CN111694218B

CN111694218B - Photosensitive resin composition and method for forming circuit pattern

Info

Publication number: CN111694218B
Application number: CN202010587896.3A
Authority: CN
Inventors: 内藤一也; 松田隆之
Original assignee: Asahi Kasei Corp
Current assignee: Asahi Kasei Corp
Priority date: 2014-05-21
Filing date: 2015-05-21
Publication date: 2023-09-08
Anticipated expiration: 2035-05-21
Also published as: KR20190092622A; CN111694218A; JP6470805B2; TWI623814B; JP2017223993A; CN106462068A; JPWO2015178462A1; TWI660241B; KR20210102494A; KR20160131084A; CN106462068B; KR20220148301A; TW201820036A; WO2015178462A1; TWI570513B; TW201602729A; TW201708959A

Abstract

A photosensitive resin composition and a method for forming a circuit pattern are provided. A photosensitive resin composition characterized by comprising: (A) alkali-soluble polymer: 40 to 80 mass percent, (B) photopolymerization initiator: 0.1 to 20% by mass, and (C) a compound having an olefinic double bond: 5 to 50 mass% of a photosensitive resin layer having a thickness of 25 [ mu ] m formed from the photosensitive resin composition is formed on a substrate surface, and a resist layer hem width of a resist pattern obtained by exposing and developing the substrate surface with a focus position at the time of exposure shifted from the substrate surface to the inside of the substrate in the thickness direction of the substrate is 0.01 [ mu ] m to 3.5 [ mu ] m, and the photosensitive resin composition is used for direct image exposure.

Description

Photosensitive resin composition and method for forming circuit pattern

The present application is a divisional application of application having application date of 2015, 05, 21, application number of 2015125748. X and application name of photosensitive resin composition and method for forming circuit pattern.

Technical Field

The present application relates to a photosensitive resin composition that can be developed with an aqueous alkaline solution, and a method for forming a circuit pattern using the photosensitive resin composition. More specifically, the present application relates to precision machining of metal foil for manufacturing a printed circuit board, manufacturing a flexible printed circuit board, manufacturing a lead frame for mounting an IC chip, manufacturing a metal mask, and the like; semiconductor package fabrication such as BGA (ball grid array), CSP (chip size package); manufacturing of tape-like substrates represented by TAB (tape automated bonding ) and COF (Chip On Film: a Film On which a semiconductor IC is mounted On a Film-like fine circuit board); manufacturing a semiconductor bump; a photosensitive resin composition for imparting an appropriate resist pattern for the production of ITO electrodes, address electrodes, electromagnetic wave shields and other members in the field of flat panel displays, and a method for forming a circuit pattern using the photosensitive resin composition.

Background

Conventionally, printed circuit boards, precision machining of metals, and the like have been manufactured by photolithography. Photosensitive resin compositions used in photolithography are classified into negative type compositions and positive type compositions. The photolithography method using the negative photosensitive resin composition is performed, for example, as follows:

a negative photosensitive resin composition is applied on a substrate, and pattern exposure is performed to polymerize and cure an exposed portion of the photosensitive resin composition. Then, the unexposed portions are removed with a developer to form a resist pattern on the substrate. Further, after the conductor pattern is formed by etching or plating, the resist pattern is peeled off from the substrate, and the conductor pattern is formed on the substrate.

For the photolithography, when the photosensitive resin composition is coated on a substrate, any of the following methods may be used:

(1) A method of applying a photoresist solution on a substrate and drying the same; and

(2) A method of laminating a photosensitive resin layer on a substrate using a photosensitive resin laminate in which a support, a layer formed of a photosensitive resin composition (hereinafter referred to as a "photosensitive resin layer"), and a protective layer laminated as necessary are laminated in this order. The latter method is mostly used in the manufacture of printed circuit boards.

Hereinafter, a method for manufacturing a printed wiring board using the photosensitive resin laminate will be briefly described.

First, the protective layer is peeled from the photosensitive resin laminate. Next, using a laminator, the photosensitive resin layer and the support are laminated on a substrate such as a copper-clad laminate in this order. Then, the photosensitive resin layer is exposed through a photomask having a desired wiring pattern, and the exposed portion is polymerized and cured. Then, the support is peeled off. Then, the unexposed portions of the photosensitive resin layer are dissolved or dispersed and removed by a developer, thereby forming a resist pattern on the substrate.

As the protective layer, for example, a polyethylene film or the like is preferably used;

as the support, for example, a polyethylene terephthalate film or the like is preferably used;

as the developer, for example, an aqueous solution having weak alkalinity is preferably used.

The step of dissolving or dispersing and removing the photosensitive resin layer in the unexposed portion by the developer is referred to as a developing step. The amount of dissolution of the unexposed portion of the photosensitive resin composition in the developer increases each time the developing process is repeated. Therefore, when the developing process is repeated, foamability of the developer tends to be high. The foamability of the developer significantly reduces the working efficiency in the developing process.

Then, etching treatment or pattern plating treatment is performed using the resist pattern formed by the development step as a protection mask. Finally, the resist pattern is peeled off from the substrate, thereby manufacturing a substrate (i.e., a printed circuit board) having a conductor pattern.

In recent years, with miniaturization and weight reduction of electronic devices, miniaturization and higher density of wiring lines/spaces (L/S) are advancing. Further, the demand for a laminated substrate (Build up substrate) having a multilayer wiring structure is also increasing. In the lamination process, a technique for accurately aligning the positions of the multilayer substrates is required, and thus a photosensitive resin layer to which a Direct Imaging (DI) method having excellent alignment accuracy can be applied is becoming a mainstream. Therefore, the photosensitive resin is required to have high sensitivity and high resolution.

In this regard, patent documents 1 and 2 describe photosensitive resin compositions containing a specific alkali-soluble polymer, a specific monomer, and a photopolymerization initiator, and describe that the above-mentioned high sensitivity and high resolution can be achieved by the photosensitive resin compositions. Patent document 3 reports that polyalkylene glycol is used as an additive for a photosensitive resin composition in order to suppress foamability of a developer.

Prior art literature

Patent literature

Patent document 1: international publication No. 2009/147913

Patent document 2: international publication No. 2010/098175

Patent document 3: japanese patent application laid-open No. 2012-159551

Disclosure of Invention

Problems to be solved by the invention

In order to cope with the miniaturization and densification of wiring, it is required to stably realize the finishing line width of the etched wire (e.g., copper wire). For this reason, the resist width after development needs to be stable. However, a slight skirt extension phenomenon called "resist skirt" is often seen at the bottom of the developed resist (see fig. 1). The presence of the resist bottom mark is a factor of fluctuation in the width of the etched conductive line. In addition, the presence of the resist layer skirt also significantly affects the adhesion of the resulting conductor pattern to the substrate in the method of manufacturing a conductor pattern by the pattern plating process. These phenomena are remarkable particularly in the DI type exposure system used in recent years, and are a new problem that arises with the progress of technology.

The mechanism by which the generation of resist layer runout becomes remarkable in DI exposure is considered as follows. The present invention is not limited to the following theory.

DI exposure is a method of performing exposure by scanning a laser focus. The irradiation intensity of the laser focus is based on gaussian distribution. Therefore, regions with a small exposure amount (weak exposure regions) are generated at both end portions of the exposure pattern. Since the cured resist layer in the weak exposure region has reduced developer resistance, it is partially dissolved in the subsequent development step. It is considered that the dissolved residue at this time is precipitated and deposited on the bottom of the resist, and thus a resist bottom swing is generated.

This faint exposure area is a particular problem for DI using multiple exposures of the focus. More importantly, the width of the weak light region is determined to be a fixed value, so the narrower the design line width is, the more obvious the problem is. In order to improve the resolution, manufacturers of exposure machines have made efforts to improve the laser focal diameter and the resolution between focal points. However, in reality, the performance of the exposure machine does not meet the specifications required for increasingly high-performance printed circuit boards.

In addition, patent document 3 (japanese patent application laid-open No. 2012-159551) discloses a method of adding a polyalkylene glycol as an antifoaming agent to a photosensitive resin composition in order to suppress foamability in a developing process. However, according to the technique of patent document 3, since the density of the monomer is reduced by the addition of the defoaming agent, photopolymerization efficiency by exposure tends to be lowered, and sensitivity tends to be lowered.

Accordingly, an object of the present invention is to provide a photosensitive resin composition for direct imaging, which is excellent in stability of a width of a wire after etching, adhesion of a wire after plating, or both, and a method for forming a circuit pattern using the photosensitive resin composition.

Solution for solving the problem

The present inventors have conducted intensive studies to solve the above problems and repeated experiments. As a result, the present invention has been completed by finding that the above problems can be solved by the following technical means.

The present invention discloses the following embodiments.

[1] A photosensitive resin composition characterized by comprising:

(A) Alkali-soluble polymer: 40 to 80 mass percent,

(B) Photopolymerization initiator: 0.1 to 20 mass%, and

(C) Compounds having an olefinic double bond: 5 to 50 mass percent,

a photosensitive resin layer having a thickness of 25 μm formed from the photosensitive resin composition is formed on the surface of a substrate,

the resist pattern obtained by exposing and developing the substrate with the position of the focus at the time of exposure shifted from the substrate surface to the inside of the substrate in the thickness direction of the substrate has a resist layer skirt width of 0.01 to 3.5 μm,

The photosensitive resin composition is used for direct image exposure.

[2] The photosensitive resin composition according to the above [1], wherein when a photosensitive resin layer having a thickness of 25 μm formed from the above photosensitive resin composition is formed on a surface of a substrate, the photosensitive resin layer is exposed with an exposure amount having a highest residual film level of 6 levels when the exposure is performed with a Sichuan-type 21 exposure rule as a mask and then development is performed,

the average number of olefinic double bonds in the compound (C) is Q, and the P X Q/100 value is 0.7 or more when the reaction rate of olefinic double bonds in the compound (C) after the exposure is P.

[3] The photosensitive resin composition according to the above [1] or [2], wherein when a photosensitive resin layer having a thickness of 25 μm formed from the above photosensitive resin composition is formed on a substrate surface, the photosensitive resin layer is exposed to an exposure of 1/10 of the exposure amount having the highest residual film level of 6 levels when the exposure is performed with a Situff 21 level exposure scale as a mask and then development is performed,

the average number of olefinic double bonds in the compound (C) is Q, and the P '. Times.Q/100 value is 0.3 or more when the reaction rate of olefinic double bonds in the compound (C) after the exposure is P'.

[4]According to the above [1]]～[3]The photosensitive resin composition according to any one of (A) wherein the alkali-soluble polymer has a Tg of weight average value Tg ^total Is 30 ℃ to 125 ℃.

[5] The photosensitive resin composition according to any one of [1] to [4], wherein the compound (C) contains a compound having 3 or more methacryloyl groups in one molecule.

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

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

{ in n ₁ 、n ₂ 、n ₃ And n ₄ Each independently represents an integer of 1 to 25, n ₁ +n ₂ +n ₃ +n ₄ Is an integer of 9 to 60, and the number of the components is equal to 9,

R ₁ 、R ₂ 、R ₃ and R is ₄ Each independently of the other represents an alkyl group,

R ₅ 、R ₆ 、R ₇ and R is ₈ Each independently represents an alkylene group, R ₅ 、R ₆ 、R ₇ And R is ₈ When there are plural R ₅ 、R ₆ 、R ₇ And R is ₈ Same or different }.

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

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

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

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

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

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

[14] A photosensitive resin composition characterized by comprising:

(A) Alkali-soluble polymer: 40 to 80 mass percent,

(B) Photopolymerization initiator: 0.1 to 20 mass%, and

(C) Compounds having an olefinic double bond: 5 to 50 mass percent,

the compound (C) contains a compound having 3 or more methacryloyl groups in one molecule.

[15] The photosensitive resin composition according to item [14], wherein when a photosensitive resin layer having a thickness of 25 μm formed from the above-mentioned photosensitive resin composition is formed on the surface of a substrate, the photosensitive resin layer is exposed to light with an exposure amount having a highest residual film level of 6 levels when the exposure is performed with a Sichuan-type 21 exposure rule as a mask and then development is performed,

[16] The photosensitive resin composition according to [14] or [15], wherein when a photosensitive resin layer having a thickness of 25 μm formed from the above photosensitive resin composition is formed on a substrate surface, the photosensitive resin layer is exposed to light with an exposure amount of 1/10 of the exposure amount having the highest residual film level of 6 levels when the exposure is performed with a Situff 21 level exposure scale as a mask and then development is performed,

[17] The photosensitive resin composition according to any one of [14] to [16], wherein the compound (C) contains a compound having 4 or more methacryloyl groups in one molecule.

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

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

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

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

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

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

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

[25]According to the foregoing [14]]～[24]The photosensitive resin composition according to any one of (A) wherein the alkali-soluble polymer has a Tg of weight average value Tg ^total Is 30 ℃ to 125 ℃.

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

[27] A method of forming a circuit pattern, comprising:

a step of forming a layer of the photosensitive resin composition according to any one of the above [1] to [26] on a substrate;

exposing and developing the layer of the photosensitive resin composition to form a resist pattern; and

and etching or plating the substrate on which the resist pattern is formed.

[28] The method according to the aforementioned [27], wherein the aforementioned exposure is performed by direct image-wise exposure.

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention can provide a photosensitive resin composition which is excellent in stability of the width of a wire (e.g., copper wire) after etching and adhesion of the wire after plating by suppressing occurrence of a resist layer runout and which is applicable to a circuit pattern formation by a direct imaging method, and a method for forming a circuit pattern using the photosensitive resin composition.

Drawings

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

Detailed Description

Hereinafter, embodiments (hereinafter, simply referred to as "embodiments") for carrying out the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.

< photosensitive resin composition >

One embodiment provides a photosensitive resin composition (photosensitive resin composition for direct image-wise exposure), comprising:

(A) Alkali-soluble polymer: 40 to 80 mass percent,

(B) Photopolymerization initiator: 0.1 to 20 mass%, and

(C) Compounds having an olefinic double bond: 5 to 50 mass percent,

the photosensitive resin composition is used for direct image exposure.

Another embodiment provides a photosensitive resin composition, comprising:

(A) Alkali-soluble polymer: 40 to 80 mass percent,

(B) Photopolymerization initiator: 0.1 to 20 mass%, and

(C) Compounds having an olefinic double bond: 5 to 50 mass percent,

The photosensitive resin composition for direct image-wise exposure of the present disclosure is a composition for providing the above-described specific resist layer skirt width to a resist pattern obtained by exposure and development under the above-described conditions. A resist pattern having a resist layer of a photosensitive resin composition having a thickness of 25 μm is formed on the surface of a substrate, and the resist pattern is obtained by exposing and developing the substrate while moving the position of the focus at the time of exposure from the surface of the substrate to the inside of the substrate in the thickness direction of the substrate, and a resist layer skirt width of 0.01 to 3.5 μm is an important condition for reducing fluctuation in the width of a wire after etching and improving adhesion of a wire after plating. From the viewpoint of improving the adhesion of the cured resist, the width of the resist skirt is preferably 0.01 μm or more; this value is advantageously 3.5 μm or less from the viewpoint of reducing fluctuation in wire width after etching and from the viewpoint of improving adhesion of the wire after plating. The resist layer skirt width is preferably 0.02 μm or more, more preferably 0.03 μm or more, preferably 2.5 μm or less, more preferably 2.0 μm or less, further preferably 1.5 μm or less, particularly preferably 1.2 μm or less, and most preferably 1 μm or less.

More specific steps of the above-described exposure and development are based on the method described in the [ example ] item or a method equivalent thereto, which can be understood by those skilled in the art.

It is to be understood that the specific resist layer skirt width can be achieved by using the components (a) to (C) in specific ratios, for example, by the following exemplary method (not limited thereto). The components contained in the photosensitive resin composition according to the present embodiment will be described in order.

Alkali-soluble Polymer

The alkali-soluble polymer (a) of the present embodiment is a polymer that can be dissolved in an alkali aqueous solution. Examples thereof include: the vinyl polymer having a carboxyl group is preferably a copolymer of monomers selected from the group consisting of (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, and (meth) acrylamide.

(A) The alkali-soluble polymer preferably contains a carboxyl group and has an acid equivalent weight of 100 to 600. The acid equivalent means the mass in grams of the alkali-soluble polymer having 1 equivalent of carboxyl group therein. The acid equivalent is preferably set to 100 or more from the viewpoint of improving development resistance, resolution and adhesion, and is preferably set to 600 or less from the viewpoint of improving development property and releasability. The acid equivalent amount can be measured by a potentiometric titration method using a sodium hydroxide aqueous solution of 0.1mol/L using a titration apparatus (for example, a methane automatic titration apparatus (COM-555) manufactured by methane industry Co., ltd.). (A) The acid equivalent of the alkali-soluble polymer is more preferably 250 to 450.

(A) The weight average molecular weight of the alkali-soluble polymer is preferably 5000 to 500000. The weight average molecular weight is preferably 5000 or more from the viewpoint of the properties of the developed aggregate and the properties of the unexposed film such as edge fusibility and chipping property of the photosensitive resin laminate, and is preferably 500000 from the viewpoint of improving the solubility in the developer. Edge fusion is a property of suppressing a phenomenon in which a photosensitive resin composition layer is squeezed out from an end surface of a roll when a photosensitive resin laminate is wound into a roll. The chipability is a property of suppressing scattering of chips when an unexposed film is cut by a cutter. When the chip property is poor, the following problems occur: the scattered chips adhere to, for example, the upper surface of the photosensitive resin laminate, and the chips are transferred to the mask in the subsequent exposure step, which causes defects. (A) The weight average molecular weight of the alkali-soluble polymer is more preferably 5000 to 300000, still more preferably 10000 to 200000.

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

(A) The alkali-soluble polymer has an aromatic hydrocarbon group, which can provide advantages of improved resolution and adhesion, reduced generation of aggregates during development, and improved etching resistance.

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

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

The first monomer is a carboxylic acid or anhydride having one polymerizable unsaturated group in the molecule. Examples thereof include: (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half esters, and the like. (meth) acrylic acid is particularly preferred. Here, (meth) acryl means acryl or methacryl.

(A) The copolymerization ratio of the first monomer of the alkali-soluble polymer can be easily calculated from the desired acid equivalent value of the alkali-soluble polymer. (A) The copolymerization ratio of the first monomer of the alkali-soluble polymer is preferably 10 to 50 mass% based on the total mass of the total monomer components. From the viewpoint of exhibiting good developability, controlling edge fusion, and the like, it is preferable that the copolymerization ratio is 10 mass% or more. The copolymerization ratio is preferably 50 mass% or less from the viewpoint of improving resolution, suppressing occurrence of resist runout, and the like, more preferably 30 mass% or less, further preferably 25 mass% or less, and particularly preferably 20 mass% or less from the viewpoint of improving resolution.

The second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule. Examples thereof include: esters of methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, and vinyl alcohol; vinyl acetate; (meth) acrylonitrile; aromatic vinyl compounds, and the like. Examples of the aromatic vinyl compound include styrene and styrene derivatives.

As the second monomer, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene derivatives, and benzyl (meth) acrylate among the above are preferable. Among them, styrene derivatives, and benzyl (meth) acrylate are particularly preferable from the viewpoints of improvement of resolution, improvement of adhesion, good development aggregation (small amount of aggregate), and etching resistance.

As the copolymer component in the alkali-soluble polymer (a), an aromatic monomer such as an aromatic vinyl compound or a (meth) acrylate compound having a benzyl group can be used. (A) The copolymerization ratio of the aromatic monomer compound in the alkali-soluble polymer is preferably 20 to 85 mass% based on the total mass of the total monomer components. The copolymerization ratio is preferably 20 mass% or more, more preferably 25 mass% or more, still more preferably 30 mass% or more, particularly preferably 40 mass% or more, from the viewpoints of improving resolution and adhesion, suppressing the occurrence of aggregates during development, improving etching resistance, and the like. From the viewpoint of exhibiting proper developability, the copolymerization ratio is preferably 85 mass% or less. In view of cost, the aromatic vinyl compound is more preferable, and the copolymerization ratio of the copolymer component in the alkali-soluble polymer (a) is preferably 20 to 70 mass% based on the total mass of the total monomer components. The copolymerization ratio is preferably 20 mass% or more, more preferably 25 mass% or more, still more preferably 30 mass% or more, particularly preferably 40 mass% or more, from the viewpoints of improvement in resolution, improvement in adhesion, good development aggregation, etching resistance, and the like. From the viewpoint of proper developability and cured film flexibility, the copolymerization ratio is preferably 70 mass% or less, more preferably 60 mass% or less. In order to put these points into consideration, the copolymerization ratio of the aromatic vinyl compound is more preferably 20 to 50% by mass, and particularly preferably 20 to 30% by mass.

In one embodiment, examples of the aromatic vinyl compound include styrene and styrene derivatives. Examples of the styrene derivative include: styrene oxide, hydroxystyrene, acetoxystyrene, alkylstyrene, haloalkylstyrene, and the like.

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

Unlike the above, in order to obtain excellent resolution, the copolymerization ratio of the aromatic vinyl compound is preferably 40 to 60 mass% based on the total mass of the total monomer components. As the comonomer in this case, styrene or a styrene derivative is preferably contained, and methyl (meth) acrylate and/or (meth) acrylic acid are contained.

In one embodiment, the weight average Tg of the alkali-soluble polymer (A) in the photosensitive resin composition ^total The temperature may be in the range of 30 to 125 ℃, preferably 50 to 110 ℃, more preferably 50 to 105 ℃, and even more preferably 50 to 90 ℃. The weight average value of Tg is preferably 30 ℃ or higher from the viewpoint of controlling edge fusion properties, and is preferably 110 ℃ or lower from the viewpoint of controlling occurrence of resist runout. Weight average Tg of Tg in the present disclosure ^total Is a value obtained by the following equation (Fox equation):

Tg ^total ＝Σ _i (W _i ×Tg _i )/W ^total

{ here, W _i Is the solid mass of each alkali-soluble polymer,

Tg _i the glass transition temperature of each alkali-soluble polymer was determined by Fox formula,

W ^total is the total value of the solid mass of each alkali-soluble polymer }. Here, each was obtained from Fox formulaGlass transition temperature Tg of the alkali-soluble Polymer _i In this case, tg of a homopolymer formed from a comonomer which forms each alkali-soluble polymer is required. In the present disclosure, this value is obtained using literature values (Brandrup, J.Immergut, E.H., polymer handbook, third edition, john wiley&sons,1989,Chapter VI"Glass transition temperatures of polymers", page 209).

Tg of each comonomer used in the examples for calculation _i Shown in Table 4.

The following is considered as a mechanism for suppressing the resist runout at the time of DI exposure by using the alkali-soluble polymer (a) having the above composition. The present invention is not limited to the following theory.

In DI exposure, a weak exposure region appears on both sides of the exposure pattern. The reaction rate of the resist in the weak exposure area is reduced. As a result, the developer resistance of the cured resist layer in this region is lowered, and thus is partially dissolved in the subsequent development step. It is assumed that the dissolved residues at this time precipitate and accumulate at the bottom of the resist layer, thereby generating a resist layer skirt.

Therefore, in order to suppress the occurrence of the resist layer runout, it is considered necessary to efficiently cure the monomer in the resist even in the weak exposure region. It is considered that the reaction rate of the monomers is influenced by the diffusion rate of the monomers from each other, and the diffusion rate is governed by the free volume in the resist.

It is considered that the composition and structure of the alkali-soluble polymer (a) are designed so that the free volume in the resist layer increases, thereby improving the reaction rate of the monomer and suppressing the resist runout in the weak exposure region.

As an index of the free volume, a glass transition temperature Tg is generally used. Tg is the temperature at which the ratio of free volume to total volume of the polymer begins to increase. It is therefore believed that at temperatures above Tg, the free volume increases gradually in proportion to the temperature difference of Tg.

Under the same temperature conditions, the higher the Tg of the material, the smaller the free volume becomes, and the lower the Tg, the larger the free volume becomes. Therefore, it is considered that, with respect to a resist composition having a high Tg, the monomer reaction rate is easily lowered, and thus a resist composition having a low Tg can suppress the generation of a resist skirt.

For this reason, (A) weight average Tg of alkali-soluble polymer ^total Low is preferred, tg is the case if control of edge fusion is taken into account ^total High is preferred. Considering their balance of compatibility, the result is Tg ^total The preferable range of (2) may be exemplified by the above range.

In one embodiment, the amount of the alkali-soluble polymer (a) blended in the photosensitive resin composition is preferably in the range of 40 to 80 mass%, more preferably 50 to 70 mass%, based on 100 mass% of the total solid content of the photosensitive resin composition. The blending amount is preferably 40 mass% or more from the viewpoint of controlling edge fusion properties, and is preferably 80 mass% or less from the viewpoint of controlling development time.

Photopolymerization initiator (B)

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

As the photopolymerization initiator (B) of the present embodiment, for example, 1 or more selected from the group consisting of an acridine compound, an N-aryl- α -amino acid compound, and a triarylimidazole dimer can be used. From the viewpoint of exhibiting high sensitivity and also from the viewpoint of suppressing the occurrence of a runout in the resist layer, an acridine compound is preferable;

From the viewpoint of more reliably suppressing the occurrence of a runout in the resist layer, triarylimidazole dimer is preferable.

The acridine compound may be, for example: 1, 7-bis (9, 9' -acridinyl) heptane, 9-phenylacridine, 9-methylacridine, 9-ethylacridine, 9-chloroethyl acridine, 9-methoxyacridine, 9-ethoxyacridine, 9- (4-methylphenyl) acridine, 9- (4-ethylphenyl) acridine, 9- (4-n-propylphenyl) acridine, 9- (4-n-butylphenyl) acridine, 9- (4-methoxyphenyl) acridine, 9- (4-ethoxyphenyl) acridine, 9- (4-acetylphenyl) acridine, 9- (4-dimethylaminophenyl) acridine, 9- (4-chlorophenyl) acridine, 9- (4-bromophenyl) acridine, 9- (3-methylphenyl) acridine, 9- (3-tert-butylphenyl) acridine, 9- (3-dimethylphenyl) acridine, 9- (3-bromophenyl) acridine, 9- (2-pyridyl) acridine, 9- (3-pyridyl) acridine, 9- (4-pyridyl) acridine. Among them, 1, 7-bis (9, 9' -acridinyl) heptane or 9-phenylacridine is preferable from the viewpoints of sensitivity, resolution, availability, and the like.

Examples of the N-aryl- α -amino acid compound include: n-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, and the like. N-phenylglycine has a high sensitization effect, and is particularly preferable.

Examples of triarylimidazole dimers include: 2,4, 5-triarylimidazole dimers such as 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4, 5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer, and 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer.

The sensitivity of the acridine compound is higher than that of the triarylimidazole dimer compound. Further, when a urethane compound is used as the compound (C) having an olefinic double bond, it is preferable in that foaming property and development aggregation property can be simultaneously suppressed in combination therewith.

N-phenylglycine and its derivatives are preferred from the viewpoint of improvement in sensitivity. The N-phenylglycine or its derivative is particularly preferable in that the occurrence of resist layer runout can be more surely suppressed when the N-phenylglycine or its derivative is used in combination with an acridine compound.

For the preferred embodiment, the photopolymerization initiator (B) preferably contains 1 or more selected from the group consisting of acridine compounds, N-phenylglycine, and N-phenylglycine derivatives. The acridine compound preferably contains 1 or more selected from the group consisting of 9-phenylacridine represented by the following formula (I) and a compound represented by the following general formula (II):

(wherein R is ₁ An alkylene group having 1 to 12 carbon atoms).

These compounds are advantageous from the viewpoint of improving sensitivity at the time of DI exposure. From the standpoint of solubility, R in the general formula (II) ₁ The carbon number of (2) is advantageously 1 to 12. R is R ₁ More preferably 4 to 10.

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

As the photopolymerization initiator (B) of the present embodiment, only 1 or more selected from the group consisting of an acridine compound, N-phenylglycine or a derivative thereof, and triarylimidazole dimer may be used, and other photopolymerization initiators may be included.

Further examples of the photopolymerization initiator (B) include, for example: aromatic ketones such as benzophenone, N '-tetramethyl-4, 4' -dimethylaminobenzophenone (michler's ketone), N' -tetraethyl-4, 4 '-diaminobenzophenone, 4-methoxy-4' -dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone;

quinones such as 2-ethylanthraquinone, phenanthrenequinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1, 2-benzanthrone, 2, 3-benzanthrone, 2-phenylanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1, 4-naphthoquinone, 9, 10-phenanthrenequinone, 2-methyl-1, 4-naphthoquinone, and 2, 3-dimethylanthraquinone;

Benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether;

benzil derivatives such as benzilmethyl ketal;

coumarin-based compounds;

4,4' -bis (diethylamino) benzophenone;

pyrazoline derivatives such as 1-phenyl-3- (4-tert-butylstyryl) -5- (4-tert-butylphenyl) pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butylphenyl) pyrazoline, and 1-phenyl-3- (4-biphenyl) -5- (4-tert-octylphenyl) pyrazoline.

(B) The photopolymerization initiator may be used alone or in combination of 1 or more than 2.

When the total solid content mass of the photosensitive resin composition is 100 mass%, the blending amount of the photopolymerization initiator (B) in the photosensitive resin composition is 0.1 to 20 mass%. The blending amount is set to 0.1 mass% or more from the viewpoint of obtaining an exposure pattern having a sufficient residual film ratio after development, and is set to 20 mass% or less from the viewpoint of obtaining high resolution by sufficiently transmitting light to the bottom surface of the resist layer and from the viewpoint of suppressing development aggregation in the developer. The preferable range of the compounding amount is 0.3 to 10 mass%.

(B) When the photopolymerization initiator contains an acridine compound, the amount of the acridine compound to be blended is preferably 0.01 to 5% by mass based on the mass of the total solid content of the photosensitive resin composition. From the viewpoint of obtaining good sensitivity, the blending amount is preferably 0.01 mass% or more. The amount of the compound is more preferably 0.1 mass% or more, and particularly preferably 0.2 mass% or more. On the other hand, from the viewpoint of adjusting the resist layer shape to be rectangular and improving the hue stability of the photosensitive resin composition, the blending amount is preferably 5 mass% or less. The amount of the compound is more preferably 3% by mass or less, and particularly preferably 2% by mass or less.

(B) When the photopolymerization initiator contains an N-aryl- α -amino acid compound, the content of the N-aryl- α -amino acid compound is preferably 0.001 to 5% by mass relative to the mass of the total solid content of the photosensitive resin composition. From the viewpoint of obtaining good sensitivity, the blending amount is preferably 0.001 mass% or more. When the N-aryl- α -amino acid compound and the acridine compound are used in combination, the N-aryl- α -amino acid compound is particularly preferable in view of more reliably suppressing the occurrence of resist runout. The blending amount is more preferably 0.01 mass% or more, still more preferably 0.05 mass% or more, and particularly preferably 0.1 mass% or more. On the other hand, from the viewpoint of improving resolution and improving the hue stability of the photosensitive resin composition, the blending amount is preferably 5 mass% or less. The amount of the compound is more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

(B) When the photopolymerization initiator contains a triarylimidazole dimer, the content of the triarylimidazole dimer is preferably 0.1 to 15% by mass relative to the mass of the total solid content of the photosensitive resin composition. From the viewpoint of obtaining good sensitivity, the blending amount is preferably 0.1 mass% or more. The amount of the compound is more preferably 1% by mass or more, and particularly preferably 3% by mass or more. On the other hand, from the viewpoint of obtaining high resolution and suppressing aggregation in the developer, the blending amount is preferably 15 mass% or less. The amount of the compound is more preferably 10 mass% or less, and particularly preferably 6 mass% or less.

(C) Compounds having an olefinic double bond ]

In an embodiment of the present invention, the photosensitive resin composition contains (C) a compound having an olefinic double bond. Preferable examples of the compound include a compound (polyfunctional monomer) having a methacrylate group having 3 or more functions (having 3 or more methacryloyl groups in one molecule) and a molecular weight of 500g/mol or more and 5000g/mol or less. The compound (C) is more preferably a compound having a methacrylate group having 4 or more functions (having 4 or more methacryloyl groups in one molecule).

The mechanism by which the resist layer runout at the time of DI exposure can be suppressed by using the above-described (C) compound is considered as follows. The present invention is not limited to the following theory.

As described above, in DI exposure, a weak exposure region appears on both sides of the exposure pattern. Further, it is estimated that the reaction rate of the resist existing in the region is lowered, and thus the developer resistance is lowered, and the resist layer is lowered. Therefore, in order to suppress occurrence of the resist runout, it is necessary to increase the reaction rate of the compound (C) even in the weak exposure region to increase the crosslinking density and thereby improve the developer resistance.

In order to crosslink the resist, it is necessary to react one double bond in a certain polyfunctional monomer and then further react the other unreacted double bond in the same monomer. Therefore, the more double bonds the (C) compound has and the fewer unreacted double bonds remain after exposure, the greater the crosslink density.

However, the double bond reacted multifunctional monomer is absorbed into the high molecular weight growing polymer chain. Therefore, in order to react two or more double bonds in the multifunctional monomer molecule, it is necessary to react the double bonds pendant from the growing polymer chain with other monomers or the growing polymer. The steric hindrance of this reaction is large, which is disadvantageous. In order to alleviate the steric hindrance of such a reaction to promote the reaction, it is necessary to lengthen the length of the molecular chain between the double bonds in the compound (C). Therefore, the molecular weight of the compound (C) is preferably large. On the other hand, if the molecular weight is too large, the reaction rate of the double bond of the compound (C) increases, but the amount of the double bond in the composition decreases, and therefore, in this case, the crosslink density also decreases.

Therefore, it is considered that in order to suppress the resist runout at the time of DI exposure, a methacrylate monomer which is a high molecular weight body and has a large number of functional groups is particularly effective.

From such a viewpoint, the compound (C) of the present embodiment has an optimal molecular weight and number of functional groups. (C) The molecular weight of the compound is preferably 500g/mol or more and 5000g/mol or less, more preferably 600g/mol or more and 4000g/mol or less, and still more preferably 700g/mol or more and 3000g/mol or less.

The number of functional groups in the compound (C) is preferably 3 or more, more preferably 4 or more from the viewpoints of improving the crosslinking density, improving the resolution and the adhesion, and suppressing the occurrence of resist runout. From the viewpoint of suppressing edge fusion, it is preferably 3 or more functions, and more preferably 4 or more functions. From the viewpoint of the peeling property, it is preferably 10 or less functions, more preferably 6 or less functions, further preferably 5 or less functions, and particularly preferably 4 or less functions. Therefore, in order to improve resolution, suppress occurrence of resist runout, control of edge fusion, and peeling property at a high level, it is most preferable to use 4-functional.

In addition, from the viewpoint of developer resistance of the monomer cross-linked body, a methacrylate monomer having low hydrolyzability is effective. From the viewpoints of improvement of resolution and adhesion, suppression of occurrence of resist runout, and control of edge fusion property, the methacrylate monomer is preferable.

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

{ in n ₁ 、n ₂ And n ₃ Each independently is an integer of 1 to 25, wherein n ₁ +n ₂ +n ₃ Is an integer of 3 to 75,

R ₁ 、R ₂ and R is ₃ Each independently alkyl }.

In the general formula (V), n ₁ +n ₂ +n ₃ The value of (2) is preferably 3 to 50. From the viewpoint of suppressing occurrence of resist runout, imparting flexibility to the cured film, and improving puncture resistance (tent film puncture-resistance) of the support film, n is preferably used ₁ +n ₂ +n ₃ When the number is 3 or more, n is preferably selected from the viewpoint of obtaining high resolution, adhesion and good peeling property ₁ +n ₂ +n ₃ The value is 50 or less. n is n ₁ +n ₂ +n ₃ More preferably, the range of (2) is 6 to 40, and still more preferably, the range is 9 to 30.

Specific examples of the compound represented by the general formula (III) include:

a trimethacrylate obtained by adding an average of 3 moles of ethylene oxide to the hydroxyl end of trimethylolpropane,

A trimethacrylate obtained by adding 9 moles of ethylene oxide on average to the hydroxyl end of trimethylolpropane,

A trimethacrylate obtained by adding an average of 15 moles of ethylene oxide to the hydroxyl end of trimethylolpropane,

And trimethylol acrylate obtained by adding 30 moles of ethylene oxide to the hydroxyl end of trimethylolpropane.

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

{ in n ₁ 、n ₂ 、n ₃ And n ₄ Each independently represents an integer of 1 to 25, n ₁ +n ₂ +n ₃ +n ₄ Is an integer of 4 to 100,

In the general formula (IV), n ₁ +n ₂ +n ₃ +n ₄ Preferably 9 to 60 inclusive. From the viewpoint of suppressing occurrence of resist runout, improving puncture resistance of the support film, and imparting flexibility to the cured film, n is preferably selected from the viewpoint of ₁ +n ₂ +n ₃ +n ₄ Set to 9 or more, the otherIn terms of improving resolution and adhesion, obtaining good peeling properties, and controlling edge fusion, n is preferably used ₁ +n ₂ +n ₃ +n ₄ The ratio is 60 or less. Further, n ₁ +n ₂ +n ₃ +n ₄ More preferably 9 to 40, still more preferably 15 to 40, and particularly preferably 15 to 28.

R as in the formula (IV) ₅ 、R ₆ 、R ₇ And R is ₈ The monomer may be 1, 2-ethylene, 1, 2-propylene, butylene, or the like, and 1, 2-ethylene is preferable from the viewpoint of imparting flexibility to the cured film, from the viewpoint of improving puncture resistance of the support film, from the viewpoint of suppressing development aggregation, and from the viewpoint of improving reactivity of the olefinic double bond. Therefore, as the compound represented by the general formula (IV), a compound represented by the following general formula (V) is preferable:

[ wherein n ₁ 、n ₂ 、n ₃ And n ₄ Each independently is an integer of 1 to 25, wherein n ₁ +n ₂ +n ₃ +n ₄ Is an integer of 4 to 100,

R ₁ 、R ₂ 、R ₃ and R is ₄ Each independently alkyl }. n is n ₁ +n ₂ +n ₃ +n ₄ The preferred ranges of (a) are the same as those described above.

Specific examples of the compound represented by the general formula (IV) include, for example: :

a tetramethyl acrylate obtained by adding 9 moles of ethylene oxide to the hydroxyl end of pentaerythritol,

A tetramethyl acrylate obtained by adding an average of 12 moles of ethylene oxide to the hydroxyl end of pentaerythritol,

A tetramethyl acrylate obtained by adding an average of 15 moles of ethylene oxide to the hydroxyl end of pentaerythritol,

A tetramethyl acrylate obtained by adding an average of 20 moles of ethylene oxide to the hydroxyl end of pentaerythritol,

Tetramethyl acrylate obtained by adding an average of 28 moles of ethylene oxide to the hydroxyl end of pentaerythritol,

And tetramethyl acrylate obtained by adding an average of 35 moles of ethylene oxide to the hydroxyl end of pentaerythritol.

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

{ in which R ₃ And R is ₄ Each independently is a hydrogen atom or a methyl group;

n ₉ and n ₁₁ Each independently is an integer of 0 to 20, and n ₉ +n ₁₁ Is an integer of 0 to 20;

n ₈ and n ₁₀ Each independently is an integer of 1 to 20, and n ₈ +n ₁₀ Is an integer of 2 to 20;

-(C ₂ H ₄ o) -and- (C ₃ H ₆ The arrangement of the repeating units of O) -being random or block, - (C) ₂ H ₄ O) -and- (C ₃ H ₆ O) -may also be bonded to bisphenol structure }.

In the general formula (VI), n ₈ +n ₉ +n ₁₀ +n ₁₁ Preferably 2 or more and 40 or less. From the viewpoint of obtaining flexibility of the cured film, n is preferably selected from ₈ +n ₉ +n ₁₀ +n ₁₁ When the number is 2 or more, n is preferably selected from the viewpoint of obtaining resolution ₈ +n ₉ +n ₁₀ +n ₁₁ Is set to 40 or less. Furthermore, in order to obtain chemical resistance, n ₈ +n ₉ +n ₁₀ +n ₁₁ More preferably in the range of 4 to 20, still more preferably in the range of 6 to 12And (3) downwards. In addition, n is for obtaining covering property ₈ +n ₉ +n ₁₀ +n ₁₁ More preferably, the range of (2) is 16 to 40, and still more preferably, the range is 30 to 40. n is n ₉ +n ₁₁ Is an integer of 1 to 20, n ₈ +n ₁₀ More preferably an integer of 2 to 20.

Specific examples of the compound represented by the general formula (VI) include, for example: :

an average of 2 moles of ethylene oxide was added to each of the two ends of bisphenol A to give ethylene glycol dimethacrylate,

An average of 5 moles of ethylene oxide was added to each of the two ends of bisphenol A to give ethylene glycol dimethacrylate,

A dimethacrylate of an alkylene glycol obtained by adding an average of 6 moles of ethylene oxide and an average of 2 moles of propylene oxide to both ends of bisphenol A,

And an alkylene glycol dimethacrylate which is an alkylene glycol dimethacrylate obtained by adding an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide to both ends of bisphenol A.

In one embodiment, the photosensitive resin composition may contain other compounds (C) in addition to the compounds having an olefinic double bond, which are represented by the general formulae (III), (IV) and (VI) above.

As the other compound (C), an ethylenically unsaturated compound which can be photopolymerized can be used. Examples of such photopolymerizable ethylenically unsaturated compounds include compounds having 1 olefinic double bond, compounds having 2 olefinic double bonds, and compounds having 3 or more olefinic double bonds.

Examples of the compound having 1 olefinic double bond include a compound obtained by adding (meth) acrylic acid to one end of a polyalkylene oxide;

And a compound in which one end of a polyalkylene oxide is added with (meth) acrylic acid and the other end is etherified with an alkyl group or an allyl group.

Examples of the compound having 2 olefinic double bonds in the molecule include compounds having (meth) acryloyl groups at both ends of an alkylene oxide chain;

a compound having (meth) acryloyl groups at both ends of an alkylene oxide chain obtained by bonding an ethylene oxide unit and a propylene oxide unit randomly, alternately or in blocks;

and compounds having (meth) acryloyl groups at both ends of bisphenol A modified with alkylene oxide.

Among them, a compound having (meth) acryloyl groups at both ends of bisphenol a modified with an alkylene oxide is preferable from the viewpoints of resolution and adhesion. Examples of the alkylene oxide modification include: ethylene oxide modification, propylene oxide modification, butylene oxide modification, pentylene oxide modification, hexylene oxide modification, and the like. More preferred is a compound having (meth) acryloyl groups at both ends of bisphenol A modified with ethylene oxide.

The compound having 3 or more olefinic double bonds in the molecule can be obtained, for example, as follows:

as the central skeleton, a compound having 3 or more moles of a group capable of adding an alkylene oxide group in the molecule is used, and an alkylene oxide group such as an ethyleneoxy group, propyleneoxy group, butyleneoxy group or the like is added to the compound to obtain an alcohol, and a (meth) acrylate is produced from the alcohol. In this case, examples of the compound capable of forming a central skeleton include: glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, a compound having an isocyanurate ring, and the like.

Specific examples of the compound having 3 or more olefinic double bonds in the molecule include: polypropylene glycol di (meth) acrylate, polyethylene glycol (meth) acrylate, 2-di (p-hydroxyphenyl) propane (meth) acrylate, glycerol tri (meth) acrylate, trimethylol tri (meth) acrylate, polyoxypropylene trimethylol propane tri (meth) acrylate, polyoxyethylene trimethylol propane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylpropane triglycidyl ether tri (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, and the like.

The other compounds (C) may be used alone or in combination of 2 or more.

When the total solid content mass of the photosensitive resin composition is set to 100 mass%, the blending amount of the compound (C) having an olefinic double bond in the photosensitive resin composition is 5 to 50 mass%. The blending amount of 5 mass% or more is based on the viewpoint of improving sensitivity, resolution and adhesion, while the blending amount of 50 mass% or less is based on the viewpoint of suppressing edge fusion and the viewpoint of suppressing peeling delay of the cured resist. The amount of the compound is more preferably 25 to 45 mass%.

(C) When the compound having an olefinic double bond contains a compound represented by the above formula (III), the amount of the compound to be blended 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, based on 100 mass% of the total solid content of the photosensitive resin composition.

(C) When the compound having an olefinic double bond contains the compound represented by the above formula (IV), the amount of the compound to be blended 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, based on 100 mass% of the total solid content of the photosensitive resin composition.

(C) When the compound having an olefinic double bond contains the compound represented by the above formula (VI), the amount of the compound to be blended is preferably 2% by mass or more and 40% by mass or less, more preferably 5% by mass or more and 30% by mass or less, and still more preferably 10% by mass or more and 20% by mass or less, based on 100% by mass of the total solid content of the photosensitive resin composition.

< leuco dye, fluoran-based dye, coloring matter >

The photosensitive resin composition of the present invention may contain 1 or more selected from leuco dyes, fluoran dyes, and coloring materials. The photosensitive resin composition contains these components, whereby the exposed portion develops color. Therefore, it is preferable from the viewpoint of visibility. Further, it is also advantageous in that the contrast between the exposed portion and the unexposed portion is increased and the alignment mark for exposure is easily recognized when the alignment mark is read by an inspection machine or the like.

Examples of the leuco dye include tris (4-dimethylaminophenyl) methane [ leuco crystal violet ], bis (4-dimethylaminophenyl) phenyl methane [ leuco malachite green ], and the like. In particular, from the viewpoint of improving contrast, leuco crystal violet is preferably used as a leuco dye.

The content of the leuco dye in the photosensitive resin composition is preferably 0.1 to 10 mass% based on 100 mass% of the total solid content of the photosensitive resin composition. From the viewpoint of improving the contrast between the exposed portion and the unexposed portion, the content is preferably 0.1 mass% or more. The content is more preferably 0.2 mass% or more, and still more preferably 0.3 mass% or more. On the other hand, from the viewpoint of maintaining the storage stability of the photosensitive resin composition and suppressing the occurrence of aggregates during development, the content is preferably 10 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 material include: magenta, phthalocyanine GREEN, gold amine base, parared (para magenta), crystal violet, methyl orange, nile blue 2B, victoria blue, malachite GREEN (registered trademark) MALACHITE GREEN, basic blue 20, malachite GREEN (registered trademark) DIAMOND GREEN GH, manufactured by the company baogu chemical).

The content of the coloring material in the photosensitive resin composition is preferably 0.001 to 1% by mass based on 100% by mass of the total solid content of the photosensitive resin composition. The content is preferably set to 0.001 mass% or more from the viewpoint of improving handleability, and is preferably set to 1 mass% or less from the viewpoint of maintaining storage stability.

< halide >

In the photosensitive resin composition of the present embodiment, a leuco dye and the following halide are preferably used in combination from the viewpoints of adhesion and contrast.

Examples of the halide include: bromopentane, bromoisopentane, bromoisobutylene, ethylene bromide, benzhydryl bromide, benzyl bromide, dibromomethane, tribromomethyl phenyl sulfone, carbon tetrabromide, tris (2, 3-dibromopropyl) phosphate, trichloroacetamide, iodopentane, iodoisobutane, 1-trichloro-2, 2-bis (p-chlorophenyl) ethane, chlorinated triazine compounds, and the like. Tribromomethyl phenyl sulfone is particularly preferred. In view of the large effect, the improvement of resolution, the improvement of adhesion, the improvement of sensitivity, the improvement of contrast, the improvement of puncture resistance of the support film, the suppression of the occurrence of a lower hem of the resist layer, and the improvement of etching resistance when used in combination with the acridine compound, halides such as tribromomethyl phenyl sulfone are preferable.

From the above viewpoints, the content of the halide in the photosensitive resin composition is preferably 0.01 mass% based on 100 mass% of the total solid content of the photosensitive resin composition. The content is more preferably 0.1 mass% or more, still more preferably 0.3 mass% or more, and particularly preferably 0.5 mass% or more. In addition, from the viewpoint of maintaining the storage stability of the hue of the photosensitive layer and suppressing the occurrence of aggregates at the time of development, the content is preferably 3 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, the photosensitive resin composition may further contain at least 1 or more compounds selected from the group consisting of radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles in order to improve the thermal stability and storage stability of the photosensitive resin composition.

Examples of the radical polymerization inhibitor include: p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, t-butylcatechol, bisphenol, cuprous chloride, 2, 6-di-t-butyl-p-cresol, 2 '-methylenebis (4-methyl-6-t-butylphenol), 2' -methylenebis (4-ethyl-6-t-butylphenol), 4 '-thiobis (6-t-butyl-m-cresol), 4' -butylidenebis (3-methyl-6-t-butylphenol), 1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, styrenated phenols (e.g., SP by Sichuan Kabushiki Kaisha, trade name "), tribenzylphenols (e.g., TBP, phenol compounds having 1 to 3 benzyl groups), nitrosophenylhydroxylamine aluminum salts, diphenylnitrosoamine, and the like.

Examples of the benzotriazole include: 1,2, 3-benzotriazole, 1-chloro-1, 2, 3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1, 2, 3-methylbenzotriazole, 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) aminoethylenecarboxybenzotriazole, and the like.

The total content of the radical polymerization inhibitor, the benzotriazole, and the carboxybenzotriazole is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass, based on the total content of the total solid content of the photosensitive resin composition, based on 100% by mass of the total solid content of the photosensitive resin composition. The content is preferably set to 0.01 mass% or more from the viewpoint of imparting storage stability to the photosensitive resin composition, and is preferably set to 3 mass% or less from the viewpoint of maintaining sensitivity and suppressing dye discoloration.

< plasticizer >

The photosensitive resin composition of the present embodiment may contain a plasticizer as needed. Examples of the plasticizer include: ethylene glycol esters such as polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxypropylene monoethyl ether, and polyoxyethylene polyoxypropylene monoethyl ether;

phthalic acid esters such as diethyl phthalate;

o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, acetyl tri-n-propyl citrate, acetyl tri-n-butyl citrate and the like;

propylene glycol having propylene oxide added to both ends of bisphenol a, ethylene glycol having ethylene oxide added to both ends of bisphenol a, and the like. They may be used alone or in combination of 1 or more than 2.

In particular, p-toluenesulfonamide is preferably used as a plasticizer from the viewpoint of improving peeling characteristics, the viewpoint of less deterioration in resolution and adhesion, the viewpoint of being able to suppress occurrence of resist runout, the viewpoint of improving flexibility of a cured film, and the viewpoint of improving puncture resistance of a support film.

The content of the plasticizer in the photosensitive resin composition is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, based on 100% by mass of the total solid content of the photosensitive resin composition. The content is preferably 1 mass% or more from the viewpoint of suppressing delay in development time and imparting flexibility to the cured film, and is preferably 50 mass% or less from the viewpoint of suppressing insufficient curing and edge fusion.

< solvent >

The photosensitive resin composition can be dissolved in a solvent to be used as a solution. Examples of the solvent to be used include:

ketones typified by Methyl Ethyl Ketone (MEK);

alcohols such as 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 to the support film becomes 500 to 4000mpa·s at 25 ℃.

< Property of photosensitive resin composition >

In the photosensitive resin composition of the present embodiment, when a photosensitive resin layer having a thickness of 25 μm formed from the photosensitive resin composition is formed on the surface of a substrate, the photosensitive resin layer is exposed to light with an exposure amount having a highest residual film number of 6 when the exposure is performed with a Sichuan-type 21 scale exposure as a mask and then development is performed,

The value of PxQ/100 is preferably 0.7 or more, where Q is the average number of olefinic double bonds in the compound (C) and P is the reaction rate of olefinic double bonds in the compound (C) after the exposure.

This important condition is preferable for curing a resist pattern to sufficiently react olefinic double bonds to achieve a sufficient crosslinking density and to suppress occurrence of resist runout in a weak exposure region. In order to suppress occurrence of resist runout as much as possible, the value of p×q/100 is more preferably 1.0 or more, still more preferably 1.5 or more, still more preferably 1.7 or more, particularly preferably 2.0 or more, and most preferably 2.5 or more. On the other hand, in order to easily peel off the resist pattern used after forming the circuit pattern, the value of p×q/100 is more preferably 5.0 or less, still more preferably 4.0 or less, and particularly preferably 3.5 or less.

From the same point of view as described above, when a photosensitive resin layer having a thickness of 25 μm formed from the photosensitive resin composition of the present embodiment is formed on the surface of a substrate, the photosensitive resin layer is exposed to an exposure amount of 1/10 of the exposure amount having the highest residual film level of 6 levels when the exposure is performed using a schiff 21 level exposure scale as a mask and then development is performed,

The value of P '×q/100 is preferably 0.3 or more, where Q is the average number of olefinic double bonds in the compound (C) and P' is the reaction rate of olefinic double bonds in the compound (C) after the exposure. The exposure amount at this time is a value obtained in consideration of the exposure amount of the weak exposure area. From the same viewpoint as described above, the value of 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, particularly preferably 1.6 or more, and most preferably 1.9 or more.

More preferably 5.0 or less, still more preferably 3.0 or less, and particularly preferably 2.5 or less.

When the transmittance at 405nm (h-rays) at peeling of the polyethylene film of the photosensitive resin laminate is less than 65%, the above-mentioned value of p×q/100 is measured under the exposure condition of a direct drawing exposure machine using h-rays. When the transmittance at 405nm (h-rays) at peeling of the polyethylene film of the photosensitive resin laminate is 65% or more, the above-mentioned value of p×q/100 is measured under the exposure condition of a direct drawing exposure machine using i-rays.

The above-mentioned P'. Times.Q/100 value can be measured under the exposure condition of the exposure machine of the ultra-high pressure mercury lamp.

< photosensitive resin laminate >

A photosensitive resin laminate can be formed using the photosensitive resin composition of the present disclosure. Typically, the photosensitive resin laminate has a support film and a photosensitive resin layer formed of the photosensitive resin composition laminated on the support film. The photosensitive resin laminate may have a protective layer on the surface of the support film opposite to the support film side, if necessary.

As the support film, a transparent film that transmits light emitted from the exposure light source is preferable. Examples of such a support film include: polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film, and the like. These films may be stretched as needed.

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

When the thickness of the support film is small, it is advantageous from the viewpoints of image formability and economy, and in view of the function of maintaining strength, it is preferably 10 to 30. Mu.m.

An important characteristic of the protective layer for the photosensitive resin laminate is to have an appropriate adhesion force. That is, the adhesion force of the protective layer to the photosensitive resin layer is preferably sufficiently smaller than the adhesion force of the support film to the photosensitive resin layer, and the protective layer can be easily peeled from the photosensitive resin laminate. As the protective layer, for example, a polyethylene film, a polypropylene film, a film excellent in peelability disclosed in japanese unexamined patent publication No. 59-202457, or the like can be used.

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

The thickness of the photosensitive resin layer in the photosensitive resin laminate varies depending on the application, and is preferably 5 to 100. Mu.m, more preferably 7 to 60. Mu.m. The thinner the photosensitive resin layer, the higher the resolution, and the thicker the thickness, the higher the film strength.

< method for producing photosensitive resin laminate >

The photosensitive resin laminate can be produced by sequentially laminating photosensitive resin layers and, if necessary, protective layers on a support film. As a method thereof, a known method can be employed. For example, a photosensitive resin composition for a photosensitive resin layer is mixed with a solvent for dissolving the photosensitive resin composition to prepare a uniform solution-like coating liquid. Then, the coating liquid is applied to a support film using a bar coater or a roll coater, and then dried, whereby a photosensitive resin layer formed of the photosensitive resin composition can be laminated on the support film. Next, a protective layer is laminated on the photosensitive resin layer as necessary, whereby a photosensitive resin laminate can be produced.

< method of Forming Circuit pattern >

Another embodiment of the present invention provides a method of forming a circuit pattern, including:

a step (laminating step) of forming a layer of the photosensitive resin composition of the present disclosure on a substrate;

a step of exposing and developing the layer of the photosensitive resin composition to form a resist pattern (exposure step and development step); and

and a step of etching or plating the substrate on which the resist pattern is formed (etching step or plating step). After the series of steps, a stripping step of stripping the resist pattern from the laminate is preferably further provided.

In a preferred embodiment, the layer of the photosensitive resin composition is formed using the photosensitive resin laminate.

Next, an example of a method of forming a circuit pattern using a photosensitive resin laminate and a copper-clad laminate as a substrate will be described.

(1) Lamination process

The method comprises the following steps: the protective layer of the photosensitive resin composition is peeled off and bonded to a substrate such as a copper-clad laminate or a flexible substrate using, for example, a hot roll laminator.

(2) Exposure process

The method comprises the following steps: a step of exposing the photosensitive resin composition layer formed on the substrate with a mask film having a desired wiring pattern interposed therebetween in a state of being adhered to the layer;

Exposing the desired wiring pattern by a direct imaging exposure method; or alternatively

And exposing the image of the photomask by an exposure method in which the image is projected through a lens. The photosensitive resin composition of the present embodiment is advantageous in that it is more remarkably useful in a direct imaging exposure method using direct drawing of a wiring pattern or in an exposure method in which an image of a photomask is projected through a lens, and is particularly remarkably useful in a direct imaging exposure method, and therefore, in the exposure step, a direct imaging exposure method is preferably used.

(3) Development process

The method comprises the following steps: after the exposure step, the support on the photosensitive resin layer is peeled off, and then the unexposed portion is developed and removed by using a developer of an alkaline aqueous solution, thereby forming a resist pattern on the substrate.

As the alkaline aqueous solution, na may be used ₂ CO ₃ Or K ₂ CO ₃ Is a solution of (a) and (b). The alkali aqueous solution may be appropriately selected depending on the characteristics of the photosensitive resin layer, but it is preferable to use Na at a concentration of about 0.2 to 2 mass% and at a temperature of about 20 to 40 ℃ ₂ CO ₃ An aqueous solution.

Through the above steps, a resist pattern can be obtained. After these steps, a heating step may be performed at about 100 to 300 ℃ for 1 minute to 5 hours, as the case may be. By performing this heating step, the adhesion of the resulting cured resist pattern can be further improved. For heating in this case, a heating furnace of a hot air type, an infrared type, or a far infrared type, for example, may be used.

(4) Etching or plating

The substrate surface (e.g., copper surface of the copper-clad laminate) exposed by the development is etched or plated to produce a conductor pattern.

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

(5) Stripping process

Thereafter, the laminate is treated with an aqueous solution having an alkali property stronger than that of the developer, and the resist pattern is peeled off from the substrate. The alkaline aqueous solution for stripping is not particularly limited. Aqueous solutions of NaOH or KOH having a concentration of about 2 to 5 mass% and a temperature of about 40 to 70 ℃ are generally used. A small amount of a water-soluble solvent may be added to the stripping solution.

Examples

The present invention will be described more specifically with reference to examples and comparative examples.

First, the method for producing the samples for evaluation of examples and comparative examples will be described, and then the method for evaluating the obtained samples and the evaluation results will be described.

(1) Evaluation of alkali-soluble Polymer

< determination of weight average molecular weight >

The weight average molecular weight of the polymer was determined as a polystyrene equivalent using a Gel Permeation Chromatograph (GPC) manufactured by japan light splitting corporation. The equipment configuration and the reagents used are as follows.

And (3) a pump: gulliver, model PU-1580

Column: 4 Shodex (registered trademark) KF-807, KF-806M, KF-806M, and KF-802.5 manufactured by Showa Denko Co., ltd. Are used in series

Flowable layer solvent: tetrahydrofuran (THF)

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

(2) Method for producing sample for evaluation

Evaluation samples of examples and comparative examples were prepared as follows.

< preparation of photosensitive resin laminate >

The components shown in table 1 below (wherein the numbers in the component columns indicate the amounts (parts by mass) blended as solid components) and the solvent were sufficiently mixed by stirring, to prepare a photosensitive resin composition blend. To the photosensitive resin composition blends of examples 1 to 19 and comparative examples 1 to 8, the following were added in addition to the components shown in table 1:

0.05 parts by mass of diamond green as a coloring substance;

0.6 parts by mass of leuco crystal violet as a leuco dye;

0.2 part by mass of a 1:1 (mass ratio) mixture of 1- (2-di-n-butylaminomethyl) -5-carboxybenzotriazole and 1- (2-di-n-butylaminomethyl) -6-carboxybenzotriazole as benzotriazoles;

0.05 parts by mass of diglycidyl ether of hydrogenated bisphenol A as an antioxidant;

0.004 parts by mass of an aluminum salt added with 3 moles of nitrosophenyl hydroxylamine as a radical polymerization inhibitor; and

2 parts by mass of p-toluenesulfonamide as a plasticizer.

To the photosensitive resin composition blend solutions other than comparative example 1 and comparative example 2, 0.7 parts by mass of tribromomethyl phenylsulfone as a halide was added.

The photosensitive resin composition blends of examples 20 to 44 and comparative examples 9 to 12 were not blended with the additional components except those described in table 1.

All of the photosensitive resin composition solutions further contain a solvent brought from the alkali-soluble polymer solution blended in the solution, and a solvent added for adjusting the concentration.

A16 μm thick polyethylene terephthalate film (GR-16, manufactured by Di-dufin Co.) was used as a support film, and each of the above-prepared solutions was uniformly applied to the surface thereof by a bar coater, and dried in a dryer at 95℃for 2.5 minutes to form a photosensitive resin composition layer. The dry thickness of the photosensitive resin composition layer was adjusted to 25. Mu.m. Next, a 19 μm thick polyethylene film (GF-18, manufactured by fak-me corporation) was adhered as a protective layer to the surface of the photosensitive resin composition layer (on the other side surface of the polyethylene terephthalate film), thereby obtaining a photosensitive resin laminate.

Table 2 below shows the names of the components indicated in table 1.

< substrate surface Regulation >

A copper-clad laminate of 0.4mm thickness, on which a rolled copper foil of 35 μm thickness was laminated, was used as an evaluation substrate for image properties, resist skirt width, etching properties, and peeling time. The substrate was treated with CPE-900 (registered trademark, manufactured by Lingjiang chemical Co., ltd.) and then 10% by mass of H ₂ SO ₄ The surface was cleaned, rinsed with pure water, and then supplied to the user.

< lamination >

The polyethylene film of the photosensitive resin laminate was peeled off, and the laminate was surface-conditioned and laminated on a copper-clad laminate sheet preheated to 60℃with a hot roll laminator (AL-700, manufactured by Asahi Kabushiki Kaisha Co., ltd.) at a roll temperature of 105℃to obtain various laminates for evaluation. The air pressure was set to 0.35MPa, and the lamination speed was set to 1.5 m/min.

The evaluation was performed on the samples produced under the conditions described in the items of the various evaluation methods using the laminated laminate, except for those described in the following evaluation methods. The general operation method for exposure, development, etching and stripping is described below.

< exposure >

For exposure other than "(x) P'. Times.Q/100", an exposure machine (DE-1 DH, light source: gaN blue-violet diode (dominant wavelength: 405.+ -. 5 nm) manufactured by Hitachi-Pond Co., ltd.) was used for direct drawing, and a Sichuan-Chart 21 scale exposure rule or a prescribed mask pattern for DI exposure was used, and the exposure was performed at an illuminance of 80mW/cm ² Exposure is performed under the condition of (2). The exposure was performed with an exposure amount of 6 steps of the highest residual film stage number when the exposure was performed using the schlieren's 21-step exposure rule as a mask.

For a substrate for evaluating items other than the width of the resist layer skirt, the position of the focus at the time of exposure was made to coincide with the substrate surface,

for a substrate for evaluating the width of the resist layer skirt, the position of the focus at the time of exposure was shifted from the substrate surface toward the inside of the substrate by 200 μm in the thickness direction of the substrate.

< development >

After the polyethylene terephthalate film of the evaluation substrate thus exposed was peeled off, the temperature was adjusted to 30℃by an alkali developing machine (developing machine for dry film, manufactured by Fuji corporation) to 1% by mass of Na ₂ CO ₃ The aqueous solution was sprayed for a predetermined period of time, and then sprayed with pure water for a predetermined period of time, followed by washing with water, to dissolve and remove the unexposed portions of the photosensitive resin layer, thereby producing a cured resist pattern.

The development time and the water washing time were set to 2 times the minimum development time, respectively.

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

< etching >

For the evaluation substrate on which the cured resist pattern was formed by the development, a copper chloride etching apparatus (copper chloride etching apparatus manufactured by tokyo chemical industry co., ltd.) was used, and a copper chloride etching solution having a temperature adjusted to 50 ℃ was sprayed for 1.3 times the minimum etching time, so that the copper foil on the copper-clad laminate at the portion not covered with the resist pattern was dissolved and removed.

The cuprous chloride etching solution is a solution with the concentration of cuprous chloride of 250g/L and the concentration of hydrochloric acid of 3 mol/L. The minimum etching time is a time required for the copper foil on the substrate to be completely dissolved and removed.

< peeling >

For the evaluation substrate after the etching, a 3 mass% aqueous sodium hydroxide solution having a temperature adjusted to 50 ℃ was sprayed to peel off the cured resist pattern.

(3) Method for evaluating sample

Next, a method for evaluating a sample will be described.

(i) Sensitivity evaluation

The substrate for sensitivity evaluation after 15 minutes from lamination was exposed to light through a mask of a schwank 21-level exposure rule. Next, development was performed with a time 2 times the shortest development time.

The above operation was repeated while changing the exposure amount, and the exposure amount was examined with the highest number of residual film stages being 6.

For examples 1 to 19 and comparative examples 1 to 8, the exposure amount of the highest residual film stage number of 6 was classified by the following criteria.

O (good): the exposure of the highest residual film stage number of 6 stages is less than 20mJ/cm ² Is the case of (2)

X (bad): the exposure of the highest residual film stage number of 6 stages is 20mJ/cm ² The above situation

The exposure values of the highest residual film stage number of 6 are shown in Table 1 for examples 20 to 44 and comparative examples 9 to 12. For the applications envisaged in these examples, the exposure of 70mJ or less can be evaluated as good, and the sensitivity is preferably 40mJ or less, more preferably 30mJ or less, and still more preferably 20mJ or less.

(ii) Resolution evaluation (1)

The substrate for evaluation after 15 minutes had passed after lamination was exposed to a pattern of lines and spaces having a width ratio of 1:1 between the exposed portion and the unexposed portion. Then, development was performed for a development time 2 times the shortest development time, to obtain a cured resist pattern. The minimum mask line width in the cured resist pattern at which the wired and spatial patterns were normally formed was investigated.

For examples 1 to 19 and comparative examples 1 to 8, the values of the minimum mask line width were classified according to the following criteria.

O (good): the minimum mask line width is 25 μm or less

Delta (pass): the minimum mask line width is greater than 25 μm and less than 30 μm

X (bad): the case where the value of the minimum mask line width is greater than 30 μm

The values of the minimum mask line widths are shown in table 1 for examples 20 to 44 and comparative examples 9 to 12. For the applications envisaged in these examples, the minimum mask line width is 60 μm or less, and it can be evaluated that the resolution (1) is good, preferably 35 μm or less, more preferably 25 μm or less, still more preferably 20 μm or less, and particularly preferably 16 μm or less.

(iii) Resolution evaluation (2)

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

That is, the evaluation substrate after 15 minutes from lamination was exposed to a pattern in which the unexposed portion was space. Next, development was performed with a development time 2 times the shortest development time, to obtain a cured resist pattern. At this time, the value of the minimum space width of the space where the unexposed portion is normally formed is taken as the value of the resolution (positive independent mold release).

When the minimum space 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 particularly preferably 20 μm or less.

(iv) Evaluation of adhesion

The substrate for evaluation after 15 minutes from lamination was exposed to light to form a pattern of lines in the exposed portion. Next, development was performed with a development time 2 times the shortest development time, to obtain a cured resist pattern. The minimum mask line width at which the cured resist line was normally formed was investigated.

For examples 1 to 19 and comparative examples 1 to 8, the minimum mask line widths were classified according to the following criteria.

O (good): the minimum mask line width is 25 μm or less

The values of the minimum mask line widths are shown in table 1 for examples 20 to 44 and comparative examples 9 to 12. For the applications envisaged in these examples, the minimum mask line width of 70 μm or less is evaluated as good adhesion, preferably 30 μm or less, more preferably 25 μm or less, even more preferably 20 μm or less, and particularly preferably 10 μm or less.

(v) Evaluation of resist skirt Width

The substrate for evaluation after 15 minutes had passed after lamination was exposed to a pattern of lines and spaces having a width ratio of 1:1 between the exposed portion and the unexposed portion. In exposure, the position of the focus at the time of exposure was shifted 200 μm from the substrate surface toward the inside of the substrate in the thickness direction of the substrate. By this measure, the weak exposure area at the exposed pattern end is enlarged, and the width of the resist layer skirt can be easily compared.

After the exposed substrate was developed with a development time 2 times the shortest development time, the exposed portion of the copper base material of the substrate was subjected to soft etching for 60 seconds with a 200g/L ammonium persulfate aqueous solution, thereby obtaining a sample for evaluating the width of the resist layer skirt. The width of the bottom projecting portion of the line pattern was obtained by observing a line pattern portion of the sample having a ratio of L/s=45 μm/45 μm of 1:1 by a scanning electron microscope (S-3400N, manufactured by hitachi).

For examples 1 to 19 and comparative examples 1 to 8, the values were classified based on resist line widths by the following criteria:

very good: the width of the resist layer lower hem is 1.5 μm or less

O (good): the width of the resist layer is greater than 1.5 μm and less than 2.5 μm

Delta (pass): the width of the resist layer is greater than 2.5 μm and less than 3.5 μm

X (bad): the width of the resist layer lower hem is greater than 3.5 μm

The values of the resist bottom width are shown in table 1 for examples 20 to 44 and comparative examples 9 to 12. For the applications envisaged in these examples, the resist layer skirt width was evaluated to be 10 μm or less, and it was evaluated that the adhesion was good, preferably 3 μm or less, more preferably 2.5 μm or less, still more preferably 2 μm or less, still more preferably 1.5 μm or less, and particularly preferably 1 μm or less.

The method for measuring the width of the resist layer bottom swing is shown in fig. 1.

(vi) Evaluation of etching Property

The substrate for evaluation after 15 minutes had passed after lamination was exposed to a pattern of lines and spaces having a width ratio of 1:1 between the exposed portion and the unexposed portion. The resist pattern was developed with a development time 2 times the minimum development time, etched with a time 1.3 times the minimum etching time, and then the cured resist pattern was peeled off with an aqueous sodium hydroxide solution, whereby a conductor pattern was obtained. The shape of the conductor pattern was examined by observing the conductor pattern with an optical microscope (MM-800, manufactured by nikon corporation), and the conductor pattern was classified according to the following criteria:

o (good): a conductor pattern is formed linearly, and no wave (etching) is observed

Delta (pass): the conductor pattern was linearly formed, but a small amount of etching solution was penetrated

X (bad): at least one of cases in which the conductor pattern was not formed linearly and cases in which the etching liquid penetrated was remarkably seen was observed.

(vii) Evaluation of foamability of developer

The foregoing is followed<Production of photosensitive resin laminate>The photosensitive resin laminate produced in (1) was cut into a sheet having an area of 0.048m ² The photosensitive resin layer after peeling the protective layer and the support film was immersed in 120ml of 1 mass% Na ₂ CO ₃ In the aqueous solution, thereby obtaining a solution in which the resin layer is dissolved. The solution was placed in a gas absorption tank having a capacity of 500ml, and foaming was performed with 6000 ml/min of nitrogen gas passing through a glass filter of G3. The time until the generated bubbles overflowed from the gas absorption tank was measured, and the results were classified by the following criteria.

Very good: with 100 seconds of no overflow

O (good): in case of overflow in more than 30 seconds and in 100 seconds

X (bad): overflow within 30 seconds

(viii) Pressure flow test (Press flow test)

The photosensitive resin laminate produced in the above < production of photosensitive resin laminate > was cut into 2.5cm squares, the protective layer was peeled off, and then sandwiched between 10cm squares of polyethylene terephthalate film, and a force of 100kg was applied for 5 minutes by a press heated to 40 ℃. Thereafter, the extrusion width of the photosensitive resin layer was measured in 4 directions (8 total), and the average value was obtained. For this test, n=2 was used, and the average value of n=2 was obtained and used as the value of the pressure flow test.

It is found from experience that when the value is large, edge fusion is likely to occur, and it is substantially impossible to stably laminate the film on the substrate during lamination.

(ix)P×Q/100

The transmittance at 405nm (h-rays) at peeling the polyethylene film of the photosensitive resin laminate was less than 65% in all examples and comparative examples. Thus, the value of PXQ/100 is determined under the exposure conditions of a direct-delineation exposure machine using h-rays.

Using a direct drawing exposure machine (Hitachi-En, DE-Equiz Co., ltd.)1DH, light source: gaN blue-violet diode (dominant wavelength 405.+ -.5 nm) from the foregoing<Production of photosensitive resin laminate>The polyethylene terephthalate film (support layer) side of the photosensitive resin laminate produced in (a) was subjected to direct image-wise exposure. At this time, the position of the focus at the time of exposure was made to coincide with the bottom of the resist layer. The illuminance at the time of exposure was set to 80mW/cm ² . The exposure amount at this time was performed by using the schlieren's 21-level exposure rule as a mask and performing exposure by the method described above, and then performing development with the highest residual film level being 6-level (ordinary exposure).

The reaction rate P of the olefinic double bonds of the cured resist obtained by the above procedure was determined by FT-IR (manufactured by Thermo SCIENTIFIC, NICOLET 380). The wave number was measured to be 810cm ^-1 The peak height below, this value was taken as the amount of olefinic double bonds.

The average number of olefinic double bonds (number of functional groups) in the compound (C) was calculated and this value was defined as Q. When the compound (C) is a mixture of a plurality of compounds, Q is obtained in consideration of the mass of each component.

The value of PxQ/100 was obtained from the above P and Q.

(x)P’×Q/100

By using an ultra-high pressure mercury lamp (HMW-801 manufactured by the Co., ltd.),from the foregoing<Preparation of photosensitive resin laminate Acting as>Photosensitive resin laminate produced by the processThe polyethylene terephthalate film (support layer) side of (a) was exposed to light. Exposure to light of the above<(ix)P×Q/100>The exposure amount (less than a decimal point) of 1/10 of the exposure amount. Otherwise, the reaction rate P' of the olefinic double bonds of the cured resist layer at 1/10 exposure (weak exposure) was determined by FT-IR in the same manner as described above.

The P 'value and the Q value calculated in the same manner as described above were used to determine the P' ×q/100 value at the time of weak exposure.

(xi) Hue stability of photosensitive resin composition blend

The transmittance at 630nm of the photosensitive resin laminate was measured using an ultraviolet-visible light (UV-Vis) measuring device (a spectrophotometer model U-3010, manufactured by hitachi, hitachi), as follows:

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

(ii) A photosensitive resin laminate was produced using a blended solution of the photosensitive resin composition after storage at 40℃for 3 days, and the polyethylene film of the photosensitive resin laminate was peeled off to measure the transmittance at 630nm, and the obtained value was used as the transmittance after storage (T _af )。

The color phase stability was found by the following formula:

T _af -T _in 。

(xii) Peeling time

Rectangular patterns of 5cm×6cm were exposed on the evaluation substrate after 15 minutes from lamination. Next, development was performed with a development time 2 times the shortest development time, to obtain a cured resist pattern.

The cured resist pattern on the substrate obtained by this operation was immersed in a 2 mass% NaOH aqueous solution at 50 ℃, and the time until the resist layer was completely peeled off the substrate was measured and taken as the peeling time.

(xiii) Softness of cured film

A photosensitive resin laminate was laminated on NIKAFLEX F-30VC1 25C 1/2 (manufactured by the company of the king industry) to expose a pattern having a width of 2.5cm and a length of 30 cm. Next, development was performed with a development time 2 times the shortest development time, and a long sample was prepared.

They were respectively put on SUS rods having contact diameters of 1, 2, 3, 4, 5 and 6mm phi in the substrate side in such a manner that they contacted the SUS rods. Then, both ends of the long sample were held so that the bending angle became 90 degrees, and the long sample was wrinkled back and forth 10 times.

At this time, the diameter of the largest SUS rod on which no crack appears on the resist layer was examined and classified as follows.

O (good): no cracking at 4mm phi

Delta (pass): cracks appear at 4mm phi, but no cracks appear at 5mm phi

(xiiv) support film puncture elongation Properties

The photosensitive resin laminate was laminated on both sides of a substrate formed of a 1.6mm thick copper-clad laminate having an opening with a diameter of 6mm, and the entire surfaces of both sides were exposed. Next, development was performed with a development time 2 times the shortest development time, thereby obtaining a cured resist pattern.

Then, the puncture strength and elongation of the membrane at the opening portion of the substrate were measured by RTM-500, manufactured by toxiong corporation, using a cylinder having an insertion diameter of 1.5 mm.

(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 in table 1 by short. The alkali-soluble polymers shown in table 2 were all supplied to the compounding as methyl ethyl ketone solutions having the solid content concentrations described in the table. The abbreviations in the columns of the functional groups in the compounds having an olefinic double bond in Table 2 are each defined as follows.

A: acrylic ester group

MA: methacrylate group

Table 3 shows glass transition temperatures (literature values) when respective monomers for synthesizing the alkali-soluble resin were made into homopolymers.

TABLE 1

Table 1 (Table 1 of the 11 total tables)

(Table 1 has follow-up)

TABLE 2

Table 1 (Table 2 of the 11 total)

(Table 1 has follow-up)

TABLE 3

Table 1 (3 rd of the 11 tables)

(Table 1 has follow-up)

TABLE 4

Table 1 (4 th of the 11 tables)

(Table 1 has follow-up)

TABLE 5

Table 1 (5 th of the 11 tables)

(Table 1 has follow-up)

TABLE 6

Table 1 (6 th of the 11 tables)

(Table 1 has follow-up)

TABLE 7

Table 1 (7 th of the 11 tables)

(Table 1 has follow-up)

TABLE 8

Table 1 (8 th of the 11 tables)

(Table 1 has follow-up)

TABLE 9

Table 1 (9 th of the 11 tables)

(Table 1 has follow-up)

TABLE 10

TABLE 11

TABLE 12

TABLE 13

Table 2 (Table 2 of the total 4)

(Table 2 has follow-up)

TABLE 14

TABLE 15

Table 2 (4 th of the total 4 tables)

(end of Table 2)

TABLE 16

Industrial applicability

The photosensitive resin composition of the present embodiment, and the photosensitive resin laminate, resist pattern, and circuit pattern produced using the same can be suitably used for the production of printed wiring boards and flexible printed wiring boards; a semiconductor package such as a lead frame, a metal mask, a BGA, or a CSP for mounting an IC chip; and the manufacture of tape substrates such as TAB and COF, semiconductor bumps, ITO electrodes, address electrodes, electromagnetic wave shields, and the like.

Claims

1. A photosensitive resin composition characterized by comprising:

(A) Alkali-soluble polymer: 40 to 80 mass percent,

(B) Photopolymerization initiator: 0.1 to 20 mass%, and

(C) Compounds having an olefinic double bond: 5 to 50 mass percent,

the photosensitive resin composition is used for direct imaging exposure,

the alkali-soluble polymer (A) has a weight average molecular weight of 5000 or more and 500000 or less,

the compound (C) comprises a compound having 3 or more methacryloyl groups in one molecule.

2. The photosensitive resin composition according to claim 1, wherein when a photosensitive resin layer having a thickness of 25 μm formed from the photosensitive resin composition is formed on a surface of a substrate, the photosensitive resin layer is exposed to light with an exposure amount having a highest residual film level of 6 levels when the exposure is performed with a Situff 21 level exposure scale as a mask and then development is performed,

3. The photosensitive resin composition according to claim 1 or 2, wherein when a photosensitive resin layer having a thickness of 25 μm formed from the photosensitive resin composition is formed on a surface of a substrate, the photosensitive resin layer is exposed to light with an exposure amount of 1/10 of an exposure amount having a highest residual film level of 6 levels when exposed to light with a Situff 21 level exposure scale as a mask and then developed,

4. The photosensitive resin composition according to claim 1 or 2, wherein the weight average Tg of the (a) alkali-soluble polymer ^total Is 30 ℃ to 125 ℃.

5. The photosensitive resin composition according to claim 1 or 2, wherein the (B) photopolymerization initiator comprises a compound having a 3-ring structure.

6. The photosensitive resin composition according to claim 1 or 2, wherein the (C) compound having an olefinic double bond comprises a compound having an aromatic group.

7. The photosensitive resin composition according to claim 1 or 2, wherein the (C) compound comprises a compound having 4 or more methacryloyl groups in one molecule.

8. The photosensitive resin composition according to claim 1 or 2, wherein the (C) compound comprises a compound represented by the following general formula (IV):

in the formula (IV), n ₁ 、n ₂ 、n ₃ And n ₄ Each independently represents an integer of 1 to 25, n ₁ +n ₂ +n ₃ +n ₄ Is an integer of 9 to 60, and the number of the components is equal to 9,

R ₅ 、R ₆ 、R ₇ and R is ₈ Each independently represents an alkylene group, R ₅ 、R ₆ 、R ₇ And R is ₈ When there are plural R ₅ 、R ₆ 、R ₇ And R is ₈ The same or different.

9. The photosensitive resin composition according to claim 8, wherein n in the general formula (IV) ₁ +n ₂ +n ₃ +n ₄ Is an integer of 15 to 40.

10. The photosensitive resin composition according to claim 8, wherein in the formula (IV), n ₁ +n ₂ +n ₃ +n ₄ Is an integer of 15 to 28.

11. The photosensitive resin composition according to claim 1 or 2, wherein the (B) photopolymerization initiator comprises an acridine compound.

12. The photosensitive resin composition according to claim 1 or 2, further comprising a halide.

13. The photosensitive resin composition according to claim 1 or 2, wherein the (B) photopolymerization initiator comprises N-phenylglycine or a derivative thereof.

14. The photosensitive resin composition according to claim 1 or 2, wherein the alkali-soluble polymer (a) has an aromatic hydrocarbon group.

15. A photosensitive resin composition, characterized in that the photosensitive resin composition comprises:

(A) Alkali-soluble polymer: 40 to 80 mass percent,

(B) Photopolymerization initiator: 0.1 to 20 mass%, and

(C) Compounds having an olefinic double bond: 5 to 50 mass percent,

the (B) photopolymerization initiator comprises a compound having a 3-ring structure,

the (C) compound comprises a compound having 4 or more methacryloyl groups in one molecule.

16. The photosensitive resin composition according to claim 15, wherein when a photosensitive resin layer having a thickness of 25 μm formed from the photosensitive resin composition is formed on a surface of a substrate, the photosensitive resin layer is exposed with an exposure amount having a highest residual film level of 6 levels when the exposure is performed using a Situff 21 level exposure scale as a mask and then development is performed,

17. The photosensitive resin composition according to claim 15 or 16, wherein when a photosensitive resin layer having a thickness of 25 μm formed from the photosensitive resin composition is formed on a surface of a substrate, the photosensitive resin layer is exposed to an exposure amount of 1/10 of an exposure amount having a highest residual film level of 6 levels when the exposure is performed with a Situff 21 level exposure scale as a mask and then development is performed,

18. The photosensitive resin composition according to claim 15 or 16, wherein the (C) compound comprises a compound represented by the following general formula (IV):

19. The photosensitive resin composition according to claim 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 claim 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 claim 15 or 16, wherein the (B) photopolymerization initiator comprises an acridine compound.

22. The photosensitive resin composition according to claim 15 or 16, wherein the (C) compound having an olefinic double bond comprises a compound having an aromatic group.

23. The photosensitive resin composition according to claim 15 or 16, further comprising a halide.

24. The photosensitive resin composition according to claim 15 or 16, wherein the (B) photopolymerization initiator comprises N-phenylglycine or a derivative thereof.

25. The photosensitive resin composition according to claim 15 or 16, wherein the alkali-soluble polymer (a) has an aromatic hydrocarbon group.

26. The photosensitive resin composition according to claim 15 or 16, wherein the weight average Tg of the (a) alkali-soluble polymer ^total Is 30 ℃ to 125 ℃.

27. The photosensitive resin composition according to claim 15 or 16, which is used for direct image-wise exposure.

28. A method of forming a circuit pattern, comprising:

A step of forming a layer of the photosensitive resin composition according to any one of claims 1 to 27 on a substrate;

and etching or plating the substrate on which the resist pattern is formed.

29. The method of claim 28, wherein the exposing is performed by direct imaging exposure.