JP2005303016A - Manufacturing method of printed wiring substrate and its wiring substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide the manufacturing method of a printed wiring board which enables near ultraviolet exposure and weak alkali development, that is, development only with weak alkali such as sodium carbonate water solution is enabled, and uses a positive type photosensitive resist material which resists a plurality of times of exposure, development and etching process by using the same resist without peeling the resist. <P>SOLUTION: In the manufacturing method of the printed wiring board, a positive type photosensitive resist liquid is applied to a laminated board whose at least one surface is a metallic layer, and a photosensitive resist film is formed uniformly in the surface of the laminated board by drying the resist liquid. Thereafter, two or more cycles of following processes (1) to (3) are repeated. In a process (1): the photosensitive resist film is exposed via a photomask; in a process (2), development is carried out; and in a process (3), the metallic layer is etched. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for manufacturing a printed wiring board and a wiring board obtained by the method.

  Currently, printed wiring boards and the like are manufactured by applying a photoresist to a substrate, attaching a mask, irradiating near-ultraviolet light, performing etching, and drawing wiring on the substrate.

  Currently, a negative photosensitive resist material is mainly used as the photoresist material used in the manufacture of printed circuit boards and the like, and a composition comprising a polycarboxylic acid resin, an ethylenically unsaturated compound, and a photopolymerization initiator is used. It is common. After applying this composition to the substrate, applying a mask, irradiating near ultraviolet rays (hereinafter referred to as exposure) to cure the resin, and then immersing it in a developing solution such as a 1% aqueous sodium carbonate solution, the unexposed portion is developed. The pattern is formed by dissolving in the solution and leaving the exposed portion of the photosensitive resist material. A method of removing the mask and etching the resulting pattern is used.

  On the other hand, a pattern forming method using a positive photosensitive resist material that can be finely processed has been proposed. As a positive photosensitive resist material that has been widely used in the semiconductor field, a naphthoquinone diazide-based photosensitive material has been proposed. There is. However, the naphthoquinone diazide-based photosensitive material may have insufficient resolution for forming a fine pattern. Furthermore, naphthoquinone diazide compounds are expensive and have problems in cost for printed circuit board applications. On the other hand, as a positive photosensitive resist material that changes to a quinonediazide type, a compound that generates an acid by light and a compound or resin that undergoes hydrolysis or the like to change its solubility in alkaline water have been proposed. The difference in solubility between the exposed area and the exposed area is small and the resolution is poor, or the image cannot be developed without using an organic alkali agent such as tetraalkylammonium hydride for development, or an expensive photoacid such as an onium salt In many cases, a generator must be used, and it has not yet been put to practical use in pattern formation of a printed wiring board using a positive photosensitive resist material.

  In recent years, as information portable devices have become more sophisticated and lighter, thinner and smaller, printed wiring boards mounted on these electronic devices are also required to have higher integration, higher speed, and smaller size, and circuit patterns continue to become finer. There is a demand for a circuit board that requires fine processing, such as forming an advanced fine pattern or providing a step in a conductor circuit. For this reason, the conductor circuit is formed by changing the etching method and conditions and performing etching a plurality of times. However, in this method, as long as the negative photosensitive resist material is used, once the first etching is completed, after the resist film is peeled off, the photosensitive resist is applied again on the conductor circuit, and exposure, development, and etching are performed. It is necessary to apply a photosensitive resist a plurality of times, and in the second and subsequent exposures, it is extremely difficult to perform exposure without causing a positional shift from the original pattern. On the other hand, the positive type photosensitive resist material can be exposed using the same resist film without being peeled after the first etching is completed. However, in the conventional general positive type photosensitive resist material, Many developing solutions such as about 1% sodium carbonate aqueous solution cannot be developed, and even if development is possible, the resist film is attacked by the developing solution in the second and subsequent exposures and development, resulting in fine patterns. It cannot be formed. In other words, a positive photosensitive resist material that can be developed only with a weak alkali such as an aqueous solution of sodium carbonate and that can withstand multiple development and etching processes using the same resist without peeling off the resist. It has not been delivered.

  According to the present invention, in particular, by using a high-resistance positive resist composition that can be exposed with near-ultraviolet exposure and developed with weak alkali, that is, with only weak alkali such as an aqueous sodium carbonate solution, a resist can be obtained. The same resist can be used for a plurality of times of exposure, development, and etching without peeling off, a fine resist pattern can be formed, and a printed circuit board with a fine circuit can be manufactured. Furthermore, by using a positive resist, exposure in the through hole is unnecessary, and it can be applied to a through hole substrate, and furthermore, by using the most common positive resist that can be developed with sodium carbonate. The printed wiring board can be manufactured without changing any conventional printed wiring board processing equipment.

  In view of the situation as described above, the object of the present invention is to allow exposure with near-ultraviolet exposure and weak alkali development, that is, development with only weak alkali such as an aqueous sodium carbonate solution, and without peeling off the resist. This is a printed wiring board manufacturing method that uses the same resist and uses a positive photosensitive resist material that can withstand multiple exposure, development, and etching processes. It also has excellent sensitivity and resolution, and is a conventional circuit. An object of the present invention is to provide a method for manufacturing a printed wiring board using a positive photosensitive resist material that can be processed at a low cost by using a processing step.

As a result of intensive studies to achieve the above object, the present inventors have completed the present invention.
That is, the present invention
After applying a positive photosensitive resist solution to a laminate having at least one surface of a metal layer and drying the resist solution, the photosensitive resist film is uniformly formed on the surface of the laminate, and then the next step It is a method for manufacturing a printed wiring board, wherein (1) to step (3) are repeated as two or more cycles as one cycle.
Step (1) Exposure of the photosensitive resist film through a photomask Step (2) Development step (3) Etching the metal layer

    The positive photosensitive resist composition used in the present invention can be developed with a weak alkali capable of repeating the steps (1) to (3) a plurality of times, and is highly resistant to a developer. Any of them can be used. That is, it is most common to perform spray development for about 1 minute or 2 minutes at 30 ° C. using a 1% by weight sodium carbonate aqueous solution. In order to enable development that is repeated a plurality of times, it is necessary to endure development for at least 5 minutes under the above development conditions.

    The positive photosensitive resist composition contains (A) an acid functional copolymer, (B) a compound that generates an acid by irradiation with active energy rays, and (C) an organic solvent.

    Examples of the acid functional copolymer (A) include an acrylic copolymer in which a carboxyl group is generated in the presence of an acid, and preferably a first structural unit represented by the following general formula (1):

(In formula (1), X represents a hydrogen atom or a methyl group)
A second structural unit represented by the following general formula (2);

(In Formula (2), R ¹ represents a hydrogen atom or a methyl group, R ² represents a straight chain or branched unsubstituted alkyl group having 1 to 6 carbon atoms, or a straight chain having 1 to 6 carbon atoms substituted with a hydroxy group. A linear or branched alkyl group having 1 to 6 carbon atoms substituted with a halogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms substituted with a cyano group, or a dialkylamino group Represents a linear or branched alkyl group having 1 to 6 carbon atoms and substituted with
A third structural unit represented by the following general formula (3);

(In Formula (3), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a hydrogen atom, a halogen atom, or a linear or branched unsubstituted alkyl group having 1 to 6 carbon atoms, Y represents a hydrogen atom, Represents a linear or branched unsubstituted alkyl group having 1 to 6 carbon atoms or a linear or branched substituted alkyl group having 1 to 6 carbon atoms; Z represents a linear or branched unsubstituted alkyl group having 1 to 6 carbon atoms; Or an acid-sensitive copolymer comprising a linear or branched substituted alkyl group having 1 to 6 carbon atoms; Y and Z may be bonded to form a ring structure, provided that a, b and c represent composition ratios, a represents 0.05 to 0.3, b represents a rational number of 0.1 to 0.7, c represents a rational number of 0.2 to 0.8, and the sum of a, b, and c is 1. Can be mentioned.
(B) The acid-generating compound preferably contains 0.05 to 20 parts by mass of (B) with respect to 100 parts by mass of the acid-sensitive copolymer (A) described above. It is preferable to contain 1-10 mass parts.
The liquid specific gravity of the positive photosensitive resist composition is preferably 0.800 to 0.990, more preferably 0.850 to 0.950.

  In the method for producing a printed wiring board according to the present invention, first, a laminate having at least one surface of a metal layer is immersed in a photosensitive resist solution, and the photosensitive resist solution is applied onto the laminate by pulling up. Next, by drying the photosensitive resist solution, a photosensitive resist film is uniformly formed on the surface of the laminate.

Next, using the laminated plate on which the photosensitive resist film is formed, a step (1) of exposing through a photomask, a step (2) of developing, and a step (3) of etching the metal layer are performed. By using a resist having a high resistance to a developing solution, it is possible to repeatedly perform the steps (1) to (3) a plurality of times with the same resist. Furthermore, a conventional circuit processing apparatus can be used by using a positive photosensitive resist material that can be developed only with a weak alkali such as an aqueous sodium carbonate solution and that can perform fine metal circuit processing.
In general formula (1), X is a hydrogen atom or a methyl group. A methyl group is preferred in terms of developer resistance.

R ¹ in the general formula (2) is a hydrogen atom or a methyl group. R ² in the general formula (2) is a linear or branched unsubstituted, hydroxy-substituted, halogen-substituted, cyano-substituted or dialkylamino-substituted alkyl group having 1 to 6 carbon atoms. Unsubstituted alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclohexyl group or cyclopentyl group, hydroxymethyl group, 1- Hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxy n-propyl group, 2-hydroxy n-propyl group, 3-hydroxy n-propyl group, 1-hydroxyisopropyl group, 2,3-dihydroxy-n-propyl, 1-hydroxy n-butyl group, 2-hydroxy n-butyl group, 3-hydroxy n-butyl group or -Hydroxy-substituted alkyl group such as hydroxy n-butyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2,2,2 ', 2', 2'-hexafluoroisopropyl group, 2 , 2,3,4,4,4-hexafluorobutyl group, 2-chloroethyl group, trichloroethyl group, 3-bromoethyl group or heptafluoroisopropyl group or other halogen-substituted alkyl group, 2-cyanoethyl group or other cyano-substituted alkyl group Group or a dialkylamino-substituted alkyl group such as 2- (dimethylamino) ethyl group, 3- (dimethylamino) propyl group, or 3-dimethylaminoneopentyl group.

Preferably, it is a linear or branched unsubstituted, hydroxy-substituted, halogen-substituted, cyano-substituted or dialkylamino-substituted alkyl group having 1 to 4 carbon atoms, specifically a methyl group, ethyl group, n-propyl group, isopropyl Group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-hydroxyethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group and the like.
More preferably, it is a linear or branched unsubstituted, hydroxy-substituted, halogen-substituted, cyano-substituted or dialkylamino-substituted alkyl group having 1 to 3 carbon atoms, specifically a methyl group, an ethyl group, an n-propyl group, An isopropyl group, a trifluoromethyl group, a 2-hydroxyethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, and the like can be given.

R ³ in the general formula (3) is a hydrogen atom or a methyl group. In the general formula (3), R ⁴ is a hydrogen atom, a halogen atom or a linear or branched unsubstituted alkyl group having 1 to 6 carbon atoms, and Z is a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. An unsubstituted or substituted alkyl group, and Y is a linear or branched unsubstituted or substituted alkyl group having 1 to 6 carbon atoms, or Y and Z may be bonded to each other to have a ring structure. .

Specifically, R ⁴ is a hydrogen atom, a fluorine atom, or a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, or the like. A chain or branched unsubstituted alkyl group, and Y is a linear or branched group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group or tert-butyl group An unsubstituted, hydroxy-substituted, halogen-substituted, cyano-substituted or dialkylamino-substituted alkyl group, etc., and Z is a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group Or a linear or branched unsubstituted, hydroxy-substituted, halogen-substituted, cyano-substituted or dialkyl group such as tert-butyl group Roh is a substituted alkyl group or the like.

More specifically, when R ⁴ , C 1, O 2, Y and Z of the alkoxyalkyl ester group portion of the general formula (3) are collectively expressed, 1-methoxyethyl group, 1-ethoxyethyl group, 1-n -Propoxyethyl group, 1-isopropoxyethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1-sec-butoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 2 -Isopropoxyethyl group, 2-n-butoxyethyl group, 2-isobutoxyethyl group, 2-sec-butoxyethyl group, 1-methoxypropyl group, 1-ethoxypropyl group, 1-n-propoxypropyl group, 1 -Isopropoxypropyl group, 1-n-butoxypropyl group, 1-isobutoxypropyl group, 1-sec-butoxypropyl group, 1-tert-butyl group Xoxypropyl group, 2-methoxypropyl group, 2-ethoxypropyl group, -n-propoxypropyl group, 2-isopropoxypropyl group, 2-n-butoxypropyl group, 2-isobutoxypropyl group, 2-sec-butoxypropyl Group, 2-tert-butoxypropyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-n-propoxypropyl group, 3-isopropoxypropyl group, 3-n-butoxypropyl group, 3-isobutoxypropyl group Group, unsubstituted alkyl group such as 3-sec-butoxypropyl group, 3-tert-butoxypropyl group, 1-methoxy-1-hydroxymethyl group, 1- (1-hydroxy) methoxymethyl group, 1- (1- Hydroxy) hydroxy-substituted alkoxy groups such as methoxyethyl group, trifluoromethoxy group A halogen-substituted alkoxy group such as 1-methoxy-2,2,2-trifluoroethyl group, 1-trifluoromethoxy-2,2,2-trifluoroethyl group, 1-methoxy-1-cyanomethyl group, Cyano-substituted alkoxy groups such as 1- (1-cyano) methoxymethyl group and 1- (1-cyano) methoxyethyl group, dialkylamino-substituted alkoxy groups such as 1,1-dimethylaminomethoxymethyl group, tetrahydrofuran-2-yloxy Group, unsubstituted cyclic ether such as tetrahydropyran-2-yloxy group, 2-methyltetrahydropyran-2-yloxy group, alkyl-substituted cyclic ether such as 2-methyltetrahydropyran-2-yloxy group, or 2-fluorotetrahydrofuran- 2-yloxy group, 2-fluorotetrahydrofuran-2 A halogen-substituted cyclic ethers such as yloxy group.

  The general formula (2) or (3) may have not only one type of structural unit but also two or more types of structural units. That is, four or more structural units are represented as in the copolymer having the structural units represented by the general formula (1), two or more general formulas (2) and two or more general formulas (3). The copolymer which has is also contained in the copolymer of this invention.

In the copolymer of the present invention, the composition ratio of the structural units represented by the general formula (1), the general formula (2), and the general formula (3) is extremely important. In such a case, the composition ratio of the general formula (1) is 0.05 or more, more preferably 0.15 or more, 0.3 or less, and more preferably 0.25 or less. Moreover, the composition ratio of General formula (2) is 0.1 or more, 0.15 or more is more preferable, it is 0.7 or less, and less than 0.5 is more preferable. The composition ratio of the general formula (3) is 0.2 or more, more preferably 0.3 or more, 0.8 or less, and more preferably 0.7 or less. In addition, when using 2 or more types of structural units shown by General formula (2) or General formula (3), a composition ratio is the sum total of the composition ratio of each structural unit. The composition ratio of the three structural units can be measured by, for example, ¹ H-NMR and ¹³ C-NMR.

The acid-sensitive copolymer used in the present invention is composed of three structural units even if the structural units represented by the general formula (1), the general formula (2) and the general formula (3) are randomly copolymerized. May be copolymerized alternately or may be block copolymerized.
The weight average molecular weight (Mw) of the acid-sensitive copolymer used in the present invention varies depending on the purpose of use of the copolymer and is not uniform, but is preferably 3,000 or more, more preferably 4,000 or more. 80,000 or less is preferable, and 60,000 or less is more preferable. Furthermore, the molecular weight dispersity (Mw / Mn, where Mn is the number average molecular weight) is preferably 1.0 or more, 5.0 or less, more preferably 4.0 or less, and even more preferably 3.0 or less. In addition, a weight average molecular weight and molecular weight dispersion degree can be measured by polystyrene conversion, for example using gel permeation chromatography (GPC) etc.
The acid-sensitive copolymer used in the present invention comprises 4- (1-methylethenyl) phenol and / or 4-ethenylphenol, (meth) acrylic acid esters, and (meth) acrylic acid alkoxyalkyl esters. And a radical polymerization initiator and a solvent are mixed so that the molar ratio of the monomers in the monomer mixture is predetermined, and heated.
Specific examples of (meth) acrylic esters used in the present invention include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, Acrylic acid unsubstituted alkyl ester such as sec-butyl acrylate, tert-butyl acrylate, cyclohexyl acrylate or cyclopentyl acrylate, hydroxymethyl acrylate, 1-hydroxyethyl acrylate, 2-hydroxyethyl acrylate, acrylic acid 1 -Hydroxy n-propyl, 2-hydroxy n-propyl acrylate, 3-hydroxy n-propyl acrylate, 1-hydroxyisopropyl acrylate, 2,3-dihydroxypropyl acrylate, 1-hydroxy n-butyl acrylate Hydroxy-substituted alkyl esters of acrylic acid such as 2-hydroxy n-butyl acrylate, 3-hydroxy n-butyl acrylate or 4-hydroxy n-butyl acrylate, trifluoromethyl acrylate, 2,2,2-acrylate Trifluoroethyl, hexafluoroisopropyl acrylate, 2,2,3,4,4,4-hexafluorobutyl acrylate, 2-chloroethyl acrylate, trichloroethyl acrylate, 3-bromoethyl acrylate or heptafluoroacrylate Acrylic halogen-substituted alkyl esters such as 2-propyl, cyano-substituted alkyl esters such as 2-cyanoethyl acrylate, 2- (dimethylamino) ethyl acrylate, 3- (dimethylamino) propyl acrylate or 3-acrylate Jime Dialkylamino-substituted alkyl esters such as ruaminoneopentyl, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, methacrylic acid Unsubstituted methacrylic acid alkyl ester such as tert-butyl, cyclohexyl methacrylate or cyclopentyl methacrylate, hydroxymethyl methacrylate, 1-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate, 1-hydroxy n-propyl methacrylate, methacrylic acid 2-hydroxy n-propyl, 3-hydroxy n-propyl methacrylate, 1-hydroxyisopropyl methacrylate, 2,3-dihydroxypropyl methacrylate 1-hydroxy n-butyl methacrylate, 2-hydroxy n-butyl methacrylate, 3-hydroxy n-butyl methacrylate or 4-hydroxy n-butyl methacrylate, hydroxy-substituted alkyl esters such as trifluoromethyl methacrylate 2,2,2-trifluoroethyl methacrylate, hexafluoroisopropyl methacrylate, 2,2,3,4,4,4-hexafluorobutyl methacrylate, 2-chloroethyl methacrylate, trichloroethyl methacrylate, methacrylic acid Methacrylic acid halogen-substituted alkyl esters such as 3-bromoethyl or heptafluoro-2-propyl methacrylate, methacrylic acid cyano-substituted alkyl esters such as 2-cyanoethyl methacrylate, 2- (dimethylamino) ethyl methacrylate And dialkylamino-substituted alkyl esters of methacrylic acid such as 3- (dimethylamino) propyl methacrylate or 3-dimethylaminoneopentyl methacrylate.

  In addition, the (meth) acrylic acid esters as described above can be used alone or in combination of two or more, and in this case, two or more structural units represented by the general formula (2) A copolymer having a structure in which is randomly copolymerized is obtained. At this time, the composition ratio of the general formula (2) is the sum of the composition ratios of the structural units represented by two or more kinds of the general formula (2).

  Specific examples of (meth) acrylic acid alkoxyalkyl esters which are another raw material of the acid-sensitive copolymer used in the present invention include, for example, 1-methoxyethyl acrylate, 1-ethoxy acrylate. Ethyl, 1-n-propoxyethyl acrylate, 1-isopropoxyethyl acrylate, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl acrylate, 1-sec-butoxyethyl acrylate, 2-ethoxy acrylate Ethyl, 2-n-propoxyethyl acrylate, 2-isopropoxyethyl acrylate, 2-n-butoxyethyl acrylate, 2-isotopoxyethyl acrylate, 2-sec-butoxyethyl acrylate, 1-methoxy acrylate Propyl, 1-ethoxypropyl acrylate, 1-n-propoxyacrylate Xylpropyl, 1-isopropoxypropyl acrylate, 1-n-butoxypropyl acrylate, 1-isobutoxypropyl acrylate, 1-sec-butoxypropyl acrylate, 1-tert-butoxypropyl acrylate, 2-methoxy acrylate Propyl, 2-ethoxypropyl acrylate, 2-n-propoxypropyl acrylate, 2-isopropoxypropyl acrylate, 2-n-butoxypropyl acrylate, 2-isobutoxypropyl acrylate, 2-sec-butoxy acrylate Propyl, 2-tert-butoxypropyl acrylate, 3-methoxypropyl acrylate, 3-ethoxypropyl acrylate, 3-n-propoxypropyl acrylate, 3-isopropoxypropyl acrylate, 3-n-butoxy acrylate Unsubstituted alkyl alkoxylates such as propyl, 3-isobutoxypropyl acrylate, 3-sec-butoxypropyl acrylate or 3-tert-butoxypropyl acrylate, 1-methoxy-1-hydroxymethyl acrylate, acrylic acid Hydroxy-substituted alkoxylates such as 1- (1-hydroxy) methoxymethyl or 1- (1-hydroxy) methoxyethyl acrylate, trifluoromethoxymethyl acrylate, 1-methoxy-2,2,2-triacrylate Acrylic acid halogen-substituted alkoxylates such as 1-trifluoromethoxy-2,2,2-trifluoroethyl acrylate, 1-methoxy-1-cyanomethyl acrylate, 1- (1-cyano) methoxymethyl acrylate Or Acrylic acid cyano-substituted alkoxylates such as 1- (1-cyano) methoxyethyl acrylate, dialkylamino-substituted alkoxylates such as 1,1-dimethylaminomethoxymethyl acrylate, tetrahydro-2-yloxy acrylate or acrylic acid Acrylic acid unsubstituted cyclic oxalate such as tetrahydropyran-2-yloxy or alkyl acrylate substituted cyclic oxalate such as 2-methyltetrahydropyran-2-yloxy acrylate or 2-methyltetrahydropyran-2-yloxy acrylate Acrylic acid halogen-substituted cyclic oxalate such as fluorotetrahydrofuran-2-yloxy, methoxymethyl methacrylate, ethoxymethyl methacrylate, n-propoxymethyl methacrylate, methacrylate Isopropoxymethyl methacrylate, n-butoxymethyl methacrylate, isobutoxymethyl methacrylate, sec-butoxymethyl methacrylate, tert-butoxymethyl methacrylate, 1-methoxyethyl methacrylate, 1-ethoxyethyl methacrylate, methacrylic acid 1 -N-propoxyethyl, 1-isopropoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 1-isobutoxyethyl methacrylate, 1-sec-butoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2 methacrylic acid 2 -N-propoxyethyl, 2-isopropoxyethyl methacrylate, 2-n-butoxyethyl methacrylate, 2-isobutoxyethyl methacrylate, 2-sec butoxyethyl methacrylate, 1-methoxypropyl methacrylate 1-ethoxypropyl methacrylate, 1-n-propoxypropyl methacrylate, 1-isopropoxypropyl methacrylate, 1-n-butoxypropyl methacrylate, 1-isobutoxypropyl methacrylate, 1-sec-butoxypropyl methacrylate, 1-tert-butoxypropyl methacrylate, 2-methoxypropyl methacrylate, 2-ethoxypropyl methacrylate, 2-n-propoxypropyl methacrylate, 2-isopropoxypropyl methacrylate, 2-n-butoxypropyl methacrylate, methacryl 2-isobutoxypropyl acid, 2-sec-butoxypropyl methacrylate, 2-tert-butoxypropyl methacrylate, 3-methoxypropyl methacrylate, 3-ethoxypropyl methacrylate, methacryl 3-n-propoxypropyl, 3-isopropoxypropyl methacrylate, 3-n-butoxypropyl methacrylate, 3-isobutoxypropyl methacrylate, 3-sec-butoxypropyl methacrylate, 3-tert-butoxypropyl methacrylate, etc. Methacrylic acid unsubstituted alkyl alkoxylate, 1-methoxy-1-hydroxymethyl methacrylate, 1- (1-hydroxy) methoxymethyl methacrylate, 1- (1-hydroxy) methoxyethyl methacrylate, etc. Methacrylic acid such as alkoxylate, trifluoromethoxymethyl methacrylate, 1-methoxy-2,2,2-trifluoroethyl methacrylate or 1-trifluoromethoxy-2,2,2-trifluoroethyl methacrylate Halogen-substituted alkoxylates, methacrylic acid cyano-substituted alkoxylates such as 1-methoxy-1-cyanomethyl methacrylate, 1- (1-cyano) methoxymethyl methacrylate or 1- (1-cyano) methoxyethyl methacrylate, methacrylic acid 1 Dialkylamino-substituted alkoxylates such as 1,1-dimethylaminomethoxymethyl, methacrylic acid-free cyclic oxalate such as tetrahydrofuran-2-yloxy methacrylate or tetrahydropyran-2-ylmethacrylate, 2-methyltetrahydrofuran-2 methacrylate -An alkyl methacrylate-substituted cyclic oxalate such as yloxy or 2-methyltetrahydropyran-2-yloxy methacrylate, or 2-fluorotetrahydrofuran methacrylate 2-methacrylate fluorinated cyclic oxalate such as yloxy and the like.

  The (meth) acrylic acid alkoxyalkyl esters as described above can be used alone or in combination of two or more. In this case, two or more structural units represented by the general formula (3) can be used. A copolymer having a structure in which is randomly copolymerized is obtained. The composition ratio at this time is the sum of the composition ratios of the structural units represented by two or more types of general formula (3).

  In addition, 4- (1-methylethenyl) phenol, (meth) acrylic acid esters, and (meth) acrylic acid alkoxyalkyl esters contain an alkaline compound such as potassium hydroxide or a polymerization inhibitor as a stabilizer. These are preferably used after carrying out normal purification operations such as recrystallization and distillation to remove the stabilizer, but commercially available products can also be used as they are without performing purification operations.

  The amount of these 4- (1-methylethenyl) phenol, (meth) acrylic acid esters and (meth) acrylic acid alkoxyalkyl esters is preferably adjusted to the desired composition ratio of the copolymer. With respect to 1 mol part in total, 4- (1-methylethenyl) phenol is preferably 0.05 mol part or more, more preferably 0.15 mol part or more, more preferably 0.3 mol part or less and 0.25 part or less. preferable. The (meth) acrylic acid esters are 0. 1 mol part or more is preferable, 0.15 mol part or more is more preferable, 0.7 mol part or less is preferable, and less than 0.5 mol part is more preferable. Furthermore, 0.2 mol part or more is preferable, (meth) acrylic-acid alkoxyalkylester is more preferable 0.3 mol part or more, 0.8 mol part or less is preferable and 0.7 mol part or less is more preferable.

  In addition, when the number of (meth) acrylic acid esters is two or more, the total number of moles is preferably within the above range, and when the number of (meth) acrylic acid alkoxyalkyl esters is two or more, The total number of moles is preferably within the above range.

  Examples of the radical polymerization initiator in the method of the present invention include azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, azobis-2-amidinopropane hydrochloride, dimethyl azobisisobutyrate, Azo initiator such as azobisisobutylamidine hydrochloride or 4,4′-azobis-4-cyanovaleric acid, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, di-tert-butyl peroxide, lauroyl peroxide Acetyl peroxide, diisopropyl dicarbonate, cumene hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, p-menthane hydroperoxide, pinane hydroperoxide, methyl ethyl ketone peroxide, cyclohexano Peroxide based initiators such as peroxide, diisopropylperoxydicarbonate, tert-butylperoxylaurate, di-tert-butylperoxyphthalate, dibenzyloxide or 2,5-dimethylhexane-2,5-dihydroperoxide, or And redox initiators such as benzoyl peroxide-N, N-dimethylaniline or peroxodisulfuric acid-sodium hydrogen sulfite.

  Of these, azo initiators or peroxide initiators are preferable, and azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, dimethyl azobisisobutyrate, Benzoyl oxide, 2,4-dichlorobenzoyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, diisopropyl dicarbonate or acetyl peroxide.

  The radical polymerization initiators as described above may be used alone or in combination of two or more simultaneously or sequentially. These usage amounts are based on the total usage amount of 4- (1-methylethenyl) phenol, (meth) acrylic acid esters and (meth) acrylic acid alkoxyalkyl esters at the start of heating the copolymer raw material. 0. 0001 mol times or more is preferable, 0. 001 mole times or more is more preferable. 005 mol times or more is more preferable, while 0. 1 mol times or less is preferable, 0. 05 mol times or less are more preferable. If the total use amount of the radical polymerization initiator is this amount, the whole amount may be charged from the start of heating, or the whole amount or a part of it may be additionally used after the start of heating.

  The polymerization method of the acid-sensitive copolymer used in the present invention is not particularly limited, and 4- (1-methylethenyl) phenol, (meth) acrylic acid esters, and (meth) acrylic acid alkoxy Any method may be used as long as the alkyl ester, radical polymerization initiator, solvent, and the like are effectively mixed and contacted, and any of a batch method, a semi-batch method, and a continuous flow method may be used. For example, a method in which these compounds are collectively inserted into a reaction vessel and heating is started, or a monomer, a radical polymerization initiator and a solvent are continuously or intermittently inserted into a reactor in which at least a part of the solvent is inserted. The method of performing is usually employed.

  After completion of the polymerization reaction, the produced copolymer can be isolated from the reaction mixture by an ordinary method such as a solvent extraction method, a fractional precipitation method, or a thin film evaporation method. Moreover, the solution containing the produced | generated copolymer can also be used as a resist raw material, without isolating the copolymer which is a target object as needed.

    As the compound that generates an acid by irradiation with active energy rays, a compound that generates an acid by irradiation of active energy rays to be used can be arbitrarily selected and used. Specifically, for example, onium salts such as sulfonium salt, chloronium salt, bromonium salt, iodonium salt, diazonium salt, pyridinium salt, 2,4,6-tris (trichloromethyl) -s-triazine, 2- ( 4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-α-naphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3 , 4-methylenedioxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, piperonyl-1-trichloromethyl 3,5-s-triazine, 2- (3-bromo-4-methoxyphenyl)- 4,6-bis (trichloromethyl) -s-triazine, 2- (2-methoxyphenylethenyl) -4,6-bis (trichloro Til) -s-triazine, 2- (3-methoxyphenylethenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenylethenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (4-hydroxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethylene glycol monoethyl ether phenyl) -4,6-bis (trichloro) Halogenated triazine compounds such as tris (trihalomethyl) -s-triazines, such as methyl) -s-triazine, or α, α-dichloro-4-phenoxyacetophenone, 4,4 ′-(α, α-dichloroacetyl) ) Acyl halides such as diphenyl ether, or derivatives of sulfonic acid, tri (methanesulfonyloxy) Benzene derivatives, bissulfonyldiazomethanes, sulfonyl carbonyl alkanes, sulfonyl carbonyl diazomethanes, disulfone compounds, and iron arene complexes.

    The total addition amount of the compounds that generate an acid upon irradiation with active energy rays is preferably 0.05 parts by weight or more, more preferably 0.2 parts by weight or more with respect to 100 parts by weight of the total amount of the acid-sensitive copolymer. On the other hand, it is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less. If the addition amount is within this range, it is preferable because a pattern can be formed satisfactorily during development. Furthermore, for the purpose of improving sensitivity, benzophenone, anthraquinone, thioxanthone, or other sensitizing dyes such as ketocoumarin, merocyanine, pyrene, and perylene can be added as necessary. . Examples of the photosensitizer include quinones such as ethyl anthraquinone and t-butyl anthraquinone, thioxanthones such as diethyl thioxanthone and isopropyl thioxanthone, benzoic acid or p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, Known sensitizers such as tertiary amines such as 2-dimethylaminoethyl benzoate and benzophenone can be used alone or in combination. Further, coumarin derivatives such as 7-diethylamino-4-methylcoumarin and 4,6-diethyl-7-ethylaminocoumarin, and other sensitizing dyes such as carbocyanine dyes and xanthene dyes can also be used.

  Examples of the solvent used in the positive photosensitive resist composition of the present invention include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, methyl isoamyl ketone, 2-heptanone or methyl-2-n-amyl ketone, and ethanol. N-propanol, isopropanol, 1-butanol, 2-butanol, 3-methoxybutanol, 3-methyl-3-methoxybutanol, alcohols such as 1-methoxy-2-propanol or 1-ethoxy-2-propanol, ethylene Polyhydric alcohols such as glycol, propylene glycol or dipropylene glycol, ethylene glycol ethylene, propylene glycol, glycol monoacetate, diethylene glycol monoacetate, propylene Polymethyl alcohol derivatives such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, monophenyl ether, dimethyl ether or diethyl ether of lenglycol monoacetate or dipropylene glycol monoacetate, cyclic ethers such as tetrahydrofuran or dioxane, Esters such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, tert-butyl acetate or tert-butyl propionate , Aromatic hydrocarbons such as benzene, toluene or xylene, or halogenated aromatic hydrocarbons such as chlorobenzene or orthodichlorobenzene. I can get lost.

  Of these, ketones, alcohols, polyhydric alcohols, derivatives of polyhydric alcohols, cyclic ethers, esters, or aromatic hydrocarbons are preferable, and acetone, methyl ethyl ketone, methyl isobutyl ketone are more preferable. , Cyclohexanone, ethanol, isopropanol, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, ethyl acetate, ethyl lactate or toluene. These solvents may be used alone or in combination of two or more.

  In addition, in order to improve the film forming property of the photosensitive resist solution, improve viscosity, developability, storage stability, heat resistance, etc., for example, styrene resin, styrene and acrylic acid, polyvinyl formal, polyvinyl butyral, novolac resin Polymer binders such as vinyl acetate resin, polyvinyl pyrrolidone, a copolymer of methacrylic acid or maleic anhydride, a copolymer of alkene and maleic anhydride, and a vinyl alcohol copolymer can be used.

  In the positive photosensitive resist composition of the present invention, the color tone of the coating film is changed by the acid generated by the exposure because of the confirmation of the pattern after the exposure and the confirmation of the consistency between the pattern position and the through hole position. It is also possible to add a pH indicator that changes color with, for example, methyl orange, methyl red, methyl violet, dinitrophenol, thymol blue, bromophenol blue, and the like.

  When the positive photosensitive resist material obtained above is used as an etching resist for forming a circuit pattern on a printed wiring board, it is first adjusted to a viscosity suitable for the coating method as necessary, and then a mother board, a package substrate, It is applied to a copper-clad multilayer substrate for flexible printed circuit boards or a copper-clad laminate substrate with through-holes by screen printing, curtain coating, roll coating, spray coating, dip coating, etc. It can be used with thin substrates (thickness of 0.1 mm or less), can be applied to the end face without being influenced by the surface shape, and can be applied to the inner surface of the through hole reliably. Dozens of substrates can be processed simultaneously, processing efficiency is extremely good, and the tact time per substrate can be greatly reduced. In, the coating method by a dip coating method is particularly preferred.

  Moreover, since the photosensitive resist solution of the present invention has a sufficiently low viscosity, it is preferably substantially Newtonian. The photosensitive resist solution applied to the substrate by the dip method as described above is dried and then exposed, and only the exposed portion is removed by development. Since the photosensitive resist solution of the present invention uses an organic solvent having a low boiling point as a main solvent, it is not necessary to perform aggressive drying, but in order to perform rapid drying, a drying means such as blowing or heating is employed. May be. In addition, the exposure method is not particularly limited, and a conventionally performed method can be employed. For example, a method of exposing a photo tool directly or indirectly to a dried film, a laser beam, For example, a direct drawing method can be used.

  After applying the positive photosensitive resist solution of the present invention to the conductor surface of the substrate by application such as dip coating, the solvent is dried by heating at 50 to 120 ° C. for 5 to 30 minutes. Is volatilized to form a positive-type photosensitive coating layer having no tack that enables contact exposure. Next, a mask having a predetermined pattern is brought into intimate contact with the coating, and exposed to near ultraviolet light (300-450 nm) through the mask, and then developed with an alkaline developer such as a 1% sodium carbonate aqueous solution. A desired pattern can be formed on the printed circuit board. The copper-clad laminate with a predetermined resist pattern formed on the copper surface is then etched with an acidic etchant to remove unnecessary copper, resulting in a circuit with the desired conductor circuit surface coated with a resist film. It is done. Next, using the resist film left on the conductor circuit, again adhere a mask having a predetermined pattern on this film, through this mask again exposed to near ultraviolet light, then develop, Etch the exposed copper surface. In this case, if the etching is stopped halfway, a circuit pattern having a step is obtained. Or if it etches completely, a finer circuit pattern will be formed. Further, using the same resist, repeated exposure, development and etching can be performed three times and four times. As described above, when a positive photosensitive resist composition having high development resistance is used, the same resist can be used, and multiple exposures, developments, and etchings can be performed.

  Usually, after etching is completed, the resist film is removed with a strong alkaline aqueous solution such as sodium hydroxide or potassium hydroxide to form a predetermined conductor circuit pattern. Conventionally, methods such as exposure, development processing, and etching processing can be employed. Special equipment and processes are not required, and conventional processes can be used as they are. Even if a type photosensitive resist composition is used, the cost can be reduced.

  Printed wiring boards to which the manufacturing method of the present invention can be applied include single-sided wiring boards, double-sided wiring boards, multilayer core boards and multilayer wiring boards, build-up wiring boards, semiconductor package wiring boards, landless wiring boards, and flexible wiring boards. And a rigid flexible wiring board.

    EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not restrict | limited by these Examples.

(Resist Solution Preparation Example 1)
200 ml of tetrahydrofuran was charged into a 1,000-ml four-necked flask equipped with a stirrer, thermometer, condenser and dropping funnel with an inner volume of 500 ml, and the external temperature was adjusted to 80 with a water bath while stirring. The mixture was heated to reflux and refluxed. Separately, 100 g (0.75 mol) of 4- (1-methylethenyl) phenol (hereinafter abbreviated as PIPE) purified by crystallization from a 2-ethylhexanol solution was purified by distillation in a 1,000 ml Erlenmeyer flask. 129 grams (1.50 moles) of methyl acrylate and 216 grams (1.50 moles) of 1-ethoxyethyl acrylate, 16.4 grams (0.10 moles) of azobisisobutyronitrile as a radical polymerization initiator, and As a solvent, 200 ml of tetrahydrofuran was charged.

  After this solution was stirred and dissolved, the entire amount was divided into two portions and transferred to a dropping funnel, and dropped into the above four-necked flask at such a rate that the reflux state continued. Although the internal temperature at the initial stage of the reaction was 72 ° C., the internal temperature increased during the polymerization and was 80 ° C. after 8 hours. The water bath was removed while continuing stirring, and after cooling to room temperature (25 ° C.) over 2 hours, the polymerization reaction solution was charged into 2 liters of n-hexane in a 5 liter beaker to precipitate the produced polymer. . The precipitated polymer was filtered and separated, and then dissolved again in 400 ml of tetrahydrofuran and charged into 2 liters of n-hexane to precipitate a solid. This filtration / separation / precipitation operation was further repeated twice. After the last filtration / separation, it was dried under reduced pressure at 100 mmHg and 100 ° C. for 2 hours to obtain 356 grams of a white polymer.

The obtained white polymer was a target copolymer from the results of ¹ H-NMR analysis, ¹³ C-NMR analysis, and elemental analysis, and had a molar ratio almost the same as the raw material charge ratio. As a result of GPC analysis using polystyrene as a standard, the weight average molecular weight (Mw) was 15,000. The obtained copolymer was dissolved in methyl ethyl ketone so as to be 50% by weight to obtain an acid-sensitive copolymer solution.

  1 part by weight of 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine as a photoacid generator with respect to 100 parts by weight of the obtained acid-sensitive copolymer solution, 0.2 parts by weight of coloring dye UV-Blue236 (manufactured by Mitsui Chemicals) was added and dissolved to prepare a positive photosensitive resist composition (resist 1) which can be dip coated. The specific gravity of this positive photosensitive resist composition was 0.941.

(Example 1)
Copper foil thickness of 18 μm 0. 5mm thick FR-4 Double-sided copper-clad laminate using resist 1 and coated with a dip coater to a film thickness of 7μm after drying and dried for 10 minutes until tack free with an 80 ° C dryer did. Thereafter, a patterning film having a model pattern of line / space = 200/200 μm was brought into close contact with the coated surface, and irradiated with 100 mJ / cm ² with a 3 kw ultra-high pressure mercury lamp. A 0% by weight aqueous sodium carbonate solution was sprayed for 1 minute with a developer whose temperature was adjusted to 30 ° C. Further, this developing operation was repeated 5 times.
That is, the resist film remained on the substrate without any deterioration by development for a total of 5 minutes. On the other hand, the same coating is performed on the same substrate as described above, dried and a resist film is formed, and a patterning film having a model pattern of line / space = 200/200 μm is adhered to the coated surface in the same manner as described above. And immediately after irradiation with 100 mJ / cm 2 with a 3 kw ultra high pressure mercury lamp, 1. A 0% by weight aqueous sodium carbonate solution was sprayed for 1 minute with a developer whose temperature was adjusted to 30 ° C. After washing with water, an etching process was subsequently performed with a known cupric chloride-based copper etching line. Next, a patterning film having a model pattern of line / space = 40/40 μm was brought into intimate contact with the coated surface, and again irradiated with 100 mJ / cm ² with a 3 kw ultrahigh pressure mercury lamp in the same manner as described above. A 0 wt% aqueous sodium carbonate solution was sprayed for 1 minute with a developer adjusted to a temperature of 30 ° C., washed with water, and then etched using a known cupric chloride-based copper etching line. Then, 3. The resist material was peeled off with a 0% by weight aqueous caustic soda spray, washed with water and dried to observe the circuit formation state. Despite repeated exposure, development and etching twice using the same resist film, the resist film was not deteriorated and a desired fine circuit could be formed. Characteristic evaluation of the positive photosensitive resist film was performed by the following characteristic evaluation method. The results are shown in Table 1.

(Resist Solution Preparation Examples 2 to 10)
The methyl acrylate used in Preparation Example 1 was changed as shown in Table 1, or 1-ethoxyethyl acrylate was changed as shown in Table 1, and all other conditions were the same as in Preparation Example 1. Processed. In the same manner as in Preparation Example 1, the weight average molecular weight (Mw) of the obtained copolymer was measured. Further, in the same manner as in Preparation Example 1, the obtained copolymer was dissolved in methyl ethyl ketone so as to be 50% by weight to obtain an acid-sensitive copolymer solution. 1 part by weight of 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine as a photoacid generator with respect to 100 parts by weight of the obtained acid-sensitive copolymer solution, 0.2 parts by weight of a coloring dye UV-Blue 236 (Mitsui Chemicals) was added and dissolved to prepare a positive photosensitive resist composition (resist 2 to 10) capable of dip coating, and the specific gravity was measured.

(Examples 2 to 10)
In the same manner as in Example 1, the resists 2 to 10 were subjected to repeated exposure, development and etching twice to evaluate the characteristics of the film of the positive photosensitive resist composition. The results are shown in Table 1.

(Comparative preparation example 1 of resist solution)
The amount of PIPE used in Preparation Example 1 was changed to 251.9 g (1.88 mol), the amount of 1-ethoxyethyl acrylate was changed to 270.7 g (1.88 mol), and methyl acrylate was changed. A reaction and a positive photosensitive resist composition (resist 11) were prepared in the same manner as in Preparation Example 1 except that they were not used.

(Comparative Example 1)
In the same manner as in Example 1, the characteristics were evaluated using the resist 11. The resistance of the developer is low, and after 1 minute, the resist film is deteriorated and cannot withstand a plurality of developments. The characteristic evaluation results are shown in Table 1 together with the results of Examples 1-10.

(Comparative preparation example 2 of resist solution)
The amount of methyl acrylate used in Preparation Example 1 was changed to 77.4 g (0.90 mol), the amount of 1-ethoxyethyl acrylate was changed to 302.4 g (2.10 mol), and PIPE was changed. A reaction and a positive photosensitive resist composition (resist 12) were prepared in the same manner as in Preparation Example 1 except that they were not used.

(Comparative Example 2)
The characteristics were evaluated using the resist 12 in the same manner as in Example 1. The resistance of the developer is low, and after 2 minutes, the resist film is deteriorated and cannot withstand a plurality of developments. The characteristic evaluation results are shown in Table 1 together with the results of Examples 1-10.
(Characteristic evaluation method)
1) Specific gravity: measured by the buoy method 2) Development resistance: exposure was performed using a pattern of line / space = 200/200 μm, and development was performed several times under the following conditions. Observe the condition and measure the time in minutes when degradation was observed.
3) Etching resistance: After the first exposure, development and etching, the substrate after the second exposure, development and etching is completed. The resist material was peeled off with an aqueous solution of 0% by weight caustic soda, washed with water and dried, then the circuit formation state was confirmed, and the following judgment was made.
○ When the copper surface of the pattern is not attacked at all
× When the copper surface of the pattern is affected and there is a lack of copper
i) Exposure condition: 100 mJ / cm 2 irradiation with 3 kw ultra high pressure mercury lamp
ii) Development conditions: Spray development is performed for 60 seconds using a 1.0% by weight sodium carbonate aqueous solution at 30 ° C. and a pressure of 0.18 Pa.
iii) Etching conditions: Spray etching is performed at a temperature of 0.20 Pa at a known cupric chloride etchant at 45 ° C. until copper having a thickness of 18 μm can be removed.

  In the manufacturing method of the present invention, the same resist is used without peeling the resist, and a plurality of exposure, development, and etching processes are performed. Therefore, a fine pattern is formed or a step is provided in the conductor circuit. Thus, it becomes possible to form a circuit board that requires fine processing.

Claims (5)

After applying a positive photosensitive resist solution to a laminate having at least one surface of a metal layer and drying the resist solution, the photosensitive resist film is uniformly formed on the surface of the laminate, and then the next step (1)-The process (3) is made into 1 cycle, and it repeats 2 cycles or more, The manufacturing method of the printed wiring board characterized by the above-mentioned.
Step (1) Exposure of the photosensitive resist film through a photomask Step (2) Development step (3) Etching the metal layer The photosensitive resist solution contains (A) an acid functional copolymer, (B) a compound that generates an acid upon irradiation with active energy rays, and (C) an organic solvent,
(A) an acid functional copolymer, the first structural unit represented by the following general formula (1),


(In formula (1), X represents a hydrogen atom or a methyl group)
A second structural unit represented by the following general formula (2);



(In Formula (2), R ¹ represents a hydrogen atom or a methyl group, R ² represents a straight chain or branched unsubstituted alkyl group having 1 to 6 carbon atoms, or a straight chain having 1 to 6 carbon atoms substituted with a hydroxy group. A linear or branched alkyl group having 1 to 6 carbon atoms substituted with a halogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms substituted with a cyano group, or a dialkylamino group Represents a linear or branched alkyl group having 1 to 6 carbon atoms and substituted with
A third structural unit represented by the following general formula (3);


(In Formula (3), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a hydrogen atom, a halogen atom, or a linear or branched unsubstituted alkyl group having 1 to 6 carbon atoms, Y represents a hydrogen atom, Represents a linear or branched unsubstituted alkyl group having 1 to 6 carbon atoms or a linear or branched substituted alkyl group having 1 to 6 carbon atoms; Z represents a linear or branched unsubstituted alkyl group having 1 to 6 carbon atoms; Or an acid-sensitive copolymer comprising a linear or branched substituted alkyl group having 1 to 6 carbon atoms; Y and Z may be bonded to form a ring structure, provided that a, b and c represent composition ratios, a represents 0.05 to 0.3, b represents a rational number of 0.1 to 0.7, c represents a rational number of 0.2 to 0.8, and the sum of a, b, and c is 1)
The method for producing a printed wiring board according to claim 1, wherein: 3. (A) 0.05 to 20 parts by weight of (B) a compound capable of generating an acid upon irradiation with an active energy ray with respect to 100 parts by weight of the acid-sensitive copolymer. The manufacturing method of the printed wiring board of description. 4. The method for producing a printed wiring board according to claim 2, wherein the positive specific gravity of the photosensitive resist composition is 0.800 to 0.990. The printed wiring board manufactured by the manufacturing method in any one of Claims 1-4.