparative Example 2

Now, a comparative example 2 will be described with reference to FIGS 9a to 9c described.

A substance for an alkaline development type solder resist film having the above-mentioned formula 2 was prepared by screen printing on a printed circuit board 3 with a conductor track formed on it 2 to thereby form a first photo-curable resist film 7 train.

Then a negative film 17 with the same pattern as the second light-curable resist pattern 11 of the example 1 in close contact with the top of the first photo-curable resist film 7 brought. Thereafter, the entire surface of the first photo-curable resist film became 7 through a high pressure mercury vapor lamp through the negative film ( 17 in the 19a ) through with ultraviolet radiation 12 irradiated. The drawing time was 30 seconds.

Then unexposed sections 13 of the first photo-curable resist film by developing with an aqueous solution of 1% sodium carbonate of 30 ° C. This became one with the first light-curable resist pattern 5 coated printed circuit board 3 received (see the 9c ).

In this Comparative Example 2, the total irradiation was performed by the high pressure mercury vapor lamp. So the productivity was excellent. However, partly due to dimensional changes of the negative film 17 due to the temperature and relative humidity, the position of the first photohardenable resist pattern 5 in terms of the conductor pattern 2 inaccurate, so that the position accuracy was poor.

Claims (12)

Method for producing a resist pattern with the following steps: Making a first light-curable Resistfilms, the light of a wavelength in a first sensitivity wavelength range is sensitive, on a semiconductor chip or a conductor pattern a circuit board; Producing a second light-curable Resistfilms, the light of a wavelength in the first sensitivity wavelength range locks and on light of a wavelength in a second sensitivity wavelength range is sensitive to the first light-curable resist film; Dithering of laser light of a wavelength in the second sensitivity wavelength range over a range the second light-curable Resistfilms that becomes a mask pattern to the area of the second light-curable To expose resist film that is to become the mask pattern; Develop the second light-curable Resistfilms through a development solution where he is not with the first photocurable Resist film overlaps, to form the mask pattern; Exposure of the first light-curable Resist film using light of a wavelength in the first sensitivity wavelength region, with the membrane body as a mask; and Develop the first light-curable Resistfilms to on the semiconductor chip or the circuit board with form the resist pattern formed thereon a resist pattern. Method according to claim 1, characterized in that when the second photo-curable resist film is formed on the first photo-curable resist film, made over a cover film that transmits light of a wavelength in the first sensitivity wavelength region; and during the development step for the first photo-curable resist film, first the cover film is peeled off to remove the mask pattern. Method according to claim 2, characterized in that that while of the development step for the first light-curable Resistfilm also unexposed sections of the first light-curable Resistfilms be removed. Method according to claim 2 or 3, characterized that a laminate with the cover film and the first photocurable Resist film is mounted on the wiring pattern and the second light-curable resist film is made on the cover film. Method according to one of claims 1 to 4, characterized that when scanning laser light of a wavelength in the second Sensitivity wavelength range over the Area to become the mask pattern around the area of the second one Light-curable To expose resist film that is to become the mask pattern in advance a correction of a position shift is performed on the conductor pattern and then the laser light of a wavelength in the second sensitivity wavelength range is scanned to the mask pattern on the trace pattern train. Method according to one of claims 1 to 5, characterized that For the first light-curable Resistfilm a material with sensitivity to ultraviolet radiation is used and the first light-curable resist film by ultraviolet radiation is exposed; and For the second light-curable Resistfilm a material with sensitivity to visible light is used and the second light-curable resist film by visible Laser light is exposed. Method according to one of claims 1 to 6, characterized that the second photo-curable resist film fine particles of titanium oxide, calcium carbonate and / or zinc oxide contains. Method according to claim 7, characterized in that that at least one species of said fine particles has a average particle size of 0.01 .mu.m to 0.05 .mu.m. Method according to one of claims 1 to 8, characterized that For the second light-curable Resistfilm a water-developable material is used; and Water is used as the second development solution. Method according to one of claims 1 to 9, characterized as the first light-curable resist film a solder resist film is used. Method according to one of claims 1 to 9, characterized as the first light-curable resist film a plating resist film is used. Method according to one of claims 1 to 9, characterized as the first light-curable resist film an etching resist film is used.