TWI623814B - Photosensitive resin composition and method for forming circuit pattern - Google Patents

Abstract

The photosensitive resin composition of the present invention is characterized in that it contains (A) an alkali-soluble polymer: 40 to 80% by mass, (B) a photopolymerization initiator: 0.1 to 20% by mass, and (C) has ethylene Compound with a double bond: 5 to 50% by mass, and a photosensitive resin layer containing the photosensitive resin composition having a thickness of 25 μm is formed on the substrate surface, and the focus at the time of exposure is from the substrate surface to the substrate. The resist foot width of the resist pattern obtained by exposure and development under the condition that the thickness direction is shifted toward the inside of the substrate by 200 μm is 0.01 μm to 3.5 μm, and is used for direct image exposure.

Description

Photosensitive resin composition and method for forming circuit pattern

The present invention relates to a photosensitive resin composition that can be developed with an alkaline aqueous solution, and a method for forming a circuit pattern using the photosensitive resin composition. More specifically, the present invention relates to providing metal foils suitable for manufacturing printed wiring boards, manufacturing flexible printed wiring boards, manufacturing lead frames for IC (Integrated Circuit) chip mounting, and manufacturing metal masks. Precision processing; BGA (Ball Grid Array, Ball Grid Array), CSP (Chip Scale Package) and other semiconductor package manufacturing; TAB (Tape Automated Bonding, tape and tape automatic bonding) and COF (Chip On Film (film (Flip-Chip): Manufacturing of tape and reel substrates represented by film-shaped micro-wiring boards (including semiconductor ICs); manufacturing of semiconductor bumps; ITO (Indium Tin Oxide) electrodes in the field of flat panel displays , A photosensitive resin composition of a resist pattern for manufacturing an address electrode, an electromagnetic wave mask, and other components, and a circuit pattern forming method using the photosensitive resin composition.

Previously, the manufacture of printed wiring boards, precision machining of metals, etc. were manufactured by the photolithography method. The photosensitive resin composition used in the photolithography method is classified into a negative composition and a positive composition. The photolithography method using a negative-type photosensitive resin composition is performed, for example, as follows: a negative-type photosensitive resin composition is coated on a substrate, pattern exposure is performed, and an exposure portion of the photosensitive resin composition is performed. Polymer hardening. Then, a non-exposed part is removed with a developing solution, and a resist pattern is formed on a board | substrate. Furthermore, after performing an etching or plating process, After the conductor pattern is formed, the resist pattern is peeled off from the substrate to form a conductor pattern on the substrate.

In the photolithography method, when the photosensitive resin composition is coated on a substrate, any one of the following methods is used: (1) a method of coating a photoresist solution on a substrate and drying it, and ( 2) The photosensitive resin layer is formed by sequentially laminating a support and a layer containing a photosensitive resin composition (hereinafter referred to as a "photosensitive resin layer") and a protective layer as necessary, Method for laminating on a substrate. In the manufacture of printed wiring boards, the latter method is often used.

Hereinafter, a method for manufacturing a printed wiring board using the above-mentioned photosensitive resin laminated body will be briefly described.

First, a protective layer is peeled from a photosensitive resin laminated body. Then, using a bonding machine, a photosensitive resin layer and a support volume layer are formed on a substrate such as a copper foil laminated board in the order of the substrate, the photosensitive resin layer, and the support. Then, the photosensitive resin layer is exposed through a photomask having a desired wiring pattern, and the exposed portion is polymerized and hardened. Then, the support is peeled. Then, a resist pattern is formed on the substrate by dissolving or dispersing and removing unexposed portions of the photosensitive resin layer using a developing solution.

As the protective layer, for example, a polyethylene film is preferably used; as a support, for example, a polyethylene terephthalate film is preferably used; as a developing solution, for example, an aqueous solution having a weak alkali is preferably used. Wait.

The step of dissolving or dispersing and removing the photosensitive resin layer in the unexposed portion using a developing solution is referred to as a developing step. This development step is performed repeatedly each time, and the amount of dissolution of the unexposed portion of the photosensitive resin composition in the developing solution is increased. Therefore, if the development step is repeated, the foamability of the developer tends to increase. The foamability of the developing solution will significantly reduce the working efficiency of the developing step.

Next, using the resist pattern formed through the development step as a protective mask, An etching process or a pattern plating process is performed. Finally, by peeling the resist pattern from the substrate, a substrate (ie, a printed wiring board) having a conductor pattern is manufactured.

In recent years, with the miniaturization and weight reduction of electronic devices, the miniaturization and high density of wiring lines / gap (L / S) have been continuously developed. Furthermore, the demand for a build-up substrate having a multilayer wiring structure has also increased. In the build-up method, since a technique for accurately aligning the positions between the multi-layer substrates is required, a photosensitive resin layer capable of applying a direct imaging (DI, Correct Image) method with excellent alignment accuracy is becoming mainstream. Therefore, high sensitivity and high resolution of the photosensitive resin are required.

In this regard, in Patent Documents 1 and 2, a photosensitive resin composition containing a specific alkali-soluble polymer, a monomer, and a photopolymerizable initiator is described, and it is described that the photosensitive resin composition, Realize the above-mentioned high sensitivity and high resolution. In Patent Document 3, a method of using polyalkylene alcohol as an additive for a photosensitive resin composition is reported in order to suppress the foamability of a developing solution.

[Prior technical literature] [Patent Literature]

[Patent Document 1] International Publication No. 2009/147913

[Patent Document 2] International Publication No. 2010/098175

[Patent Document 3] Japanese Patent Laid-Open No. 2012-159651

In order to cope with the miniaturization and high density of wiring, it is required that the final line width of the conductor wire (for example, copper wire) after etching can be stably produced. For this reason, the width of the resist after development needs to be relatively stable. However, at the bottom of the resist after development, a tiny skirt-like bottom phenomenon called "resist foot part" is often seen (see FIG. 1). In addition, the presence of this resist foot portion becomes a factor that causes uneven widths of the conductor lines after the etching. In addition, regarding the existence of the resist foot portion, in the manufacturing method of forming a conductor pattern by pattern plating, the obtained conductor is also subjected to The pattern greatly affects the adhesion of the substrate. These phenomena, especially in the DI-type exposure methods used in recent years, are significant phenomena, and have become new issues that have arisen with the advancement of technology.

Regarding the mechanism by which the generation of the resist foot portion becomes apparent in the DI exposure, it is considered as follows. However, the present invention is not limited to the following theory.

DI exposure is an exposure method that uses laser scanning. The irradiation intensity of the laser points is based on a Gaussian distribution. Therefore, a region (a weakly exposed region) with a small exposure amount is generated at both ends of the exposure pattern. The hardened resist in this weakly exposed area is partially dissolved in the subsequent development step because the resistance to the developing solution is reduced. It is considered that since the dissolved residue at this time precipitated on the bottom of the resist and accumulated, a resist foot portion was generated.

This weakly exposed area is a unique problem in DI of multiple exposures using points. More importantly, because the width of the weak light area is determined by a fixed value, the narrower the line width of the design becomes, the more surface the problem becomes. In order to improve the resolution, each exposure machine manufacturer is committed to improving the laser spot diameter and the resolution between spots. However, the current state of the art is that the performance of the exposure machine does not follow the required specifications of the printed circuit boards that are constantly being improved.

In addition, in the above-mentioned Patent Document 3 (Japanese Patent Laid-Open No. 2012-159651), it is reported that a polyalkylene alcohol as a defoamer is added to the photosensitive resin composition in order to suppress foaming in the developing step. Method. However, according to the technique of Patent Document 3, since the density of the monomer is reduced by adding an antifoaming agent, there is a tendency that the efficiency of photopolymerization due to exposure decreases and the sensitivity decreases.

Therefore, an object of the present invention is to provide a photosensitive resin composition for direct imaging with excellent stability of the conductor line width after etching, the adhesion of the conductor wire after plating, or both, and the use of the photosensitive property. A method for forming a circuit pattern of a resin composition.

In order to solve the above-mentioned problems, the inventors of the present invention conducted diligent research and repeated experiments. As a result, it was found that the above-mentioned problems can be solved by the following technical methods, thereby completing Cost invention.

The present invention discloses the following embodiments.

[1] A photosensitive resin composition, characterized in that it contains (A) an alkali-soluble polymer: 40 to 80% by mass, (B) a photopolymerization initiator: 0.1 to 20% by mass, and (C) A compound having an ethylenic double bond: 5 to 50% by mass, and a photosensitive resin layer having a thickness of 25 μm containing the photosensitive resin composition is formed on the substrate surface, and the focus position at the time of exposure is from the substrate surface to the substrate. The width of the resist foot of the resist pattern obtained by exposing and developing under the condition that the substrate thickness direction is shifted toward the inside of the substrate by 200 μm is 0.01 μm to 3.5 μm, and is used for direct image exposure.

[2] The photosensitive resin composition as described in the above [1], wherein a photosensitive resin layer having a thickness of 25 μm containing the photosensitive resin composition is formed on the surface of the substrate so as to classify Stouffer 21 The exposure meter is used as a mask for exposure, and then the maximum residual film level during development is an exposure amount of level 6. When this photosensitive resin layer is exposed, the average number of vinylic double bonds in the (C) compound is exposed. The number is Q, and the value of P × Q / 100 when the reaction rate of the ethylenic double bond in the (C) compound after the exposure is set to P is 0.7 or more.

[3] The photosensitive resin composition described in the above [1] or [2], wherein a photosensitive resin layer having a thickness of 25 μm including the photosensitive resin composition is formed on the surface of the substrate, so that Stufe 21 Exposure meter as a mask to perform exposure, and then the highest residual film level during development is an exposure amount that is 1/10 of the exposure amount of level 6. When the photosensitive resin layer is exposed, the above (C) compound is exposed. The average number of ethylenic double bonds is Q, and the value of P '× Q / 100 when the reaction rate of the ethylenic double bonds in the above-mentioned (C) compound after the exposure is set to P' It is 0.3 or more.

[4] The above [1] to [3] The photosensitive resin composition according to any one of, wherein the Tg of the weight of (A) an alkali-soluble polymer of average Tg of above 30 ℃ ^Total 125 ℃ or less and .

[5] The photosensitive resin composition according to any one of the above [1] to [4], wherein the compound (C) includes a compound having three or more methacrylfluorenyl groups in one molecule.

[6] The photosensitive resin composition according to any one of the above [1] to [5], wherein the compound (C) includes a compound having four or more methacrylfluorenyl groups in one molecule.

[7] The photosensitive resin composition according to any one of the above [1] to [6], wherein the compound (C) includes a compound represented by the following general formula (IV),

{In the formula, n ₁ , n ₂ , n ₃ , and n ₄ each independently represent an integer of 1 to 25, n ₁ + n ₂ + n ₃ + n ₄ is an integer of 9 to 60, and R ₁ , R ₂ , R ₃ , and R ₄ each independently represent an alkyl group, and R ₅ , R ₆ , R ₇ , and R ₈ each independently represent an alkylene group. In the case where a plurality of R ₅ , R ₆ , R ₇ , and R ₈ exist, respectively The plurality of R ₅ , R ₆ , R ₇ , and R ₈ may be the same or different from each other}.

[8] The photosensitive resin composition according to the above [7], wherein in the general formula (IV), n ₁ + n ₂ + n ₃ + n ₄ is an integer of 15 to 40.

[9] The photosensitive resin composition according to the above [7], wherein in the formula (IV), n ₁ + n ₂ + n ₃ + n ₄ is an integer of 15 to 28.

[10] The photosensitive resin composition according to any one of the above [1] to [9], wherein the (B) photopolymerization initiator includes an acridine-based compound.

[11] The photosensitive resin composition according to any one of the above [1] to [10], further comprising a halogen compound.

[12] The photosensitive resin composition according to any one of the above [1] to [11], wherein the (B) photopolymerization initiator includes N-phenylglycine or a derivative thereof.

[13] The photosensitive resin composition according to any one of the above [1] to [12], wherein the (A) alkali-soluble polymer has an aromatic hydrocarbon group.

[14] A photosensitive resin composition, comprising: (A) an alkali-soluble polymer: 40 to 80% by mass; (B) a photopolymerization initiator: 0.1 to 20% by mass; and (C) Compound having an ethylenic double bond: 5 to 50% by mass, and the compound (C) includes a compound having three or more methacryl groups in one molecule.

[15] The photosensitive resin composition described in the above [14], wherein a photosensitive resin layer having a thickness of 25 μm containing the photosensitive resin composition is formed on a substrate surface, and a Stuffe 21-level exposure meter is used as When the photosensitive resin layer is exposed by exposing the mask and then developing the highest residual film level to an exposure level of 6, the average number of vinylic double bonds in the (C) compound is set as Q, and the value of P × Q / 100 when the reaction rate of the ethylenic double bond in the compound (C) after the exposure is set to P is 0.7 or more.

[16] The photosensitive resin composition as described in the above [14] or [15], wherein a photosensitive resin layer having a thickness of 25 μm containing the photosensitive resin composition is formed on the surface of the substrate, so that Stufe 21 Level exposure meter as a mask to perform exposure, and then the exposure amount of the highest residual film level during development to 1/10 of the level 6 exposure level is performed on the photosensitive resin layer During exposure, the average number of ethylenic double bonds in the (C) compound is set to Q, and the reaction rate of the ethylenic double bonds in the (C) compound after the above exposure is set to P ' In this case, the value of P '× Q / 100 is 0.3 or more.

[17] The photosensitive resin composition according to any one of the above [14] to [16], wherein the compound (C) includes a compound having four or more methacrylfluorenyl groups in one molecule.

[18] The photosensitive resin composition according to any one of the above [14] to [17], wherein the compound (C) includes a compound represented by the following general formula (IV),

{In the formula, n ₁ , n ₂ , n ₃ , and n ₄ each independently represent an integer of 1 to 25, n ₁ + n ₂ + n ₃ + n ₄ is an integer of 9 to 60, and R ₁ , R ₂ , R ₃ , and R ₄ each independently represent an alkyl group, and R ₅ , R ₆ , R ₇ , and R ₈ each independently represent an alkylene group. In the case where a plurality of R ₅ , R ₆ , R ₇ , and R ₈ exist, respectively The plurality of R ₅ , R ₆ , R ₇ , and R ₈ may be the same or different from each other}.

[19] The photosensitive resin composition according to the above [18], wherein in the formula (IV), n ₁ + n ₂ + n ₃ + n ₄ is an integer of 15 to 40.

[20] The photosensitive resin composition according to the above [18], wherein in the formula (IV), n ₁ + n ₂ + n ₃ + n ₄ is an integer of 15 to 28.

[21] The photosensitive resin composition according to any one of the above [14] to [20], wherein the (B) photopolymerization initiator includes an acridine-based compound.

[22] The photosensitive resin composition according to any one of the above [14] to [21], further comprising a halogen compound.

[23] The photosensitive resin composition according to any one of the above [14] to [22], wherein the (B) photopolymerization initiator includes N-phenylglycine or a derivative thereof.

[24] The photosensitive resin composition according to any one of the above [14] to [23], wherein the (A) alkali-soluble polymer has an aromatic hydrocarbon group.

[25] As the above-mentioned [14] to [24] The photosensitive resin composition according to any one of, wherein the Tg of the weight of (A) an alkali-soluble polymer of average Tg of above 30 ℃ ^Total 125 ℃ and less .

[26] The photosensitive resin composition according to any one of the above [14] to [25], which is used for direct imaging exposure.

[27] A method for forming a circuit pattern, comprising the steps of: forming a layer of the photosensitive resin composition according to any one of the above [1] to [26] on a substrate; A step of exposing and developing a layer of the resin composition to form a resist pattern; and a step of etching or plating the substrate on which the resist pattern is formed.

[28] The method as described in [27] above, wherein the exposure is performed by direct imaging exposure.

The present invention can provide stability of the width of a conductor wire (such as a copper wire) after etching and excellent adhesion of the conductor wire after plating by suppressing the occurrence of a resist foot portion, and can be suitably applied to use A photosensitive resin composition for forming a circuit pattern by a direct imaging method, And a method for forming a circuit pattern using the photosensitive resin composition.

FIG. 1 is a schematic cross-sectional view for explaining the definition of the width of the foot of the resist.

Hereinafter, the form (hereinafter, abbreviated as "embodiment") for implementing this invention is demonstrated in detail. The present invention is not limited to the following embodiments, and can be implemented with various changes within the scope of the gist thereof.

<Photosensitive resin composition>

An embodiment provides a photosensitive resin composition (a photosensitive resin composition for direct imaging exposure), which is characterized in that it contains (A) an alkali-soluble polymer: 40 to 80% by mass, and (B) a photopolymerization initiation Agent: 0.1-20% by mass and (C) Compound having an ethylenic double bond: 5-50% by mass, and a photosensitive resin layer containing the photosensitive resin composition with a thickness of 25 μm is formed on the substrate surface, and The width of the resist foot of the resist pattern obtained by exposing and developing the position of the focal point at the time of exposure from the surface of the substrate to the inside of the substrate by 200 μm in the thickness direction of the substrate is 0.01 μm to 3.5 μm , And for direct imaging exposure.

Another embodiment provides a photosensitive resin composition characterized in that it contains (A) an alkali-soluble polymer: 40 to 80% by mass, (B) a photopolymerization initiator: 0.1 to 20% by mass, and ( C) A compound having an ethylenic double bond: 5 to 50% by mass, and the compound (C) includes a compound having three or more methacrylfluorenyl groups in one molecule.

The photosensitive resin composition for direct image exposure of the present invention is a composition for forming the above-mentioned specific resist foot width by using a resist pattern obtained by exposure and development under the above conditions. A 25 μm-thick photosensitive resin layer containing a photosensitive resin composition is formed on the surface of the substrate, and the focus position at the time of exposure is shifted from the surface of the substrate in the thickness direction of the substrate to the inside of the substrate by 200 μm. The resist foot width of the resist pattern obtained by development is 0.01 μm to 3.5 μm, which is necessary to reduce unevenness in the width of the conductor lines after etching and improve the adhesion of the conductor lines after plating. condition. The width of the resist foot portion is 0.01 μm or more is advantageous from the viewpoint of improving the adhesion of the hardened resist; the value of 3.5 μm or less is the viewpoint of reducing unevenness in the width of the conductor line after etching and improving the plating This is advantageous from the viewpoint of the tightness of the coated conductor wire. The width of the resist foot portion is preferably 0.02 μm or more, more preferably 0.03 μm or more, more preferably 2.5 μm or less, even more preferably 2.0 μm or less, still more preferably 1.5 μm or less, and even more preferably 1.2 μm or less. It is preferably 1 μm or less.

The more specific order of the above-mentioned exposure and development is based on the method described in the item of [Example] or a method equivalent to that understood by those skilled in the art.

It is understood that the specific resist foot width described above can be achieved by using the components (A) to (C) at a specific ratio and, for example, a method (not limited to these) as exemplified below. Hereinafter, each component contained in the photosensitive resin composition of this embodiment is demonstrated in order.

<(A) Alkali-soluble polymer>

The so-called (A) alkali-soluble polymer in this embodiment is a polymer that is soluble in an alkaline aqueous solution. For example, a vinyl-based polymer containing a carboxyl group may be mentioned, and a monomer selected from (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide) is preferable Copolymer.

(A) The alkali-soluble polymer preferably contains a carboxyl group and has an acid equivalent of 100 to 600. The so-called acid equivalent refers to the mass in grams of an alkali-soluble polymer having one equivalent of a carboxyl group therein. on From the viewpoint of improving development resistance, resolution, and adhesion, it is preferable to set the acid equivalent to 100 or more. On the other hand, from the viewpoint of improving developability and peelability, it is preferable to set the acid equivalent to Below 600. The acid equivalent can be measured using a titration device (for example, Hiranuma Industry Co., Ltd., Hiranuma Automatic Titration Device (COM-555)) and a potentiometric titration method using 0.1 mol / L sodium hydroxide aqueous solution. (A) The acid equivalent of the alkali-soluble polymer is more preferably 250 to 450.

The weight-average molecular weight of the (A) alkali-soluble polymer is preferably 5,000 or more and 500,000 or less. From the viewpoint of developing the properties of the aggregates and the properties of the unexposed film such as the edge melting properties of the photosensitive resin laminate and the dicing wafer property, it is preferable to set the weight average molecular weight to 5,000 or more. From the viewpoint of improving the solubility in a developing solution, the weight-average molecular weight is preferably 500,000 or less. The edge meltability is a property that suppresses the phenomenon that the photosensitive resin composition layer overflows from the end surface of the roll when the photosensitive resin laminate is wound into a roll shape. The so-called wafer dicing property is a property that suppresses the phenomenon of wafer flying out when a non-exposed film is cut by a cutter. If the dicing of the wafer is poor, problems such as scattering of the wafer adhere to the upper surface of the photosensitive resin laminated body, etc., and the wafer is transferred to the mask in the subsequent exposure step, causing a defect. (A) The weight average molecular weight of the alkali-soluble polymer is more preferably 5,000 or more and 300,000 or less, and still more preferably 10,000 or more and 200,000 or less.

(A) The alkali-soluble polymer preferably has an aromatic hydrocarbon group.

Since (A) the alkali-soluble polymer has an aromatic hydrocarbon group, it has the advantages of improving resolution and adhesion, reducing the amount of agglomerates generated during development, and improving etching resistance.

By using an aromatic vinyl compound, a (meth) acrylate compound having a benzyl group, and the like for a part of the monomers used in the synthesis, an aromatic hydrocarbon group can be introduced into the (A) alkali-soluble polymer.

(A) The alkali-soluble polymer can be obtained by copolymerizing one or two or more monomers selected from the following two monomers.

The first monomer is a carboxylic acid or anhydride having one polymerizable unsaturated group in the molecule. Examples include (meth) acrylic acid, fumaric acid, cinnamic acid, butenoic acid, itaconic acid, maleic anhydride, maleic acid half ester, and the like. Especially preferred is (meth) acrylic acid. Here, (meth) acrylic acid means acrylic acid or methacrylic acid.

(A) The copolymerization ratio of the first monomer in the alkali-soluble polymer can be easily calculated based on the value of the required acid equivalent in the alkali-soluble polymer. (A) The copolymerization ratio of the first monomer in the alkali-soluble polymer is preferably 10 to 50% by mass based on the total mass of all the monomer components. From the viewpoint of exhibiting good developability and controlling the meltability of the edge, it is preferable that the copolymerization ratio is 10% by mass or more. From the viewpoint of improving the resolution and the viewpoint of suppressing the generation of the resist foot portion, it is preferable to set the copolymerization ratio to 50% by mass or less, and more preferably 30% by mass from the viewpoints. Hereinafter, it is more preferably 25% by mass or less, and particularly preferably 20% by mass or less.

The second monosystem is a monomer which is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth) ) Isobutyl acrylate, tertiary butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Benzyl (meth) acrylate, vinyl alcohol esters; vinyl acetate; (meth) acrylonitrile; aromatic vinyl compounds, and the like. Examples of the aromatic vinyl-based compound include styrene and a styrene derivative.

As the second monomer, among the above, preferred are methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, a styrene derivative, and benzyl (meth) acrylate. Among these, styrene, a styrene derivative, and (formaldehyde) are particularly preferred from the viewpoints of improving resolution, improving adhesion, and good development cohesiveness (less amount of aggregates) and etching resistance. Group) benzyl acrylate.

As the copolymer component in the (A) alkali-soluble polymer, an aromatic monomer such as an aromatic vinyl compound or a (meth) acrylate compound having a benzyl group can be used. About (A) Alkali The copolymerization ratio of the compound of the aromatic monomer in the soluble polymer is preferably 20 to 85% by mass based on the total mass of all the monomer components. From the viewpoints of improving resolution and adhesion, suppressing generation of aggregates during development, and improving etching resistance, the copolymerization ratio is preferably 20% by mass or more, and more preferably 25% by mass. The above is more preferably 30% by mass or more, and even more preferably 40% by mass or more. From the viewpoint of exhibiting moderate developability, the copolymerization ratio is preferably 85% by mass or less. From the viewpoint of cost, aromatic vinyl compounds are more preferred. Among the (A) alkali-soluble polymers, the copolymerization ratio is preferably 20 based on the total mass of all monomer components as a reference. ~ 70% by mass. From the viewpoints of improving resolution, improving adhesion, and exhibiting good development cohesiveness and etching resistance, the copolymerization ratio is preferably 20% by mass or more, and more preferably 25% by mass. % Or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more. From the viewpoint of exhibiting moderate developability and cured film flexibility, the copolymerization ratio is preferably 70% by mass or less, and more preferably 60% by mass or less. When these viewpoints are taken seriously, the copolymerization ratio of the aromatic vinyl compound is more preferably 20 to 50% by mass, and even more preferably 20 to 30% by mass.

In one embodiment, examples of the aromatic vinyl-based compound include styrene and a styrene derivative. Examples of the styrene derivative include oxystyrene, hydroxystyrene, ethoxylated styrene, alkylstyrene, and halogenated alkylstyrene.

(A) The alkali-soluble polymer is preferably a copolymer containing a monomer mixture of styrene or a styrene derivative, methyl (meth) acrylate, and (meth) acrylic acid as a comonomer.

Different from the above, in order to obtain excellent resolvability, the copolymerization ratio of the aromatic vinyl compound is preferably 40 to 60% by mass based on the total mass of all monomer components. It is preferable to include styrene or a styrene derivative, methyl (meth) acrylate, and / or (meth) acrylic acid as a comonomer in this case.

In one embodiment, the weight average Tg ^{total (} Tg ^total ) of the Tg of the (A) alkali-soluble polymer in the photosensitive resin composition may be set within a range of 30 to 125 ° C, preferably 50 to 110 ° C, and more preferably 50 ~ 105 ° C, more preferably 50 to 90 ° C. From the viewpoint of controlling the meltability of the edges, it is preferable to set the average weight of Tg to 30 ° C or higher. On the other hand, from the viewpoint of suppressing the occurrence of the resist foot, it is preferably set to 110 ° C. the following. The weight average value of Tg in the present invention, Tg ^total , is a value obtained according to the following formula (Fox formula): Tg ^total = Σ _i (W _i × Tg _i ) / W ^total

{Here, W _i is the solid mass of each alkali-soluble polymer, Tg _i is the glass transition temperature determined by the Fox formula for each alkali-soluble polymer, and W ^total is the total value of the solid mass of each alkali-soluble polymer. }. Here, when the glass transition temperature Tg _i is determined by the Fox formula for each alkali-soluble polymer, it is necessary to include Tg of a homopolymer that forms a copolymerization monomer of each alkali-soluble polymer. In the present invention, a document value (Brandrup, J. Immergut, EH editor, Polymer handbook, Third edition, John Wiley & sons, 1989, Chapter VI "Glass transition temperatures of polymers", p209) is used as the value.

The Tg _i of each comonomer used in the calculations in the examples is shown in Table 4.

Regarding the mechanism for suppressing the resist foot portion during DI exposure by using the (A) alkali-soluble polymer having the above-mentioned composition, the following is considered. However, the present invention is not limited to the following theory.

In DI exposure, weakly exposed areas are generated on both sides of the exposure pattern. The response rate of the resist in the weakly exposed area is reduced. Thereby, the developing solution resistance of the hardened resist in this region is lowered, so that it is partially dissolved in the subsequent development step. It is presumed that since the dissolved residue at this time was deposited on the bottom of the resist and accumulated, a resist foot portion was generated.

Therefore, it is considered that in order to suppress the occurrence of the resist foot portion, it is necessary to efficiently harden the monomer in the resist even in the weakly exposed area. It is considered that the reaction rate of the monomers is affected by the diffusion speed of the monomers, and the diffusion speed is restricted by the free volume in the resist.

In view of the above, it is thought that by designing the composition and structure of the (A) alkali-soluble polymer in such a way as to increase the free volume in the resist, the reaction rate of the monomer can be increased and the resist in weakly exposed areas can be suppressed. Foot.

As an indicator of the free volume, a glass transition temperature Tg can be generally used. Tg is the temperature at which the ratio of free volume to the total volume of the polymer begins to increase. Therefore, it is considered that at a temperature above Tg, the free volume increases in proportion to the temperature difference from Tg.

At the same temperature, the higher the Tg of a substance, the smaller the free volume, and the lower the Tg, the larger the free volume. Therefore, it is considered that, for a resist composition having a higher Tg, the reaction rate of the monomer is likely to be lowered, so that a resist foot portion is generated, and a resist composition having a lower Tg suppresses the generation of the resist foot portion.

For this reason, (A) the weight-average Tg of the alkali-soluble polymer is preferably lower when the ^total Tg ^{total is} lower, but if the control of the edge melting is considered, the higher Tg ^total is better. Considering the balance of these melting properties, the above range can be exemplified as a preferred range of Tg ^total .

In one embodiment, the blending amount of the (A) alkali-soluble polymer in the photosensitive resin composition is preferably set to 100% by mass of the total solid component content of the photosensitive resin composition. The range is 40 to 80% by mass, and more preferably 50 to 70% by mass. Setting the blending amount to 40% by mass or more is advantageous from the viewpoint of controlling edge melting properties, while setting the blending amount to 80% by mass or less is advantageous from the viewpoint of controlling the development time.

<(B) Photopolymerization initiator>

In the embodiment of the present invention, as the (B) photopolymerization initiator, various materials that can be used as a photopolymerization initiator for a photosensitive resin can be used.

As the (B) photopolymerization initiator in this embodiment, for example, one selected from the group consisting of an acridine-based compound, an N-aryl-α-amino acid compound, and a triarylimidazole dimer can be used. 1 or more. An acridine-based compound is preferred from the viewpoint of exhibiting a higher sensitivity and the viewpoint of simultaneously achieving high sensitivity and suppression of the generation of the resist's foot. The acridine-based compound is more reliably suppressed; From the viewpoint of production, a triarylimidazole dimer is preferred.

Examples of the acridine-based compound include 1,7-bis (9,9'-acridyl) heptane, 9-phenylacridine, 9-methylacridine, 9-ethylacridine, 9 -Chloroethylacridine, 9-methoxyacridine, 9- Ethoxyacridine, 9- (4-methylphenyl) acridine, 9- (4-ethylphenyl) acridine, 9- (4-n-propylphenyl) acridine, 9- (4 -N-butylphenyl) acridine, 9- (4-third butylphenyl) acridine, 9- (4-methoxyphenyl) acridine, 9- (4-ethoxyphenyl) Acridine, 9- (4-ethylamidophenyl) acridine, 9- (4-dimethylaminophenyl) acridine, 9- (4-chlorophenyl) acridine, 9- (4- Bromophenyl) acridine, 9- (3-methylphenyl) acridine, 9- (3-third-butylphenyl) acridine, 9- (3-ethylamidophenyl) acridine, 9 -(3-dimethylaminophenyl) acridine, 9- (3-diethylaminophenyl) acridine, 9- (3-chlorophenyl) acridine, 9- (3-bromobenzene Group) acridine, 9- (2-pyridyl) acridine, 9- (3-pyridyl) acridine, and 9- (4-pyridyl) acridine. Among these, 1,7-bis (9,9'-acridyl) heptane or 9-phenylacridine is preferable from the viewpoints of sensitivity, resolvability, and availability.

Examples of the N-aryl-α-amino acid compound include N-phenyl glycine, N-methyl-N-phenyl glycine, and N-ethyl-N-phenyl glycine Wait. In particular, the sensitizing effect of N-phenylglycine is higher and better.

Examples of the triarylimidazole dimer include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis (methoxy) Phenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole di Polymer, 2, (4-methoxyphenyl) -4,5-diphenylimidazole dimer, etc. 2,4,5-triarylimidazole dimer.

Acridine compounds are more sensitive than triarylimidazole dimer compounds. Further, when a urethane compound is used as the compound having an ethylenic double bond in (C), it is preferable from the viewpoint of suppressing both foaming properties and development cohesiveness by combining them.

N-phenylglycine and its derivatives are preferred from the viewpoint of improving sensitivity. In particular, when N-phenylglycine or a derivative thereof is used in combination with an acridine-based compound, it is preferable from the viewpoint that the generation of the resist foot portion can be more surely suppressed.

In a preferred aspect, (B) the photopolymerization initiator preferably contains one selected from the group consisting of an acridine-based compound, N-phenylglycine, and an N-phenylglycine derivative. More than that. The acridine-based compound preferably contains a compound selected from the following formula (I):

9-phenylacridine represented by the following general formula (II):

(Wherein R ₁ represents an alkylene group having 1 to 12 carbon atoms)

One or more of the groups represented by the compounds represented. These compounds are advantageous from the viewpoint of improving sensitivity in DI exposure. The number of carbon atoms of R ₁ in the general formula (II) is preferably 1 to 12 from the viewpoint of solubility. The carbon number of R ₁ is more preferably 4 to 10.

As the acridine-based compound, 9-phenylacridine represented by the formula (I) is preferably used.

As the (B) photopolymerization initiator in this embodiment, only a group selected from the group consisting of an acridine-based compound, N-phenylglycine or a derivative thereof, and a triarylimidazole dimer can be used. One or more of them may further contain photopolymerization initiators other than these.

Further examples of the (B) photopolymerization initiator include benzophenone, N, N'-tetramethyl-4,4'-dimethylaminobenzophenone (Michele Ketone), N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2 -Dimethylamino-1- (4-morpholinylphenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinyl-acetone Aromatic ketones such as -1; 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-benzoanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1 , 4-naphthoquinone, 2,3-dimethylanthraquinone and other quinones; benzoin methyl ether, benzoin ether, benzoin phenyl ether and other benzoin ether compounds; benzoin methyl ketal derivatives such as benzoin acetophenone; coumarol Voxel-based compounds; 4,4'-bis (diethylamino) benzophenone; 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl -Phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-third butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-third octyl-phenyl)- Pyrazoline derivatives such as pyrazoline and the like.

(B) A photopolymerization initiator may be used individually by 1 type, and may use 2 or more types together.

When the total solid component content of the photosensitive resin composition is 100% by mass, the amount of the (B) photopolymerization initiator in the photosensitive resin composition is 0.1 to 20% by mass. Setting the blending amount to 0.1% by mass or more is based on the viewpoint that an exposure pattern having a sufficient residual film ratio is obtained after development. On the other hand, setting the blending amount to 20% by mass or less is based on the sufficient transmission of light to the resist. From the viewpoint of obtaining a high resolving power on the bottom surface of the agent, and from the viewpoint of suppressing the development cohesiveness in the developer. A preferable range of the blending amount is 0.3 to 10% by mass.

In the case where the (B) photopolymerization initiator contains an acridine-based compound, the compounded amount of the acridine-based compound is preferably 0.01% by mass to 5% by mass relative to the mass of the entire solid content of the photosensitive resin composition. . From the viewpoint of obtaining a good sensitivity, it is preferable to adjust the tone The compounding amount is set to 0.01% by mass or more. The blending amount is more preferably 0.1% by mass or more, and even more preferably 0.2% by mass or more. On the other hand, from the viewpoint of adjusting the resist shape to a rectangular shape and improving the hue stability of the photosensitive resin composition, it is preferable that the blending amount is 5 mass% or less. The blending amount is more preferably 3% by mass or less, and even more preferably 2% by mass or less.

In the case where the (B) photopolymerization initiator contains an N-aryl-α-amino acid compound, the N-aryl-α-amino acid is relative to the total solid component content of the photosensitive resin composition. The content of the compound is preferably from 0.001% by mass to 5% by mass. From the viewpoint of obtaining good sensitivity, it is preferable that the blending amount is 0.001% by mass or more. In particular, when this N-aryl-α-amino acid compound is used in combination with an acridine-based compound, it is preferable from the viewpoint that the generation of the resist foot can be more surely suppressed. The blending amount is more preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more. On the other hand, from the viewpoint of improving the resolution and improving the hue stability of the photosensitive resin composition, it is preferable that the blending amount is 5 mass% or less. The blending amount is more preferably 1% by mass or less, and even more preferably 0.5% by mass or less.

In the case where the (B) photopolymerization initiator contains a triarylimidazole dimer, the content of the triarylimidazole dimer is preferably 0.1% by mass to the total solid content of the photosensitive resin composition. 15% by mass. From the viewpoint of obtaining a good sensitivity, it is preferable to set the blending amount to 0.1% by mass or more. The blending amount is more preferably 1% by mass or more, and even more preferably 3% by mass or more. On the other hand, from the viewpoint of obtaining high resolution and suppressing cohesiveness in the developer, it is preferable that the blending amount is 15% by mass or less. The blending amount is more preferably 10% by mass or less, and even more preferably 6% by mass or less.

<(C) Compound having ethylenic double bond>

In the embodiment of the present invention, the photosensitive resin composition contains (C) a compound having an ethylenic double bond. As a preferable example of the compound, a methacrylate group having three or more functions (three or more methacryl groups in one molecule), and a molecular weight of 500 g / mol can be mentioned. Compounds (multifunctional monomers) above 5,000 g / mol. The compound (C) is more preferably a compound having a tetrafunctional or higher methacrylate group (4 or more methacrylfluorenyl groups in one molecule).

Regarding the mechanism for suppressing the resist foot portion during DI exposure by using the (C) compound described above, the following is considered. However, the present invention is not limited to the following theory.

As described above, in DI exposure, weakly exposed areas are generated on both sides of the exposure pattern. In addition, it is presumed that since the reaction rate of the resist existing in this area is reduced, the resistance to the developing solution is lowered and a resist foot portion is generated. Therefore, in order to suppress the occurrence of the resist foot portion, it is also necessary to increase the reaction rate of the (C) compound in the weakly exposed area, increase the crosslinking density, and improve the developer resistance.

In order to crosslink the resist, it is necessary to react one of the double bonds in a multifunctional monomer and then further react the other unreacted double bonds in the same monomer. Therefore, the (C) compound has a large number of double bonds, and the fewer unreacted double bonds remaining after exposure, the higher the crosslinking density.

However, a multifunctional monomer obtained by performing a single reaction of a double bond is introduced into a high-molecular-weight growing polymer chain. Therefore, in order to make two or more of the double bonds in the polyfunctional monomer molecule react, the double bonds dangling to the growing polymer chain need to react with other monomers or growing polymers. This reaction has a large steric hindrance. In order to alleviate the steric hindrance of such a reaction and promote the reaction, it is necessary to lengthen the length of the molecular chain between the double bonds in the compound (C). Therefore, it is preferable that the molecular weight of the (C) compound is large. On the other hand, if it is a polymer with an excessively high molecular weight, the reaction rate of the double bond in the (C) compound is increased, but the amount of the double bond in the composition is reduced. Therefore, the crosslinking density is also reduced in this case. .

Therefore, in order to suppress the resist foot portion during DI exposure, a methacrylate monomer having a high molecular weight and having a large number of functional groups is considered to be particularly effective.

From such a viewpoint, the compound (C) in the present embodiment has a range of the optimal molecular weight and the number of functional groups. (C) The molecular weight of the compound is preferably 500 g / mol or more and 5,000 g / mol or less, more preferably 600 g / mol or more and 4,000 g / mol or less, still more preferably 700 g / mol or more and 3,000 g / mol or less.

Regarding the number of functional groups in the (C) compound, from the viewpoint of increasing the cross-linking density, improving the resolvability and adhesion, and the viewpoint of suppressing the occurrence of the resist foot portion, it is preferably tri-functional or more, more preferably 4 or more functional. From the viewpoint of controlling the meltability of the edge, it is also preferably trifunctional or more, and more preferably tetrafunctional or more. Moreover, from a viewpoint of a peeling property, 10-functionality or less is more preferable, 6-functionality or less is more preferable, 5-functionality or less is more preferable, and 4-functionality or less is more preferable. Therefore, in order to show improvement in resolution at a higher level, suppression of the formation of resist foot portions, control of edge melting properties, and all of the peeling properties, it is most preferably a four-functionality.

Furthermore, from the viewpoint of the developing solution resistance of the monomer crosslinked body, a methacrylate monomer having a low hydrolyzability is more effective. The methacrylate monomer is excellent from the viewpoints of improvement in resolvability and adhesion, suppression of generation of a resist foot, and control of edge melting.

In the embodiment of the present invention, the photosensitive resin composition preferably contains a compound represented by the following general formula (III) as a compound having (C) an ethylenic double bond,

{Where n ₁ , n ₂ , and n ₃ are each independently an integer from 1 to 25, where n ₁ + n ₂ + n ₃ is an integer from 3 to 75, and R ₁ , R ₂ , and R ₃ are independent Is alkyl}.

In the general formula (V), the value of n ₁ + n ₂ + n ₃ is preferably 3 or more and 50 or less. From the viewpoint of suppressing the occurrence of the resist foot portion, the viewpoint of imparting flexibility to the cured film, and the viewpoint of improving the puncture resistance of the cover film, it is preferable to set n ₁ + n ₂ + n ₃ to 3 or more. On the other hand, from the viewpoint of obtaining higher resolution and adhesion, and good peeling characteristics, it is preferable to set n ₁ + n ₂ + n ₃ to 50 or less. A more preferable range of n ₁ + n ₂ + n ₃ is 6 or more and 40 or less, and a more preferable range is 9 or more and 30 or less.

Specific examples of the compound represented by the general formula (III) include a trimethacrylate having an average of 3 moles of ethylene oxide added to the terminal of the hydroxyl group of trimethylolpropane, and trihydroxymethylpropane. Methylpropane hydroxyl groups are added with an average of 9 moles of ethylene oxide trimethacrylate, and trimethylolpropane hydroxyl groups are added with an average of 15 moles of ethylene oxide triple Methacrylate, trimethacrylate with an average of 30 moles of ethylene oxide added to the end of the hydroxyl group of trimethylolpropane.

In one embodiment, the photosensitive resin composition preferably contains a compound represented by the following general formula (IV) as a compound having (C) an ethylenic double bond,

{In the formula, n ₁ , n ₂ , n ₃ , and n ₄ each independently represent an integer of 1 to 25, n ₁ + n ₂ + n ₃ + n ₄ is an integer of 4 to 100, and R ₁ , R ₂ , R ₃ , and R ₄ each independently represent an alkyl group, and R ₅ , R ₆ , R ₇ , and R ₈ each independently represent an alkylene group. In the case where a plurality of R ₅ , R ₆ , R ₇ , and R ₈ exist, respectively The plurality of R ₅ , R ₆ , R ₇ , and R ₈ may be the same or different from each other}.

In the general formula (IV), n ₁ + n ₂ + n ₃ + n _{4 is} preferably 9 or more and 60 or less. From the viewpoint of suppressing the occurrence of the resist foot portion, the viewpoint of improving the puncture resistance of the cover film, and the viewpoint of imparting flexibility to the cured film, it is preferable to set n ₁ + n ₂ + n ₃ + n ₄ It is 9 or more. On the other hand, from the viewpoint of improving resolution and adhesion, obtaining good peeling characteristics, and controlling edge fusion, it is preferable to use n ₁ + n ₂ + n ₃ + n ₄ It is set to 60 or less. Furthermore, a more preferable range of n ₁ + n ₂ + n ₃ + n ₄ is 9 or more and 40 or less, a more preferable range is 15 or more and 40 or less, and a more preferable range is 15 or more and 28 or less.

R ₅ , R ₆ , R ₇ , and R ₈ in the general formula (IV) may be 1,2-ethene, 1,2-propane, and butylene, respectively. From the viewpoint of flexibility, the viewpoint of improving the puncture resistance of the cover film, the viewpoint of suppressing the development cohesiveness, and the viewpoint of improving the reactivity of the ethylenic double bond, 1,2-ethanyl is preferred. Therefore, as the compound represented by the general formula (IV), a compound represented by the following general formula (V) is preferred,

[Where n ₁ , n ₂ , n ₃ , and n ₄ are each independently an integer of 1 to 25, where n ₁ + n ₂ + n ₃ + n ₄ is an integer of 4 to 100, and R ₁ , R ₂ , R ₃ , and R ₄ are each independently alkyl}. The preferable range of n ₁ + n ₂ + n ₃ + n ₄ is the same as the above.

Specific examples of the compound represented by the general formula (IV) include, for example, a tetramethacrylate having an average of 9 moles of ethylene oxide added to a terminal of a hydroxyl group of pentaerythritol, and a terminal of a hydroxyl group of pentaerythritol. Tetramethacrylate with an average of 12 moles of ethylene oxide, tetramethacrylate with an average of 15 moles of ethylene oxide, and a terminal of the hydroxyl group of pentaerythritol Tetramethacrylate with an average of 20 moles of ethylene oxide, tetramethacrylate with an average of 28 moles of ethylene oxide, and a terminal of the hydroxyl group of pentaerythritol Additions include an average of 35 moles of ethylene oxide, tetramethacrylate, and the like.

In one embodiment, the photosensitive resin composition preferably contains a compound represented by the following general formula (VI) as a compound having (C) an ethylenic double bond,

{In the formula, R ₃ and R ₄ are each independently a hydrogen atom or a methyl group; n ₉ and n ₁₁ are each independently an integer of 0 to 20, and n ₉ + n ₁₁ is an integer of 0 to 20; n ₈ and n ₁₀ Each is independently an integer of 1-20, and n ₈ + n ₁₀ is an integer of 2-20; the arrangement of repeating units of-(C ₂ H ₄ O)-and-(C ₃ H ₆ O)-can be random It may be a block, and either one of-(C ₂ H ₄ O)-and-(C ₃ H ₆ O)-may be bonded to a bisphenol structure}.

In the general formula (VI), n ₈ + n ₉ + n ₁₀ + n ₁₁ is preferably 2 or more and 40 or less. From the viewpoint of obtaining the flexibility of the cured film, it is preferable to set n ₈ + n ₉ + n ₁₀ + n ₁₁ to 2 or more. On the other hand, from the viewpoint of obtaining resolution, it is more preferable to set n ₈ + n ₉ + n ₁₀ + n _{11 is} set to 40 or less. Furthermore, in order to obtain chemical resistance, a more preferable range of n ₈ + n ₉ + n ₁₀ + n ₁₁ is 4 or more and 20 or less, and a more preferable range is 6 or more and 12 or less. In order to obtain hiding properties, a more preferable range of n ₈ + n ₉ + n ₁₀ + n ₁₁ is 16 or more and 40 or less, and a more preferable range is 30 or more and 40 or less. Further preferably, n ₉ + n ₁₁ is an integer of 1-20, and n ₈ + n ₁₀ is an integer of 2-20.

Specific examples of the compound represented by the general formula (VI) include, for example, dimethacrylic acid of ethylene glycol obtained by adding an average of 2 moles of ethylene oxide to both ends of bisphenol A, respectively. Esters, ethylene glycol dimethacrylates obtained by adding an average of 5 moles of ethylene oxide to both ends of bisphenol A, and an average of 6 moles of bisphenol A at both ends Of ethylene oxide and an average of 2 moles of propylene oxide, a dimethacrylate of an alkylene glycol, with an average of 15 moles of ethylene oxide added to both ends of bisphenol A and an average of 2 moles of propylene oxide, dimethacrylate of alkylene glycol, etc.

In one embodiment, as the photosensitive resin composition, only the compounds represented by the general formulae (III), (IV), and (VI) may be used as the (C) compound having an ethylenic double bond. It may further contain other (C) compounds.

As the other (C) compound, a photopolymerizable ethylenically unsaturated compound can be used. Examples of such photo-polymerizable ethylenically unsaturated compounds include: A compound having one ethylenic double bond, a compound having two ethylenic double bonds, and a compound having three or more ethylenic double bonds.

Examples of the compound having one ethylenic double bond include a compound having (meth) acrylic acid added to one end of a polyalkylene oxide; and a (methyl group) added to one end of a polyalkylene oxide. ) Acrylic acid, and a compound obtained by etherifying or allyl ethering the other terminal alkyl group.

Examples of the compound having two ethylenic double bonds in the molecule include a compound having a (meth) acrylfluorenyl group at both ends of an alkylene oxide chain; and random randomization between an ethylene oxide unit and a propylene oxide unit. Compounds with (meth) acrylfluorenyl groups at both ends of alkylene oxide chains bonded by alternating, alternating, or block methods; (methyl) at both ends of alkylene oxide-modified bisphenol A ) Acrylic fluorenyl compounds and the like.

Among these, a compound having a (meth) acrylfluorenyl group at both ends of the alkylene oxide-modified bisphenol A is preferred from the viewpoint of resolvability and adhesion. Examples of the alkylene oxide modification include ethylene oxide modification, propylene oxide modification, butylene oxide modification, pentylene oxide modification, and hexane oxide modification. More preferred is a compound having (meth) acrylfluorenyl groups at both ends of bisphenol A modified with ethylene oxide.

A compound having three or more ethylenic double bonds in the molecule can be obtained, for example, by adding a compound having 3 mol or more of an alkylene oxide-based group as a central skeleton, and adding the compound. Alkyloxy groups such as ethoxy, propoxy, and butoxy, and the obtained alcohol is made into (meth) acrylate. In this case, examples of the compound that can serve as a central skeleton include glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, and a compound having an isocyanurate ring.

Specific examples of the compound having three or more ethylenic double bonds in the molecule include polypropylene glycol di (meth) acrylate, polyethylene glycol (meth) acrylate, and 2-di (P-hydroxyphenyl) propane (meth) acrylate, glyceryl tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyoxypropyltrimethylolpropane tri (methyl) Acrylate, polyoxyethyltrimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylpropane triglycidyl ether tri (methyl) Acrylate), phenoxy polyethylene glycol (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, and the like.

The other (C) compounds may be used alone or in combination of two or more.

When the mass of all solid components in the photosensitive resin composition is set to 100% by mass, the compounding amount of the compound (C) having an ethylenic double bond in the photosensitive resin composition is 5 to 50% by mass. Setting the blending amount to 5 mass% or more is based on the viewpoint of improving sensitivity, resolution, and adhesiveness. On the other hand, setting the blending amount to 50 mass% or less is based on the viewpoint of suppressing edge fusion and suppressing hardening resistance Etching of peeling retardation. The blending amount is more preferably 25 to 45% by mass.

In the case where (C) the compound having an ethylenic double bond includes the compound represented by the formula (III), the compounding amount of the compound is set to 100% by mass of the total solid component content of the photosensitive resin composition In this case, it is preferably 2 mass% or more and 40 mass% or less, more preferably 5 mass% or more and 30 mass% or less, and still more preferably 10 mass% or more and 20 mass% or less.

When the compound having an ethylenic double bond (C) includes the compound represented by the formula (IV), the compounding amount of the compound is set to 100% by mass of the total solid component content of the photosensitive resin composition. In this case, it is preferably 2 mass% or more and 40 mass% or less, more preferably 5 mass% or more and 30 mass% or less, and still more preferably 10 mass% or more and 20 mass% or less.

In the case where (C) the compound having an ethylenic double bond includes the compound represented by the formula (VI), the compounding amount of the compound is set to 100% by mass of the total solid component content of the photosensitive resin composition In this case, it is preferably set to 2% by mass or more and 40% by mass or more. Hereinafter, it is more preferably 5 mass% or more and 30 mass% or less, and still more preferably 10 mass% or more and 20 mass% or less.

<Hygrochrome, fluorescent yellow matrix dye, coloring substance>

The photosensitive resin composition of the present invention may contain one or more selected from the group consisting of a leuco dye, a fluorescent yellow matrix dye, and a coloring substance. When the photosensitive resin composition contains these components, the exposed portion develops color. Therefore, it is preferable from the viewpoint of visibility. Furthermore, when a registration mark for exposure is read by an inspection machine or the like, it is also advantageous from the viewpoint of increasing the contrast between the exposed portion and the unexposed portion and making it easy to identify.

Examples of the leuco dye include tris (4-dimethylaminophenyl) methane [crypto crystal violet], bis (4-dimethylaminophenyl) phenylmethane [leuco malachite green], and the like . In particular, from the viewpoint of improving the contrast, it is preferable to use leuco crystal violet as the leuco dye.

When the mass of all solid components of the photosensitive resin composition is 100% by mass, the content of the leuco dye in the photosensitive resin composition is preferably 0.1 to 10% by mass. From the viewpoint of improving the contrast between the exposed portion and the unexposed portion, the content is preferably set to 0.1% by mass or more. The content is more preferably 0.2% by mass or more, and still more preferably 0.3% by mass or more. On the other hand, from the viewpoint of maintaining the storage stability of the photosensitive resin composition and the viewpoint of suppressing the generation of aggregates during development, the content is preferably 10% by mass or less. The content is more preferably 5% by mass or less, and still more preferably 1% by mass or less.

Examples of the coloring substance include magenta, phthalocyanine green, golden amine base, para-magenta, crystal violet, methyl orange, Nero Blue 2B, Victoria Blue, and Malachite Green (manufactured by Hodogaya Chemical Co., Ltd. (Registered trademark) MALACHITE GREEN), basic blue 20, diamond green (manufactured by Hodogaya Chemical Co., Ltd., Aizen (registered trademark) DIAMOND GREEN GH), etc.

When the total solid content of the photosensitive resin composition is 100% by mass, the content of the coloring substance in the photosensitive resin composition is preferably 0.001% to 1% by mass. From the viewpoint of improving the operability, the content is preferably set to 0.001% by mass or more. On the other hand, from the viewpoint of maintaining storage stability, the content is preferably 1% by mass or less.

<Halogen compound>

In the photosensitive resin composition of this embodiment, a leuco dye is used in combination with the following halogen compound, and it is preferable from a viewpoint of adhesiveness and contrast.

Examples of the halogen compound include bromopentane, bromoisopentane, 1,2-dibromo-2-methylpropane, 1,2-dibromoethane, diphenylbromomethane, benzyl bromide, and diphenyl bromide. Methyl bromide, tribromomethylphenylphosphonium, carbon tetrabromide, tris (2,3-dibromopropyl) phosphate, trichloroacetamide, iodopentane, iodoisobutane, 1,1,1- Trichloro-2,2-bis (p-chlorophenyl) ethane, trichloride Compounds etc. Especially preferred is tribromomethylphenylphosphonium. For example, the halogen compound of tribromomethylphenylphosphonium has a greater effect when used in combination with an acridine-based compound, which improves the resolution, the adhesion, the sensitivity, the contrast, the puncture resistance of the cover film and the inhibition It is preferable from the viewpoint of the generation of the foot of the resist and improvement of the etching resistance.

From the viewpoints described above, it is preferable that the content of the halogen compound in the photosensitive resin composition is 0.01% by mass when the mass of the entire solid content of the photosensitive resin composition is 100% by mass. The content is more preferably 0.1% by mass or more, still more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more. From the viewpoint of maintaining the storage stability of the hue in the photosensitive layer and the viewpoint of suppressing the generation of aggregates during development, the content is preferably 3% by mass or less. The content is more preferably 2% by mass or less, and still more preferably 1.5% by mass or less.

<Free radical polymerization inhibitor, benzotriazoles, carboxybenzotriazoles>

In this embodiment, in order to improve the thermal stability and storage stability of the photosensitive resin composition, the photosensitive resin composition may further contain a member selected from the group consisting of a radical polymerization inhibitor, benzotriazoles, and carboxybenzotris. At least one compound in a group consisting of azoles.

Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, biphenol, cuprous chloride, 2,6 -Two-section Tributyl-p-cresol, 2,2'-methylenebis (4-methyl-6-third butylphenol), 2,2'-methylenebis (4-ethyl-6-section Tributylphenol), 4,4'-thiobis (6-third-butyl-m-cresol), 4,4'-butylenebis (3-methyl-6-third-butylphenol), 1 , 1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, styrenated phenol (for example, manufactured by Kawaguchi Chemical Industry Co., Ltd. under the trade name "Antage SP"), Tribenzylphenol (for example, manufactured by Kawaguchi Chemical Industry Co., Ltd. under the trade name "TBP", a phenol compound having 1 to 3 benzyl groups), aluminum nitrosophenylhydroxylamine, diphenylnitrosamine, etc. .

Examples of the benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, and bis (N-2-ethylhexyl) amino Methyl-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, bis (N-2-hydroxyethyl) ) Aminomethylene-1,2,3-benzotriazole and the like.

Examples of the carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N- (N, N-di 2-ethylhexyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, N- (N, N -Di-2-ethylhexyl) amino vinyl carboxybenzotriazole and the like.

Regarding the total content of the radical polymerization inhibitor, benzotriazoles, and carboxybenzotriazoles, the total content of the solid resin component of the photosensitive resin composition is set to 100% by mass. The total is preferably 0.01 to 3% by mass, and more preferably 0.05 to 1% by mass. From the viewpoint of imparting storage stability to the photosensitive resin composition, the content is preferably 0.01% by mass or more. On the other hand, from the viewpoint of maintaining sensitivity and suppressing discoloration of the dye, it is preferably The content is set to 3% by mass or less.

<Plasticizer>

The photosensitive resin composition of this embodiment may contain a plasticizer as needed. Examples of the plasticizer include polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, Polyoxyethylene monoethyl ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether and other glycol esters; Phthalates such as diethyl phthalate; o-Tosylamide, p-Tosylsulfonamide, tributyl citrate, triethyl citrate, ethyl ethyl triethyl citrate, ethyl acetate Tri-n-propyl citrate, tri-n-butyl ethoxylate, etc .; propylene glycol with propylene oxide added to both ends of bisphenol A, and ethylene oxide with bisphenol A added to both ends Glycol, etc.

These can be used alone or in combination of two or more.

In particular, from the viewpoint of improving the peeling characteristics, from the viewpoint of less deterioration of the resolution and adhesion, from the viewpoint of suppressing the occurrence of the resist foot portion, from the viewpoint of improving the flexibility of the cured film, and improving the puncture resistance of the cover film From a viewpoint, it is preferable to use p-toluenesulfonamide as a plasticizer.

Regarding the content of the plasticizer in the photosensitive resin composition, when the mass of all solid components in the photosensitive resin composition is 100% by mass, it is preferably 1 to 50% by mass, and more preferably 1 to 30% by mass. %. From the viewpoint of suppressing the delay of the development time and imparting flexibility to the cured film, the content is preferably 1% by mass or more. On the other hand, from the viewpoint of suppressing insufficient curing and edge melting, it is more preferred. The content is set to 50% by mass or less.

<Solvent>

The photosensitive resin composition can be dissolved in a solvent and used as a solution. Examples of the solvent to be used include ketones typified by methyl ethyl ketone (MEK, Methyl Ethyl Ketone); alcohols typified by methanol, ethanol, and isopropanol.

The solvent is preferably added to the photosensitive resin composition so that the viscosity of the solution of the photosensitive resin composition applied on the supporting film becomes 500 to 4,000 mPa · s at 25 ° C.

<Characteristics of photosensitive resin composition>

The photosensitive resin composition of this embodiment is formed on the surface of a substrate The photosensitive resin layer with a thickness of 25 μm of the photosensitive resin composition is exposed by using a Stuffer 21-level exposure meter as a mask, and then the maximum residual film level at the time of development is an exposure amount of 6 for the photosensitive resin layer. When performing exposure, the average number of ethylenic double bonds in the compound (C) is set to Q, and the reaction rate of the ethylenic double bonds in the compound (C) after the exposure is set to P. In this case, the value of P × Q / 100 is preferably 0.7 or more.

This necessary condition is a preferable necessary condition for sufficiently reacting the ethylenic double bond in the hardened resist pattern to achieve a sufficient crosslink density, and to suppress the occurrence of the resist foot portion in the weakly exposed area. In order to suppress the occurrence of the resist foot as much as possible, the value of the above P × Q / 100 is more preferably 1.0 or more, more preferably 1.5 or more, even more preferably 1.7 or more, particularly preferably 2.0 or more, and most preferably 2.5. the above. On the other hand, after the circuit pattern is formed, in order to easily peel off the used resist pattern, the value of the P × Q / 100 is more preferably 5.0 or less, even more preferably 4.0 or less, and even more preferably 3.5 or less.

From the same viewpoint as described above, a photosensitive resin layer having a thickness of 25 μm including the photosensitive resin composition of the present embodiment is formed on the substrate surface, and exposure is performed using a Stuffer 21-level exposure meter as a mask, followed by When the maximum residual film level at the time of development becomes 1/10 of the 6th level of exposure, when the photosensitive resin layer is exposed, the average number of vinylic double bonds in the compound (C) is set as Q, and the value of P ′ × Q / 100 when the reaction rate of the ethylenic double bond in the (C) compound after the exposure is set to P ′ is preferably 0.3 or more. The exposure amount at this time is a value considering the exposure amount of the weakly exposed area. From the same viewpoint as above, the value of the above-mentioned P '× Q / 100 is more preferably 0.5 or more, more preferably 0.7 or more, still more preferably 1.0 or more, still more preferably 1.3 or more, and even more preferably 1.6 or more. , The best is 1.9 or more; more preferably 5.0 or less, even more preferably 3.0 or less, and even more preferably 2.5 or less.

When the transmittance at 405 nm (h-ray) when the polyethylene film of the photosensitive resin laminate is peeled off is less than 65%, the above-mentioned value of P × Q / 100 is based on direct drawing using h-rays The measurement was performed under exposure conditions of an exposure machine. When the transmittance at 405 nm (h-ray) is 65% or more when the polyethylene film of the photosensitive resin laminated body is peeled off, the value of the P × Q / 100 is based on the exposure using an i-ray direct drawing exposure machine. The measurement was performed under the conditions.

The above-mentioned value of P '× Q / 100 was measured under the exposure conditions of an exposure machine using an ultra-high pressure mercury lamp.

<Photosensitive resin laminated body>

The photosensitive resin composition of the present invention can be used to form a photosensitive resin laminate. Typically, the photosensitive resin laminate has a support film and a photosensitive resin layer containing the above-mentioned photosensitive resin composition laminated on the support film. This photosensitive resin laminated body may have a protective layer on the surface opposite to a support film side as needed.

As the supporting film, it is preferable to be transparent to transmit the light emitted from the exposure light source. Examples of such a support film include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, Polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film, etc. These films can also be used if necessary.

The haze of the supporting film is preferably 5 or less.

The thickness of the supporting film is advantageous in terms of image formation and economy, but if the function of maintaining strength is also considered, it is preferably 10 to 30 μm.

An important characteristic of the protective layer used in the photosensitive resin laminated body is that it has appropriate adhesion. That is, it is preferable that the adhesion of the protective layer to the photosensitive resin layer is sufficiently smaller than the adhesion of the support film to the photosensitive resin layer, and that the protective layer can be easily peeled from the photosensitive resin laminate. As the protective layer, for example, a polyethylene film, a polypropylene film, and a film having excellent peelability disclosed in Japanese Patent Laid-Open No. Sho 59-202457 can be used.

The film thickness of the protective layer is preferably 10 to 100 μm, and more preferably 10 to 50 μm.

The thickness of the photosensitive resin layer in the photosensitive resin laminate varies depending on the application. Same, but preferably 5 to 100 μm, and more preferably 7 to 60 μm. The smaller the thickness of the photosensitive resin layer, the higher the resolution, and the thicker the film strength, the higher the film strength.

<Production method of photosensitive resin laminated body>

The photosensitive resin laminated body can be produced by sequentially laminating a photosensitive resin layer and a protective layer as necessary on a support film. As a method thereof, a known method can be adopted. For example, the photosensitive resin composition used in the photosensitive resin layer is mixed with the dissolved solvent to form a uniform solution-like coating liquid. Then, the coating liquid may be applied on a support film using a bar coater or a roll coater, followed by drying, and a photosensitive resin layer containing a photosensitive resin composition may be laminated on the support film. Then, a protective layer is laminated on this photosensitive resin layer as needed, whereby a photosensitive resin laminated body can be manufactured.

<Circuit pattern formation method>

Another embodiment of the present invention provides a method for forming a circuit pattern, which includes the steps of forming a layer of the photosensitive resin composition of the present invention (a lamination step) on a substrate, and applying the photosensitive resin composition The layer is subjected to exposure and development to form a resist pattern (exposure step and development step), and a step (etching step or plating step) of etching or plating the substrate on which the resist pattern is formed.

Preferably, it further comprises the peeling step which peels a resist pattern from a laminated body after the said series of steps.

In a preferred aspect, the layer of the photosensitive resin composition is formed using the above-mentioned photosensitive resin laminate.

Hereinafter, an example of the photosensitive resin laminated body and the method of forming a circuit pattern using a copper foil laminated board as a board | substrate is demonstrated.

(1) Laminating step

This is a step of peeling the protective layer of the photosensitive resin composition on a substrate such as a copper foil laminated board, a flexible substrate, or the like, using a hot-roller bonding machine to make it adhere to it.

(2) Exposure steps

The photosensitive resin composition layer formed on the substrate is a step of exposing the mask film having a desired wiring pattern through the mask film in a state in which the mask film has a desired wiring pattern. The step of exposing a desired wiring pattern, or the step of exposing by a projection method of projecting a mask image through a lens.

The advantages of the photosensitive resin composition of this embodiment are more prominent in a direct imaging exposure method using direct drawing of a wiring pattern or an exposure method in which a mask image is projected through a lens. In particular, it is particularly significant, so it is preferable to use a direct imaging exposure method in the exposure step.

(3) Development step

It is a step of forming a resist pattern on a substrate after removing the support on the photosensitive resin layer and developing and removing the unexposed portion using a developing solution of an alkaline aqueous solution after the exposure step.

As the alkaline aqueous solution, an aqueous solution of Na ₂ CO ₃ or K ₂ CO ₃ can be used. The alkaline aqueous solution is appropriately selected depending on the characteristics of the photosensitive resin layer, and it is preferable to use an aqueous Na ₂ CO ₃ solution having a concentration of about 0.2 to 2% by mass and a temperature of about 20 to 40 ° C.

A resist pattern can be obtained through the above steps. Depending on the situation, after these steps, a heating step of about 1 minute to 5 hours can be performed at about 100 ° C to 300 ° C. By implementing this heating step, the adhesiveness or chemical resistance of the obtained hardened resist pattern can be further improved. In this case, for example, a heating furnace using hot air, infrared, or far-infrared can be used for heating.

(4) Etching step or plating step

By performing the substrate surface exposed by development (such as the copper surface of a copper foil laminate) Etching or plating to make a conductor pattern.

In the case of the etching step, the resist pattern formed through the above steps is sprayed with an etchant from above, and the copper surface not covered by the resist pattern is etched to form a desired circuit pattern. . Examples of the etching method include acid etching and alkaline etching. The etching method is performed by a method suitable for the photosensitive resin laminate to be used.

(5) Stripping step

After that, the laminated body is treated with an aqueous solution having an alkalinity stronger than that of the developing solution, and the resist pattern is peeled from the substrate. There is no particular limitation on the alkaline aqueous solution for peeling. Generally, an aqueous solution of NaOH or KOH with a concentration of about 2 to 5 mass% and a temperature of about 40 to 70 ° C is used. A small amount of a water-soluble solvent may be added to the peeling solution.

[Example]

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.

First, a method for preparing evaluation samples of Examples and Comparative Examples will be described, and then evaluation methods and evaluation results related to the obtained samples will be shown.

(1) Evaluation of alkali-soluble polymers <Measurement of weight average molecular weight>

The weight average molecular weight of the polymer is determined in the form of a polystyrene conversion value using Gel Permeation Chromatography (GPC, manufactured by JASCO Corporation). The equipment configuration and the reagents used are as follows.

Pump: made by Gulliver, PU-1580

Column: made by Showa Denko Co., Ltd., 4 Shodex (registered trademark) KF-807, KF-806M, KF-806M, and KF-802.5 are connected in series and used

Mobile layer solvent: tetrahydrofuran

Calibration curve: prepared using a polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Denko Corporation)

(2) Preparation method of evaluation samples

The evaluation samples in the examples and comparative examples were prepared as follows.

<Production of photosensitive resin laminated body>

The components shown in the following Table 1 (where the numbers in each component column indicate the blending amount (parts by mass) in terms of solid components) and the solvent are sufficiently mixed to prepare a photosensitive resin composition.物 调 液。 Mixing liquid. To the photosensitive resin composition blending liquids of Examples 1 to 19 and Comparative Examples 1 to 8, 0.05 parts by mass of diamond green as a coloring substance and the components described in Table 1 were added; as a leuco dye 0.6 parts by mass of leuco crystal violet; 1- (2-di-n-butylaminomethyl) -5-carboxybenzotriazole and 1- (2-di-n-butylamine) as benzotriazoles Methylmethyl) -6-carboxybenzotriazole in a 1: 1 (mass ratio) mixture of 0.2 parts by mass; 0.05 parts by mass of diglycidyl ether of hydrogenated bisphenol A as an antioxidant; addition of a radical polymerization inhibitor 0.004 parts by mass of an aluminum salt of 3 moles of nitrosophenylhydroxylamine; and 2 parts by mass of p-toluenesulfonamide as a plasticizer.

0.7 parts by mass of tribromomethylphenylfluorene as a halogen compound was further added to the photosensitive resin composition preparation liquids other than Comparative Examples 1 and 2.

In the photosensitive resin composition preparation liquids of Examples 20 to 26, 28 to 44, and Comparative Examples a, 9 to 12, except for those described in Table 1, the above-mentioned additional components were not formulated.

In addition, all the photosensitive resin composition preparation liquids further contain a carry-in solvent derived from an alkali-soluble polymer solution prepared in the preparation liquid, or a solvent added to adjust the concentration.

A 16 μm-thick polyethylene terephthalate film (manufactured by Teijin Dupont Films Co., Ltd., GR-16) was used as a support film, and each of the preparations described above was evenly coated using a bar coater on its surface. The prepared solution was dried in a dryer at 95 ° C. for 2.5 minutes to form a photosensitive resin composition layer. The dry thickness of the photosensitive resin composition layer was adjusted to 25 μm. Then, on the surface of the photosensitive resin composition layer (and polyterephthalic acid) On the surface of the opposite side of the ethylene glycol film), a 19 μm-thick polyethylene film (manufactured by Tamapoly Co., Ltd., GF-18) was laminated as a protective layer, thereby obtaining a photosensitive resin laminate.

In Table 2 below, the names of the components indicated by abbreviations in Table 1 are disclosed.

<Substrate surface treatment>

A copper foil laminate having a thickness of 0.4 mm and a rolled copper foil having a thickness of 35 μm was used as an evaluation substrate for imageability, resist width, etching properties, and peeling time. This substrate was processed with CPE-900 (registered trademark, manufactured by Lingjiang Chemical Co., Ltd.), and then the surface was cleaned with 10% by mass of H ₂ SO ₄ , and then rinsed with pure water before being used.

<Laminate>

The polyethylene film of the photosensitive resin laminated body was peeled off, and the copper foil laminated board which had been surface-treated and preheated at 60 ° C was heated on a roll by a hot roll laminator (manufactured by Asahi Kasei Co., Ltd., AL-700). Lamination was performed at a temperature of 105 ° C to obtain laminated bodies for various evaluations. The air pressure system was set to 0.35 MPa, and the lamination speed was set to 1.5 m / min.

Evaluations other than those specifically described in the following evaluation methods are performed on samples prepared under the conditions described in the items of the various evaluation methods using the laminated body. General operation methods of exposure, development, etching, and peeling are described below.

<Exposure>

For exposures other than the following "(x) P '× Q / 100", a direct drawing exposure machine (Hitachi Via Mechanics Co., Ltd., DE-1DH, light source: GaN blue-violet diode (dominant wavelength 405 ± 5nm)), using a Stoffe 21-level exposure meter or a mask pattern for specific DI exposure, exposure was performed at an illumination of 80 mW / cm ² . This exposure is performed by using the above-mentioned Stoffe 21-level exposure meter as a mask to perform exposure, and the highest residual film level at the time of development is an exposure amount of 6 levels.

For substrates used to evaluate items other than the width of the resist foot, align the position of the focal point during exposure with the surface of the substrate. For the substrate for evaluating the width of the resist foot portion, the position of the focal point at the time of exposure was shifted from the surface of the substrate in the thickness direction of the substrate to the inside of the substrate by 200 μm.

<Development>

After peeling the polyethylene terephthalate film of the evaluation substrate subjected to exposure as described above, the temperature was adjusted to a concentration of 1 mass at 30 ° C using an alkaline developing machine (manufactured by Fujikiko, a developing machine for dry film) After spraying a Na ₂ CO ₃ aqueous solution at a specific time for a specific time, pure water is sprayed for a specific time and washed with water, and the unexposed portion of the photosensitive resin layer is dissolved and removed to produce a hardened resist pattern.

The development time and the water washing time are set to twice the minimum development time, respectively.

The minimum development time is the minimum time required to completely dissolve the photosensitive resin layer in the unexposed portion.

<Etch>

A copper chloride etching device (manufactured by Tokyo Chemical Industry Co., Ltd., a copper chloride etching device) was used on the evaluation substrate on which the hardened resist pattern was formed by the above development, and sprayed for a period of 1.3 times the minimum etching time. The copper chloride etching solution adjusted to 50 ° C. was used to dissolve and remove the copper foil on the copper foil laminate plate from the portion not covered with the resist pattern.

The copper chloride etching solution is a solution in which the concentration of copper chloride is 250 g / L and the concentration of hydrochloric acid is 3 mol / L. The so-called minimum etching time refers to the time required until the copper foil on the substrate is completely dissolved and removed.

<Stripping>

The cured resist pattern was peeled by spraying a 3% by mass sodium hydroxide aqueous solution adjusted to 50 ° C. on the evaluation substrate after the above-mentioned etching was performed.

(3) Evaluation method of samples

Next, the evaluation method of the sample will be described.

(i) Sensitivity evaluation

Sensitivity evaluation substrate for 15 minutes after lamination, with a 21-step exposure chart Mask for exposure. Then, the development is performed at a time twice as long as the minimum development time.

While changing the exposure amount, the above operation was repeated, and the exposure amount at which the highest residual film level became 6 steps was investigated.

Regarding Examples 1 to 19 and Comparative Examples 1 to 8, the exposure amount in which the above-mentioned highest residual film level became 6 levels was classified according to the following criteria.

○ (Good): In the case where the highest residual film level is 6 levels, the exposure amount does not reach 20 mJ / cm ²

× (defective): when the highest residual film level is 6 and the exposure is 20mJ / cm ² or more

Regarding Examples 20 to 26, 28 to 44, and Comparative Examples a, 9 to 12, the values of the exposure amounts in which the above-mentioned highest residual film levels are 6 steps are described in the first table. In the applications assumed in these examples, when the exposure is 70 mJ or less, it can be evaluated as a good sensitivity, preferably 40 mJ or less, more preferably 30 mJ or less, and even more preferably 20 mJ or less.

(ii) Evaluation of resolution (1)

For the evaluation substrate that had passed 15 minutes after lamination, a pattern of lines and gaps that became a ratio of 1: 1 between the width of the exposed portion and the unexposed portion was exposed. Then, development is performed at a development time which is twice the minimum development time, and a hardened resist pattern is obtained. The minimum mask line width of the lines and gap patterns in the hardened resist pattern was normally formed.

Regarding Examples 1 to 19 and Comparative Examples 1 to 8, the above-mentioned minimum mask line width values were classified according to the following criteria.

○ (Good): When the minimum mask line width is 25 μm or less

△ (Possible): When the minimum mask line width exceeds 25 μm and is less than 30 μm

× (defective): when the minimum mask line width exceeds 30 μm

Regarding Examples 20 to 26, 28 to 44, and Comparative Examples a, 9 to 12, the values of the minimum mask line widths are described in the first table. In the applications assumed in these examples, when the minimum mask line width is 60 μm or less, it can be evaluated as good resolution (1), preferably 35 μm or less, more preferably 25 μm or less, and further preferably 20 μm. Hereinafter, it is particularly preferably 16 μm or less.

(iii) Resolution evaluation (2)

Regarding some of the examples and comparative examples, in addition to the resolution evaluation (1) of (ii) above, the resolution evaluation of the positive independent demolding was also performed.

That is, the unexposed part was exposed as a pattern of gaps about the evaluation substrate 15 minutes after lamination. Then, development is performed with a development time which is 2 times the minimum development time to obtain a hardened resist pattern. At this time, the value of the minimum gap width of the gap in which the unexposed portions are normally formed is set to the value of the resolution (positive independent release).

When the minimum gap width is 45 μm or less, it can be evaluated that the resolution (2) is good, preferably 35 μm or less, more preferably 30 μm or less, still more preferably 25 μm or less, and even more preferably 20 μm or less.

(iv) Tightness evaluation

For the evaluation substrate that had passed 15 minutes after lamination, the exposed portion was exposed as a line pattern. Then, development is performed with a development time which is 2 times the minimum development time to obtain a hardened resist pattern. Investigate the smallest mask line width where the hardened resist line is normally formed.

Regarding Examples 1 to 19 and Comparative Examples 1 to 8, the above-mentioned minimum mask line width is classified according to the following criteria.

○ (Good): When the minimum mask line width is 25 μm or less

△ (Possible): When the minimum mask line width exceeds 25 μm and is less than 30 μm

× (defective): when the minimum mask line width exceeds 30 μm

Regarding Examples 20 to 26, 28 to 44, and Comparative Examples a, 9 to 12, the values of the minimum mask line widths are described in the first table. In the applications assumed in these examples, when the minimum mask line width is 70 μm or less, it can be evaluated as good adhesion, preferably 30 μm or less, more preferably 25 μm or less, and even more preferably 20 μm or less. It is particularly preferably 10 μm or less.

(v) Evaluation of resist foot width

For the evaluation substrate 15 minutes after lamination, a pattern of lines and gaps having a ratio of 1: 1 between the width of the exposed portion and the unexposed portion was exposed. During exposure, the position of the focal point during exposure is shifted from the surface of the substrate in the thickness direction of the substrate to the inside of the substrate by 200 μm. By With this measure, the weakly exposed area at the end of the exposure pattern is enlarged, and it is easy to compare the width of the resist foot portion.

After developing the exposed substrate at a development time twice as long as the minimum development time, the exposed portion of the copper base material of the substrate was subjected to soft etching for 60 seconds by using a 200 g / L ammonium persulfate aqueous solution to obtain an evaluation resistance. Etching foot width sample. A scanning electron microscope (made by Hitachi High-Technologies, S-3400 N) was used to observe the line pattern portion of the sample at a ratio of 1: 1 of L / S = 45 μm / 45 μm to obtain the skirt shape of the line pattern. The width of the bottom part.

Regarding Examples 1 to 19 and Comparative Examples 1 to 8, this value was set as the line width of the resist, and graded by the following criteria:

◎ (Excellent): When the width of the foot of the resist is 1.5 μm or less

○ (Good): When the width of the foot of the resist exceeds 1.5 μm and is 2.5 μm or less

△ (Possible): When the width of the resist foot portion exceeds 2.5 μm and is 3.5 μm or less

× (defective): When the width of the resist foot portion exceeds 3.5 μm

Regarding Examples 20 to 26, 28 to 44 and Comparative Examples a, 9 to 12, the values of the width of the resist foot portions are described in the first table. In the applications assumed in these examples, when the value of the width of the foot of the resist is 10 μm or less, it can be evaluated as good adhesion, preferably 3 μm or less, more preferably 2.5 μm or less, and further preferably It is 2 μm or less, more preferably 1.5 μm or less, and particularly preferably 1 μm or less.

For a method of measuring the width of the resist foot portion, refer to FIG. 1.

(vi) Etching evaluation

For the evaluation substrate 15 minutes after lamination, a pattern of lines and gaps having a ratio of 1: 1 between the width of the exposed portion and the unexposed portion was exposed. This is developed with a development time that is twice the minimum development time, and after etching is performed at a time that is 1.3 times the minimum etching time, the hardened resist pattern is peeled off with an aqueous sodium hydroxide solution, thereby obtaining a conductor pattern. The conductor pattern was observed with an optical microscope (manufactured by Nikon, MM-800), and the Shape, and graded by:

○ (Good): The conductor pattern was formed linearly, and no fluctuations or infiltration of the etching solution were seen.

△ (Possible): The conductor pattern is formed linearly, but the penetration of the etching solution is slightly visible

× (defective): At least one of a case where a conductor pattern is not formed linearly, and a case where penetration of an etchant is clearly visible

(vii) Evaluation of developer foamability

The photosensitive resin laminated body produced in the above-mentioned "Production of the photosensitive resin laminated body" was cut into an area of 0.048 m ² , and the photosensitive resin layer after the protective layer and the supporting film were peeled off was immersed in 120 ml of 1% by mass Na ₂ CO ₃ aqueous solution to obtain a solution in which a resin layer is dissolved. This solution was added to a gas absorption tank with a capacity of 500 ml, and a nitrogen gas of 6000 ml / min passed through a glass filter of G3 was passed. The time taken for the generated bubbles to overflow from the gas absorption tank was measured, and the results were ranked according to the following criteria.

◎ (Excellent): No overflow in 100 seconds

○ (Good): In case of overflow within 30 seconds and within 100 seconds

× (Bad): In case of overflow within 30 seconds

(viii) Pressurized flow test

The photosensitive resin laminated body produced in the above-mentioned "Production of the photosensitive resin laminated body" was cut into a 2.5 cm square, the protective layer was peeled off, and it was sandwiched in the center of a 10 cm square polyethylene film. A force of 100 kg was applied for 5 minutes by an oil hydraulic press heated to 40 ° C. Then, the overflow width of the photosensitive resin layer was measured in 4 directions (8 points), and the average value was calculated | required. This test was performed with n = 2, and the average value of n = 2 was calculated, and this average value was made into the value of a pressure flow test.

It is known from experience that if the value is large, edge melting is likely to occur, and essentially, it cannot be stably laminated on the substrate during lamination.

(ix) P × Q / 100

When the polyethylene film of the photosensitive resin laminate was peeled, the transmittance at 405 nm (h-ray) was less than 65% in all Examples and Comparative Examples. Therefore, the value of P × Q / 100 is measured under exposure conditions using a direct-drawing exposure machine using h-rays.

From the side of the polyethylene terephthalate film (supporting layer) of the photosensitive resin laminate produced in the above-mentioned "Production of the photosensitive resin laminate", a direct drawing exposure machine (manufactured by Hitachi Via Mechanics Co., Ltd., DE-1DH, light source: GaN blue-violet diode (main wavelength: 405 ± 5nm)), direct imaging exposure. At this time, the position of the focal point at the time of exposure is aligned with the bottom of the resist. The illuminance at the time of exposure was set to 80 mW / cm ² . The exposure amount at this time is performed by the method described above, using the Stoffe 21-level exposure meter as a mask, and then performing the exposure with a maximum residual film level of 6 during development (normal exposure).

FT-IR (Fourier Transform Infrared Radiation, Fourier Transform Infrared Spectroscopy) (Thermo SCIENTIFIC, NICOLET 380) was used to obtain the reaction rate P of the ethylenic double bond of the hardened resist obtained by the above operation. The peak height at a wavenumber of 810 cm ^-1 was measured, and the value was set to the amount of the ethylenic double bond.

The average number (the number of functional groups) of the ethylenic double bonds in the compound (C) was calculated, and this value was set to Q. When the compound (C) is a mixture of a plurality of compounds, Q is determined in consideration of the content of each component.

From the above P and Q, the value of P × Q / 100 is obtained.

(x) P '× Q / 100

From the polyethylene terephthalate film (support layer) of the photosensitive resin laminate produced in the above-mentioned "Production of the photosensitive resin laminate" , an ultra-high pressure mercury lamp (manufactured by Oak Manufacturing Co., Ltd., HMW-801) was used. Make an exposure. The exposure amount is performed at an exposure amount (rounded to the nearest decimal point) of 1/10 of the exposure amount in the above ((ix) P × Q / 100>). Other than that, the reaction rate P ′ of the ethylenic double bond of the hardened resist in 1/10 exposure (weak exposure) was determined by FT-IR in the same manner as described above.

Based on this P 'value and the value of Q calculated by the same method as above, the value of P' × Q / 100 at the time of weak exposure was obtained.

(xi) Hue stability of the blending solution of the photosensitive resin composition

Using an ultraviolet-visible light (UV-Vis) measuring device (manufactured by Hitachi High-Technologies Co., Ltd., U-3010 type spectrophotometer), the transmittance of 630 nm of the photosensitive resin laminate was measured as follows:

(i) The polyethylene film of the photosensitive resin laminate was peeled to measure the transmittance at 630 nm, and the obtained value was set as the initial transmittance (T _in ).

(ii) A photosensitive resin laminate was prepared by using a photosensitive resin composition preparation solution stored at 40 ° C for 3 days, and the polyethylene film of the photosensitive resin laminate was peeled to measure the transmittance at 630 nm. The value is set as the transmittance (T _af ) after storage.

Excellent phase stability is obtained by the following formula: T _af -T _in .

(xii) Stripping time

A 15 cm × 6 cm rectangular pattern was exposed to the evaluation substrate 15 minutes after lamination. Then, development is performed with a development time which is 2 times the minimum development time to obtain a hardened resist pattern.

The hardened resist pattern on the substrate obtained by this operation was immersed in a 50 ° C, 2% by mass aqueous NaOH solution, and the time until the resist was completely peeled from the substrate was measured, and this was set as the peeling time.

(xiii) Hardened film flexibility

The photosensitive resin laminate was laminated on NIKAFLEX F-30VC1 25C1 1/2 (manufactured by NIKKAN INDUSTRIES), and a pattern having a width of 2.5 cm and a length of 30 cm was exposed. Then, development was performed with a development time that was twice the minimum development time, and a short strip-shaped sample was prepared.

So that the substrate side and the diameter are 1, 2, 3, 4, 5, and 6mm The SUS sticks are erected separately by the way they are contacted. Then, the two ends of the short strip-shaped sample were held so that the bending angle became 90 degrees, and the short strip-shaped sample was rubbed back and forth 10 times.

At this time, the diameter of the largest SUS rod without cracks formed on the resist surface was investigated, and the grade was classified as follows.

○ (Good): at 4mm No cracks formed

△ (possible): if it is 4mm A crack is formed, but if it is 5mm No cracks are formed

(xiiv) Covering film puncture and ductility

A photosensitive resin laminate was laminated on both sides of a base material including a 1.6 mm-thick copper foil laminate having an opening portion having a diameter of 6 mm, and the entire surface of both sides was exposed. Then, development is performed with a development time that is twice the minimum development time to obtain a hardened resist pattern.

Then, using a cylinder with an insertion diameter of 1.5 mm, the puncture strength and ductility of the film in the opening portion of the substrate were measured using Tensilon (RTM-500 manufactured by Orientec).

(3) Evaluation results

The evaluation results of Examples and Comparative Examples are shown in Table 1.

Table 2 shows the names of the components indicated by abbreviations in Table 1. All the alkali-soluble polymers shown in Table 2 were prepared as methyl ethyl ketone solutions having a solid component concentration as described in the table, and were supplied to the preparation. The abbreviations in the functional group type column of the compound having an ethylenic double bond in Table 2 have the following meanings.

A: Acrylate

MA: methacrylate group

Table 3 shows the glass transition temperature (document value) of each monomer used in the synthesis of the alkali-soluble resin when each is made into a homopolymer.

[Industrial availability]

The photosensitive resin composition of this embodiment, and a photosensitive resin laminate, a resist pattern, and a circuit pattern manufactured using the same can be suitably used for the production of printed wiring boards, flexible printed wiring boards, and IC chip mounting leads. Manufacture of frames, metal masks, semiconductor packages such as BGA or CSP, tape substrates such as TAB or COF, semiconductor bumps, ITO electrodes, address electrodes, electromagnetic wave shields, etc.

Claims (24)

A photosensitive resin composition, characterized in that when the mass of all solid components of the photosensitive resin composition is 100% by mass, it contains (A) an alkali-soluble polymer: 40 to 80% by mass, (B) Photopolymerization initiator: 0.1 to 20% by mass, and (C) Compound having an ethylenic double bond: 5 to 50% by mass; a photosensitive resin having a thickness of 25 μm including the photosensitive resin composition is formed on a substrate surface Layer, the width of the resist foot of the resist pattern obtained by exposing and developing under the condition that the position of the focal point during exposure is shifted from the surface of the substrate to the inside of the substrate by 200 μm in the thickness direction of the substrate is 0.01 μm ~ 3.5μm; and a photosensitive resin layer with a thickness of 25μm containing the above-mentioned photosensitive resin composition is formed on the surface of the substrate, and exposure is performed using a Stuffer 21-level exposure meter as a mask, followed by the highest residual film level during development When the photosensitive resin layer is exposed to an exposure amount of 6 levels, the average number of vinylic double bonds in the compound (C) is set to Q, and the compound (C) after the exposure is performed. Reaction of Ethylene Double Bonds When the case of P is set to the value of P × Q / 100 of more than 0.7; and system for direct imaging exposure. For example, the photosensitive resin composition according to claim 1, wherein a photosensitive resin layer having a thickness of 25 μm containing the above-mentioned photosensitive resin composition is formed on the substrate surface, and exposure is performed using a Stufe 21-level exposure meter as a mask, and then When the maximum residual film level at the time of development becomes 1/10 of the 6th level of exposure, when the photosensitive resin layer is exposed, the average number of vinylic double bonds in the compound (C) is set as Q, and the value of P ′ × Q / 100 when the reaction rate of the ethylenic double bond in the compound (C) after the exposure is set to P ′ is 0.3 or more. The photosensitive resin composition according to claim 1 or 2, wherein the compound (C) includes a compound having three or more methacrylfluorenyl groups in one molecule. The photosensitive resin composition according to claim 1 or 2, wherein the compound (C) includes a compound having four or more methacryl groups in one molecule. The photosensitive resin composition according to claim 1 or 2, wherein the compound (C) includes a compound represented by the following general formula (IV), {In the formula, n ₁ , n ₂ , n ₃ , and n ₄ each independently represent an integer of 1 to 25, n ₁ + n ₂ + n ₃ + n ₄ is an integer of 9 to 60, and R ₁ , R ₂ , R ₃ , and R ₄ each independently represent an alkyl group, and R ₅ , R ₆ , R ₇ , and R ₈ each independently represent an alkylene group. In the case where a plurality of R ₅ , R ₆ , R ₇ , and R ₈ exist, respectively The plurality of R ₅ , R ₆ , R ₇ , and R ₈ may be the same or different from each other}. The photosensitive resin composition according to claim 5, wherein in the general formula (IV), n ₁ + n ₂ + n ₃ + n ₄ is an integer of 15 to 40. The photosensitive resin composition according to claim 5, wherein in the formula (IV), n ₁ + n ₂ + n ₃ + n ₄ is an integer of 15 to 28. The photosensitive resin composition according to claim 1 or 2, wherein the (B) photopolymerization initiator contains an acridine-based compound. The photosensitive resin composition according to claim 1 or 2, further comprising a halogen compound. The photosensitive resin composition according to claim 1 or 2, wherein the (B) photopolymerization initiator comprises N-phenylglycine or a derivative thereof. The photosensitive resin composition according to claim 1 or 2, wherein the (A) alkali-soluble polymer has an aromatic hydrocarbon group. A photosensitive resin composition, characterized in that when the mass of all solid components of the photosensitive resin composition is 100% by mass, it contains (A) an alkali-soluble polymer: 40 to 80% by mass, (B) Photopolymerization initiator: 0.1 to 20% by mass, and (C) Compound having an ethylenic double bond: 5 to 50% by mass, and the (C) compound contains 3 or more methacrylfluorenyl groups in one molecule And a photosensitive resin layer having a thickness of 25 μm containing the above-mentioned photosensitive resin composition is formed on the surface of the substrate, and exposure is performed using a Stufe 21-level exposure meter as a mask, and then the highest residual film level during development When the photosensitive resin layer is exposed to an exposure amount of 6 levels, the average number of vinylic double bonds in the compound (C) is set to Q, and the compound (C) after the exposure is performed. When the reaction rate of the ethylenic double bond is P, the value of P × Q / 100 is 0.7 or more. For example, the photosensitive resin composition of claim 12, wherein a photosensitive resin layer having a thickness of 25 μm containing the above-mentioned photosensitive resin composition is formed on the surface of the substrate, and exposure is performed using a Stufe 21-level exposure meter as a mask, followed by When the maximum residual film level at the time of development becomes 1/10 of the 6th level of exposure, when the photosensitive resin layer is exposed, the average number of vinylic double bonds in the compound (C) is set as Q, and the value of P ′ × Q / 100 when the reaction rate of the ethylenic double bond in the compound (C) after the exposure is set to P ′ is 0.3 or more. The photosensitive resin composition according to claim 12 or 13, wherein the compound (C) includes a compound having four or more methacryl groups in one molecule. The photosensitive resin composition according to claim 12 or 13, wherein the compound (C) includes a compound represented by the following general formula (IV), {In the formula, n ₁ , n ₂ , n ₃ , and n ₄ each independently represent an integer of 1 to 25, n ₁ + n ₂ + n ₃ + n ₄ is an integer of 9 to 60, and R ₁ , R ₂ , R ₃ , and R ₄ each independently represent an alkyl group, and R ₅ , R ₆ , R ₇ , and R ₈ each independently represent an alkylene group. In the case where a plurality of R ₅ , R ₆ , R ₇ , and R ₈ exist, respectively The plurality of R ₅ , R ₆ , R ₇ , and R ₈ may be the same or different from each other}. The photosensitive resin composition according to claim 15, wherein n ₁ + n ₂ + n ₃ + n ₄ is an integer of 15 to 40 in the formula (IV). The photosensitive resin composition according to claim 15, wherein n ₁ + n ₂ + n ₃ + n ₄ is an integer of 15 to 28 in the formula (IV). The photosensitive resin composition according to claim 12 or 13, wherein the (B) photopolymerization initiator includes an acridine-based compound. The photosensitive resin composition according to claim 12 or 13, further comprising a halogen compound. The photosensitive resin composition according to claim 12 or 13, wherein the (B) photopolymerization initiator comprises N-phenylglycine or a derivative thereof. The photosensitive resin composition according to claim 12 or 13, wherein the (A) alkali-soluble polymer has an aromatic hydrocarbon group. The photosensitive resin composition according to claim 12 or 13, which is used for direct imaging exposure. A method for forming a circuit pattern, comprising the steps of: forming a layer of a photosensitive resin composition as claimed in claim 1 or 12 on a substrate; and forming the layer of the photosensitive resin composition by exposing and developing the layer. A step of resist pattern; and a step of etching or plating the substrate on which the resist pattern is formed. The method of claim 23, wherein the exposure is performed by direct imaging exposure.