TWI425313B - A photosensitive resin composition, a photosensitive member, a method for forming a resist pattern, and a method for manufacturing a printed wiring board - Google Patents

Description

Photosensitive resin composition, photosensitive element, method for forming photoresist pattern, and method for producing printed wiring board

The present invention relates to a photosensitive resin composition, a photosensitive element, a method of forming a photoresist pattern, and a method of producing a printed wiring board.

In the field of the manufacture of printed wiring boards, a photosensitive element (laminate) having a photosensitive resin composition as a photoresist material for etching or plating or the like, or containing the photosensitive resin is widely used. The layer of the composition (hereinafter referred to as "photosensitive resin composition layer") is formed on the support film and has a structure in which the protective film is disposed on the photosensitive resin composition layer.

Conventionally, a printed wiring board is manufactured using the aforementioned photosensitive element, for example, in the following procedure. In other words, first, the photosensitive resin composition layer of the photosensitive element is laminated on a circuit formation substrate such as a copper clad laminate. In this case, the surface of the photosensitive resin composition layer opposite to the surface in contact with the supporting film (hereinafter referred to as "underside" of the photosensitive resin composition layer) (hereinafter referred to as "upper surface of photosensitive resin composition layer") A surface that is in close contact with a circuit that forms a substrate for circuit formation. Therefore, when the protective film is placed on the upper surface of the photosensitive resin composition layer, the layer is bonded under the peeling of the protective film. In addition, the lamination is performed by heating and pressing the photosensitive resin composition layer on the substrate for circuit formation of the underlayer (normal pressure layering).

Next, the photosensitive resin composition layer is subjected to pattern exposure by a photomask film or the like. At this time, support thinner before or after exposure The film is peeled off. Thereafter, the unexposed portion of the photosensitive resin composition layer is dissolved or dispersed in a developing solution. Next, an etching treatment or a plating treatment is applied to form a pattern, and finally, the hardened portion is removed by peeling off.

Here, the etching treatment refers to a method of etching away the metal surface of the circuit-forming substrate covered by the cured photoresist formed after development, and then peeling off the cured photoresist. On the other hand, the plating treatment refers to a metal surface of a circuit-forming substrate that is not covered by a cured photoresist formed after development, and after plating treatment such as copper or solder, the hardened photoresist is removed and the etching is performed. A method of covering a metal surface by the photoresist.

However, as a method of exposure of the aforementioned pattern, a mercury lamp is conventionally used as a light source and exposed by a photomask. In addition, in recent years, there has been proposed a direct drawing exposure method called DLP (Digital Light Processing) which is a new exposure technique, and directly draws digital data of a pattern on a photosensitive resin composition layer. This direct drawing exposure method is better in alignment accuracy than the exposure method through the photomask, and since a fine pattern can be obtained, it is gradually introduced for producing a high-density package substrate.

Pattern exposure is to shorten the exposure time as much as possible in order to increase the production throughput (Throughput). In the above-described direct drawing exposure method, when a composition having the same degree of sensitivity as that of the conventional photosensitive resin composition for the exposure method through the photomask is used, the exposure time required generally is large. Therefore, it is necessary to increase the illuminance on the side of the exposure device or to increase the sensitivity of the photosensitive resin composition.

Further, in addition to the above-described sensitivity, the photosensitive resin composition is excellent in resolution, peeling characteristics of light resistance, and adhesion. Photosensitive tree If the grease composition provides a photoresist pattern excellent in resolution and adhesion, the short circuit or disconnection between circuits can be sufficiently reduced. Further, when the photosensitive resin composition can form a photoresist having excellent peeling properties, the peeling time of the photoresist can be shortened, the formation efficiency of the resist pattern can be improved, and the size of the peeling sheet of the photoresist can be reduced. The peeling residue is reduced, and the yield of the circuit is improved.

In response to such a request, there is proposed a photosensitive resin composition which is excellent in sensitivity, resolution, and photoresist peeling properties by using a specific adhesive polymer, a photopolymerization initiator, and the like (for example, refer to Patent Documents 1 and 2).

Patent Document 1: Japanese Laid-Open Patent Publication No. 2006-234995

Patent Document 2: Japanese Laid-Open Patent Publication No. 2005-122123

Invention disclosure

However, the photosensitive resin compositions described in the above Patent Documents 1 and 2 are not capable of forming a photoresist pattern which satisfies all of the sensitivity, the resolution, and the adhesion.

Accordingly, the present invention has been made in view of the above circumstances, and an object thereof is to provide a photosensitive resin composition and a photosensitive element, a method of forming a photoresist pattern using the same, and a method of manufacturing a printed wiring board, which are formed in a conventional manner The photoresist pattern satisfies all the sensitivity, resolution and adhesion.

In order to achieve the aforementioned object, the present invention provides a photosensitive resin group A product comprising: (A) 100 parts by mass of an adhesive polymer having 10 to 65 parts by mass of a divalent group represented by the following general formula (I), represented by the following general formula (II) 5 to 55 parts by mass of the divalent group, and 15 to 50 parts by mass of the divalent group represented by the following general formula (III); (B) a photopolymerizable compound; and (C) a photopolymerization initiator.

Here, in the formulae (I), (II) and (III), R ¹ , R ³ and R ⁵ each independently represent a hydrogen atom or a methyl group, and R ² is an alkyl group having 1 to 3 carbon atoms and a carbon number of 1 to 3 alkoxy, hydroxy, amine or halogen atom. R ⁴ is an alicyclic hydrocarbon group which may have a substituent, an aromatic hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent. m is an integer from 0 to 5, and when m is from 2 to 5, a plurality of R ^{2 's} may be the same or different from each other.

The photosensitive resin composition of the present invention is constituted by combining the specific components as described above, and even if the photoresist pattern is formed by direct drawing exposure, it has sufficient sensitivity compared with the conventional one, and can have sufficient resolution and adhesion. Sex A photoresist pattern is formed. By using the adhesive polymer of the specific group of the component (A) as described above, the inventors of the present invention thought that a more sufficient effect than the conventional one can be obtained with respect to all of the sensitivity, the resolution and the adhesion as described above.

The photosensitive resin composition of the present invention has a sufficient peeling property from the photoresist pattern formed therefrom. Therefore, when the resist pattern or the printed wiring board is formed, if the photosensitive resin composition of the present invention is used, the step of the joining step is shortened, and the yield of the product can be improved.

In the photosensitive resin composition, R ⁴ is preferably a monovalent group represented by the following general formula (IV), and the sensitivity, resolution, and adhesion of the photosensitive resin composition can be further improved.

Here, in the formula (IV), R ⁶ is a hydroxyl group, an alkyl group having 1 to 12 carbon atoms or a hydroxyalkyl group having 1 to 12 carbon atoms. n is an integer from 0 to 5, and when n is from 2 to 5, a plurality of R ⁶ may be the same or different from each other.

Further, R ^{4 is} a monovalent group represented by each of the following general formulas (V), (VI), (VII), and (VIII) (hereinafter referred to as "(V) to (VIII)"). Preferably, at least one of the selected groups is suitable. Thereby, the sensitivity, resolution, and adhesion of the photosensitive resin composition can be further improved.

Here, in the formulae (V) to (VIII), R ⁷ , R ⁸ and R ⁹ each independently represent a hydroxyl group, an alkyl group having 1 to 12 carbon atoms or a hydroxyalkyl group having 1 to 12 carbon atoms. j is an integer of 0 to 4, k and p are integers of 0 to 9, and when j, k or p is 2 or more, plural R ⁷ , R ⁸ or R ⁹ may be the same or different from each other.

Further, the photosensitive resin composition of the present invention preferably contains a hexaarylbiimidazole derivative as a photopolymerization initiator. Thereby, the resolution and adhesion of the photoresist pattern can be further improved, and the sludge removal property can be further improved.

The photosensitive resin composition of the present invention preferably contains (D) a sensitizing dye. Thereby, when exposure is performed with light having a peak in a specific wavelength range, the absorption in the vicinity of the specific wavelength range can be greatly increased, and the sensitivity of the photosensitive resin composition can be further improved.

Further, the photosensitive resin composition of the present invention preferably contains an (E) amine compound. Thereby, the sensitivity of the photosensitive resin composition can be further improved.

The present invention provides a photosensitive element comprising: a support film; and a photosensitive resin composition layer formed on the support film, wherein the photosensitive resin composition layer contains the photosensitive resin composition. According to the photosensitive element, since the photosensitive resin composition layer containing the photosensitive resin composition is provided, even when the photoresist pattern is formed by direct drawing exposure, sufficient sensitivity, resolution, and adhesion can be performed. .

The present invention provides a method for forming a photoresist pattern, comprising: a lamination step of laminating a photosensitive resin composition layer containing the photosensitive resin composition on a circuit formation substrate; and irradiating active light to photosensitivity a specific portion of the resin composition layer, an exposure step of photocuring the exposed portion; and a portion other than the exposed portion of the substrate for forming a circuit on which the photosensitive resin composition layer is laminated Development step. According to the method for forming the photoresist pattern, since the photoresist pattern is formed using the photosensitive resin composition layer containing the photosensitive resin composition, even by direct drawing exposure method with a short exposure time, sufficient resolution and adhesion can be obtained. The photoresist pattern is formed.

The present invention provides a method of manufacturing a printed wiring board, comprising: a step of forming a conductor pattern by etching or plating a circuit-forming substrate on which a photoresist pattern is formed in accordance with the method for forming a photoresist pattern. According to the method of manufacturing a printed wiring board, since the circuit-forming substrate in which the photoresist pattern is formed by the above-described method of forming the photoresist pattern is used, a high-density line can be formed, and the disconnection and short-circuit can be sufficiently suppressed. Printed circuit board.

According to the present invention, it is possible to provide a photosensitive resin composition which forms a photoresist pattern which satisfies all of the sensitivity, the resolution and the adhesion more than the conventional one.

The best form for implementing the invention

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as needed. In the drawings, the same components are denoted by the same reference numerals, and the description thereof will not be repeated. In addition, the positional relationship of the up, down, left, and the like is based on the positional relationship shown in the drawing unless otherwise specified. In addition, the dimensional ratio of the drawings is not limited to the ratios shown. In the present specification, "(meth)acrylic acid" means "acrylic acid" and "methacrylic acid" corresponding thereto, and "(meth)acrylate" means "acrylic acid ester" and "methyl group" corresponding thereto. Acrylate".

The photosensitive resin composition of the present invention contains: (A) an adhesive polymer having a divalent group (hereinafter also referred to as "structural unit") represented by the above general formula (I), and the above general formula ( II) a structural unit represented by the above, and a structural unit represented by the above general formula (III); (B) a photopolymerizable compound; and (C) a photopolymerization initiator.

First, the adhesive polymer for the component (A) will be explained.

(A) The adhesive polymer of the component contains: the structural unit based on styrene or its derivative represented by the above general formula (I), and the (meth) acrylate based on the above general formula (II) The structural unit and the structural unit based on (meth)acrylic acid represented by the above general formula (III). In this way, the sensitivity of the photosensitive resin composition is excellent, and the resolution of the photosensitive resin composition layer as the structural material and the adhesion and peeling properties to the substrate for circuit formation are good.

Here, in the above formula (I), R ¹ is a hydrogen atom or a methyl group. R ² is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a hydroxyl group, an amine group or a halogen atom. m is an integer from 0 to 5.

The structural unit represented by the above general formula (I) is obtained from styrene or a derivative thereof of a polymer monomer. Specific examples of the styrene derivative include methyl styrene, ethyl styrene, hydroxystyrene, butoxy styrene, chlorostyrene, bromostyrene, and aminostyrene.

Further, in the above formula (II), R ³ is a hydrogen atom or a methyl group. R ⁴ is an alicyclic hydrocarbon group which may have a substituent, an aromatic hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent.

Examples of the alicyclic hydrocarbon group include a cyclic hydrocarbon group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group, or a derivative thereof; a dicyclopentyl group, a dicyclopentenyl group, and a diamond A group having two or more cyclic hydrocarbons such as an alkyl group or an isobornyl group or a derivative thereof.

Examples of the aromatic hydrocarbon group include a group having an aromatic ring such as a phenyl group, a biphenyl group, a triphenylmethyl group, a naphthyl group, an anthracenyl group, a condensed tetraphenyl group, a phenanthryl group, or a pyrenyl group. And other derivatives.

Examples of the heterocyclic group include an aliphatic heterocyclic group such as a tetrahydropyranyl group, a piperidinyl group, a piperazinyl group or a morpholinyl group; or a derivative thereof; a pyranyl group, a pyridyl group or a pyrimidine group; A group having an aromatic heterocyclic ring such as a thiol group, a furyl group, a thienyl group, a pyrazolyl group, a pyrrolyl group, an imidazolyl group, an oxazolyl group, or a thiazolyl group, or a derivative thereof.

From the viewpoint of further improving the sensitivity, resolution, and adhesion of the photosensitive resin composition, R ^{4 is} preferably an alicyclic hydrocarbon group which may have a substituent or an aliphatic heterocyclic group which may have a substituent.

Further, from the viewpoint of further improving the sensitivity, resolution, and adhesion of the photosensitive resin composition, R ⁴ is preferably a group represented by the above general formula (IV).

Here, in the formula (IV), R ⁶ is a hydroxyl group, an alkyl group having 1 to 12 carbon atoms or a hydroxyalkyl group having 1 to 12 carbon atoms. n is an integer from 0 to 5, and when n is from 2 to 5, a plurality of R ⁶ may be the same or different from each other.

From the standpoint of obtaining a more reliable and effective effect of the present invention, R ^{6 is} preferably a hydroxyl group, an alkyl group having 1 to 5 carbon atoms or a hydroxyalkyl group having 1 to 5 carbon atoms, and an alkyl group having 1 to 3 carbon atoms or carbon. The hydroxyalkyl group having 1 to 3 is particularly preferred, and more preferably a hydroxyl group, a methyl group or a hydroxymethyl group. Further, n is preferably 0 to 3, and particularly preferably 0 to 2.

In the general formula (II), when R ⁴ is a group represented by the above general formula (IV), the structural unit is obtained from a cyclohexyl (meth)acrylate or a derivative thereof of a polymerizable monomer. Specific examples of the cyclohexyl (meth)acrylate derivative include methylcyclohexyl (meth)acrylate, dimethylcyclohexyl (meth)acrylate, and trimethyl (meth)acrylate. Hexyl ester, hydroxycyclohexyl (meth) acrylate, methyl hydroxycyclohexyl (meth) acrylate.

Further, from the viewpoint of further improving the sensitivity, resolution, and adhesion of the photosensitive resin composition, R ^{4 is} a group consisting of a monovalent group represented by each of the above general formulas (V) to (VIII). It is preferred to use at least one of the selected ones.

Here, in the above formulae (V) to (VIII), R ⁷ , R ⁸ and R ⁹ each independently represent a hydroxyl group, an alkyl group having 1 to 12 carbon atoms or a hydroxyalkyl group having 1 to 12 carbon atoms. j is an integer from 0 to 4, and k and p are integers from 0 to 9. When j, k or p is 2 or more, a plurality of R ⁷ , R ⁸ or R ⁹ may be the same or different from each other.

From the viewpoint of obtaining more effective and effective effects of the present invention, R ⁷ , R ⁸ and R ^{9 are} preferably a hydroxyl group, an alkyl group having 1 to 5 carbon atoms or a hydroxyalkyl group having 1 to 5 carbon atoms, and having a carbon number of 1 to The alkyl group of 3 or the hydroxyalkyl group having 1 to 3 carbon atoms is particularly preferred, and more preferably a hydroxyl group, a methyl group or a hydroxymethyl group. In addition, j is preferably 0 to 2. k and p are preferably from 0 to 5, particularly preferably from 0 to 2.

In the general formula (II), when R ⁴ is a group represented by the above general formula (V), the structural unit is obtained from a tetrahydropyran (meth)acrylate or a derivative thereof of a polymerizable monomer. Further, when R ⁴ is a group represented by the above general formula (VI), the structural unit is obtained from adamantyl (meth)acrylate or a derivative thereof of a polymerizable monomer. Further, when R ⁴ is a group represented by the above general formula (VII), the structural unit is obtained from dicyclopentyl (meth)acrylate or a derivative thereof of a polymerizable monomer. Further, when R ⁴ is a group represented by the above general formula (VIII), the structural unit is obtained from an isobornyl (meth)acrylate of a polymerizable monomer.

From the viewpoint of further improving the sensitivity, resolution, and adhesion of the photosensitive resin composition, R ^{4 is particularly} preferably a monovalent group represented by the above general formula (IV).

Further, in the above formula (III), R ⁵ is a hydrogen atom or a methyl group, specifically, a structural unit based on acrylic acid or methacrylic acid.

The content ratio of the structural unit represented by the above general formula (I) in the component (A) is from 10 to 65 parts by mass, preferably from 15 to 55 parts by mass, based on 100 parts by mass of the total of the component (A). It is particularly preferably 50 parts by mass, more preferably 25 to 45 parts by mass. Thereby, the adhesion of the photoresist pattern and the peeling property are excellent. When the content ratio is less than 10 parts by mass, the adhesion tends to be insufficient, and if it exceeds 65 parts by mass, the peeling property is Reduce the trend.

The content ratio of the structural unit represented by the above general formula (II) in the component (A) is 5 to 55 parts by mass, preferably 10 to 50 parts by mass, based on 100 parts by mass of the total of the component (A). It is particularly preferably 45 parts by mass, more preferably 20 to 40 parts by mass. Thereby, the adhesion of the photoresist pattern and the peeling property are excellent. When the content ratio is less than 5 parts by mass, the adhesion tends to be insufficient, and when it exceeds 55 parts by mass, the peeling property tends to be lowered.

The content ratio of the structural unit represented by the above general formula (III) in the component (A) is 15 to 50 parts by mass, preferably 20 to 45 parts by mass, based on 100 parts by mass of the total amount of the component (A). It is particularly preferably 40 parts by mass, more preferably 27 to 35 parts by mass. Thereby, the peeling property and the developability of the photoresist pattern are more excellent. When the content ratio is less than 15 parts by mass, the peeling sheet becomes large as the alkali solubility of the resist pattern decreases, and the peeling time tends to become long. Further, when the content ratio exceeds 50 parts by mass, the resolution tends to be insufficient. The structural unit represented by the above general formula (III) is obtained from a (meth)acrylic acid of a polymerizable monomer.

In the present invention, the term "styrene derivative" means that a hydrogen atom in a phenyl group of styrene is substituted with a substituent (organic group such as an alkyl group, a hydroxyl group or a halogen atom). In addition, the "cyclohexyl (meth) acrylate derivative" means a substituent of a hydrogen atom in a cyclohexyl group of cyclohexyl (meth) acrylate (alkyl group having 1 to 12 carbon atoms and carbon number 1 to 12) Substituted by hydroxyalkyl).

When the adhesive polymer is used to form a photosensitive resin composition layer, A single adhesive polymer may be used, and any combination of two or more adhesive polymers may be used. The adhesive polymer used in combination of two or more types may be, for example, two or more kinds of different copolymerized components (containing different repeating units as constituent components), an adhesive polymer, and different weight average molecular weights. Two or more kinds of adhesive polymers, two or more kinds of adhesive polymers having different degrees of dispersion, and the like. Further, a polymer having a multimode molecular weight distribution described in JP-A-H11-327137 can also be used.

(A) The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the adhesive polymer can be determined by gel permeation chromatography (GPC) (converted from a calibration curve using standard polystyrene). According to this measurement, the Mw of the adhesive polymer is preferably from 5,000 to 300,000, more preferably from 10,000 to 150,000, even more preferably from 20,000 to 80,000. When the Mw is at 5,000, the development liquid resistance tends to decrease. If it exceeds 300,000, the development time tends to be prolonged.

Further, the dispersion (Mw/Mn) of the (A) adhesive polymer is preferably from 1.0 to 3.0, more preferably from 1.0 to 2.0. When the degree of dispersion exceeds 3.0, the adhesion and resolution tend to decrease.

The adhesive polymer of the present invention can be produced, for example, by subjecting the above polymerizable monomer to radical polymerization.

The above (A) adhesive polymer may contain structural units other than the structural unit represented by the above general formulas (I) to (III). In this case, the polymerizable monomer which is a structural unit other than the structural unit represented by the above general formulas (I) to (III) may, for example, be an acrylonitrile such as diacetone acrylamide. Ethyl alcohol esters such as amines, acrylonitrile, vinyl n-butyl ether, alkyl (meth)acrylates, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, Diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3 (meth)acrylic acid -tetrafluoropropyl ester, α-bromo (meth)acrylic acid, α-chloro(meth)acrylic acid, β-furyl (meth)acrylic acid, β-styryl (meth)acrylic acid, maleic acid, horse Maleic acid monoesters such as phthalic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, croton Acid, propionic acid. These may be used alone or in combination of two or more.

In addition, the (meth)acrylic acid alkyl ester may, for example, be a compound represented by the following general formula (IX); and a compound obtained by substituting an alkyl group of these compounds with a hydroxyl group, an epoxy group, a halogen atom or the like.

CH ₂ =C(R ¹⁰ )-COOR ¹¹ (IX)

Here, in the above general formula (IX), R ¹⁰ is a hydrogen atom or a methyl group, and R ¹¹ is an alkyl group having 1 to 12 carbon atoms. The alkyl group having 1 to 12 carbon atoms represented by R ¹¹ may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group or an eleven group. Alkyl, dodecyl and such structural isomers. Examples of the polymerizable monomer represented by the above general formula (IX) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. Amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, bismuth (meth)acrylate Ester, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate. These polymerizable single systems may be used alone or in combination of two or more.

The content ratio of the component (A) in the structural unit other than the structural unit represented by the above general formulas (I) to (III) is within the range of the purpose of the invention, and is not particularly limited. However, the content ratio is preferably from 0 to 40 parts by mass, more preferably from 0 to 20 parts by mass, even more preferably from 0 to 10 parts by mass, per 100 parts by mass of the total of the component (A).

In the present invention, (A) the adhesive polymer is preferably one or two or more kinds of polymers having a carboxyl group, from the viewpoint of developability in alkali development using an alkali solution. The (A) adhesive polymer can be produced, for example, by radical polymerization of a polymerizable monomer having a carboxyl group and another polymerizable monomer.

The acid value of the (A) adhesive polymer is preferably from 30 to 220 mgKOH/g, more preferably from 50 to 200 mgKOH/g, still more preferably from 80 to 180 mgKOH/g. If the acid value is less than 30 mgKOH/g, the development time tends to be long. When it exceeds 220 mgKOH/g, the development resistance of the photocured photoresist is lowered. Further, when solvent development is carried out as a developing step, it is preferred to prepare a small amount of a polymerizable monomer having a carboxyl group.

Further, the (A) adhesive polymer may have a photosensitive property group in the molecule as needed.

The amount of the component (A) in the photosensitive resin composition of the present invention is preferably 30 to 70 parts by mass, and preferably 35 to 65 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). More preferably, it is preferably 40 to 60 parts by mass. If the amount is less than 30 parts by mass, it is difficult to obtain light. When the tendency of the good shape of the resist pattern is more than 70 parts by mass, there is a tendency that it is difficult to obtain good sensitivity or resolution. (A) The components may be used alone or in combination of two or more.

Further, the photosensitive resin composition of the present invention may be used in combination with the resin other than the above component (A) in order to achieve the object of the invention. Examples of such a resin include an acrylic resin, a styrene resin, an epoxy resin, a guanamine resin, a guanamine epoxy resin, an alkyd resin, and a phenol resin. Among them, an acrylic resin is preferred from the viewpoint of alkali developability. In addition, these resins may be used alone or in combination of two or more.

Next, the photopolymerizable compound of the component (B) will be described.

The photopolymerizable compound of the component (B) may, for example, be a compound obtained by reacting a polyhydric alcohol with an α,β-unsaturated carboxylic acid, a bisphenol A-based (meth) acrylate compound, or a glycidyl group-containing compound. a compound obtained by reacting an α,β-unsaturated carboxylic acid, an amine ester monomer such as a (meth) acrylate compound having an urethane bond in the molecule, a nonyl phenoxy poly ethoxy acrylate, or a neighbor A phthalic acid compound or an alkyl (meth)acrylate. These compounds may be used alone or in combination of two or more.

The compound obtained by reacting a polyol with an α,β-unsaturated carboxylic acid as described above may, for example, be a polyethylene glycol di(meth)acrylate having an ethyl group number of 2 to 14, and a propyl group of 2 to 14 Polypropylene glycol di(meth) acrylate, polyethylene glycol-polypropylene glycol di(meth) acrylate, trimethylolpropane di(a) having an ethyl group number of 2 to 14 and a propyl group number of 2 to 14. Acrylate, trimethylolpropane tri(meth)acrylate , EO modified trimethylolpropane tri(meth)acrylate, PO modified trimethylolpropane tri(meth)acrylate, EO and PO modified trimethylolpropane tri(meth)acrylate , tetramethylol methane tri (meth) acrylate, tetramethylol methane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate. These compounds may be used alone or in combination of two or more. Here, the term "EO" means ethylene oxide, and the EO-modified compound means a block structure having an oxirane group. In addition, the "PO" means propylene oxide, and the PO modified compound means a block structure having an oxypropylene group.

The bisphenol A-based (meth) acrylate compound may, for example, be 2,2-bis(4-((meth)propenyloxypolyethoxy)phenyl)propane, 2,2-double (4-((meth)propenyloxypolypropoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxy)oxy)phenyl)propane, 2, 2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane or the like. As the above 2,2-bis(4-((meth)propenyloxypolyethoxy)phenyl)propane, for example, 2,2-bis(4-((meth)propenyloxy) Diethoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxy)triethoxy)phenyl)propane, 2,2-bis(4-((methyl)) Propylene decyloxytetraethoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxypentaethoxy)phenyl)propane, 2,2-bis(4-( (methyl)propenyloxyhexaethoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxyheptaethoxy)phenyl)propane, 2,2-double (4-((Methyl) propylene methoxy octaethoxy) phenyl) propane, 2,2-bis(4-((methyl) propylene oxy) pentoxide) Propane, 2,2-bis(4-((meth)propenyloxylethoxy)phenyl)propane, 2,2-bis(4-((methyl)propenyloxy) Ethoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxydodecyloxy)phenyl)propane, 2,2-bis(4-((methyl)) Propylene decyloxytritethoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxytetradecyloxy)phenyl)propane, 2,2-bis(4) -((Meth)propenyloxypentadecylethoxy)phenyl)propane, 2,2-bis(4-((meth)propenyloxyhexadecyloxy)phenyl)propane.

The above 2,2-bis(4-(methacryloxypentapentaethoxy)phenyl)propane is commercially available as BPE-500 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name) or FA-321M ( Hitachi Chemical Co., Ltd., trade name), the aforementioned 2,2-bis(4-(methacryloxypentadecane)-p-ethoxy)phenyl)propane can be commercially obtained as BPE-1300 (Xinzhongcun Chemical Industry) Social system, trade name). The above 2,2-bis(4-((meth)propenyloxypolyethoxy)phenyl)propane has an ethylene oxide group number of 1 to 20, preferably 8 to 15 Especially good. These compounds may be used alone or in combination of two or more.

The (meth) acrylate compound having an amine ester bond in the above-mentioned molecule may, for example, be a (meth)acrylic monomer having a hydroxyl group at the β-position and a diisocyanate compound (isophorone diisocyanate, 2, 6 Addition reactant of -toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexamethylene diisocyanate, etc., tris((meth)acryloxytetramethylene isocyanate) hexamethylene Isoisocyanurate, EO modified amine ester di(meth)acrylate, EO and PO modified amine ester di(meth)acrylate. Make In the above-mentioned EO-modified amine ester di(meth)acrylate, for example, UA-11 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name) can be mentioned. In addition, as the above-mentioned EO and PO-modified amine ester di(meth)acrylate, for example, UA-13 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name) can be mentioned. These compounds may be used alone or in combination of two or more.

Examples of the above mercaptophenoxy poly(ethoxy acrylate) include mercaptophenoxytetraethylene ethoxyacrylate, nonylphenoxy pentaethoxy acrylate, and mercaptophenoxy group. Hexagonal ethoxy acrylate, nonylphenoxy heptaethylene ethoxy acrylate, nonylphenoxy octaethoxy ethoxylate, nonylphenoxy hexaethoxy acrylate, mercapto benzene Oxetyl ethoxy acrylate, nonyl phenoxy eleven ethoxy acrylate. These compounds may be used alone or in combination of two or more.

Examples of the phthalic acid-based compound include γ-chloro-β-hydroxypropyl phthalate β′-(meth) propylene methoxyethyl ester and β-hydroxyalkyl phthalate β. '-(Methyl) propylene decyloxyalkyl ester. For the related phthalic acid-based compound, for example, FA-MECH (trade name, manufactured by Hitachi Chemical Co., Ltd.) can be obtained. These compounds may be used alone or in combination of two or more.

Further, as the component (B) of the present invention, a (meth) acrylate containing a bisphenol A-based (meth) acrylate compound or an amine ester bond in the molecule is used from the viewpoint of plating resistance and adhesion. Compounds are preferred. Further, from the viewpoint of improving sensitivity and resolution, it is particularly preferable to contain a bisphenol A-based (meth) acrylate compound.

In addition, in the component (B) of the present invention, the cured film can be improved. From the viewpoint of flexibility, a polyalkylene glycol di(meth)acrylate having both an ethylene glycol chain and a propylene glycol chain in the molecule is preferred. The (meth) acrylate is not particularly limited as long as it has an ethylene glycol chain and a propylene glycol chain (n-propylene glycol chain or isopropyl diol chain) as the intramolecular alkanediol chain. Further, the (meth) acrylate may further have a n-butylene glycol chain, an isobutylene glycol chain, a n-pentanediol chain, a hexanediol chain, and the structural isomers thereof having a carbon number of 4 to 6 Approximately alkanediol chain.

When the number of the ethylene glycol chain and the propylene glycol chain is plural, the plurality of ethylene glycol chains and the propylene glycol chain are not necessarily continuous and block-formed, and may be randomly present. Further, in the isopropyl glycol chain, the propyl group-derived carbon may be bonded to the oxygen atom, or the first-order carbon may be bonded to the oxygen atom.

Examples of the polyalkylene glycol di(meth)acrylate having both an ethylene glycol chain and a propylene glycol chain in the component (B) include, for example, the following general formulas (X), (XI) and (XII). The compound represented.

Here, in the general formulae (X), (XI) and (XII), R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. EO represents an ethylene glycol chain and PO represents a propylene glycol chain. M1 to m4 and n1 to n4 are each independently an integer of 1 to 30. These compounds may be used alone or in combination of two or more.

Examples of the alkyl group having 1 to 3 carbon atoms in the above general formulas (X), (XI) and (XII) include a methyl group, an ethyl group, a n-propyl group and an isopropyl group.

Further, the total number of repeating amounts of the ethylene glycol chains (m1+m2, m3, and m4) in the above general formulas (X), (XI), and (XII) are each an integer of 1 to 30, and an integer of 1 to 10 is used. Preferably, it is preferably from 4 to 9 integers, more preferably from 5 to 8 integers. If the number of repetitions exceeds 30, the reliability of the cap hole and the shape of the photoresist tend to deteriorate.

Further, the total number of repeating amounts of the propylene glycol chains (n1, n2+n3, and n4) in the above general formulas (X), (XI), and (XII) are each an integer of from 1 to 30, preferably an integer of from 5 to 20. It is particularly preferably an integer of 8 to 16, and more preferably an integer of 10 to 14. If the number of repetitions exceeds 30, the resolution is deteriorated and the tendency of sludge generation occurs.

Specific examples of the compound represented by the above general formula (X) include a vinyl compound ( Hitachi, R ¹² = R ¹³ = methyl group, m1 + m2 = 4 (average value), and n1 = 12 (average value). Chemical Industrial Co., Ltd., trade name "FA-023M"). Further, specific examples of the compound represented by the above general formula (XI) include a vinyl compound having R ¹⁴ = R ¹⁵ = methyl group, m 3 = 6 (average value), and n 2 + n 3 = 12 (average value). (The product name "FA-024M", manufactured by Hitachi Chemical Co., Ltd.). Further, specific examples of the compound represented by the above general formula (XII) include a vinyl compound (R ¹⁶ = R ¹⁷ = hydrogen atom, m4 = 1 (average value), and n4 = 9 (average value) (new Nakamura Chemical Industry Co., Ltd., trade name "NK ester HEMA-9P"). These compounds may be used alone or in combination of two or more.

(B) In the above-mentioned photopolymerizable compound, it is preferable to use two kinds of compounds having two photopolymerizable bonds in one molecule and one compound having one photopolymerizable bond in one molecule. For example, when the component (B) is a (meth) acrylate, two (meth) acrylate compounds having two (meth)acrylic groups in one molecule are combined, and one (meth) is contained in one molecule. One type of (meth) acrylate compound based on acrylic acid is particularly preferably used.

Thereby, the light sensitivity, the adhesion, the resolution, and the peeling property can be balancedly improved.

The amount of the photopolymerizable compound as the component (B) is preferably 30 to 70 parts by mass, more preferably 35 to 65 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). 40 to 60 parts by mass is more preferable. If the amount is less than 30 parts by mass, there is a tendency that good sensitivity or resolution cannot be obtained, and if it exceeds 70 parts by mass, there is a tendency that a good shape cannot be obtained. (B) The components may be used alone or in combination of two or more.

Next, a photopolymerization initiator for the component (C) will be described.

The photopolymerization initiator of the component (C) may, for example, be 4,4'-bis(diethylamino)benzophenone, benzophenone or 2-benzyl-2-dimethylamino group. 1-(4-(N-morpholinyl)phenyl)-butanone-1,2-methyl-1-[4-(methylthio) An aromatic ketone such as phenyl]-2-(N-morpholinyl)-acetone-1; an anthracene such as an alkyl group; a benzoin ether compound such as a benzoin alkyl ether; a benzoin, an alkyl group; Benzoin compounds such as benzoin; benzyl derivatives such as benzyl dimethyl ketal; 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chloro Phenyl)-4,5-bis(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxybenzene) 2,4,5-triarylimidazole dimer such as 4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer An acridine derivative such as 9-phenyl acridine or 1,7-bis(9,9'-acridinyl)heptane.

Further, the substituent of the aryl group of the two 2,4,5-triarylimidazole dimers of the two 2,4,5-triarylimidazoles may be the same as the target compound, or may be formed into asymmetrical Compound. Further, from the viewpoint of adhesion and sensitivity, the photopolymerization initiator is preferably a derivative of a hexaarylbiimidazole using a 2,4,5-triarylimidazole dimer. These photopolymerization initiators may be used alone or in combination of two or more.

Further, the amount of the photopolymerization initiator of the component (C) is preferably 0.1 to 10 parts by mass, more preferably 2 to 6 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). It is more preferably 3.5 to 5 parts by mass. When the amount is less than 0.1 part by mass, it is difficult to obtain good sensitivity or resolution, and if it exceeds 10 parts by mass, there is a tendency that a desired good shape resist pattern cannot be obtained. The photopolymerization initiator of the component (C) may be used alone or in combination of two or more.

The photosensitive resin composition of the present invention preferably contains (D) a sensitizing dye and/or an (E) amine compound in addition to the above components (A) to (C). .

The component (D) sensitizing dye in the present invention can effectively utilize the absorption wavelength of the active light for exposure, and it is preferable to absorb a compound having a wavelength of 370 to 420 nm. The present invention utilizes such a sensitizing dye to have a sufficiently high sensitivity to light exposed by direct exposure exposure. When the maximum absorption wavelength of the sensitizing dye is less than 370 nm, the sensitivity to light directly exposed is lowered. When it exceeds 420 nm, the stability tends to decrease even in a yellow light environment.

Examples of the sensitizing dye include pyrroline, anthracene, coumarin, xanthone, oxazole, benzoxazole, thiazole, benzothiazole, and triazole. Styrenes, triazines, thiophenes, naphthoquinone imines. From the viewpoint of improving resolution, adhesion, and sensitivity, the sensitizing dye preferably contains hydrazine.

The amount of the sensitizing dye is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, even more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). . If the amount is less than 0.01 parts by mass, there is a tendency that good sensitivity or resolution cannot be obtained, and if it exceeds 10 parts by mass, there is a tendency that a desired good shape resist pattern cannot be obtained. The sensitizing dyes of the component (D) may be used alone or in combination of two or more.

The amine-based compound of the component (E) is not particularly limited as long as it has an amine group in the molecule which can improve the sensitivity of the photosensitive resin composition. As such a specific example, bis[4-(dimethylamino)phenyl]methane, bis[4-(diethylamino)phenyl]methane, and colorless crystal violet (leuco) may be mentioned. Crystal violet).

The amount of the amine compound is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, even more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the total of the components (A) and (B). . If the amount is less than 0.01 parts by mass, there is a tendency that good sensitivity is not obtained. When the amount is more than 10 parts by mass, the component (E) tends to precipitate as a foreign matter after the film is formed. The amine compound of the component (E) may be used alone or in combination of two or more.

The photosensitive resin composition of the present invention may contain, if necessary, a photopolymerizable compound (such as an oxetane compound) having at least one cyclic ether group capable of undergoing cationic polymerization, a cationic polymerization initiator, Malachite green and other dyes, tribromophenyl hydrazine, colorless crystal violet and other photochromic agents, thermal color development inhibitors, p-toluenesulfonamide and other plasticizers, pigments, fillers, defoamers, flame retardant Agent, stabilizer, adhesion imparting agent, leveling agent, peeling accelerator, antioxidant, fragrance, developer (Imaging Agent), thermal crosslinking agent. Each of the components may be contained in an amount of from 0.01 to 20 parts by mass per 100 parts by mass of the total of the components (A) and (B). These may be used alone or in combination of two or more.

Further, the photosensitive resin composition of the present invention may be dissolved in methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide A solvent such as propylene glycol monomethyl ether or a mixed solvent thereof is used to prepare a solution having a solid content of about 30 to 60% by mass. This solution can be applied as a layer of a photosensitive resin composition for forming a photosensitive member. Use cloth liquid.

Further, the coating liquid may be applied as a liquid photoresist coating on the surface of a metal plate in addition to the photosensitive resin composition layer for forming the photosensitive element, and after drying, the protective film may be coated. The material of the metal plate may, for example, be an iron-based alloy such as copper, a copper-based alloy, nickel, chromium, iron or stainless steel, and preferably copper, a copper-based alloy or an iron-based alloy.

Next, the photosensitive element of the present invention will be described. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a preferred embodiment of a photosensitive member of the present invention. The photosensitive element 1 shown in FIG. 1 is composed of a support film 2, a photosensitive resin composition layer 3 containing the photosensitive resin composition formed on the support film 2, and laminated to a photosensitive resin. The protective film 4 on the composition layer 3.

As the support film 2, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, or polyester can be used. As a commercially available product, for example, Alphan MA-410, E-200C (trade name) manufactured by Oji Paper Co., Ltd.; a polypropylene film manufactured by Shin-Etsu Film Co., Ltd.; and a PS series manufactured by Teijin Co., Ltd. (for example, trade name: PS-25) A polyethylene terephthalate film, etc., but is not limited thereto.

Further, the thickness of the support film 2 is preferably from 1 to 100 μm, particularly preferably from 5 to 25 μm. If the thickness is less than 1 μm, the support film tends to be broken when the support film is peeled off before development, and if it exceeds 100 μm, the resolution tends to decrease. Further, the support film 2 may be used as a support of the photosensitive resin composition layer, and the other protective film as a photosensitive resin composition may be laminated on both surfaces of the photosensitive resin composition layer.

The photosensitive resin composition layer 3 is preferably obtained by dissolving the photosensitive resin composition in a solution (coating liquid) having a solid content of about 30 to 60% by mass as described above, and applying the solution to the support film. 2, formed by drying. For the coating system, for example, a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, a bar coater, or the like can be used. The known method is carried out. The drying system can be carried out at 70 to 150 ° C for about 5 to 30 minutes. In addition, from the viewpoint of preventing the diffusion of the organic solvent in the subsequent step, the amount of the residual organic solvent in the photosensitive resin composition is preferably 2% by mass or less.

Further, the thickness of the photosensitive resin composition layer 3 varies depending on the use of the photosensitive element, but the thickness after drying is preferably from 1 to 100 μm, particularly preferably from 1 to 50 μm. When the thickness is less than 1 μm, there is a tendency that coating is difficult in the industry. If it exceeds 100 μm, the effect of the present invention becomes small, and the adhesion and resolution tend to decrease.

The transmittance of the photosensitive resin composition layer 3 to light having a wavelength of 365 nm or 405 nm is preferably from 5 to 75%, more preferably from 7 to 60%, still more preferably from 10 to 40%. If the penetration rate is less than 5%, the adhesion tends to be inferior, and if it exceeds 75%, the resolution tends to be inferior. The transmittance is measured by a UV spectrometer, and the UV spectrometer is, for example, a Hitachi 228A W beam spectrophotometer (trade name).

The protective film 4 is preferably one in which the adhesion between the photosensitive resin composition layer 3 and the protective film 4 is smaller than the adhesion between the photosensitive resin composition layer 3 and the support film 2, and the fish eye is low. ) The film is suitable . In addition, the term "fisheye" refers to a method in which a material is thermally melted and a film is produced by kneading, extrusion, two-axis stretching, casting, or the like, and foreign matter, undissolved matter, oxidative degradation, or the like of the material enters the film.

As the protective film 4, for example, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, or polyester can be used. As a commercially available product, for example, Alphan MA-410, E-200C (trade name) manufactured by Oji Paper Co., Ltd.; a polypropylene film manufactured by Shin-Etsu Film Co., Ltd.; and a PS series manufactured by Teijin Co., Ltd. (for example, trade name: PS-25) And the like, but not limited to polyethylene terephthalate.

The thickness of the protective film 4 is preferably from 1 to 100 μm, more preferably from 5 to 50 μm, even more preferably from 5 to 30 μm, still more preferably from 15 to 30 μm. When the thickness is less than 1 μm and the laminate is laminated, the protective film tends to be broken, and when it exceeds 100 μm, the inexpensiveness tends to decrease.

Further, the photosensitive element 1 of the present invention may further have an intermediate layer such as a buffer layer, an adhesive layer, a light absorbing layer, and a gas barrier layer. Further, the obtained photosensitive element 1 can be stored in a sheet form or wound up in a roll shape in a roll shape. Further, at this time, it is preferable to wind up so that the support film 1 becomes the outermost side. From the viewpoint of protecting the end face, it is preferable that the end face of the roll-shaped photosensitive element roll is provided with an end face separation piece, and it is preferable to provide a moisture-proof end face separation piece from the viewpoint of resistance to melting. Further, as the packing method, it is preferable to package the black steel sheet which is small in moisture permeability. Examples of the winding core include plastics such as a polyethylene resin, a polypropylene resin, a polystyrene resin, a polyvinyl chloride resin, and an ABS resin (acrylonitrile-butadiene-styrene copolymer).

Next, a method of forming the photoresist pattern of the present invention will be described.

The method for forming a photoresist pattern of the present invention comprises at least a lamination step of laminating a photosensitive resin composition layer containing the photosensitive resin composition on a circuit formation substrate; and irradiating active light to a photosensitive resin composition An exposure step of photohardening the exposed portion of the specific portion of the layer; and a developing step of removing the photosensitive resin composition from the portion other than the exposed portion on the substrate for forming a circuit. In addition, the "circuit formation substrate" means a substrate including an insulating layer and a conductor layer formed on the insulating layer. Further, the circuit-forming substrate may be formed in a plurality of layers and formed with a wiring inside, or may have a small-diameter through hole.

The lamination method of laminating the photosensitive resin composition layer on the circuit formation substrate in the lamination step may be, for example, the following method. First, the protective film is gradually peeled off from the photosensitive resin composition layer, and at the same time, the surface of the photosensitive resin composition layer which is gradually exposed is adhered to the surface of the circuit for forming the substrate for circuit formation. Next, the photosensitive resin composition layer is heated, and the photosensitive resin composition is laminated on the circuit formation substrate to be laminated. In addition, from the viewpoint of improving adhesion and followability, it is preferable to laminate the laminate under reduced pressure. The lamination of the photosensitive element is preferably performed by heating the photosensitive resin composition layer and/or the substrate for circuit formation to 70 to 130 ° C, and the pressing pressure is about 0.1 to 1.0 MPa (about 1 to 10 kgf/cm ² ). It is advisable, but not particularly limited by these conditions. In addition, when the photosensitive resin composition layer is heated to 70 to 130 ° C as described above, it is not necessary to preheat the substrate for circuit formation in advance, but in order to further improve the laminate property, the substrate for substrate formation may be preheated. deal with.

As a method of forming an exposure portion in the exposure step, for example, by being A method of illuminating an image of active light by a negative or positive reticle pattern called Artwork (mask exposure method). At this time, when the active light penetrates the support film existing on the photosensitive resin composition layer, the active light can be irradiated through the support film, and when the support film is light-shielding, after the support film is removed, the active light is irradiated onto the photosensitive resin. Layer of matter. Further, a method of directing the active light to an image by a direct direct exposure method such as laser direct exposure or DLP (Digital Light Processing) exposure may be employed.

As the light source of the active light, a known light source such as a carbon arc lamp, a mercury vapor arc lamp, a high pressure mercury lamp, a xenon lamp, an argon laser or the like, and a YAG (yttrium aluminum garnet) can be used. Stone) Solid lasers such as lasers, semiconductor electric radiation, etc., effectively emit ultraviolet light, visible light, and the like.

In the case where a portion other than the exposed portion is removed in the development step, for example, when the support film is present in the photosensitive resin composition layer, the support film is removed, and the portion other than the exposed portion is removed by wet development or dry development. The method of developing is carried out in portions. Thereby a photoresist pattern is formed.

For example, the wet development system uses a developing solution corresponding to a photosensitive resin composition such as an alkaline aqueous solution, an aqueous developing solution, or an organic solvent developing solution, and is immersed, brushed, and scraped by, for example, a dipping method, a pulverizing method, a spraying method, shaking, dipping, brushing, and scraping. The development is carried out by a known method such as rubbing. In order to improve the resolution, the development method is most suitable by a high pressure spray method. Further, two or more development methods may be used in combination as needed.

As the developer, it is possible to use a safe, stable, and operability alkaline. Aqueous solution, etc. As the base of the alkaline aqueous solution, for example, an alkali hydroxide such as a hydroxide of lithium, sodium or potassium; a carbonate such as a carbonate of lithium, sodium, potassium or ammonium or a hydrogencarbonate; a base such as potassium phosphate or sodium phosphate; Metal phosphate; alkali metal pyrophosphate such as sodium pyrophosphate or potassium pyrophosphate; borax.

Further, as the alkaline aqueous solution used for development, a diluted solution of 0.1 to 5% by mass of sodium carbonate, a diluted solution of 0.1 to 5% by mass of potassium carbonate, and a diluted solution of 0.1 to 5% by mass of sodium hydroxide, A diluted solution of 0.1 to 5% by mass of sodium tetraborate (borax) is preferred. Further, the pH of the alkaline aqueous solution is preferably in the range of from 9 to 11, and the temperature is adjusted in accordance with the developability of the photosensitive resin composition layer. Further, a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be added to the alkaline aqueous solution.

The aqueous developing solution may, for example, be a developing solution formed of water or an aqueous alkaline solution and one or more organic solvents. Here, as the base of the alkaline aqueous solution, in addition to the above substances, for example, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxyl can be mentioned. Methyl-1,3-propanediol, 1,3-diaminopropanol-2, morpholine. The pH of the developer is preferably as small as possible in the range in which the photoresist development can be sufficiently performed, preferably from pH 8 to 12, particularly preferably from pH 9 to 10.

Examples of the organic solvent include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethanol, isopropanol, butanol, diethylene glycol monomethyl ether, and diethylene glycol. Alcohol monoethyl ether, diethylene glycol monobutyl ether. These may be used alone or in combination of two or more. The concentration of the organic solvent is usually 2 to 90% by mass, which is compatible with developability. Adjustment. Further, a surfactant, an antifoaming agent, or the like may be added in a small amount in the aqueous developing solution.

Further, examples of the organic solvent-based developing solution using an organic solvent alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, and cyclohexanone. , methyl isobutyl ketone, γ-butyrolactone. In order to prevent ignition, it is preferable to add water in the range of 1 to 20% by mass in such an organic solvent-based developing solution.

As the treatment after development, the photoresist pattern may be further cured by heating at about 60 to 250 ° C or about 0.2 to 10 J/cm ² as needed.

Next, a method of manufacturing the printed wiring board of the present invention will be described.

The method for producing a printed wiring board according to the present invention is a method of forming a conductor pattern by etching or plating a circuit-forming substrate on which a photoresist pattern is formed according to the method for forming a photoresist pattern according to the present invention.

The etching and plating of the circuit-forming substrate are performed by using the formed photoresist pattern as a photomask, a conductor layer of the circuit-forming substrate, and the like. Examples of the etching liquid to be etched include a copper chloride solution, a ferric chloride solution, an alkaline etching solution, and a hydrogen peroxide etching solution. Among these, in view of the fact that the etch factor is good, it is preferred to use a ferric chloride solution. Further, as a plating method for plating, for example, copper plating such as copper sulfate plating or copper pyrophosphate plating; tin plating such as high-thickness tin plating; and Watt bath (nickel sulfate-chlorination) Nickel plating, nickel sulfonate, etc.; nickel plating; hard gold plating, soft gold plating, etc.

After etching or plating, the photoresist pattern can be compared to the alkali used for development. The aqueous solution is more alkaline and the aqueous solution is peeled off. As the strongly alkaline aqueous solution, for example, a 1 to 10% by mass aqueous sodium hydroxide solution and a 1 to 10% by mass aqueous potassium hydroxide solution can be used. Examples of the peeling method include a dipping method, a spraying method, and the like, and the dipping method and the spraying method may be used alone or in combination. According to the foregoing, a printed wiring board is available.

The preferred embodiments of the present invention have been described above, but the present invention is not limited to the foregoing embodiments.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto.

[Synthesis of Adhesive Polymer ((A) Component) 1]

A flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel and a nitrogen inlet tube, and 500 g of a solution of methyl cellosolve and toluene in a mass ratio of 3:2, stirred under nitrogen, and heated to 80 ° C . On the other hand, a solution of 150 g of methacrylic acid as a copolymer monomer, 175 g of cyclohexyl methacrylate, 175 g of styrene, and 12.5 g of azobisisobutyronitrile is prepared (hereinafter referred to as "solution" a"). The solution a was added dropwise to the solution of methyl cellosolve and toluene having a mass ratio of 3:2 prepared in advance for 4 hours, and then kept at 80 ° C for 2 hours while stirring. Further, a solution in which 1.0 g of azobisisobutyronitrile was dissolved was dropped into 250 g of a solution of methyl cellosolve and toluene in a mass ratio of 3:2 over 10 minutes. The solution after the dropwise addition was stirred at 80 ° C for 3 hours, and then heated to 90 ° C for 30 minutes. After being kept at 90 ° C for 2 hours, it was cooled to obtain a sticky layer. Polymer (A-1).

The non-volatile matter (solid content) of the adhesive polymer (A-1) was 46% by mass, and the weight average molecular weight was 40,000. Further, the weight average molecular weight was measured by gel permeation chromatography and derived from a calibration curve using standard polystyrene. The GPC conditions are as follows.

Pump: Hitachi L-6000 (made by Hitachi, Ltd., trade name)

Pipe column: Gelpack GL-R420+Gelpack GL-R430+Gelpack GL-R440 (3 in total) (above, manufactured by Hitachi Chemical Co., Ltd., trade name)

Eluent: tetrahydrofuran

Measuring temperature: 40 ° C

Flow rate: 2.05mL/min

Detector: Hitachi L-3300 RI (made by Hitachi, Ltd., trade name)

Further, the adhesive polymers (A-2) to (A-6) were synthesized in the same manner as in the synthesis of the above-mentioned adhesive polymer (A-1), as shown in the following Table 1.

[Synthesis of Adhesive Polymer ((A) Component) 2]

In a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel and a nitrogen inlet tube, 450 g of a solution of methyl cellosolve and toluene in a mass ratio of 3:2 was added, and the mixture was stirred under nitrogen and heated to 80. °C. On the other hand, a solution of 150 g of methacrylic acid as a copolymer monomer, 175 g of tetrahydropyranyl methacrylate, and 175 g of styrene, and 9.0 g of azobisisobutyronitrile are prepared (hereinafter referred to as It is "solution b"). The previously prepared solution of propylene glycol monomethyl ether and toluene having a mass ratio of 3:2 was added dropwise to the solution b in 4 hours, and then kept at 80 ° C for 2 hours while stirring. Further, a solution in which 1.2 g of azobisisobutyronitrile was dissolved was dropped into 100 g of a formulation of propylene glycol monomethyl ether and toluene in a mass ratio of 3:2 over 10 minutes. The solution after the dropwise addition was stirred at 80 ° C for 3 hours, and then heated to 90 ° C for 30 minutes. After cooling at 90 ° C for 2 hours, it was cooled to obtain an adhesive polymer (A-7).

The nonvolatile matter (solid content) of the adhesive polymer (A-7) was 47.8% by mass, and the weight average molecular weight was 41,000.

Further, the adhesive polymers (A-8) to (A-12) were synthesized in the same manner as in the synthesis of the above-mentioned adhesive polymer (A-7), as shown in the following Table 2.

* Malonic acid monomethyl ether / toluene (3 / 2) solution (solid content: 47.8%)

(Preparation of photosensitive resin composition)

The above-mentioned adhesive polymers (A-1) to (A-6) and the following materials were blended at a mass ratio as shown in Table 3 to prepare photosensitive resins of Examples 1 to 3 and Comparative Examples 1 to 3. a solution of the composition. Further, the above-mentioned adhesive polymers (A-7) to (A-12) and the following materials were blended at a mass ratio as shown in Table 4 to prepare a solution of the photosensitive resin compositions of Examples 4 to 9. .

<Photopolymerizable Compound ((B) Component)>

B-1: 2,2-bis(4-(methacryloxypentapentaethoxy)phenyl)propane (manufactured by Hitachi Chemical Co., Ltd., trade name: FA-321M)

B-2: a compound represented by the above general formula (V), a vinyl compound having R ¹¹ = R ¹² = methyl group, m1 + m2 = 4 (average value), and n1 = 12 (average value) (Hitachi Chemical Industry Co., Ltd. System, the product name "FA-023M")

B-3: γ-chloro-β-hydroxypropyl phthalate β-methyl propylene methoxyethyl ester (manufactured by Hitachi Chemical Co., Ltd., trade name “FA-MECH”)

B-4: a compound represented by the above general formula (XI), a vinyl compound having R ¹¹ = R ¹² = methyl group, n 2 + n 3 = 12 (average value), and m 3 = 6 (average value) (Hitachi Chemical Industry Co., Ltd. System, the product name "FA-024M").

B-5: 4-n-decylphenoxy octaethylene glycol acrylate (manufactured by Toagosei Co., Ltd., trade name "M-114")

<Photopolymerization initiator ((C) component)>

C-1: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole (manufactured by Hampford Co., Ltd., trade name: BCIM)

<sensitizing pigment ((D) component)>

D-1: 9,10-dibutoxy oxime (manufactured by Kawasaki Chemical Industry Co., Ltd., trade name: DBA, indicating the wavelength of absorption maximum [λ n] = 368 nm, 388 nm, 410 nm)

<(E) developer (amine compound)>

E-1: colorless crystal violet (manufactured by Yamada Chemical Co., Ltd.)

<dye>

Malachite Green (Osaka Organic Chemical Industry Co., Ltd.)

<solvent>

acetone

Toluene

Methanol

(A) The composition represents the amount of solid matter, and the values of the components represent the mass ratio.

(A) The composition represents the amount of solid matter, and the values of the components represent the mass ratio.

(Making photosensitive elements)

Each of the obtained photosensitive resin composition solutions was uniformly applied onto a 16 μm-thick polyethylene terephthalate film as a support film. Thereafter, it was dried by a hot air convection dryer at 70 ° C and 110 ° C to form a photosensitive resin composition layer having a film thickness of 25 μm after drying. Next, the protective film was laminated on the photosensitive resin composition layer by roll press, and the photosensitive elements of each of Examples 1 to 9 and Comparative Examples 1 to 3 were obtained.

(making a test piece)

Then, a copper-clad laminate (available from Hitachi Chemical Co., Ltd.), which is a glass epoxy material having a copper foil (thickness: 35 mm) laminated on both sides, was polished using a grinder (manufactured by Sankyo Co., Ltd.) having a brush corresponding to #600. The copper surface of the product name: MCL-E-67), after washing with water, is dried by air flow to obtain a copper-clad laminate (substrate). After the copper-clad laminate is heated to 80° C., the protective film of each of the photosensitive elements is removed from the copper-clad laminate, and laminated under a pressure of 4 kgf/cm ² at 120° C. to form each photosensitive resin composition. The layer was adhered to the surface of the copper clad laminate to prepare a test piece.

(evaluation characteristics)

<Light sensitivity>

When the copper-clad laminate in which the photosensitive elements are laminated is cooled to 23 ° C, 41 steps of a concentration range of 0.00 to 2.00, a concentration stage of 0.05, a plate size of 20 mm × 187 mm, and a size of 3 mm × 12 mm in each stage are obtained. A step tool of a step tablet is attached to the support film. Direct-drawing machine DE-1AH (trade name) manufactured by Hitachi Via Mechanics Co., Ltd., which uses a 405 nm blue-violet laser diode as a light source, is exposed (photographed) to photosensitivity through a photographic tool and a supporting film at a specific exposure amount. Resin composition layer. In addition, the measurement of the illuminance was performed using an ultraviolet illuminometer (manufactured by Ushio Electric Co., Ltd., trade name: UIT-150) to which a 405 nm corresponding probe was applied.

Next, the support film was peeled off, and a 1% by mass aqueous sodium carbonate solution was sprayed at 30 ° C for 24 seconds to remove the unexposed portion of the photosensitive resin composition layer, and development was carried out. Thereafter, the number of stages of the stage exposure plate of the photocured film remaining on the copper clad laminate was measured. The number of segments of this stage exposure plate is evaluated as the light sensitivity of the 11-segment exposure amount. The smaller the exposure, the higher the light sensitivity. The results obtained are shown in Tables 5 and 6.

<adhesion>

The adhesion was evaluated by exposure using a photographing tool having a line pattern having a line width/pitch width of 10/10 to 22/22 (unit: μm) as a negative film for adhesion evaluation. Here, the adhesion is a minimum value (unit: μm) of the line width/pitch width formed by the development process after the exposure to cleanly remove the unexposed portion, and the line width and the pitch width are not formed as the evaluation index. Further, the exposure amount was adjusted so that the number of remaining segments of the stage exposure plate after the development process was 9 segments, 11 segments, and 13 segments, and the adhesion was evaluated for each exposure amount. The smaller the evaluation coefficient value of the adhesion is, the better the value is. The results obtained are shown in Tables 6 and 7.

<resolution (disengagement)>

The resolution was evaluated by exposing with a specific exposure amount using a photographing tool having a line pattern having a line width/pitch width of 400/10 to 400/22 (unit: μm) as a negative for evaluation of the resolution. Here, the resolution is the minimum value (unit: μm) between the lines of the portion after the unexposed portion is cleanly removed from the photoresist pattern formed by the development after the exposure, as the evaluation index. Further, the exposure amount was adjusted so that the number of remaining segments of the stage exposure plate after the development process was 9 segments, 11 segments, and 13 segments, and the resolution was evaluated for each exposure amount. The smaller the evaluation coefficient value of the resolution is, the better the value is. The results obtained are shown in Tables 6 and 7.

<peelability>

The peelability was evaluated by the following method. First, the photosensitive resin composition layers of the respective examples and comparative examples were formed on a copper-clad laminate, and each photosensitive resin composition layer was exposed and developed at a specific exposure amount to prepare a photocured film having a size of 40 mm × 50 mm. . Next, peeling was performed using a 3% sodium hydroxide aqueous solution. The peeling property was measured as the peeling time as the peeling time from the time when the photocured film was completely peeled off from the copper clad laminate, and it was used as an evaluation index. Further, the exposure amount is the exposure amount of the stage exposure plate after the development processing becomes the exposure amount of 11 stages. Table 5 shows the conditions of the stripping step. In addition, the results obtained are shown in Tables 6 and 7.

<evaluation result>

As shown in Table 4, in Examples 1 and 2, the photosensitivity, adhesion, and resolution were excellent, and the peeling time was also moderately shortened, and the balance was good. As a result of Example 3, although the peeling time was long, the photosensitivity, adhesion, and resolution were excellent. On the other hand, in Comparative Example 1, in particular, since the adhesion was not good, the photoresist pattern could not be formed. In addition, the result of Comparative Example 2 is a solution. The image and peelability are good, but the adhesion is poor. In Comparative Example 3, although the peeling property and the resolution were excellent, the adhesion was not particularly good.

Further, as shown in Table 7, Examples 4, 5, and Example 9 were excellent in light sensitivity, adhesion, and resolution, and the peeling time was also moderately shortened, and the balance was good. As a result of Examples 6 to 8, the peeling time was long, but the photosensitivity, adhesion, and resolution were excellent.

Industrial availability

According to the present invention, it is possible to provide a photosensitive resin composition which forms a photoresist pattern which satisfies all of the sensitivity, the resolution and the adhesion more than the conventional one.

1‧‧‧Photosensitive components

2‧‧‧Support film

3‧‧‧Photosensitive resin composition layer

4‧‧‧Protective film

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a preferred embodiment of a photosensitive member of the present invention.

Claims (9)

A photosensitive resin composition comprising: (A) 100 parts by mass of an adhesive polymer having a divalent group represented by the following general formula (I): 20 to 65 parts by mass, the following general formula (II) 5 to 55 parts by mass of the divalent group represented by the above, and 15 to 50 parts by mass of the divalent group represented by the following general formula (III); (B) photopolymerizable compound; and (C) photopolymerization a starting agent, wherein the (C) photopolymerization initiator contains a hexaarylbiimidazole derivative [In the formula (I), the formula (II) and the formula (III), R ¹ , R ³ and R ⁵ each independently represent a hydrogen atom or a methyl group, and R ² is an alkyl group having 1 to 3 carbon atoms and a carbon number of 1 to 3 alkoxy group, hydroxyl group, amine group or halogen atom, R ⁴ is an alicyclic hydrocarbon group which may have a substituent, an aromatic hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent, m is 0 to An integer of 5, when m is 2 to 5, a plurality of R ² may be the same or different from each other]. The photosensitive resin composition of the first aspect of the invention, wherein the (B) photopolymerizable compound contains a bisphenol A-based (meth) acrylate compound. The photosensitive resin composition of the first aspect of the invention, wherein the R ⁴ is a monovalent group represented by the following general formula (IV). [In the formula (IV), R ⁶ is a hydroxyl group, an alkyl group having 1 to 12 carbon atoms or a hydroxyalkyl group having 1 to 12 carbon atoms, n is an integer of 0 to 5, and when n is 2 to 5, a plurality of R ⁶ Can be the same or different from each other]. The photosensitive resin composition of claim 1, wherein R ⁴ is a monovalent group represented by each of the following general formulas (V), (VI), (VII) and (VIII); At least one of the selected groups of the group, [In the formulae (V), (VI), (VII) and (VIII), R ⁷ , R ⁸ or R ⁹ are each independently a hydroxyl group, an alkyl group having 1 to 12 carbon atoms or a hydroxyalkyl group having 1 to 12 carbon atoms. j is an integer of 0 to 4, k and p are integers of 0 to 9, and when j, k or p is 2 or more, plural R ⁷ , R ⁸ or R ⁹ may be the same or different from each other]. The photosensitive resin composition of claim 1, which further contains (D) a sensitizing dye. The photosensitive resin composition of claim 1, which further contains (E) an amine compound. A photosensitive element comprising: a support film; and a photosensitive resin composition layer formed on the support film, the photosensitive resin composition layer containing the photosensitive material of any one of claims 1 to 6. Resin composition. A method for forming a resist pattern, comprising the step of laminating a photosensitive resin composition layer containing a photosensitive resin composition according to any one of claims 1 to 6 on a substrate for forming a circuit a step of exposing the active light to a specific portion of the photosensitive resin composition layer to photoharden the exposed portion; and removing the photosensitive layer from the substrate for forming a circuit layer on which the photosensitive resin composition layer is laminated A developing step of a portion other than the aforementioned exposed portion of the resin composition layer. A method of producing a printed wiring board, comprising: a step of forming a conductor pattern by etching or plating a circuit-forming substrate on which a photoresist pattern is formed in accordance with a method for forming a photoresist pattern according to claim 8 of the patent application.