KR20180042842A - Photosensitive resin composition - Google Patents

Abstract

 A photosensitive resin composition comprising an alkali-soluble polymer, a compound having an ethylenic double bond, and a photopolymerization initiator was coated on a copper-clad laminate having a copper foil having a thickness of 18 탆 laminated thereon, Thick, and subjected to light irradiation and development processing in the form of a line / space = 50 占 퐉 / 30 占 퐉 pattern to form a cured resist pattern, followed by 55 seconds of copper etching treatment at 50 占 폚, And the bottom width of the copper line pattern obtained by removing the copper line pattern is 38 占 퐉 or more.

Description

[0001] PHOTOSENSITIVE RESIN COMPOSITION [0002]

≪ Technical Field of the Invention <

A first embodiment of the present invention relates to a photosensitive resin composition.

≪ Technical Field of the Second Embodiment of the Present Invention &

A second embodiment of the present invention relates to a photosensitive resin composition or the like.

≪ Technical Field of the Third Embodiment of the Present Invention &

A third embodiment of the present invention relates to a photosensitive resin composition, and the like.

<Technical Field of the Fourth Embodiment of the Present Invention>

A fourth embodiment of the present invention relates to a photosensitive resin composition.

&Lt; Background Art of First Embodiment of the Present Invention &gt;

The printed wiring board is generally manufactured by photolithography. Photolithography is a technique in which a layer made of a photosensitive resin composition is formed on a substrate, a resist pattern is formed by pattern exposure and development on the coating film, a conductor pattern is formed by etching or plating, Thereby forming a desired wiring pattern on the substrate.

In this photolithography, a method of removing a solvent after applying a composition solution when forming a photosensitive resin composition layer on a substrate, a method of forming a photosensitive element or a dry film resist by laminating a support and a photosensitive resin composition layer on a substrate A method of peeling the support after lamination is known.

In the production of a printed wiring board, a photosensitive element is often used. There are many known methods for forming a wiring pattern using the photosensitive element and a photosensitive resin composition suitable for the method.

For example, Patent Document 1 discloses a method capable of easily forming a copper wiring pattern having a good cross-sectional shape, and a photosensitive resin composition used in the method;

Patent Document 2 discloses a photosensitive resin composition containing an addition polymerizable monomer having a specific ethylenic double bond.

However, in recent years, in order to increase the density of the printed wiring board, the substrate is often multilayered. In the multi-layer substrate, through-holes are formed so as to be stacked on top of each other and to be electrically connected to each other. In the case of forming a wiring pattern by photolithography on a substrate having a through hole used for a multilayer substrate, a resist film (tent film) formed on the through hole is torn by the spray pressure at development, (Tentability of the inner tent membrane or tentability).

In this respect, Patent Document 3 discloses a photosensitive resin composition containing a binder polymer having a small degree of dispersion (Mw / Mn) and a photopolymerizable compound and an acridine compound, It is described that a film can be formed.

&Lt; Background Art of Second Embodiment of the Present Invention &gt;

The printed wiring board is generally manufactured by photolithography. Photolithography is a technique in which a coating film including a layer made of a photosensitive resin composition is formed on a substrate, a resist pattern is formed by pattern exposure and development of the coating film, and then a conductor pattern is formed by etching or plating, And removing the resist pattern to form a desired wiring pattern on the substrate.

In photolithography, a method of removing a solvent after applying a composition solution when forming a photosensitive resin layer on a substrate, a method of laminating a photosensitive element or a dry film resist comprising a support and a photosensitive resin layer laminated on a substrate And a method of peeling the support afterward.

In the production of a printed wiring board, a photosensitive element is often used. There are many known methods for forming a wiring pattern using the photosensitive element and a photosensitive resin composition suitable for the method.

For example, Patent Document 1 discloses a method capable of easily forming a copper wiring pattern having a good cross-sectional shape and a photosensitive resin composition used in the method, and Patent Document 4 discloses a method of forming a copper wiring pattern having a specific cross- And photosensitive resin compositions containing addition polymerizable monomers are disclosed, respectively.

&Lt; Background Art of Third Embodiment of the Present Invention &gt;

Conventionally, printed wiring boards are generally manufactured by photolithography. In the photolithography method, first, the photosensitive resin composition layer laminated on the substrate is pattern-exposed. The exposed part of the photosensitive resin composition is solubilized (in the case of a positive type) for the polymerization curing (in the case of the negative type) or the developing solution. Next, the unexposed portion (in the case of the negative type) or the exposure portion (in the case of the positive type) is removed with a developer to form a resist pattern on the substrate. Further, after the conductor pattern is formed by performing the etching or plating treatment, the resist pattern is peeled off from the substrate. Through these processes, a conductor pattern is formed on the substrate.

In the photolithography method, generally, a method of applying a solution of a photosensitive resin composition to a substrate and drying it, or a method of laminating a photosensitive resin composition layer of a dry film resist (a photosensitive resin laminate on which a photosensitive resin composition layer is laminated on a support) One of the methods is used. In the production of a printed wiring board, the latter is commonly used.

Background Art [0002] With the recent miniaturization of interconnection spacing in printed wiring boards, various properties have been required for dry film resists. Along with the miniaturization of the interconnection interval, the thickness of the dry film resist also tends to be reduced. However, toughness is still required to protect the through holes on the substrate.

Further, when the resist pattern is developed, the resist component is eluted between the patterns due to the water remaining between the patterns, resulting in a water residual short defect. In order to reduce the water residual shot defects, it is necessary to improve the hydrophobicity of the cured resist.

In order to improve the resist properties, various photosensitive resin compositions have been proposed (Patent Documents 5 and 6).

&Lt; Background Art of Fourth Embodiment of the Present Invention &gt;

The printed wiring board is generally manufactured by photolithography. Photolithography is a technique in which a layer made of a photosensitive resin composition is formed on a substrate, a resist pattern is formed by pattern exposure and development on the coating film, a conductor pattern is formed by etching or plating, Thereby forming a desired wiring pattern on the substrate.

In photolithography, a method of removing a solvent after applying a composition solution when forming a photosensitive resin layer on a substrate, a method of laminating a photosensitive element or a dry film resist comprising a support and a photosensitive resin layer laminated on a substrate And a method of peeling the support afterward.

In the production of a printed wiring board, a photosensitive element is often used. A method of forming a wiring pattern using this photosensitive element, and a photosensitive resin composition suitable for this method are known (Patent Documents 1 and 2). Patent Document 1 describes a general method of forming a copper wiring pattern having a good sectional shape and a photosensitive resin composition used therefor. Patent Document 2 discloses a photosensitive resin composition comprising an addition polymerizable monomer having a specific ethylenic unsaturated bond.

[0005] In recent years, along with miniaturization of interconnection spacing in recent printed wiring boards, characteristics such as resolution have been required for dry film resists. For example, various photosensitive resin compositions have been proposed to improve the resist pattern characteristics (Patent Documents 5 and 6).

Japanese Laid-Open Patent Publication No. 2011-233769 International Publication No. 2009/022724 Japanese Laid-Open Patent Publication No. 2013-109321 Japanese Laid-Open Patent Publication No. 2015-60120 International Publication No. 2015/098870 Japanese Patent Application Laid-Open No. 2014-048340

<Problems to be Solved by the First Embodiment of the Present Invention>

In recent years, the production of a wiring board is usually carried out by a line process in which a substrate is sequentially transported while being transported in a certain direction. Here, when a conductor pattern of, for example, a line / space pattern is formed on a substrate, in the case where the lines of the conductor are parallel to each other (the line in the MD direction) ), And a case where it is inclined. When a conductor pattern of a line / space pattern is formed by a line process using a resist material of the prior art, the line widths in the lines in the MD direction and the line direction in the TD direction are different from each other. In many cases, the line in the MD direction tends to be penetrated by the etching solution more than the line in the TD direction, and therefore, the etching amount increases and the wiring width tends to become narrow. In order to form a fine conductor pattern by the line process, it is preferable that the wiring width difference between the wiring in the MD direction and the wiring in the TD direction is reduced.

However, in the conventional techniques represented by the above-described Patent Documents 1 to 3, such a point of view has not been studied, and a resist material for reducing the vertical / horizontal difference in wiring width is not known.

The first embodiment of the present invention is made in consideration of the present situation. Therefore, an object of the first embodiment of the present invention is to provide a resist material in which the vertical and horizontal differences in wiring width are suppressed in forming a fine conductor pattern by a line process.

<Problems to be Solved by the Second Embodiment of the Present Invention>

In order to form a resist pattern using the photosensitive resin composition, a development step is performed. In this developing step, a resist pattern is formed by dissolving and removing the composition in the exposure area in the positive composition and the composition in the exposure area in the negative composition. In this developing step, not all of the composition in the unnecessary region is &quot; dissolved &quot; in the developing solution, and at least a part thereof is removed from the substrate by being dispersed in the developing solution while being insoluble. Therefore, every time the developing process is repeated, the amount of the unnecessary matter in the developing solution increases, and in some cases, the insoluble component, which has poor dispersibility, forms an aggregate. Such aggregates adhere to and remain on the substrate to be developed later, and may cause defective shot or the like.

Therefore, it is strongly desired that the developer dispersion of the photosensitive resin composition to be used is good in terms of improvement in product yield in the development step, and further reduction in manufacturing cost of the printed wiring board.

In recent years, however, demands for miniaturization and refinement of printed wiring boards have become more intense. Therefore, a photosensitive resin composition used for forming the printed wiring board is required to be capable of forming a fine pattern. Here, since the minimum size of the pattern formed on the substrate depends on the exposure wavelength, it is logically very difficult to form a fine pattern by adopting a photosensitive polymerization initiator according to the used exposure wavelength no. On the other hand, for example, a fine pattern formed by exposure at a size of several tens of micrometers or less sometimes peels off from the substrate in a subsequent step such as a developing step, and as a result, the fineness of the printed wiring board is limited .

Therefore, in order to form a fine printed wiring board, a photosensitive resin composition having high adhesion of a fine pattern is required.

However, in the photosensitive resin compositions described in Patent Documents 1 and 4, there is still room for improvement in this field because both of the development dispersibility and the adhesion of fine patterns can not withstand today's harsh demands.

The second embodiment of the present invention is made in consideration of the present situation.

Therefore, an object of the second embodiment of the present invention is to provide a novel photosensitive material having a high level of performance generally required for a photosensitive material, such as resolution, and excellent in development dispersibility and adhesion to a fine pattern .

&Lt; Problem to be solved by the third embodiment of the present invention &

Patent Document 5 discloses that in the photosensitive resin composition, the structural unit of (meth) acrylic acid, the structural unit of styrene or? -Methylstyrene, and the structural unit of (meth) acrylic acid are preferably used in view of the developability of the photosensitive resin composition and the resolution, A binder polymer having a structural unit of a (meth) acrylic acid hydroxyalkyl ester having a hydroxyalkyl group having 1 to 12 carbon atoms and a polymer having a structural unit number of 1 to 20 and a structural unit number of 0 to 7 A combination of bisphenol type di (meth) acrylate monomers is being studied.

In Patent Document 6, from the viewpoint of the space width and tent property of the positive resist pattern, 30 mass% or more is proposed as the content of the structural unit of the styrene or styrene derivative in the alkali-soluble polymer, and the weight average molecular weight Of at least 1,100 are proposed.

In both of Patent Documents 5 and 6, a photosensitive resin composition containing a specific monomer and a polymer having a structural unit of styrene at a specific ratio is focused on. However, the photosensitive resin composition described in Patent Documents 5 and 6 is a resist pattern tent And also has room for improvement from the viewpoint that both the performance and the water-poor residual short-circuit inhibition are satisfied.

Therefore, a problem to be solved by the third embodiment of the present invention is to provide a photosensitive resin composition capable of achieving both a tent property of a resist pattern and a water-poor short-circuit inhibiting property.

&Lt; Problem to be solved by the fourth embodiment of the present invention &

In recent years, the production of a wiring board is usually carried out by a line process in which a substrate is sequentially transported while being transported in a certain direction. At this time, the treatment of the developer or etchant on the substrate is carried out by spraying. In forming a resist pattern by photolithography, it is important that the resist line width after development does not vary. However, in the formation of the resist pattern by the spraying phenomenon, when the developing time is short, deviation of the developing solution in the substrate plane easily occurs. In such a case, the above problem may arise.

Here, the developing time is a time period during which the substrate stays in the developing chamber and is subjected to development processing, for example, a time such as twice the minimum developing time. The minimum developing time refers to the minimum time required until the unexposed portion of the photosensitive resin layer is completely dissolved and removed and is changed depending on the concentration or temperature of the developing solution, the spray direction or spray amount, the pressure, do.

Here, it is considered that the dissolution reaction of the resist due to the development is generally caused by the diffusion rate of the developer. Therefore, from the viewpoint of promoting the development, it is necessary to actively supply the developer onto the substrate by spraying or the like. This supply takes some time. Therefore, when the development time is short, it is considered that the supply of the developing solution does not sufficiently reach the entire surface of the substrate, and the deviation of the resist line width becomes remarkably large. On the other hand, when the developing time is long, it is considered that the supply of the developer on the substrate becomes uniform, and thus the deviation of the line width becomes small. Therefore, it is considered that the use of a photosensitive resin composition having a slow minimum developing time itself is effective from the viewpoint of suppressing the deviation of line width.

Patent Document 5 discloses that in the photosensitive resin composition, the structural unit of (meth) acrylic acid, the structural unit of styrene or? -Methylstyrene, and the structural unit of (meth) acrylic acid are preferably used in view of the developability of the photosensitive resin composition and the resolution, A binder polymer having a structural unit of a (meth) acrylic acid hydroxyalkyl ester having a hydroxyalkyl group having 1 to 12 carbon atoms and a polymer having a structural unit number of 1 to 20 and a structural unit number of 0 to 7 A combination of bisphenol type di (meth) acrylate monomers is being studied.

In Patent Document 6, from the viewpoint of the space width and tent property of the positive resist pattern, 30 mass% or more is proposed as the content of the structural unit of the styrene or styrene derivative in the alkali-soluble polymer, and the weight average molecular weight Of at least 1,100 are proposed.

Both Patent Documents 5 and 6 have focused on a polymer having styrene structural units at a specific ratio and a photosensitive resin composition containing a specific monomer. However, the photosensitive resin compositions described in Patent Documents 5 and 6 are excellent in the resist pattern But also had room for improvement in terms of both resolution and prolongation of the minimum development time.

Therefore, a problem to be solved by the fourth embodiment of the present invention is to provide a photosensitive resin composition capable of satisfactory resolution of a resist pattern and prolongation of a minimum development time.

&Lt; Means for solving the first problem &

The present inventors have found out that the above object can be achieved by the following technical means, and have reached the first embodiment of the present invention. The first embodiment of the present invention is as follows.

[One]

Each of the following components (A) to (C)

(A) Component: alkali-soluble polymer,

(B): a compound having an ethylenic double bond, and

(C): Photopolymerization initiator

Wherein the photosensitive resin composition comprises

A photosensitive resin layer composed of the above photosensitive resin composition was laminated to a thickness of 25 mu m on a copper clad laminate in which copper foils having a thickness of 18 mu m were laminated and subjected to light irradiation and development processing in a pattern of line / space = 50 mu m / 30 mu m Wherein the copper line pattern obtained by removing the cured resist pattern after forming a cured resist pattern and performing copper etching treatment at 50 占 폚 for 55 seconds is 38 占 퐉 or more.

[2]

The photosensitive resin composition according to [1], wherein the component (A) is a copolymer having a (meth) acrylic acid unit content of 10 mass% or more and 24 mass% or less.

[3]

The photosensitive resin composition according to [1] or [2], wherein the component (A) is a copolymer having a styrene unit content of 32 mass% or more and 60 mass% or less.

[4]

The photosensitive resin composition according to any one of [1] to [3], wherein the component (C) contains an acridine compound.

[5]

The photosensitive resin composition according to any one of [1] to [4], wherein the component (B) contains a pentaerythritol compound.

[6]

The photosensitive resin composition according to any one of [1] to [5], wherein the component (B) contains a trimethylolpropane compound.

[7]

The photosensitive resin composition according to any one of [1] to [6], wherein the component (B) contains a bisphenol A compound.

[8]

Each of the following components (A) to (C)

(A) Component: alkali-soluble polymer,

(B): a compound having an ethylenic double bond, and

(C): Photopolymerization initiator

Wherein the photosensitive resin composition comprises

The component (A) includes a copolymer having a (meth) acrylic acid unit content of 10 mass% or more and 24 mass% or less and a styrene unit content of 32 mass% or more,

The component (C) is a compound containing an acridine compound

Sensitive resin composition.

[9]

Wherein the component (A) comprises a copolymer having a (meth) acrylic acid unit content of 10 mass% or more and 24 mass% or less and a styrene unit content of 32 mass% or more and 60 mass% or less. The photosensitive resin composition described above.

[10]

The photosensitive resin composition according to [8] or [9], wherein the component (B) contains a pentaerythritol compound.

[11]

The photosensitive resin composition according to any one of [8] to [10], wherein the component (B) contains a trimethylolpropane compound.

[12]

The photosensitive resin composition according to any one of [8] to [11], wherein the component (B) contains a bisphenol A compound.

[13]

A photosensitive element in which a photosensitive resin layer comprising the photosensitive resin composition according to any one of [1] to [12] is laminated on a support.

[14]

A lamination step of laminating the photosensitive resin layer of the photosensitive element described in [13] on a conductor substrate,

An exposure step of exposing the laminated photosensitive resin composition layer, and

A developing step of removing the unexposed portion after the exposure with a developer,

And forming a resist pattern on the resist pattern.

[15]

Wherein the lamination step is a step of laminating a photosensitive resin layer of the photosensitive element on a conductive substrate through a wetting agent.

[16]

A lamination step of laminating the photosensitive resin composition layer of the photosensitive element described in [13] on a conductor substrate,

An exposure step of exposing the laminated photosensitive resin composition layer,

A developing step of removing the unexposed portion after the exposure with a developer,

A conductor pattern forming step of etching or plating a conductor substrate on which a resist pattern is formed by the above phenomenon, and

A peeling step of peeling the resist pattern,

And a step of forming the wiring board.

[17]

The laminate process is a process for laminating a photosensitive resin layer of a photosensitive element on a conductive substrate through a wetting agent.

&Lt; Means for solving the second problem &

The present inventors have found out that the above object can be achieved by the following technical means, and have reached the second embodiment of the present invention. The second embodiment of the present invention is as follows.

[One]

Each of the following components (A) to (C)

Component (A): an alkali-soluble polymer having an acid equivalent weight of 100 to 600,

(B): a compound having an ethylenic double bond, and

(C): Photopolymerization initiator

Wherein the photosensitive resin composition comprises

Wherein the component (A) contains a copolymer containing 50% by mass or more of styrene units,

Wherein the component (B) is a compound represented by the following general formula (I):

[Chemical Formula 1]

Wherein n is an integer of 0 to 30, provided that n1 + n2 + n3? 6 is an integer of 1 to 4, Wherein the content of the compound represented by the general formula (I) is 5% by mass or more based on the solid content of the photosensitive resin composition, and the component (C) is acridine Wherein the photosensitive resin composition contains the compound.

[2]

The photosensitive resin composition according to [1], wherein n1, n2 and n3 in the general formula (I) satisfy 20? N1 + n2 + n3> 9.

[3]

The photosensitive resin composition according to [1] or [2], wherein all of R in the general formula (I) is a hydrogen atom.

[4]

The photosensitive resin composition according to any one of [1] to [3], wherein the component (B) further contains a pentaerythritol-modified monomer.

[5]

A photosensitive element in which a photosensitive resin layer composed of the photosensitive resin composition described in any one of [1] to [4] is laminated on a support.

[6]

A lamination step of laminating a photosensitive resin layer of the photosensitive element described in [5] on a conductor substrate,

An exposure step of exposing the laminated photosensitive resin layer, and

A developing step of removing the unexposed portion after the exposure with a developer,

And forming a resist pattern on the resist pattern.

[7]

A lamination step of laminating a photosensitive resin layer of the photosensitive element described in [5] on a conductor substrate,

An exposure step of exposing the laminated photosensitive resin layer,

A developing step of removing the unexposed portion after the exposure with a developer,

A conductor pattern forming step of etching or plating a conductor substrate on which a resist pattern is formed by the above phenomenon, and

A peeling step of peeling the resist pattern,

And a step of forming the wiring board.

&Lt; Means for solving the third problem &

The present inventor has found that the above problems can be solved by the following technical means. A third embodiment of the present invention is as follows.

[One]

(A) an alkali-soluble polymer;

(B) an ethylenically unsaturated bond-containing compound; and

(C) a photopolymerization initiator;

A photosensitive resin composition,

The alkali-soluble polymer (A) is a polymer comprising 10 to 24 mass% of a structural unit of (meth) acrylic acid and 35 to 90 mass% of structural units based on the total mass of the monomers constituting the alkali- Styrene &lt; / RTI &gt;

Wherein the ethylenically unsaturated bond-containing compound (B) has a weight average molecular weight of 1,200 or more.

[2]

The photosensitive resin composition according to [1], wherein the ethylenically unsaturated bond-containing compound (B) has a weight average molecular weight of 1,300 or more.

[3]

Wherein at least 40 mass% of the ethylenically unsaturated bond-containing compound (B) satisfies the following formula (II):

(2)

Wherein R ₃ and R ₄ each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , n ₁ , n ₂ , n ₃ and n ₄ are , n ₁ + n ₂ + n ₃ + n ₄ = 2 to 50, and the arrangement of repeating units of - (AO) - and - (BO) - may be random or block, , Any one of - (AO) - and - (BO) - may be a bisphenyl group side}

Is an alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the following formula (1) or (2).

[4]

The photosensitive resin composition according to [3], wherein n ₁ , n ₂ , n ₃ and n ₄ in the general formula (II) satisfy a relationship of n ₁ + n ₂ + n ₃ + n ₄ = 30 to 50.

[5]

The photosensitive resin composition according to [3], wherein n ₁ , n ₂ , n ₃ and n ₄ in the general formula (II) satisfy a relationship of n ₁ + n ₂ + n ₃ + n ₄ = 2 to 10.

[6]

The ethylenically unsaturated bond-containing compound (B) is a compound represented by the following general formula (III):

(3)

Wherein R ₅ , R ₆ and R ₇ each independently represent a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, m ₂ , m ₃ and m ₄ each independently M ₂ + m ₃ + m ₄ is 1 to 40, and when m ₂ + m ₃ + m ₄ is 2 or more, the plural Xs are the same or different from each other I can do it}

The photosensitive resin composition according to [1] or [2], further comprising a tri (meth) acrylate compound represented by the following formula

[7]

The ethylenically unsaturated bond-containing compound (B) is represented by the following general formula (IV):

[Chemical Formula 4]

(Wherein R ₈ and R ₉ each independently represent a hydrogen atom or a methyl group, Y represents an alkylene group having 2 to 6 carbon atoms, Z represents a divalent organic group, and s and t represent The photosensitive resin composition according to [1] or [2], further comprising a urethane di (meth) acrylate compound represented by the following formula:

[8]

The photosensitive resin composition according to any one of [1] to [7], wherein the alkali-soluble polymer (A) further comprises a structural unit of butyl (meth) acrylate.

[9]

The photosensitive resin composition according to any one of [1] to [8], which is for direct imaging exposure.

[10]

A laminating step of laminating a photosensitive resin layer comprising the photosensitive resin composition described in any one of [1] to [9] on a support;

An exposure step of exposing the photosensitive resin layer;

A developing step of developing the exposed photosensitive resin layer;

And forming a resist pattern on the resist pattern.

[11]

A laminating step of laminating a photosensitive resin layer made of the photosensitive resin composition described in any one of [1] to [9] on a substrate;

An exposure step of exposing the photosensitive resin layer;

A developing step of developing the exposed photosensitive resin layer to obtain a substrate on which a resist pattern is formed;

A conductor pattern forming step of etching or plating the substrate on which the resist pattern is formed;

A peeling step of peeling the resist pattern;

And a step of forming the wiring board.

&Lt; Means for solving the fourth problem &

The inventors of the present invention have found that the above objects can be achieved by the following technical means, leading to the fourth embodiment of the present invention. The fourth embodiment of the present invention is as follows.

[One]

(A) an alkali-soluble polymer;

(B) an ethylenically unsaturated bond-containing compound; and

(C) a photopolymerization initiator;

A photosensitive resin composition,

The alkali-soluble polymer (A) contains a first copolymer having a content of acid monomer units of less than 25 mass% and a content of aromatic monomer units of not less than 30 mass%

Wherein the ethylenically unsaturated bond-containing compound (B) has a weight average molecular weight of 900 or less,

The photosensitive resin composition.

[2]

The photosensitive resin composition according to [1], wherein the (C) photopolymerization initiator comprises an acridine compound.

[3]

The photosensitive resin composition according to [1] or [2], wherein the alkali-soluble polymer (A) comprises a second copolymer having a content of aromatic monomer units of 45 mass% to 90 mass%.

[4]

The ethylenically unsaturated bond-containing compound (B) is a compound represented by the following general formula (III):

[Chemical Formula 5]

Wherein R ₅ , R ₆ and R ₇ each independently represent a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, m ₂ , m ₃ and m ₄ each independently M ₂ + m ₃ + m ₄ is 0 to 40, and when m ₂ + m ₃ + m ₄ is 2 or more, the plural Xs are the same or different from each other I can do it}

The photosensitive resin composition according to any one of [1] to [3], which comprises a tri (meth) acrylate compound represented by the following formula

[5]

The ethylenically unsaturated bond-containing compound (B) is represented by the following general formula (II):

[Chemical Formula 6]

Wherein R ₃ and R ₄ each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , n ₁ , n ₂ , n ₃ and n ₄ are , n ₁ + n ₂ + n ₃ + n ₄ = 2 to 50, and the arrangement of repeating units of - (AO) - and - (BO) - may be random or block, , Any one of - (AO) - and - (BO) - may be a bisphenyl group side}

The photosensitive resin composition according to any one of [1] to [4], wherein the photosensitive resin composition comprises an alkylene oxide-modified bisphenol A type di (meth) acrylate compound.

[6]

As the hindered phenol, a compound represented by the following general formula (V):

(7)

(Wherein R ⁵¹ represents a linear alkyl group, a branched alkyl group, an aryl group, a cyclohexyl group, a linear alkyl group having a divalent linking group, a branched alkyl group having a divalent linking group, a divalent linking group, And R ⁵² , R ⁵³ and R ⁵⁴ are each independently hydrogen or a linear or branched alkyl group, a branched alkyl group, an aryl group, a cycloalkyl group, a cycloalkyl group, a cycloalkyl group, a cycloalkyl group, A hexyl group, a linear alkyl group having a divalent linking group, a branched alkyl group having a divalent linking group, a cyclohexyl group having a divalent linking group, or an aryl group having a divalent linking group interposed therebetween. The photosensitive resin composition according to any one of [1] to [5],

[7]

The photosensitive resin composition according to any one of [1] to [6], which is for direct emulsion exposure.

[8]

A photosensitive element in which a photosensitive resin layer composed of the photosensitive resin composition described in any one of [1] to [7] is laminated on a support.

[9]

A lamination step of laminating the photosensitive resin layer of the photosensitive element described in [8] on a conductor substrate;

An exposure step of exposing the laminated photosensitive resin layer;

A developing step of developing the exposed photosensitive resin layer;

And forming a resist pattern on the resist pattern.

[10]

A lamination step of laminating the photosensitive resin layer of the photosensitive element described in [8] on a conductor substrate;

An exposure step of exposing the laminated photosensitive resin layer;

A developing step of developing the exposed photosensitive resin layer to form a resist pattern on the conductive substrate;

A conductive pattern forming step of etching or plating the conductive substrate on which the resist pattern is formed;

A peeling step of peeling the resist pattern;

And a step of forming the wiring board.

&Lt; Effects of First Embodiment &gt;

According to the first embodiment of the present invention, in forming a fine conductor pattern by a line process, a resist material in which the vertical and horizontal differences in wiring width are suppressed is provided.

&Lt; Effects of Second Embodiment &gt;

According to the second embodiment of the present invention, there is provided a novel photosensitive material excellent in both developability of dispersibility and adhesion of a fine pattern while having a high level of performance generally required for a photosensitive material, such as sensitivity and resolution .

&Lt; Effect of Third Embodiment &gt;

According to the third embodiment of the present invention, there is provided a photosensitive resin composition capable of satisfying both the tent property of the resist pattern and the water-insoluble short-circuit inhibiting property.

&Lt; Effect of Fourth Embodiment &gt;

According to the fourth embodiment of the present invention, there is provided a photosensitive resin composition capable of securing good resolution of a resist pattern and extending a minimum developing time, and a method of forming a resist pattern or a wiring board using the same.

&Lt; First Embodiment &gt;

Hereinafter, a mode for carrying out the first embodiment of the present invention (hereinafter abbreviated as &quot; the first embodiment &quot;) will be described in detail.

<Photosensitive resin composition>

In the first embodiment, the photosensitive resin composition comprises the following components (A) to (C)

(A) Component: alkali-soluble polymer,

(B): a compound having an ethylenic double bond, and

Component (C): a photopolymerization initiator,

Lt; / RTI &gt;

[Component (A): alkali-soluble polymer]

The component (A) is not particularly limited as long as it is soluble in a developing solution described later. Preferably, it is a copolymer of (meth) acrylic acid and other monomers. The degree of dispersion of the copolymer represented by the weight average molecular weight (described later) and the number average molecular weight of the copolymer is preferably 1 or more and 6 or less.

Examples of the (meth) acrylic acid include (meth) acrylic acid, pentenoic acid, unsaturated dicarboxylic acid anhydride, and hydroxystyrene. Examples of the unsaturated dicarboxylic acid anhydride include maleic anhydride, itaconic anhydride, fumaric acid, and citraconic anhydride. Among them, (meth) acrylic acid is preferable.

The copolymerization ratio of the (meth) acrylic acid unit in the component (A) is preferably 10% by mass to 24% by mass, more preferably 15% by mass to 23% by mass relative to the total mass of all monomer units Do. When the content of the (meth) acrylic acid unit is within this range, the suppression of the etching rate at the time of forming the conductor pattern (the bottom width of the conductor line pattern described above is maintained at a certain level or more) It is preferable from the viewpoint of suppressing the difference.

Examples of other monomers include unsaturated aromatic compounds (sometimes referred to as "aromatic monomers"), (meth) acrylic acid alkyl esters, (meth) acrylic acid aralkyl esters, conjugated diene compounds, polar monomers, And the like.

Examples of the unsaturated aromatic compound include styrene,? -Methylstyrene, vinylnaphthalene, and the like. Among them, styrene is preferable.

(Meth) acrylic acid alkyl ester is a concept including both chain alkyl esters and cyclic alkyl esters, and specifically includes, for example, methyl (meth) acrylate, ethyl (meth) (Meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl Stearyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like.

Examples of (meth) acrylic acid aralkyl esters include benzyl (meth) acrylate and the like;

Examples of the conjugated diene compound include 1,3-butadiene, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene and the like.

As the polar monomer, for example,

Hydroxyl group-containing monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and pentenol;

Amino group-containing monomers such as 2-aminoethyl methacrylate;

Amide group-containing monomers such as (meth) acrylamide and N-methylol (meth) acrylamide;

Cyano group-containing monomers such as acrylonitrile, methacrylonitrile,? -Chloroacrylonitrile and? -Cyanoethyl acrylate;

Epoxy group-containing monomers such as glycidyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate;

And the like.

Examples of the crosslinkable monomer include trimethylolpropane triacrylate and divinylbenzene.

The component (A) is preferably a copolymer of (meth) acrylic acid, styrene, and other monomers.

The copolymerization ratio of the styrene unit in the component (A) is preferably 32% by mass or more, and more preferably 35% by mass or more, based on the total mass of all monomer units. The copolymerization ratio of styrene units in the component (A) is preferably 60% by mass or less, more preferably 55% by mass or less, based on the total mass of all monomer units. It is preferable to set the copolymerization ratio of styrene having high hydrophobicity and styrene which is difficult to be fused with the developing solution and the developing water to the above-mentioned range from the viewpoint of suppressing the width and width of the wiring.

The weight-average molecular weight of the component (A) (the weight-average molecular weight of the mixture as a whole when the component (A) includes plural kinds of copolymers) is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000 And more preferably from 15,000 to 100,000. Adjusting the weight average molecular weight of the component (A) within this range is preferable from the viewpoint of satisfying the developing time at the time of forming the resist pattern to the operating state of the line process to be used.

In the first embodiment, the content of the component (A) in the photosensitive resin composition is 10% by mass to 10% by mass based on the total solid content of the photosensitive resin composition (hereinafter, unless otherwise specified, , More preferably 20 mass% to 80 mass%, and still more preferably 40 mass% to 60 mass%. This content is preferably 10% by mass or more from the viewpoint of maintaining alkali developability, and is preferably 90% by mass or less from the viewpoint that the resist pattern formed by exposure sufficiently exhibits the performance as a resist.

(Meth) acrylic acid units is from 10% by mass to 24% by mass, and the content of styrene units is from 32% by mass to 60% by mass based on the total solid content of the photosensitive resin composition is not less than 8% , More preferably 10 mass% or more, and particularly preferably 13.5 / 99.19 x 100 mass% or more. (Meth) acrylic acid unit content is from 10% by mass to 24% by mass and the styrene unit content is from 32% by mass to 60% by mass based on the total solid content of the photosensitive resin composition is 50% by mass or less Or less, and may be 40 mass% or less, 30 mass% or less, 27 / 99.19 × 100 mass% or less, or 20 mass% or less.

[Component (B): a compound having an ethylenic double bond]

The component (B) may contain at least one ethylenic double bond. It is preferable to use a compound having two or more ethylenic double bonds.

Examples of the compound (B) having two ethylenic double bonds include bisphenol A compounds, especially di (meth) acrylates of polyalkylene glycols in which an average of 2 to 15 mol of an alkylene oxide is added to both ends of bisphenol A, Methacrylate and the like are preferably used.

Examples of the compound (B) having three ethylenic double bonds include trimethylolpropane compounds, particularly trimethylolpropane tri (meth) acrylate compounds having an average of 3 to 25 moles of alkylene oxide added to trimethylolpropane (Meth) acrylate and the like are preferably used.

Examples of the compound (B) having four ethylenic double bonds include pentaerythritol compounds, particularly tetra (meth) acrylates of polyols obtained by adding an average of from 4 mol to 35 mol of an alkylene oxide to pentaerythritol, Acrylate and the like are preferably used.

As commercial products thereof, for example, "BPE-500", "A-TMPT-3EO", "A-9300-1CL", etc. (all manufactured by Shin- Nakamura Chemical Co., Ltd.)

Aronix M-327 &quot; (manufactured by Toagosei Co., Ltd.), and the like.

The content of the component (B) in the photosensitive resin composition of the first embodiment is preferably 1% by mass to 70% by mass, more preferably 5% by mass to 60% by mass, still more preferably 10% Is more preferable. This content is preferably not less than 1% by mass from the viewpoint of suppressing the curing failure and retarding the developing time, and is preferably not more than 70% by mass from the viewpoint of suppressing the delamination delay of the cold flow and the cured resist.

As the component (B), it is preferable to use a high molecular weight compound having a molecular weight of 1,000 or more. The molecular weight of this high molecular weight compound is more preferably from 1,300 to 3,000. The inclusion of such a high molecular weight compound is preferable from the viewpoints of suppressing the etching rate at the time of forming the conductor pattern and suppressing the width and width of the wiring.

The proportion of such a high molecular weight compound in the component (B) is preferably 20 mass% or more, and more preferably 20 to 50 mass%.

Here, DD value is defined as an index of the double bond concentration of the component (B). The DD value is the number of double bonds per weight average molecular weight of the monomers, and has a specific value for each monomer.

When a monomer having a small DD value is used in a photosensitive resin composition, the film after photo-curing tends to become flexible.

When the component (B) is composed of plural kinds, the weighted average of the DD value and the compounding ratio of each ethylenically unsaturated bond-containing compound is regarded as the DD value of the composition. From the viewpoint of suppressing the vertical and horizontal difference in the wiring width and improving the tentability, the preferable range of the DD value of the composition is 0.10 to 0.13. More preferably 0.10 to 0.125.

[Component (C): photopolymerization initiator]

The component (C) is a component that generates a radical capable of initiating polymerization of the component (B) by irradiation of light.

Examples of such component (C) include aromatic ketone compounds, quinone compounds, benzoin ether compounds, benzoin compounds, benzyl compounds, hexaarylbisimidazole compounds, and acridine compounds. Among these, from the viewpoint of high resolution and good tentability, it is preferable to use an acridine compound.

The content of the acridine compound in the photosensitive resin composition of the first embodiment is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.2% by mass, and most preferably 0.3% , More preferably 0.4 mass%.

The content of the acridine compound in the photosensitive resin composition of the first embodiment is preferably 2.0 mass% or less, more preferably 1.8 mass% or less, even more preferably 1.7 mass% or less, and 1.6 mass% or less Is more preferable. Within this range, it is possible to provide a resist material that suppresses the vertical and horizontal difference in wiring width, which is preferable.

Examples of the acridine compound include acridine, 9-phenylacridine, 1,6-bis (9-acridinyl) hexane, 1,7- (9-acridinyl) decane, 1,11-bis (9-acridinyl) octane, 1,9-bis Undecane, 1,12-bis (9-acridinyl) dodecane, and the like.

It is preferable to use an acridine compound and a hexaarylbisimidazole compound as the component (C).

Examples of the hexaarylbisimidazole compound include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2,2 ', 5-tris (o-chlorophenyl) -4 - (3,4-dimethoxyphenyl) -4 ', 5'-diphenylimidazolyl dimer, 2,4-bis- (o-chlorophenyl) Diphenylimidazolyl dimer, 2- (o-chlorophenyl) -bis-4,5- (3,4-dichlorophenyl) Dimethoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2-fluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) Dimer, 2,2'-bis- (2,3-difluoromethylphenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) (2,4-difluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,5-difluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'- Difluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3,4-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3- Methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3,5-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) ) -Imidazolyl dimer, 2,2'-bis- (2,3,6-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) (2,4,5-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl 2 (2,4,6-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2 , 2'-bis- (2,3,4,5-tetrafluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, Tetrais- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3,4,6-tetrafluorophenyl) -4,4 ', 5,5'- '- bis- (2,3,4,5,6-pentafluorophenyl) -4,4', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer etc. The can.

The content of the component (C) in the photosensitive resin composition of the first embodiment is preferably 0.1% by mass to 2% by mass, more preferably 0.2% by mass to 1.8% by mass, still more preferably 0.3% By mass to 1.7% by mass, and particularly preferably 0.4% by mass to 1.6% by mass. Setting the content of the component (C) in such a range is preferable from the viewpoint of obtaining good light sensitivity and peeling property.

The component (C) may further contain a sensitizer in view of improvement in sensitivity and resolution. Examples of such a sensitizer include N-aryl amino acids, organic halogen compounds, and other sensitizers.

Examples of the N-arylamino acid include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like;

Examples of the organic halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenylsulfone, tetrabromocarbon, tris (2,3 (Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, chlorinated triazine compounds and the like;

Respectively.

Examples of the other sensitizer include 2-ethyl anthraquinone, octaethyl anthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, Anthraquinone, 1-chloroanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethyl anthraquinone, Quinone compounds such as methyl anthraquinone;

Aromatic ketone compounds such as benzophenone, Michler's ketone [4,4'-bis (dimethylamino) benzophenone] and 4,4'-bis (diethylamino) benzophenone;

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

Benzyldimethyl ketal, benzyldiethyl ketal, 1-phenyl-1,2-propanedione-2-O-benzoin oxime, 1-phenyl-1,2-propanedioyl- 2- (O-ethoxycarbonyl) oxime Oxime ester compounds such as &lt; RTI ID = 0.0 &gt;

And the like.

The content of the sensitizer in the first embodiment is preferably 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 3% by mass, from the viewpoints of the light sensitivity of the composition and the peelability of the resist cured film, More preferably 0.1% by mass to 2% by mass.

In the photosensitive resin composition of the first embodiment, it is preferable to use an acridine compound and an N-arylamino acid as the component (C), and to use them together within the above-mentioned ratio of use, to form a conductor pattern In view of the suppression of the etching rate at the time of etching and the suppression of the vertical and lateral difference of the wiring width.

[Other components]

The photosensitive resin composition of the first embodiment may contain other components in addition to the components (A) to (C) described above. Such other components include, for example, leuco dyes, base dyes, plasticizers, antioxidants, stabilizers, radical polymerization inhibitors, solvents and the like.

[Leuco dye]

The above-mentioned leuco dye can be compounded in the photosensitive resin composition of the first embodiment in order to impart desirable coloring property and excellent peeling property to the resist cured film.

Specific examples of the leuco dyes include, for example, leuco crystal violet (tris [4- (dimethylamino) phenyl] methane), 3,3-bis (p-dimethylaminophenyl) (1-ethyl-2-methylindole-3-yl) phthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- 3-methyl-6-dimethylaminofluororan, 3-dibutyl (2-methylbutyl) Amino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3- 2-chloroanilino) -6-dibutylaminofluorane, 3,6-dimethoxyfluoran, 3,6-di-n-butoxyfluororan, 1,2- Methyl-6- (Np-tolyl-N-ethylamino) fluororan, 1,2-benzyl- 2- 2- (3'-trifluoromethylanilino) -6-diethylaminofluororan, 3- (N-phenyl- Chloro-6-cyclohexylaminofluorane, 2-methyl-6-cyclohexylaminofluorane and 3-methoxy-4-dodecoxy-styrinoquinoline. Among them, Loico crystal violet is preferable.

The content of the leuco dye in the photosensitive resin composition of the first embodiment is preferably 0.6% by mass to 1.6% by mass, and more preferably 0.7% by mass to 1.2% by mass. By setting the usage ratio of the leuco dye within this range, it is possible to realize good coloring property and good releasability.

[Base dye]

Examples of the base dye include Basic Green 1 (CAS No.: 633-03-4) (for example, Aizen Diamond Green GH, trade name, manufactured by Hodogaya Chemical Co., Ltd.), malachite green oxalate (Aizen Malachite Green, trade name, manufactured by Hodogaya Chemical Co., Ltd.), Brilliant Green [633-03-4], fuchsin [632-99-5], methyl violet [603-47- 4], Methyl Violet 2B [8004-87-3], Crystal Violet [548-62-9], Methyl Green [82-94-0], Victoria Blue B [2580-56-5], Basic Blue 7 [2390 -60-5] (for example, Aizen Victoria Pure Blue BOH, a product of Hodogaya Chemical Co., Ltd.), rhodamine B [81-88-9], rhodamine 6G [989-38-8], basic yellow 2 [2465-27-2], diamond green, and the like. Of these, at least one selected from Basic Green 1, Malachite Green Oxalate, Basic Blue 7 and Diamond Green is preferable, and from the viewpoints of color stability and exposure contrast, Basic Green 1 is particularly preferable.

The content of the base dye in the photosensitive resin composition of the first embodiment is preferably 0.001 mass% to 3 mass%, more preferably 0.01 mass% to 2 mass%, still more preferably 0.01 Mass% to 1.2 mass%. By setting the ratio in this range, both good color development and high sensitivity can be achieved.

[menstruum]

The photosensitive resin composition of the first embodiment may be a mixture of the above components (A) to (C) and other components optionally used, or a photosensitive resin composition comprising the above components in which a suitable solvent is added It may be used as a combination liquid.

As the solvent used here, for example,

Ketone compounds such as methyl ethyl ketone (MEK);

Alcohols such as ethanol, ethanol, and isopropyl alcohol;

And the like.

The ratio of the solvent used is preferably such that the viscosity of the solution of the photosensitive resin composition combination at 25 ° C is 500 to 4,000 mPa · sec.

<Photosensitive element>

In the first embodiment, the photosensitive element is a laminate (photosensitive resin laminate) in which a photosensitive resin layer composed of the above-described photosensitive resin composition is laminated on a support. If necessary, the photosensitive resin layer may have a protective layer on the surface opposite to the support.

[Support]

As the support, a transparent substrate that transmits light emitted from an exposure light source is preferable. Examples of such a support include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film , A polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. As these films, stretched films may be used if necessary.

The haze of the support is preferably 5 or less.

Thickness of the support is advantageous from the viewpoint of image forming property and economical efficiency, but it is necessary to maintain the strength. Considering both of them, a support of 10 占 퐉 to 30 占 퐉 can be preferably used.

[Photosensitive resin composition layer]

When the photosensitive resin composition used for forming the photosensitive resin composition layer contains a solvent, the solvent is preferably removed in the photosensitive resin composition layer, but a solvent may remain.

The thickness of the photosensitive resin composition layer is preferably 5 탆 to 100 탆, and more preferably 7 탆 to 60 탆. The thinner the thickness, the better the resolution, and the thicker the film the better the film strength. Therefore, the thickness of the composition layer can be appropriately selected within the above-described range depending on the application.

[Protective layer]

An important characteristic of the protective layer is that the adhesive force between the support and the photosensitive resin composition layer is sufficiently smaller than the adhesion between the support and the photosensitive resin composition layer and can be easily peeled off. As the protective layer, for example, a polyethylene film, a polypropylene film and the like can be preferably used, and for example, a film having excellent peelability disclosed in Japanese Patent Application Laid-open No. 59-202457 can be used.

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

[Method of producing photosensitive element]

The photosensitive element can be produced by sequentially laminating a support, a photosensitive resin layer and, if necessary, a protective layer. As a method for laminating the support, the photosensitive resin layer, and the protective layer, a known method can be adopted.

For example, a photosensitive resin composition is prepared as a combination solution of the above-described photosensitive resin composition, and then applied on a support using a bar coater or roll coater and dried to form a photosensitive resin composition layer comprising a photosensitive resin composition on the support . Subsequently, if necessary, a photosensitive element can be produced by laminating a protective layer on the formed photosensitive resin composition layer.

&Lt; Method of forming resist pattern &gt;

A resist pattern can be formed on a substrate using the above-described photosensitive element.

A method of forming a resist pattern includes:

A lamination step of laminating a photosensitive resin layer of the photosensitive element on a conductor substrate,

An exposure step of exposing the laminated photosensitive resin composition layer, and

A developing step of removing the unexposed portion after the exposure with a developer,

In the order described above.

The lamination step is preferably a step of laminating the photosensitive resin layer of the photosensitive element on the conductive substrate through the wetting agent. As the wetting agent, at least one selected from pure water, deionized water, and electrolytic water, and a copper chelating agent (for example, selected from the group consisting of an imidazole compound, a triazole compound, a pyridine compound, and a pyrazole compound) At least one compound selected from the group consisting of:

In the resist pattern forming method of the first embodiment, first, a photosensitive resin composition layer is formed on a substrate by using a laminator in the lamination step. Specifically, when the photosensitive element has a protective layer, the protective layer is peeled off, and then the photosensitive resin composition layer is laminated on the surface of the substrate by heating using a laminator.

As the substrate, a metal plate or an insulating substrate having a metal coating is used. Examples of the material of the metal include copper, stainless steel (SUS), glass, indium tin oxide (ITO), and the like. These substrates may have through-holes corresponding to the multilayer substrate.

Here, the photosensitive resin composition layer may be laminated only on one side of the substrate surface, and may be laminated on both sides of the substrate, if necessary. The heating temperature at this time is preferably 40 占 폚 to 160 占 폚. It is preferable to carry out hot pressing twice or more from the viewpoint of further improving the adhesion of the obtained resist pattern to the substrate. In the case of performing the pressing twice or more, a two-stage laminator having two sets of rolls may be used. Alternatively, the laminate of the substrate and the photosensitive resin composition layer may be repeatedly passed through rolls and pressed.

Next, in the exposure step, the photosensitive resin composition layer is exposed using an exposure machine. This exposure may be carried out through the support without peeling the support, and may be carried out after peeling off the support.

By applying this exposure in the form of a pattern, a resist film (resist pattern) having a desired pattern can be obtained after passing through a developing step described later. Patternwise exposure may be performed by a method of exposure through a photomask, or a maskless exposure method. In the case of exposure through a photomask, the exposure dose is determined by the light source illuminance and the exposure time. The exposure dose may be measured using a photometer.

In maskless exposure, a photomask is not used, and exposure is performed directly on a substrate by a drawing apparatus. As the light source, a semiconductor laser having a wavelength of 350 nm to 410 nm, an ultra-high pressure mercury lamp or the like is used. In maskless exposure, the imaging pattern is controlled by a computer, and the amount of exposure is determined by the illuminance of the exposure light source and the moving speed of the substrate.

Next, in the developing step, the unexposed portion of the photosensitive resin composition layer is removed with a developer. If there is a support on the photosensitive resin composition layer after exposure, it is preferable to provide it to the development step after excluding it.

In the developing step, a developing solution composed of an aqueous alkali solution is used to develop and remove the unexposed portion, thereby obtaining a resist image. As the alkali aqueous solution, for example, an aqueous solution of Na ₂ CO ₃ , K ₂ CO _3, or the like is preferably used. The alkali aqueous solution is selected in accordance with the characteristics of the photosensitive resin composition layer, but it is preferable to use an Na ₂ CO ₃ aqueous solution having a concentration of 0.2 mass% to 2 mass%. A surfactant, a defoaming agent, and a small amount of an organic solvent for promoting the development may be mixed in the aqueous alkali solution.

The temperature of the developing solution in the developing step is preferably maintained at a constant temperature in the range of 20 캜 to 40 캜.

A resist pattern is obtained by the above-described steps. In some cases, a heating step of 100 ° C to 300 ° C may be further performed. This heating step is preferable from the viewpoint of better chemical resistance. For the heating, a heating furnace of an appropriate method such as hot air, infrared ray, and far-infrared ray can be used.

<Method of forming wiring board>

In the method for forming a wiring board according to the first embodiment,

A lamination step of laminating the photosensitive resin composition layer of the photosensitive element on a conductor substrate,

An exposure step of exposing the laminated photosensitive resin composition layer,

A developing step of removing the unexposed portion after the exposure with a developer,

A conductor pattern forming step of etching or plating a conductor substrate on which a resist pattern is formed by the above phenomenon, and

A peeling step of peeling the resist pattern,

, Preferably in the order described above.

The lamination step is preferably a step of laminating the photosensitive resin layer of the photosensitive element on the conductive substrate through the wetting agent. Examples of the wetting agent include at least one selected from pure water, deionized water and electrolytic water and at least one selected from the group consisting of copper chelating agents (for example, imidazole compounds, triazole compounds, pyridine compounds, and pyrazole compounds Compound).

In the conductor pattern forming step, a conductor pattern can be formed on a substrate surface (for example, a copper surface) exposed by a developing process on a substrate having a resist pattern formed thereon by a known etching method or a plating method.

In the peeling step, the substrate on which the conductor pattern is formed is brought into contact with an appropriate peeling liquid, whereby the resist pattern is peeled off. By this process, a desired wiring board can be obtained.

The peeling liquid used in the peeling step is preferably an aqueous alkali solution. As this alkali aqueous solution, for example, an aqueous NaOH solution or a KOH aqueous solution of 2% by mass to 5% by mass is preferably used. To the release liquid, a small amount of a water-soluble solvent such as an alcohol may be added. The temperature of the peeling liquid in the peeling step is preferably 40 占 폚 to 70 占 폚.

Generally, in the formation of a conductor pattern by etching, the etching time for adjusting a desired wiring width can be adjusted, for example, by adjusting the conveying speed of the etching line irrespective of the etching speed. However, if the etching speed is too high, the conveying speed becomes too high, which may cause a problem that the etching time can not be set practically.

In addition, in recent years, the production of the wiring board is usually carried out by a line process in which the substrate is sequentially processed while being transported in a certain direction, and when the line of the conductor is parallel to the transport direction of the substrate Line), vertical (line in the TD direction), and oblique. In particular, when the etching rate is high, the vertical / horizontal difference of the wiring width tends to become more conspicuous.

As a result of intensive studies, the present inventors have found that, in the case where a photosensitive resin composition forming a cured resist pattern has specific physical properties, in forming a fine conductor pattern by a line process, I found out I could.

That is, in the photosensitive resin composition of the first embodiment, a photosensitive resin layer composed of the photosensitive resin composition was laminated to a thickness of 25 탆 on a copper clad laminate in which copper foils having a thickness of 18 탆 were laminated, and a line / space = 50 탆 / 30 占 퐉 to form a cured resist pattern, copper etching treatment was performed at 50 占 폚 for 55 seconds, the cured resist pattern was removed, and the bottom width of the copper line pattern obtained was 38 (Preferably 38 to 50 mu m, and more preferably 40 to 45 mu m).

However, the resist pattern swells / shrinks in each of the development, the water washing process, and the etching process, and particularly swelling / shrinking in the water washing process is large. It is considered that the swelling / shrinkage of the resist pattern deteriorates the adhesion between the wiring and the resist pattern. The resist pattern formed from the photosensitive resin composition of the first embodiment has a small swelling / shrinkage in any of the development, water washing, and etching steps, and is difficult to etch at the interface between the resist pattern and the wiring, Can be suppressed.

In the first embodiment, it is possible to distinguish the specific photosensitive resin composition by focusing on characteristics (the bottom width of the conductor line width is equal to or more than a certain value) when a specific analysis method (specific etching condition) is used, As shown in FIG.

Such adjustment of the bottom width of the conductor line width can be adjusted by appropriately setting the composition of the photosensitive resin composition.

The conductor pattern (wiring) formed by the method for forming a wiring board according to the first embodiment as described above can make the vertical / horizontal difference of the wiring width of the conductor pattern very small. The vertical and horizontal difference in wiring width is the difference between the wiring width (TD) of the conductor line in the TD direction and the wiring width (MD) of the conductor line in the MD direction, represented by TD - MD.

The absolute value of the vertical / horizontal difference of the wiring width in the conductor pattern formed by the method of forming a conductor pattern of the first embodiment is preferably 0 mu m to 5 mu m, more preferably 0 mu m to 3 mu m.

The photosensitive resin composition, the photosensitive element and the method for forming a wiring board according to the first embodiment are very preferably applied to the production of a printed wiring board, a lead frame, a substrate having a concavo-convex pattern, a semiconductor package, and the like .

In addition, the measurement methods of the various parameters described above are measured according to the measurement method in Examples described later, unless otherwise specified.

&Lt; Second Embodiment &gt;

Hereinafter, a mode for carrying out the second embodiment of the present invention (hereinafter abbreviated as &quot; the second embodiment &quot;) will be described in detail.

<Photosensitive resin composition>

In the second embodiment, the photosensitive resin composition comprises the following components (A) to (C)

Component (A): an alkali-soluble polymer having an acid equivalent weight of 100 to 600,

(B): a compound having an ethylenic double bond, and

Component (C): a photopolymerization initiator,

Lt; / RTI &gt;

[Component (A): alkali-soluble polymer]

The component (A) contains a copolymer having an acid equivalent of 100 to 600 (preferably 200 to 500, more preferably 250 to 450) and containing 50 mass% or more of styrene units. Herein, in the present specification, the styrene unit means a substituted or unsubstituted styrene. The substituent is not particularly limited, and examples thereof include an alkyl group, a halogen group, and a hydroxyl group.

The component (A) is a copolymer of a styrene derivative and preferably another monomer such as an acid monomer.

Examples of the acid monomer include (meth) acrylic acid, pentenoic acid, unsaturated dicarboxylic acid anhydride, and hydroxystyrene. Examples of the unsaturated dicarboxylic acid anhydride include maleic anhydride, itaconic anhydride, fumaric acid and citraconic anhydride. Among them, (meth) acrylic acid is preferable.

Examples of other monomers include unsaturated aromatic compounds (sometimes referred to as "aromatic monomers"), (meth) acrylic acid alkyl esters, (meth) acrylic acid aralkyl esters, conjugated diene compounds, polar monomers, And the like.

As the unsaturated aromatic compound, for example, vinyl naphthalene and the like can be given.

(Meth) acrylic acid alkyl ester is a concept including both chain alkyl esters and cyclic alkyl esters, and specifically includes, for example, methyl (meth) acrylate, ethyl (meth) (Meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl Stearyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like.

Examples of (meth) acrylic acid aralkyl esters include benzyl (meth) acrylate and the like;

Examples of the conjugated diene compound include 1,3-butadiene, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene and the like;

Respectively.

As the polar monomer, for example,

Hydroxyl group-containing monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and pentenol;

Amino group-containing monomers such as 2-aminoethyl methacrylate;

Amide group-containing monomers such as (meth) acrylamide and N-methylol (meth) acrylamide;

Cyano group-containing monomers such as acrylonitrile, methacrylonitrile,? -Chloroacrylonitrile and? -Cyanoethyl acrylate;

Epoxy group-containing monomers such as glycidyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate;

And the like.

Examples of the crosslinkable monomer include trimethylolpropane triacrylate and divinylbenzene.

The component (A) is preferably a copolymer of (meth) acrylic acid, styrene, and other monomers.

The component (A) contains the copolymer 1 containing 50 mass% or more of styrene units. The amount of the styrene unit in the copolymer 1 is preferably 50% by mass to 80% by mass, more preferably 51% by mass to 70% by mass.

The component (A) in the second embodiment may be composed only of the copolymer 1, or may be a mixture of the copolymer 1 and other polymer. The content of the copolymer 1 in the component (A) is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 80% by mass, and still more preferably 20% by mass to 70% by mass.

As the other polymer, a copolymer of the acid monomer and other monomers described above and not corresponding to the copolymer 1 (copolymer 2) is preferable.

The weight average molecular weight of the component (A) when the component (A) comprises a plurality of kinds of copolymers is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000 More preferably from 15,000 to 100,000. Adjusting the weight average molecular weight of the component (A) within this range is preferable from the viewpoint of satisfying the developing time at the time of forming the resist pattern to the operating state of the line process to be used. The degree of dispersion of the copolymer represented by the ratio of the weight average molecular weight to the number average molecular weight of the component (A) is preferably 1 or more and 6 or less.

In the second embodiment, the content of the component (A) in the photosensitive resin composition is from 10% by mass to 10% by mass, based on the total solid content of the photosensitive resin composition (hereinafter, , More preferably 20 mass% to 80 mass%, and still more preferably 40 mass% to 60 mass%. This content is preferably 10% by mass or more from the viewpoint of maintaining alkali developability, and is preferably 90% by mass or less from the viewpoint that the resist pattern formed by exposure sufficiently exhibits the performance as a resist.

[Component (B): a compound having an ethylenic double bond]

The component (B) is not particularly limited as long as it has at least one ethylenic double bond. However, the component (B) in the second embodiment is a compound (B1) essentially containing the compound represented by the following general formula (I):

[Chemical Formula 8]

Wherein n is an integer of 0 to 30, provided that n1 + n2 + n3? 6 is an integer of 1 to 4, Satisfies the condition.).

In the formula (I), as R, each independently, a hydrogen atom or a methyl group is preferable, and a hydrogen atom is more preferable. n1, n2 and n3 are each independently preferably an integer of 1 to 30, more preferably an integer of 3 to 21.

In the formula (I), the value of n1 + n2 + n3 is preferably more than 9, more preferably not more than 20, and more preferably not less than 15 and not more than 20 from the viewpoint of improving development dispersibility.

In the formula (I), at least one R is preferably a hydrogen atom, and more preferably all of R is a hydrogen atom, from the viewpoint of improving the development dispersibility.

In the formula (I), it is particularly preferable that all R are hydrogen atoms and the value of n1 + n2 + n3 is 15 or more and 20 or less, from the viewpoint of achieving both development dispersibility and adhesion.

The compound represented by the formula (I) can be synthesized using a known method, for example, by adding 3 moles of (meth) acrylic acid to an adduct obtained by adding ethylene oxide of 6 equivalents or more to trimethylol propane Or ester exchange.

Specific preferred examples of the compound represented by the formula (I) include ethylene oxide (EO) -modified trimethylolpropane tri (meth) acrylate (the total number of moles of EO is 6 to 20).

The component (B) in the second embodiment may be composed solely of the compound (B1) or may be a mixture of the compound (B1) and the other component (B).

When the component (B) of the second embodiment is a mixture, the content of the compound (B1) in the mixture is preferably 10% by mass or more, more preferably 10% by mass or more, To 50% by mass, and more preferably from 15% by mass to 35% by mass.

The content of the compound (B1) in the photosensitive resin composition of the second embodiment is preferably 5% by mass or more, more preferably 5.5% by mass to 30% by mass, based on the total solid content of the photosensitive resin composition, By mass, and more preferably 6% by mass to 20% by mass.

Here, by including an alkali-soluble polymer having a specific acid equivalent and a specific amount of a styrene unit, and the component (B1) and the acridine, a photosensitive resin composition excellent in both developability of dispersibility and adhesion to a fine pattern is realized But the interaction between the styrene unit and the acridine component (due to? Electron stacking) and the interaction between the acid monomer and the above-mentioned (B1) component (due to hydrogen bonding) And that the compatibility as a whole is improved contributes to the above characteristics.

In the second embodiment, it is preferable that the component (B) contains, in addition to the compound (B1), a pentaerythritol-modified monomer (hereinafter referred to as "compound (B2)") . As the compound (B2), tetra (meth) acrylate of a polyol to which an alkylene oxide is added to pentaerythritol, preferably an average of 4 to 35 moles, more preferably 8 to 28 moles, and still more preferably 12 to 20 moles (Meth) acrylate is used.

The content of the compound (B2) in the component (B) is preferably 10% by mass to 40% by mass, and more preferably 15% by mass to 30% by mass, based on the total mass of the component (B) .

The content of the compound (B2) in the photosensitive resin composition of the second embodiment is preferably 1% by mass or more, more preferably 1% by mass to 20% by mass, still more preferably 5% 15% by mass.

The component (B) may contain a compound having an ethylenic double bond other than the compounds (B1) and (B2).

The component (B) comprises the following components:

Bisphenol A compounds such as di (meth) acrylates of polyalkylene glycols in which an average of 2 to 15 moles of alkylene oxide is added to both ends of bisphenol A, respectively;

Tri (meth) acrylates of polyalkylene thiol in which an alkylene oxide having 3 to 25 moles on average is added to trimethylolpropane, for example, a compound having three ethylenic double bonds (excluding B1);

.

The content of the component (B) in the photosensitive resin composition of the second embodiment is preferably 1 mass% to 70 mass%, more preferably 5 mass% to 60 mass%, still more preferably 10 mass% to 50 mass% Is more preferable. This content is preferably not less than 1% by mass from the viewpoint of suppressing the curing failure and retarding the developing time, and is preferably not more than 70% by mass from the viewpoint of suppressing the generation of agglomerates in the developer.

[Component (C): photopolymerization initiator]

The component (C) is a component that generates a radical capable of initiating polymerization of the component (B) by irradiation of light.

In the second embodiment, an acridine compound can be used as the photopolymerization initiator (B). Further, the acridine compound and other photopolymerization initiators may be used in combination. The acridine-based compound is preferably used for improving the sensitivity and resolution of the photosensitive resin composition of the second embodiment.

Examples of the acridine compound include 1,7-bis (9,9'-acridinyl) heptane, 9-phenylacridine, 9-methylacridine, 9- (4-methylphenyl) acridine, 9- (4-ethylphenyl) acridine, 9- (4-tert-butylphenyl) acridine, 9- (4-methoxyphenyl) acridine, 9- 9- (4-chlorophenyl) acridine, 9- (4-acetylphenyl) acridine, 9- (3-tert-butylphenyl) acridine, 9- (3-acetylphenyl) acridine, 9- (3-dimethylaminophenyl) acridine, 9- (3-bromophenyl) acridine, 9- 9- (2-pyridyl) acridine, 9- (3-pyridyl) acridine, and 9- (4-pyridyl) acridine.

As other photopolymerization initiators, for example,

(O-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2,2 ' , 5'-diphenylimidazolyl dimer, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylimidazolyl dimer, 2,4,5 2, 2, 3, 4, 5, 6-tetramethylpiperazin-1-yl) -tris (o-chlorophenyl) -diphenylimidazolyl dimer, 2- (o- Bis (2-fluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'- (2,4-difluoro-phenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'- Phenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,5- difluorophenyl) 4,4 ', 5' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,6-difluorophenyl) 5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3,4-tri Imidazolyl dimer, 2,2'-bis- (2,3,5-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) ) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3,6-trifluorophenyl) -4 , 4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,4,5-trifluorophenyl) , 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,4,6-trifluorophenyl) -4,4 ' 5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3,4,5-tetrafluorophenyl) -4,4 ' -Tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3,4,6-tetrafluorophenyl) -4,4 ', 5,5' - tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3,4,5,6-pentafluorophenyl) -4,4 ', 5,5 Hexaarylbisimidazole compounds such as' -tetrakis- (3-methoxyphenyl) -imidazolyl dimer;

2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o- (O-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- , 2,4,5-triarylimidazole dimer such as 5-diphenylimidazole dimer (except for the above hexaarylbisimidazole compound);

Benzophenone, N, N'-tetramethyl-4,4'-dimethylaminobenzophenone (Michler's ketone), N, N'-tetraethyl-4,4'-diaminobenzophenone, Methyl-1- [4- (methylthio) phenyl] -2-morpholinobenzophenone, 2-benzyl- Aromatic ketones such as polyno-propanone-1;

Diethylanthraquinone, 2,3-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-di 2-methyl anthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethyl anthraquinone Quinone compounds such as quinone;

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

Benzyl derivatives such as benzyl methyl ketal;

N-phenylglycine derivatives, coumarin-based compounds, and 4,4'-bis (diethylamino) benzophenone.

The content of the acridine compound in the photosensitive resin composition of the second embodiment is preferably 0.001 mass% to 2 mass%, more preferably 0.01 mass% to 1.5 mass%, still more preferably 0.1 mass% To 1% by mass.

The content of the component (C) (the content of the entire component (C) including the acridine compound) in the photosensitive resin composition of the second embodiment is preferably 0.1% by mass to 2% by mass, more preferably 0.2% By mass to 1.8% by mass, more preferably 0.3% by mass to 1.7% by mass, and particularly preferably 0.4% by mass to 1.6% by mass.

The component (C) may further contain a sensitizer in view of improvement in sensitivity and resolution. Examples of such a sensitizer include N-aryl amino acids, organic halogen compounds, and other sensitizers.

Examples of the N-arylamino acid include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like;

Examples of the organic halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenylsulfone, tetrabromocarbon, tris (2,3 (Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, chlorinated triazine compounds and the like;

Respectively.

As the other sensitizer, for example,

1,2-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 1, Quinone compounds such as 4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethyl anthraquinone and 3-chloro-2-methyl anthraquinone;

Aromatic ketone compounds such as benzophenone, Michler's ketone [4,4'-bis (dimethylamino) benzophenone] and 4,4'-bis (diethylamino) benzophenone;

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

Benzyldimethyl ketal, benzyldiethyl ketal, 1-phenyl-1,2-propanedione-2-O-benzoin oxime, 1-phenyl-1,2-propanedioyl- 2- (O-ethoxycarbonyl) oxime Oxime ester compounds such as &lt; RTI ID = 0.0 &gt;

And the like.

The content of the sensitizer in the photosensitive resin composition of the second embodiment is preferably from 0.01% by mass to 5% by mass, more preferably from 0.05% by mass to 3% by mass, from the viewpoint of the light sensitivity of the composition and the peelability of the resist- And more preferably 0.1% by mass to 2% by mass.

[Other components]

The photosensitive resin composition of the second embodiment may contain other components in addition to the components (A) to (C) described above. As other components, for example, a coloring material, a halogen compound, a stabilizer, a solvent and the like can be given.

Examples of the coloring material include leuco dyes and other coloring materials;

Examples of the stabilizer include a radical polymerization inhibitor, a benzotriazole compound, a carboxybenzotriazole compound and the like;

Respectively.

<Leuco dye>

Examples of the leuco dyes include tris (4-dimethylaminophenyl) methane [leuco crystal violet] and bis (4-dimethylaminophenyl) phenylmethane [leuco malachite green]. Particularly, from the viewpoint of good contrast, it is preferable to use Loico crystal violet.

The content of the leuco dye in the photosensitive resin composition is preferably 0.1% by mass to 10% by mass. It is preferable to adjust the content of the leuco dye to 0.1% by mass or more from the viewpoint of obtaining the contrast between the exposed portion and the unexposed portion. On the other hand, adjusting the content of the leuco dye to 10% .

&Lt; Other coloring materials &gt;

Examples of the other coloring materials include fuchsin, phthalocyanine green, aramine base, paradadiene, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (manufactured by Ehodogaya Chemical Co., MALACHITE GREEN), Basic Blue 20, Diamond Green (DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.), and the like.

The content of other coloring materials in the photosensitive resin composition is preferably 0.001 mass% to 1 mass%. It is preferable to adjust the content to 0.001% by mass or more from the viewpoint of improving handling properties. On the other hand, adjusting the content to 1% by mass or less is preferable from the viewpoint of maintaining storage stability.

<Halogen compounds>

Use of a combination of a leuco dye and a halogen compound in a photosensitive resin composition is a preferred embodiment from the viewpoint of adhesion and contrast.

Examples of the halogen compound include amides such as amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenylsulfone, tetrabromide carbon, tris (2,3- Trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, chlorinated triazine compounds, etc. have. Tribromomethylphenyl sulfone is particularly preferable. The content of the halogen compound in the photosensitive resin composition is preferably from 0.01% by mass to 3% by mass from the viewpoint of maintaining the color storage stability in the photosensitive layer.

<Radical polymerization inhibitor, benzotriazole compound, and carboxybenzotriazole compound>

Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert- , Methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert- butylphenol), nitrosophenylhydroxyamine aluminum salt, Diphenylnitrosamine, and the like.

Examples of the benzotriazole compound include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene- Benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, bis (N-2- hydroxyethyl) aminomethylene-1,2,3-benzotriazole And the like.

Examples of the carboxybenzotriazole compound include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N- (N, Ethylhexyl) aminomethylene carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylene carboxybenzotriazole, N- (N, Triazole, and the like.

The total content of the radical polymerization inhibitor, the benzotriazole compound and the carboxybenzotriazole compound in the photosensitive resin composition is preferably 0.01% by mass to 3% by mass, and more preferably 0.05% by mass to 1% by mass. It is preferable to adjust the content to 0.01% by mass or more from the viewpoint of imparting storage stability to the photosensitive resin composition. On the other hand, if the content is adjusted to 3% by mass or less, the sensitivity is maintained, .

<Plasticizer>

The photosensitive resin composition may contain a plasticizer, if necessary. Examples of the plasticizer include phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, triethyl acetylcitrate, tri- Tri-n-butyl, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether and the like.

The content of the plasticizer in the photosensitive resin composition is preferably 1% by mass to 50% by mass, and more preferably 1% by mass to 30% by mass. Adjustment of this content to 1% by mass or more is preferable from the viewpoint of retarding development time and imparting flexibility to the cured film. On the other hand, adjusting the content to 50% It is preferable from the viewpoint of suppressing the edge fuse.

<Solvent>

The photosensitive resin composition may contain a solvent. Examples of the solvent include ketones represented by methyl ethyl ketone (MEK), alcohols such as methanol, ethanol, and isopropanol. The solvent is preferably added to the photosensitive resin composition such that the viscosity of the solution of the photosensitive resin composition applied on the support film is from 500 mPa · s to 4,000 mPa · s at 25 ° C.

<Photosensitive element>

In the second embodiment, the photosensitive element is a laminate (photosensitive resin laminate) in which a photosensitive resin layer composed of the above-described photosensitive resin composition is laminated on a support. The photosensitive element may have a protective layer on the surface opposite to the support of the photosensitive resin layer, if necessary.

[Support]

As the support, a transparent substrate that transmits light emitted from an exposure light source is preferable. Examples of the support include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film, a polystyrene Film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. As these films, stretched films may be used if necessary.

The haze of the support is preferably 5 or less.

Thickness of the support is advantageous from the viewpoint of image forming property and economical efficiency, but it is necessary to maintain the strength. Considering both of them, a support of 10 占 퐉 to 30 占 퐉 can be preferably used.

[Photosensitive resin layer]

When the photosensitive resin composition used for forming the photosensitive resin layer contains a solvent, the solvent is preferably removed from the photosensitive resin layer, but may remain in the photosensitive resin layer.

The thickness of the photosensitive resin layer is preferably 5 mu m to 100 mu m, more preferably 7 mu m to 60 mu m. The thinner the thickness, the better the resolution, and the thicker the film the better the film strength. Therefore, the thickness of the photosensitive resin layer can be appropriately selected within the range of 5 탆 to 100 탆 according to the application.

[Protective layer]

An important characteristic of the protective layer is that the adhesion strength with the photosensitive resin layer is sufficiently smaller than the adhesion between the support and the photosensitive resin layer and can be easily peeled off. As the protective layer, for example, a polyethylene film, a polypropylene film or the like can be preferably used, and for example, a film having excellent peelability disclosed in JP-A-59-202457 can be used.

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

[Method of producing photosensitive element]

The photosensitive element can be produced by sequentially laminating a support, a photosensitive resin layer and, if necessary, a protective layer. As a method for laminating the support, the photosensitive resin layer, and the protective layer, a known method can be adopted.

For example, a photosensitive resin composition comprising a photosensitive resin composition is formed on a support by adding a solvent to a photosensitive resin composition and mixing them, preparing a combination solution, applying the composition on a support using a bar coater or a roll coater, . Then, if necessary, the photosensitive element can be produced by laminating a protective layer on the formed photosensitive resin layer.

&Lt; Method of forming resist pattern &gt;

A resist pattern can be formed on a substrate using the above-described photosensitive element.

A method of forming a resist pattern includes:

A lamination step of laminating a photosensitive resin layer of the photosensitive element on a conductor substrate,

An exposure step of exposing the laminated photosensitive resin layer, and

A developing step of removing the unexposed portion after the exposure with a developer,

In the order described above.

The laminating step is preferably a step of laminating the photosensitive resin layer of the photosensitive element on the conductive substrate through the wetting agent. Examples of the wetting agent include at least one selected from pure water, deionized water and electrolytic water and at least one selected from the group consisting of copper chelating agents (for example, imidazole compounds, triazole compounds, pyridine compounds, and pyrazole compounds Compound).

In the method for forming a resist pattern according to the second embodiment, first, a photosensitive resin layer is formed on a substrate by using a laminator in a laminating step. Specifically, when the photosensitive element has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is laminated on the surface of the substrate by heating using a laminator.

As the substrate, a metal plate or an insulating substrate having a metal coating is used. Examples of the material of the metal include copper, stainless steel (SUS), glass, indium tin oxide (ITO), and the like. These substrates may have through-holes corresponding to the multilayer substrate.

The photosensitive resin layer may be laminated only on one side of the substrate surface, and may be laminated on both sides of the substrate as required. The heating temperature at the time of lamination is preferably 40 to 160 캜. It is preferable to carry out hot pressing twice or more from the viewpoint of further improving the adhesion of the obtained resist pattern to the substrate. In the case of pressing at least two times, a two-stage laminator having two sets of rolls may be used. Alternatively, a laminate of the substrate and the photosensitive resin layer may be repeatedly passed through rolls and pressed.

Next, in the exposure step, the photosensitive resin layer is exposed using an exposure machine. The exposure may be carried out through a support without peeling off the support, and may be carried out after peeling off the support if necessary.

By applying this exposure in the form of a pattern, a resist film (resist pattern) having a desired pattern can be obtained after passing through a developing step described later. Patternwise exposure may be performed by either a method of exposing through a photomask or a maskless exposure method. In the case of exposure through a photomask, the exposure dose is determined by the light source illuminance and the exposure time. The exposure dose may be measured using a photometer.

In the maskless exposure, a photomask is not used, and the substrate is exposed directly to the substrate with an imaging apparatus. As the light source, a semiconductor laser having a wavelength of 350 nm to 410 nm, an ultra-high pressure mercury lamp or the like is used. In maskless exposure, the imaging pattern is controlled by a computer, and the amount of exposure is determined by the illuminance of the exposure light source and the moving speed of the substrate.

Next, in the developing step, the unexposed portion of the photosensitive resin layer is removed by a developer. After the exposure, if there is a support on the photosensitive resin layer, it is preferable to provide it to the development step after excluding it.

In the developing step, a developing solution composed of an aqueous alkali solution is used to develop and remove the unexposed portion, thereby obtaining a resist image. As the alkali aqueous solution, for example, an aqueous solution of Na ₂ CO ₃ , K ₂ CO _3, or the like is preferably used. The alkali aqueous solution is selected in accordance with the characteristics of the photosensitive resin layer, but it is preferable to use an aqueous solution of Na ₂ CO _{3 at} a concentration of 0.2 mass% to 2 mass%. A surfactant, a defoaming agent, and a small amount of an organic solvent for promoting development may be mixed in the alkali aqueous solution.

The temperature of the developing solution in the developing step is preferably maintained at a constant temperature in the range of 20 캜 to 40 캜.

A resist pattern is obtained by the above-described steps. In some cases, a heating step of 100 ° C to 300 ° C may be further performed. The execution of this heating step is preferable from the viewpoint of better chemical resistance. For the heating, a heating furnace of an appropriate method such as hot air, infrared ray, and far-infrared ray can be used.

<Method of forming wiring board>

In the method for forming a wiring board according to the second embodiment,

A lamination step of laminating a photosensitive resin layer of the photosensitive element on a conductor substrate,

An exposure step of exposing the laminated photosensitive resin layer,

A developing step of removing the unexposed portion after the exposure with a developer,

A conductor pattern forming step of etching or plating a conductor substrate on which a resist pattern is formed by the above phenomenon, and

A peeling step of peeling the resist pattern,

, Preferably in the order described above.

The laminating step is preferably a step of laminating the photosensitive resin layer of the photosensitive element on the conductive substrate through the wetting agent. Examples of the wetting agent include at least one selected from pure water, deionized water and electrolytic water and at least one selected from the group consisting of copper chelating agents (for example, imidazole compounds, triazole compounds, pyridine compounds, and pyrazole compounds Compound).

In the conductor pattern forming step, a conductor pattern can be formed on a substrate surface (for example, a copper surface) exposed by a developing process on a substrate having a resist pattern formed thereon by a known etching method or a plating method.

In the peeling step, the substrate on which the conductor pattern is formed is brought into contact with an appropriate peeling liquid, whereby the resist pattern is peeled off. By this process, a desired wiring board can be obtained.

The peeling liquid used in the peeling step is preferably an aqueous alkali solution. As this alkali aqueous solution, for example, an aqueous NaOH solution or a KOH aqueous solution of 2% by mass to 5% by mass is preferably used. To the exfoliating liquid, a small amount of a water-soluble solvent, for example, alcohol may be added. The temperature of the peeling liquid in the peeling step is preferably 40 占 폚 to 70 占 폚.

The photosensitive resin composition, the photosensitive element and the method for forming the wiring board in the second embodiment are very preferably applied to the production of a printed wiring board, a lead frame, a substrate having a concavo-convex pattern, a semiconductor package, and the like .

In addition, the measurement methods of the various parameters described above are measured according to the measurement method in Examples described later, unless otherwise specified.

&Lt; Third Embodiment &gt;

Hereinafter, a mode for carrying out the third embodiment of the present invention (hereinafter abbreviated as &quot; the third embodiment &quot;) will be described concretely.

<Photosensitive resin composition>

In the third embodiment, the photosensitive resin composition comprises (A) an alkali-soluble polymer, (B) an ethylenically unsaturated bond-containing compound, and (C) a photopolymerization initiator. As desired, the photosensitive resin composition may further contain other components such as (D) an additive.

(Meth) acryloyl group means acryloyl group or methacryloyl group, and the term "(meth) acryloyl group" means acryloyl group or methacryloyl group, Acrylate &quot; means &quot; acrylate &quot; or &quot; methacrylate &quot;.

(A) an alkali-soluble polymer

(A) The alkali-soluble polymer is a polymer soluble in an alkali substance. In the third embodiment, the alkali-soluble polymer (A) preferably has a mass of 10 mass% based on the total mass of the monomers constituting the alkali-soluble polymer (A), from the viewpoint of both achieving both the tent property of the resist pattern and the water- Structural units of (meth) acrylic acid of from% to 24% by mass and structural units of styrene of from 35% by mass to 90% by mass.

The content of the structural unit of the (meth) acrylic acid in the alkali-soluble polymer (A) is preferably not more than 24% by mass from the viewpoint of suppressing the water-residual short defect on the basis of the total mass of the monomers constituting the alkali-soluble polymer (A) And is preferably 10% by mass or more from the viewpoint of ensuring alkali developability and alkali peelability. The upper limit of this content is more preferably 23 mass% or 22.5 mass%, and the lower limit value is more preferably 11 mass%, 15 mass%, 18 mass% or 20 mass%. The water residual short defect is strongly correlated with the hydrophobicity of the cured resist, and it is possible to suppress the water residual short defect by increasing the hydrophobicity of the resist, that is, the water contact angle.

(A) the acid equivalent (A) of the alkali-soluble polymer (A) in the case where the component (A) contains a plurality of kinds of copolymers, Is preferably 100 or more from the viewpoints of resistance to developing of the photosensitive resin layer and development resistance, resolution and adhesion of the resist pattern, and is preferably 900 or less from the viewpoint of developability and releasability of the photosensitive resin layer . The acid equivalent of the alkali-soluble polymer (A) is more preferably from 250 to 600, and still more preferably from 350 to 500. [ The acid equivalent means the mass of the linear polymer having one equivalent of carboxyl groups therein.

The content of the structural unit of styrene in the alkali-soluble polymer (A) is preferably 90% by mass or less from the viewpoint of developability based on the total mass of the monomers constituting the alkali-soluble polymer (A) From the viewpoint of the poor defective shot property, it is preferably 35 mass% or more. The upper limit of the content is more preferably 85% by mass, 80% by mass, 70% by mass or 60% by mass from the viewpoint of development and prevention of delamination time delay, , It is more preferable that 36 mass%, 38 mass%, 40 mass%, or 42 mass% is satisfied.

From the viewpoint of improving the tent property of the resist pattern, it is preferable that the alkali-soluble polymer (A) further includes a structural unit of (meth) butyl acrylate. The structural unit of butyl (meth) acrylate is preferably a repeating unit derived from at least one selected from the group consisting of n-butyl (meth) acrylate, isobutyl (meth) acrylate and tert- .

The content of the structural unit of the (meth) butyl acrylate in the alkali-soluble polymer (A) is, from the viewpoint of compatibility between the tent and the poor residual shot defects, the content of the structural unit (A) , Preferably from 0.1% by mass to 5% by mass, and more preferably from 0.3% by mass to 1% by mass.

(A) the alkali-soluble polymer is a copolymer of (A) a structural unit of (meth) acrylic acid of from 10 to 24 mass% and a structural unit of styrene of from 35 to 90 mass% based on the total mass of the monomer constituting the alkali- May be a single kind of copolymer as long as it contains a structural unit and may be a mixture of plural kinds of copolymers and / or a mixture of plural types of homopolymers.

The alkali-soluble polymer (A) may be at least one selected from the group consisting of poly (meth) acrylic acid, poly (meth) acrylate, polystyrene, (meth) acrylic acid and / or styrene and at least one of the following first monomers and / A copolymer obtained by copolymerizing a copolymerization component comprising at least one kind of monomer, and the like.

The first monomer is a monomer containing a carboxyl group in the molecule (excluding (meth) acrylic acid). Examples of the first monomer include fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester.

The second monomer is a non-acidic monomer (excluding styrene) having at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, benzyl (meth) acrylate and vinyl acetate, (meth) acrylonitrile, polymerizable styrene derivatives and the like.

Of these, n-butyl (meth) acrylate, isobutyl (meth) acrylate or tert-butyl (meth) acrylate is preferable from the viewpoint of improving the tent property of the resist pattern, Butyl (meth) acrylate is more preferable, and polymerizable styrene derivatives are preferable from the viewpoint of improving the resolution and water residual shot defective inhibition.

Examples of polymerizable styrene derivatives include methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer and styrene trimmer.

The alkali-soluble polymer may be prepared by mixing the above monomers and adding a radical polymerization initiator, for example, benzoyl peroxide, such as benzoyl peroxide, to a solution diluted with a solvent, for example, acetone, methyl ethyl ketone, methanol, ethanol, normal propyl alcohol, or isopropanol , And azoisobutyronitrile in an appropriate amount, followed by heating and stirring. The synthesis may be carried out while dropping a part of the mixture into the reaction solution. After the completion of the reaction, a solvent may be further added to adjust the concentration to a desired level. As the synthesizing means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

The weight average molecular weight of the alkali-soluble polymer (A) when the component (A) contains a plurality of copolymers is preferably 5,000 to 500,000. The weight average molecular weight of the alkali-soluble polymer (A) is preferably not less than 5,000 from the viewpoint of uniformly maintaining the thickness of the dry film resist and obtaining resistance to a developing solution, and from the viewpoint of maintaining developability of the dry film resist, Or less. The weight average molecular weight of the alkali-soluble polymer (A) is more preferably 10,000 to 200,000, and still more preferably 20,000 to 100,000. The degree of dispersion of the alkali-soluble polymer (A) is preferably 1.0 to 6.0.

In the third embodiment, the content of the alkali-soluble polymer (A) in the photosensitive resin composition is preferably from 0.1 to 10 parts by weight, based on the total solid content of the photosensitive resin composition (hereinafter, Is in the range of 10 mass% to 90 mass%, more preferably 20 mass% to 80 mass%, and still more preferably 40 mass% to 60 mass%. The content of the alkali-soluble polymer (A) is preferably 10% by mass or more from the viewpoint of maintaining the alkali developability of the photosensitive resin layer, and more preferably 90% by mass or more from the viewpoint that the resist pattern formed by exposure, % Or less.

(B) an ethylenically unsaturated bond-containing compound

The ethylenically unsaturated bond-containing compound (B) is a compound having polymerizability by having an ethylenic unsaturated group in its structure. The ethylenically unsaturated bond is preferably a terminal ethylenically unsaturated group in terms of addition polymerizability.

In the third embodiment, from the viewpoint of ensuring the tent property of the resist pattern when (A) the alkali-soluble polymer and (B) the ethylenically unsaturated bond-containing compound are used in combination, (B) the weight of the ethylenically unsaturated bond- The average molecular weight is preferably 1,200 or more. In the present specification, the weight average molecular weight of the ethylenically unsaturated bond-containing compound (B) means the weight average molecular weight of the ethylenically unsaturated bond-containing compound derived from the structural formula (B) Means a weighted average of the weight average molecular weight of the respective ethylenically unsaturated bond-containing compounds and the compounding ratio when the (B) ethylenically unsaturated bond-containing compound is composed of plural kinds.

The weight average molecular weight of the ethylenically unsaturated bond-containing compound (B) is preferably not less than 1,300, more preferably not less than 1,400, from the viewpoint of further improving the tent property of the resist pattern, More preferably not more than 5,000, more preferably not more than 4,000, particularly preferably not more than 3,000 from the viewpoint of releasability.

(B) an unsaturated bond-containing compound is ethylenic, to _{(b 1) ~ (b 5} ):

(b ₁₎ to general formula (I):

[Chemical Formula 9]

Wherein R ₁ and R ₂ are each independently a hydrogen atom or a methyl group and m ₁ is a number satisfying 2 to 40. <

An ethylene glycol di (meth) acrylate compound represented by the following formula

(b ₂₎ represented by the following general formula (II):

[Chemical formula 10]

Wherein R ₃ and R ₄ each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , n ₁ , n ₂ , n ₃ and n ₄ are , n ₁ + n ₂ + n ₃ + n ₄ = 2 to 50, and the arrangement of repeating units of - (AO) - and - (BO) - may be random or block, , Any one of - (AO) - and - (BO) - may be a bisphenyl group side.

An alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the following formula:

(b ₃₎ represented by the following general formula (III):

(11)

(Wherein R ₅ to R ₇ each independently represent a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, m ₂ , m ₃ and m ₄ each independently represent 0 M ₂ + m ₃ + m ₄ is 1 to 40, and when m ₂ + m ₃ + m ₄ is 2 or more, the plural Xs may be the same or different from each other}

A tri (meth) acrylate compound represented by the following formula

(b ₄₎ the following general formula (IV):

[Chemical Formula 12]

(Wherein R ₈ and R ₉ each independently represent a hydrogen atom or a methyl group, Y represents an alkylene group having 2 to 6 carbon atoms, Z represents a divalent organic group, Each independently, an integer of 0 to 40, and s + t &gt; = 1)

(Meth) acrylate compound represented by the following formula

(b ₅₎ addition polymerizable monomers other than said _{(b 1) ~ (b 4} );

And at least one selected from the group consisting of

The ethylenically unsaturated bond-containing compound (B) is preferably a compound containing an ethylene glycol di (meth) acrylate compound represented by the general formula (I) (b ₁ ) from the viewpoint of adjusting the stripping time of the resist pattern and the size of the stripping piece desirable.

In the general formula (I), m ₁ is preferably 2 or more from the viewpoints of the time of peeling and the size of the peeled piece, and is preferably 40 or less from the viewpoints of resolution, tolerance to water and etching resistance. m ₁ is more preferably 4 to 20, and still more preferably 6 to 12.

General formula (I) ethylene glycol di (meth) Specific examples of the acrylate compound, m ₁ = 4 of the tetraethylene glycol di (meth) acrylate, m ₁ = 9 in the na glycol di (meth) acrylate represented by the Or polyethylene glycol di (meth) acrylate of m ₁ = 14 is preferred.

The ethylenically unsaturated bond-containing compound (B) preferably includes an alkylene oxide-modified bisphenol A-type di (meth) acrylate compound represented by the general formula (II) (b ₂ ) from the viewpoint of resolution and tent . B in the general formula (II) may be -CH ₂ CH ₂ CH ₂ - or -CH (CH ₃ ) CH ₂ -.

The hydrogen atom on the aromatic ring in formula (II) may be substituted with a hetero atom and / or a substituent.

Examples of the hetero atom include a halogen atom and the like, and examples of the substituent include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, a phenacyl group, A dialkylamino group having 2 to 20 carbon atoms, a nitro group, a cyano group, a carbonyl group, a mercapto group, an alkylmercapto group having 1 to 10 carbon atoms, an aryl group, a hydroxyl group, a hydroxyalkyl group having 1 to 20 carbon atoms , A carboxyl group, a carboxyalkyl group having 1 to 10 carbon atoms in the alkyl group, an acyl group having 1 to 10 carbon atoms in the alkyl group, an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylcarbonyl group having 2 to 10 carbon atoms , An alkenyl group having 2 to 10 carbon atoms, an N-alkylcarbamoyl group having 2 to 10 carbon atoms, a heterocyclic group, or an aryl group substituted with a substituent of these groups. These substituents may form a condensed ring, or hydrogen atoms in these substituents may be substituted with a hetero atom such as a halogen atom. When the aromatic ring in formula (II) has a plurality of substituents, the plurality of substituents may be the same or different.

R ₃ and R ₄ in the general formula (II) are, each independently, but a hydrogen atom or a methyl contribution, in terms of achieving the contrast to the exposure immediately after the photosensitive resin layer made of a photosensitive resin composition, one of R ₃ and R ₄ Or both of them are preferably hydrogen atoms, and it is more preferable that both of R ₃ and R ₄ are hydrogen atoms.

(b ₂ ) The alkylene oxide-modified bisphenol A-type di (meth) acrylate compound represented by the general formula (II) is preferably an alkylene oxide having a relatively long chain in view of tentability. More specifically, in the general formula (II), n ₁ , n ₂ , n ₃ and n ₄ preferably satisfy a relationship of n ₁ + n ₂ + n ₃ + n ₄ = 4 to 50, More preferably, the relationship of n ₁ + n ₂ + n ₃ + n ₄ = 10 to 50 is satisfied, and more preferably the relationship of n ₁ + n ₂ + n ₃ + n ₄ = 20 to 50 is satisfied, And particularly preferably satisfies a relationship of n ₁ + n ₂ + n ₃ + n ₄ = 30 to 50.

In view of the tent, (B) ethylenically unsaturated bond-containing more than 40% by weight of the compound, preferably, (b ₂₎ the formula (II) an alkylene oxide-modified bisphenol A represented by the di (meth) acrylate compound and, more preferably, the formula (II) of n _1, n _2, n ₃ and n ₄ is _{n 1 + n 2 + n 3} + n 4 = 30 ~ alkylene oxide modified to meet the 50 relationship of bisphenol A type di (meth) acrylate compound. More preferably an alkylene oxide represented by (B) ethylenically to 50% by mass of containing an unsaturated bond compounds, more preferably at least 55 mass% and, most preferably be 60 mass%, (b ₂₎ the formula (II) Modified bisphenol A type di (meth) acrylate compound.

(b ₂ ) Specific preferred examples of the alkylene oxide-modified bisphenol A-type di (meth) acrylate compound represented by the general formula (II) include bisphenol A di (meth) acrylate compounds having an average of 1 unit of ethylene oxide added to both ends of bisphenol A Di (meth) acrylate of polyethylene glycol in which an average of 2 units of ethylene oxide is added to both ends of bisphenol A, di (meth) acrylate of polyethylene glycol in which an average of 5 units of ethylene oxide is added to both ends of bisphenol A, Di (meth) acrylate of polyethylene glycol having an average of 7 units of ethylene oxide added to both ends of bisphenol A, ethylene oxide of 6 units on average and propylene oxide of 2 units on average at both ends of bisphenol A Di (meth) acrylate of the added polyalkylene glycol, bisphenol A, and bis Di (meth) acrylate of a polyalkylene glycol to which ethylene oxide is added in an average of 15 units and an average of 2 units of propylene oxide are added to both ends of bisphenol A, Acrylate, and the like.

In the general formula (II), n ₁ , n ₂ , n ₃ and n ₄ have a relationship of n ₁ + n ₂ + n ₃ + n ₄ = 2 to 10 from the viewpoints of resolution and water- And it is particularly preferable that the relationship of n ₁ + n ₂ + n ₃ + n ₄ = 2 to 4 is satisfied.

The ethylenically unsaturated bond-containing compound (B) is a compound which satisfies n ₁ + n ₂ + n ₃ + n ₄ = 30 to 50 in the general formula (II) from the viewpoint of compatibility between tent and water- , A compound in which one or both of R ₃ and R ₄ in formula (II) is a hydrogen atom, and a compound satisfying n ₁ + n ₂ + n ₃ + n ₄ = 2 to 10 in formula (II) At the same time.

The ethylenically unsaturated bond-containing compound (B) preferably contains a tri (meth) acrylate compound represented by the general formula (III) (b ₃ ) from the viewpoint of resolution and tentability. X in the general formula (III) is an alkylene group having 2 to 6 carbon atoms and may be, for example, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH (CH ₃ ) CH ₂ - .

(b ₃₎ the general formula (III) represents a tri (meth) acrylate compound preferably has an alkylene oxide portion of the tent viewpoint, relatively chapter chain. More specifically, in the general formula (III), m ₂ + m ₃ + m ₄ is preferably 10 to 40, and more preferably 20 to 40.

(b _3), examples of preferred embodiments of the indicating tri (meth) acrylate compound with the general formula (III), ethylene oxide (EO) modified trimethylolpropane tri (meth) acrylate (EO average addition molar number: 10 to 40), propylene (PO) -modified trimethylolpropane tri (meth) acrylate (PO average molar number of addition: 10 to 40).

The ethylenically unsaturated bond-containing compound (B) preferably contains a urethane di (meth) acrylate compound represented by the general formula (IV) (b ₄ ) from the viewpoint of tentability.

In the general formula (IV), Z represents a divalent organic group and includes, for example, an alkylene group having 1 to 10 carbon atoms, an alkylene oxide group having 2 to 10 carbon atoms, an alkylene oxide group having 3 to 10 carbon atoms Or an alicyclic group or the like.

In the general formula (IV), Y represents an alkylene group having 2 to 6 carbon atoms, for example, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH (CH ₃ ) CH ₂ - Or the like.

(YO) _s - and - (YO) _t - moieties in the general formula (IV) are each independently - (C ₂ H ₅ O) - (C ₃ H ₆ O) ₉ -.

(b ₄₎ of the general formula (IV) examples of the urethane di (meth) acrylate, preferred examples of the compound represented by (meth) acrylic monomers having a hydroxyl group at the β position with isopropyl isophorone diisocyanate, 2,6-toluene diisocyanate, 2 (Meth) acryloxytetraethylene glycol isocyanate), hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, and diisocyanate compounds such as diisocyanate, tetraene diisocyanate and 1,6-hexamethylene diisocyanate, Acrylate, and EO, PO-modified urethane di (meth) acrylate. Further, EO represents ethylene oxide, and the EO-modified compound has a block structure of an ethylene oxide group. In addition, PO represents propylene oxide, and the PO-modified compound has a block structure of propylene oxide group. As the EO-modified urethane di (meth) acrylate, for example, trade name "UA-11" manufactured by Shin-Nakamura Chemical Co., Ltd. and the like can be mentioned. As the EO and PO modified urethane di (meth) acrylate, for example, trade name "UA-13" manufactured by Shin-Nakamura Chemical Co., Ltd. and the like can be mentioned. These may be used singly or in combination of two or more.

(B) an ethylenically unsaturated bond-containing compound, (b ₅₎ is a _{component, (b 1) ~ (b} 4) may contain an addition-polymerizable monomer other than the component.

(b ₅₎ as components, the following:

(b ₃₎ tri (meth) other than the component acrylate, for example, trimethylolpropane tri (meth) acrylate, ethoxylated glycerin tri (meth) acrylate, ethoxy tetroxide SOCCIA press acid tri (meth) acrylate , Pentaerythritol tri (meth) acrylate and the like;

(Meth) acrylate, dipentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, Tetra (meth) acrylate and the like;

Penta (meth) acrylate, such as dipentaerythritol penta (meth) acrylate;

Hexa (meth) acrylate such as dipentaerythritol hexa (meth) acrylate, hexa (meth) acrylate in which a total of 1 to 24 moles of ethylene oxide is added to six terminals of dipentaerythritol, di Hexa (meth) acrylate in which a total of 1 to 10 moles of? -Caprolactone is added to the six terminals of pentaerythritol;

Acrylate compounds having one (meth) acryloyl group;

A compound obtained by reacting a polyhydric alcohol with an?,? - unsaturated carboxylic acid;

A compound obtained by reacting an?,? - unsaturated carboxylic acid with a glycidyl group-containing compound; and

Phthalic acid compounds such as? -Chloro-2-hydroxypropyl-? '- (meth) acryloyloxylyl-o-phthalate and? -Hydroxyalkyl-?' - (meth) Oxyalkyl-o-phthalate and the like;

.

In the third embodiment, the total content of all the ethylenically unsaturated bond-containing compounds (B) in the photosensitive resin composition is preferably 1% by mass to 70% by mass, more preferably 1% By mass to 2% by mass to 60% by mass, and more preferably 4% by mass to 50% by mass.

(C) a photopolymerization initiator

(C) The photopolymerization initiator is a compound which polymerizes monomers by light. The photosensitive resin composition includes a compound generally known in the art as a photopolymerization initiator.

The content of the photopolymerization initiator (C) in the photosensitive resin composition is preferably in the range of 0.01 to 20 mass%, more preferably 0.05 to 10 mass%, and still more preferably 0.1 to 7 mass% . The content of the photopolymerization initiator (C) is preferably 0.01 mass% or more from the viewpoint of obtaining sufficient sensitivity, and preferably 20 mass% or less from the viewpoint of sufficiently transmitting light to the bottom of the resist and obtaining good high resolution.

Examples of the photopolymerization initiator (C) as the photopolymerization initiator include quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin ethers, dialkyl ketaldehyde, thioxanthones, dialkylaminobenzoic acid esters, Esters and acridines, and further hexaarylbimidazoles, pyrazoline compounds, N-arylamino acids or ester compounds thereof (for example, N-phenylglycine), and organic halogen compounds . These may be used singly or in combination of two or more. Among them, acridines are particularly suitable for direct imaging exposure.

Examples of the acridine include acridine, 9-phenylacridine, 1,6-bis (9-acridinyl) hexane, 1,7- (9-acridinyl) decane, 1,11-bis (9-acridinyl) octane, 1,9-bis Undecane, 1,12-bis (9-acridinyl) dodecane, and the like. From the viewpoint of the suitability for direct imaging exposure, the content of acridine in the photosensitive resin composition is preferably 0.1% by mass to 5% by mass, more preferably 0.3% by mass to 3% by mass, still more preferably 0.5% Mass% to 2 mass%.

Examples of the aromatic ketones include benzophenone, Michler's ketone [4,4'-bis (dimethylamino) benzophenone], 4,4'-bis (diethylamino) benzophenone, 4-methoxy- - dimethylaminobenzophenone. These may be used singly or in combination of two or more. Of these, 4,4'-bis (diethylamino) benzophenone is preferable from the viewpoint of adhesion. From the viewpoint of the transmittance, the content of the aromatic ketones in the photosensitive resin composition is preferably in the range of 0.01% by mass to 0.5% by mass, more preferably 0.02% by mass to 0.3% by mass.

Examples of hexaarylbimidazoles include 2- (o-chlorophenyl) -4,5-diphenylbiimidazole, 2,2 ', 5-tris (o-chlorophenyl) -4- (4-methoxyphenyl) -4 ', 5'-diphenylbiimidazole, 2,4-bis- (o-chlorophenyl) , 5-tris (o-chlorophenyl) -diphenyl biimidazole, 2- (o-chlorophenyl) Bis- (2-fluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'- (2,4-difluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) ', 5,5'-tetrakis- (3-methoxyphenyl) -bimidazole, 2,2'-bis- (2,5-difluorophenyl) -4,4', 5,5'- Tetrakis- (3-methoxyphenyl) -bimidazole, 2,2'-bis- (2,6-difluorophenyl) -4,4 ', 5,5'- (2,4,6-trimethoxyphenyl) -bimidazole, 2,2'-bis- (2,3,4-trifluorophenyl) -4,4 ', 5,5'-tetrakis- 3-methoxyphenyl) -bimidazole, 2,2'-bis- (2,3,5-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) ) -Bimidazole, 2,2'-bis- (2,3,6-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) , 2,2'-bis- (2,4,5-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) Bis- (2,4,6-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- , 3,4,5-tetrafluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'- Tetrakis- (3-methoxyphenyl) -bimidazole, and 2,2'-bis- (2,3,4-tetrafluorophenyl) -4,4 ', 5,5'- Pentafluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -bimidazole, and they can be used singly or in combination of two or more May be used in combination. From the viewpoints of high sensitivity, resolution and adhesion, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer is preferable.

In the third embodiment, the content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably 0.05% by mass to 7% by mass, more preferably 0.05% by mass to 7% by mass from the viewpoint of improving the peeling property and / or sensitivity of the photosensitive resin layer Is in the range of 0.1% by mass to 6% by mass, and more preferably 1% by mass to 4% by mass.

Examples of the N-arylamino acid include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like. Among them, N-phenylglycine is particularly preferable. The content of the N-arylamino acid in the photosensitive resin composition is preferably 0.05% by mass to 5% by mass, more preferably 0.1% by mass to 2% by mass relative to the total solid content of the photosensitive resin composition from the viewpoint of improving the peeling property and / Is more preferable.

Examples of the organic halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenylsulfone, tetrabromocarbon, tris (2,3 (Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p- chlorophenyl) ethane, and chlorinated triazine compounds Among them, tribromomethylphenylsulfone is particularly preferably used. The content of the organic halogen compound in the photosensitive resin composition is preferably 0.05% by mass to 5% by mass, more preferably 0.1% by mass to 3% by mass relative to the total solid content of the photosensitive resin composition from the viewpoint of improving the peeling property and / % Is more preferable.

Other photosensitizers include, for example, 2-ethyl anthraquinone, octaethyl anthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, Anthraquinone, 1-chloroanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethyl anthraquinone, Quinone such as 2-methyl anthraquinone, benzoin ethers such as benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin, benzyl dimethyl ketal, benzyl diethyl ketal, Phenyl-1,2-propanedione-2-O-benzoin oxime, and 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime. The content of the photosensitizer in the photosensitive resin composition is preferably 0.05% by mass to 5% by mass, more preferably 0.1% by mass to 3% by mass relative to the total solid content of the photosensitive resin composition from the viewpoint of improving the peeling property and / % Is more preferable.

In the third embodiment, it is also preferable that the photosensitive resin composition contains a pyrazoline compound as a photosensitizer. Examples of the pyrazoline compound include 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert- butylphenyl) Phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert- butylphenyl) phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -pyrazoline and 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazolene are preferred.

(D) Additive

The photosensitive resin composition may contain additives such as a discoloring agent, a dye, a plasticizer, an antioxidant, a stabilizer, etc., as desired. For example, the additives listed in Japanese Laid-Open Patent Publication No. 2013-156369 and International Publication No. 2009/093706 may be used.

Examples of the discoloring agent include a leuco dye and a fluororan dye. The use of a discoloring agent is preferable from the viewpoint of visibility due to color development of the exposed portion. In the case where the inspection device or the like reads the alignment mark for exposure, it is advantageous because the position of the exposure portion is large and the contrast of the unexposed portion is easy to recognize.

Examples of the leuco dyes include tris (4-dimethylaminophenyl) methane [leuco crystal violet] and bis (4-dimethylaminophenyl) phenylmethane [leuco malachite green]. In particular, from the viewpoint of improving the contrast, it is preferable to use Loico crystal violet as the leuco dye. The content of the leuco dye in the photosensitive resin composition is preferably 0.1% by mass to 10% by mass. This content is preferably 0.1% by mass or more from the viewpoint of the contrast between the exposed portion and the unexposed portion, and is preferably 10% by mass or less from the viewpoint of maintaining the storage stability.

Examples of the base dye include Basic Green 1 (CAS No.: 633-03-4) (for example, Aizen Diamond Green GH, trade name, manufactured by Hodogaya Chemical Co., Ltd.), malachite green oxalate [ 2437-29-8] (for example, Aizen Malachite Green, trade name, manufactured by Hodogaya Chemical Co., Ltd.), Brilliant Green [633-03-4], fuchsin [632-99-5], methyl violet [603-47-4 ], Methyl Violet 2B [8004-87-3], Crystal Violet [548-62-9], Methyl Green [82-94-0], Victoria Blue B [2580-56-5], Basic Blue 7 [2390- 60-5] (for example, Aizen Victoria Pure Blue BOH, a product of Hodogaya Chemical Co., Ltd.), rhodamine B [81-88-9], rhodamine 6G [989-38-8], basic yellow 2 [ 2465-27-2]. Of these, Basic Green 1, Malachite Green Oxalate, and Basic Blue 7 are preferable, and Basic Green 1 is particularly preferable in view of improving color stability and exposure contrast.

In the third embodiment, the content of the base dye in the photosensitive resin composition is preferably 0.001 mass% to 3 mass%, more preferably 0.01 mass% to 2 mass%, still more preferably 0.01 mass% to 1 mass %. The content of the dye is preferably 0.001% by mass or more from the viewpoint of obtaining good coloring property, and is preferably 3% by mass or less from the viewpoint of maintaining the sensitivity of the photosensitive resin layer.

In the third embodiment, in order to suppress the delay of the resist pattern peeling due to the alkali-soluble polymer having a structural unit content of (meth) acrylic acid of 10% by mass to 24% by mass and to shorten the peeling time, -Toluenesulfonic acid amide, p-toluenesulfonic acid amide and the like is preferably contained in the photosensitive resin composition. The content of the toluenesulfonic acid amide in the photosensitive resin composition is preferably in the range of 0.1% by mass to 5% by mass, and more preferably in the range of 1% by mass to 4% by mass.

Examples of other plasticizers include polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, polyoxyethylene Glycol esters such as ethylene glycol monoethyl ether, polyoxypropylene monoethyl ether and polyoxyethylene polyoxypropylene monoethyl ether, phthalic acid esters such as diethyl phthalate, and the like; esters such as tributyl citrate, triethyl citrate, triethyl acetylcitrate, Tri-n-butyl acetylcitrate, tri-n-butyl acetylcitrate, propylene glycol having propylene oxide added to both sides of bisphenol A, and ethylene glycol having ethylene oxide added to both sides of bisphenol A, and the like.

From the viewpoints of thermal stability or storage stability of the photosensitive resin composition, the photosensitive resin composition preferably contains, as a stabilizer, a radical polymerization inhibitor such as p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert- 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4 -Ethyl-6-tert-butylphenol), diphenylnitrosoamine, triethylene glycol-bis (3-3-t-butyl-5-methyl-4-hydroxyphenylpropionate) Benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene- Benzyltriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, 1- (2-di- And bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole Carboxybenzotriazoles such as 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, 6-carboxy-1,2,3-benzotriazole Sol, a 1: 1 mixture of 1- (2-di-n-butylaminomethyl) -5-carboxybenzotriazole and 1- (2-di-n-butylaminomethyl) -6- , N- (N, N-di-2-hydroxyethyl) aminomethylene carboxybenzotriazole, N- (N, N- N-di-2-ethylhexyl) aminoethylene carboxybenzotriazole and the like, and alkylene oxide compounds having a glycidyl group such as neopentyl glycol diglycidyl ether (for example, (For example, Epolite 400E manufactured by Kyowa Chemical Industry Co., Ltd.), diglycidyl ether of bisphenol A-propylene oxide adduct of 2 moles (for example, ethylene glycol diglycidyl ether listen (Epolite 3002 manufactured by Kyowa Chemical Industry Co., Ltd.), hydrogenated bisphenol A diglycidyl ether (for example, Epolite 4000 manufactured by Kyowa Chemical Industry Co., Ltd.), 1,6-hexanediol diglycidyl Diallyl ether (for example, Epolite 1600 manufactured by Kyowa Chemical Industry Co., Ltd.);

And at least one selected from the group consisting of

In the third embodiment, the total content of all the stabilizers in the photosensitive resin composition is preferably 0.001 mass% to 3 mass%, more preferably 0.01 mass% to 1 mass%, still more preferably 0.05 mass% 0.7% by mass. The total content of the stabilizer is preferably 0.001% by mass or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, and is preferably 3% by mass or less from the viewpoint of maintaining the sensitivity of the photosensitive resin layer.

The additives described above can be used singly or in combination of two or more kinds.

&Lt; Photosensitive resin composition combination liquid &gt;

In the third embodiment, a solution of the photosensitive resin composition can be formed by adding a solvent to the photosensitive resin composition. Examples of the preferable solvent include ketones such as acetone, methyl ethyl ketone (MEK) and the like, and alcohols such as methanol, ethanol, isopropyl alcohol and the like. It is preferable to add a solvent to the photosensitive resin composition so that the viscosity of the solution of the photosensitive resin composition combination is from 500 mPa 占 퐏 to 4000 mPa 占 퐏 at 25 占 폚.

&Lt; Photosensitive resin laminate &

In the third embodiment, a photosensitive resin laminate having a support and a photosensitive resin layer made of the photosensitive resin composition laminated on a support may be provided. The photosensitive resin laminate may have a protective layer on the side opposite to the support side of the photosensitive resin layer as desired.

The support is not particularly limited, but is preferably transparent to transmit light emitted from an exposure light source. Examples of such a support include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film , A polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. These films may be stretched if necessary. The haze is preferably 0.01% to 5.0%, more preferably 0.01% to 2.5%, and still more preferably 0.01% to 1.0%. Thickness of the film is advantageous from the viewpoint of image forming property and economical efficiency as the film is thinner, but it is preferable that the thickness is from 10 탆 to 30 탆 in order to maintain the strength.

The important property of the protective layer used in the photosensitive resin laminate is that the protective layer is smaller than the support in adhesion to the photosensitive resin layer and can be easily peeled off. As the protective layer, for example, a polyethylene film, a polypropylene film and the like are preferable. For example, a film having excellent peelability described in JP-A-59-202457 can be used. The film thickness of the protective layer is preferably 10 탆 to 100 탆, more preferably 10 탆 to 50 탆.

In the third embodiment, the thickness of the photosensitive resin layer in the photosensitive resin laminate is preferably 5 탆 to 100 탆, more preferably 7 탆 to 60 탆. The smaller the thickness of the photosensitive resin layer, the better the resolution of the resist pattern. On the other hand, the larger the thickness of the photosensitive resin layer, the greater the strength of the cured film.

As a method for producing a photosensitive resin laminate by successively laminating a support, a photosensitive resin layer and a protective layer as desired, a known method may be used.

For example, the photosensitive resin composition combination solution is prepared, and then coated on a support using a bar coater or a roll coater, followed by drying to form a photosensitive resin layer comprising a photosensitive resin composition combination liquid on the support. Further, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer as desired.

<Method of Forming Resist Pattern>

The resist pattern forming method includes a lamination step of laminating a photosensitive resin layer made of the above-described photosensitive resin composition on a support, an exposure step of exposing the photosensitive resin layer, and a developing step of developing the exposed photosensitive resin layer, In this order. An example of a specific method of forming a resist pattern in the third embodiment will be described below.

First, in a laminating process, a photosensitive resin layer is formed on a substrate by using a laminator. Specifically, when the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is laminated by heat pressing on the surface of the substrate with a laminator. Examples of the material of the substrate include copper, stainless steel (SUS), glass, indium tin oxide (ITO), and the like.

In the third embodiment, the photosensitive resin layer may be laminated only on one side of the substrate surface, or laminated on both sides if necessary. The heating temperature at the time of laminating is generally 40 ° C to 160 ° C. In addition, adhesion of the obtained resist pattern to the substrate can be improved by performing the heat press bonding at the time of laminating two or more times. In hot pressing, a two-stage laminator having two sets of rolls may be used, or a laminate of the substrate and the photosensitive resin layer may be pressed and repeatedly passed through a roll several times.

Next, in the exposure step, the photosensitive resin layer is exposed to active light using an exposure machine. The exposure can be carried out after the support is peeled, as desired. In the case of exposure through a photomask, the exposure dose is determined by the light source illuminance and the exposure time, and may be measured using a photometer. In the exposure step, direct imager exposure may be performed. In the direct imager exposure, a photomask is not used and the substrate is directly exposed by the imaging apparatus. As the light source, a semiconductor laser or ultra-high pressure mercury lamp having a wavelength of 350 nm to 410 nm is used. When the imaging pattern is controlled by a computer, the exposure amount is determined by the illuminance of the exposure light source and the moving speed of the substrate.

Next, in the developing step, the unexposed portion or the exposed portion of the exposed photosensitive resin layer is removed by a developer using a developing apparatus. If there is a support on the photosensitive resin layer after exposure, this is excluded. Subsequently, using a developer composed of an aqueous alkali solution, the unexposed portion or the exposed portion is removed by development to obtain a resist image.

As the alkali aqueous solution, an aqueous solution such as Na ₂ CO ₃ or K ₂ CO ₃ is preferable. The alkali aqueous solution is selected in accordance with the characteristics of the photosensitive resin layer, but an Na ₂ CO ₃ aqueous solution having a concentration of 0.2 mass% to 2 mass% is generally used. In the alkali aqueous solution, a surface active agent, a defoaming agent, and a small amount of an organic solvent for promoting development may be mixed. The temperature of the developing solution in the developing step is preferably kept constant within the range of 20 占 폚 to 40 占 폚.

Although the resist pattern is obtained by the above-described process, it is also possible to carry out the heating process at 100 占 폚 to 300 占 폚, if desired. By carrying out this heating step, the chemical resistance of the resist pattern can be improved. As the heating process, a heating furnace of a type using hot air, infrared light or far-infrared light can be used.

The photosensitive resin composition of the third embodiment can be preferably used for forming a circuit of a printed board. In general, a subtractive process and a semi-additive process (SAP) are used as a circuit forming method of a printed board.

The subtractive process is a method in which only a non-circuit portion is removed by etching from a conductor disposed on the entire surface of a substrate to form a circuit.

The SAP is a method in which a resist is formed on a non-circuit portion on the conductor seed layer disposed on the entire surface of the substrate, and then only the circuit portion is formed by plating.

<Method of Manufacturing Conductor Pattern>

A method for producing a conductor pattern includes a lamination process for laminating a photosensitive resin layer made of the above-described photosensitive resin composition on a substrate such as a metal plate or a metal film insulation plate, an exposure process for exposing the photosensitive resin layer, Or a step of forming a conductive pattern by etching or plating a substrate on which a resist pattern is formed, preferably in this order.

In the third embodiment, the conductor pattern manufacturing method is carried out by forming a resist pattern by the above-mentioned resist pattern forming method using a metal plate or a metal coating insulating plate as a substrate, and then conducting a conductor pattern forming step . In the conductor pattern forming step, a conductor pattern is formed on the substrate surface (for example, copper surface) exposed by development using an etching method or a plating method already known.

Further, the third embodiment is preferably applied in, for example, the following applications.

&Lt; Manufacturing method of wiring board &gt;

A conductor pattern is produced by a method for manufacturing a conductor pattern and then a peeling step of peeling the resist pattern from the substrate with an aqueous solution having a stronger alkaline property than the developer is further carried out to obtain a wiring board having a desired wiring pattern Printed wiring board) can be obtained.

Although not particularly limited, an aqueous solution of NaOH or KOH in an amount of 2% by mass to 5% by mass, or an organic amine-based removing solution is generally used for the aqueous alkaline solution for separation (hereinafter also referred to as " do. A small amount of a water-soluble solvent may be added to the peeling solution. Examples of the water-soluble solvent include alcohols and the like. The temperature of the peeling liquid in the peeling step is preferably in the range of 40 占 폚 to 70 占 폚.

<Preparation of Lead Frame>

A lead frame can be manufactured by forming a resist pattern by a resist pattern forming method using a metal plate such as copper, a copper alloy, or an iron-based alloy as a substrate, and then performing the following steps. First, the substrate exposed by development is etched to form a conductor pattern. Thereafter, a peeling step of peeling off the resist pattern is carried out in the same manner as in the method for producing a wiring board to obtain a desired lead frame.

&Lt; Production of base material having uneven pattern &gt;

The resist pattern formed by the resist pattern forming method can be used as a protective mask member when the substrate is processed by the sandblast method. In this case, examples of the substrate include glass, silicon wafer, amorphous silicon, polycrystalline silicon, ceramic, sapphire, and metal materials. A resist pattern is formed on these substrates by the same method as the resist pattern forming method. Thereafter, a sandblasting process is performed in which the blast material is blown from the formed resist pattern image to a desired depth, and a peeling process is performed to remove the resist pattern portion remaining on the substrate from the substrate with an alkaline removing liquid, A substrate having a fine concavo-convex pattern on the substrate can be produced.

In the sand blast process, but also by using the known blast material, for example, SiC, SiO _2, Al ₂ O _3, CaCO _3, ZrO, glass, have a particle size of 2 ㎛ ~ 100 ㎛ fine particles comprising a stainless steel, etc. It is generally used.

<Fabrication of Semiconductor Package>

A semiconductor package can be manufactured by forming a resist pattern on a wafer by a resist pattern forming method using a wafer on which a large-scale integrated circuit (LSI) has been formed as a substrate, and then performing the following steps. First, the opening exposed by development is subjected to columnar plating such as copper or solder to form a conductor pattern. Thereafter, a step of peeling off the resist pattern is carried out in the same manner as the method of manufacturing the wiring board, and a step of removing the thin metal layer of the portion other than the columnar plating by etching is performed to obtain a desired semiconductor package have.

In the third embodiment, the photosensitive resin composition is used in the production of a printed wiring board, a lead frame for mounting an IC chip, a metal foil precision processing such as a metal mask production, a ball grid array (BGA) (COF), and tape automated bonding (TAB); the manufacture of semiconductor bumps; and the manufacture of flat panel displays such as ITO electrodes, address electrodes, electromagnetic shields, etc. Can be used for the production of barrier ribs.

The values of the above-described parameters are measured in accordance with the measuring method in Examples to be described later, unless otherwise specified.

&Lt; Fourth Embodiment &

Hereinafter, a mode for carrying out the fourth embodiment of the present invention (hereinafter abbreviated as &quot; the fourth embodiment &quot;) will be described concretely.

<Photosensitive resin composition>

In the fourth embodiment, the photosensitive resin composition contains (A) an alkali-soluble polymer, (B) an ethylenically unsaturated bond-containing compound, and (C) a photopolymerization initiator. As desired, the photosensitive resin composition may further contain other components such as (D) a stabilizer.

(Meth) acryloyl group means acryloyl group or methacryloyl group, and the term "(meth) acryloyl group" means acryloyl group or methacryloyl group, Acrylate &quot; means &quot; acrylate &quot; or &quot; methacrylate &quot;.

[(A) Alkali-soluble polymer]

The alkali-soluble polymer (A) contains a first copolymer having a content of acid monomer units of less than 25 mass% and a content of aromatic monomer units of 30 mass% or more from the viewpoints of resolution and prolongation of minimum developing time do. The first copolymer may contain, in addition to the acid monomer unit and the aromatic monomer unit, other monomer units, as desired. The degree of dispersion of the copolymer represented by the weight average molecular weight (described later) and the number average molecular weight of the copolymer is preferably 1 or more and 6 or less.

Examples of the acid monomer include (meth) acrylic acid, pentenoic acid, unsaturated dicarboxylic acid anhydride, and hydroxystyrene. Examples of the unsaturated dicarboxylic acid anhydride include maleic anhydride, itaconic anhydride, fumaric acid, and citraconic anhydride. Among them, (meth) acrylic acid is preferable.

The copolymerization ratio of the acid monomer units in the component (A) is preferably less than 25 mass%, more preferably 10 mass% to 24 mass%, and more preferably 15 mass% to 24 mass%, based on the total mass of all monomer units. More preferably 23 mass%. The content of the acid monomer units in the above range is preferable in view of improvement in resolution and prolongation of the minimum development time.

The aromatic monomer is also called an unsaturated aromatic compound. Examples of the aromatic monomer include styrene,? -Methylstyrene, vinylnaphthalene and the like, and (meth) acrylic acid aralkyl esters. Examples of the (meth) acrylic acid aralkyl ester include benzyl (meth) acrylate and the like.

The copolymerization ratio of the aromatic monomer unit (preferably styrene unit) in the component (A) is preferably 30% by mass or more, more preferably 32% by mass to 60% by mass relative to the total mass of all monomer units , More preferably from 35% by mass to 55% by mass. It is preferable to set the copolymerization ratio of the hydrophobic high-molecular-weight aromatic monomer and the aromatic monomer which is difficult to be fused with the developing water and the developing water to the above-described range in view of improvement of resolution and prolongation of the minimum developing time.

Examples of other monomers include (meth) acrylic acid alkyl esters, conjugated diene compounds, polar monomers, and crosslinkable monomers.

(Meth) acrylic acid alkyl ester is a concept including both chain alkyl esters and cyclic alkyl esters, and specifically includes, for example, methyl (meth) acrylate, ethyl (meth) (Meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl Stearyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like.

Examples of the conjugated diene compound include 1,3-butadiene, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene and the like.

As the polar monomer, for example,

Hydroxyl group-containing monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and pentenol; amino group-containing monomers such as 2-aminoethyl methacrylate;

Amide group-containing monomers such as (meth) acrylamide and N-methylol (meth) acrylamide;

Cyano group-containing monomers such as acrylonitrile, methacrylonitrile,? -Chloroacrylonitrile and? -Cyanoethyl acrylate;

Epoxy group-containing monomers such as glycidyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate;

And the like.

Examples of the crosslinkable monomer include trimethylolpropane triacrylate and divinylbenzene.

The first copolymer is preferably a copolymer of (meth) acrylic acid, styrene, and other monomers.

In the fourth embodiment, from the viewpoint of resolution, developability and cohesiveness, it is also preferable to include the second copolymer in which the content of the aromatic monomer units described above is 45% by mass to 90% by mass. In the second copolymer, the content of the aromatic monomer units is 45% by mass, so that the hydrophobicity of the resist pattern including the second copolymer tends to be secured. It is preferable that the weight ratio of the second copolymer to the total weight of the total copolymer is 25 mass% or more from the viewpoint of improving the cohesiveness.

The second copolymer may contain the above-described acid monomer unit and other monomer units. As the aromatic monomer for polymerizing the second copolymer, styrene is preferable from the viewpoint of hydrophobicity. The upper limit of the content ratio of the aromatic monomer units in the second copolymer is more preferably 80% by mass or 70% by mass from the viewpoint of developability.

The second copolymer may contain the above-described acid monomer unit and other monomer units, and from the viewpoints of resolution, developability and cohesiveness, the content of the acid monomer units described above is preferably 25 mass% To 50% by mass, and more preferably from 25% by mass to 40% by mass. As the acid monomer for polymerizing the second copolymer, (meth) acrylic acid is preferable from the viewpoint of developability.

The weight-average molecular weight of the component (A) (the weight-average molecular weight of the mixture as a whole when the component (A) includes plural kinds of copolymers) is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000 And more preferably from 15,000 to 100,000. Adjusting the weight average molecular weight of the component (A) within this range is preferable from the viewpoint of satisfying the developing time at the time of forming the resist pattern to the operating state of the line process to be used.

In the fourth embodiment, the content of the component (A) in the photosensitive resin composition is 10% by mass to 10% by mass, based on the total solid content of the photosensitive resin composition (hereinafter, , More preferably 20 mass% to 80 mass%, and still more preferably 40 mass% to 60 mass%. This content is preferably 10% by mass or more from the viewpoint of maintaining alkali developability, and is preferably 90% by mass or less from the viewpoint that the resist pattern formed by exposure sufficiently exhibits the performance as a resist.

It is preferable that the content of acid monomer units is less than 25 mass% and the content of aromatic monomer units is 30 mass% or more in an amount of 5 mass% or more and 50 mass% or less based on the total solid content of the photosensitive resin composition. More preferably 10% by mass or more and 40% by mass or less.

[(B) Ethylenically unsaturated bond-containing compound]

The ethylenically unsaturated bond-containing compound (B) is a compound having polymerizability by having an ethylenic unsaturated group in its structure. The ethylenically unsaturated bond is preferably a terminal ethylenically unsaturated group in terms of addition polymerizability.

In the fourth embodiment, from the viewpoint of ensuring good resolution of the resist pattern and extending the minimum developing time when the (A) alkali-soluble polymer and (B) the ethylenically unsaturated bond-containing compound are used in combination, ) The ethylenically unsaturated bond-containing compound preferably has a weight average molecular weight of 900 or less. In the present specification, the average molecular weight of the ethylenically unsaturated bond-containing compound (B) means the weight average molecular weight derived from the structural formula of the ethylenically unsaturated bond-containing compound (B) when the ethylenically unsaturated bond- Means a weighted average of the weight average molecular weight of the respective ethylenically unsaturated bond-containing compounds and the compounding ratio when the (B) ethylenically unsaturated bond-containing compound is composed of plural kinds.

The weight average molecular weight of the ethylenically unsaturated bond-containing compound (B) is preferably 850 or less, more preferably 800 or less, from the viewpoints of improvement in resolution and prolongation of the minimum development time, and in the photosensitive resin laminate Is preferably 50 or more, and more preferably 100 or more, from the viewpoint of suppressing the edge fusing property. Here, the edge fuse property is a phenomenon in which the photosensitive resin composition layer is evacuated from the end face of the roll when the photosensitive resin laminate is wound in a roll form.

(B) an ethylenically unsaturated bond-containing compound, to _{(b 1) ~ (b 6} ):

(b ₁₎ to general formula (I):

[Chemical Formula 13]

Wherein R ₁ and R ₂ are each independently a hydrogen atom or a methyl group and m ₁ is a number satisfying 2 to 40. <

An ethylene glycol di (meth) acrylate compound represented by the following formula

(b ₂₎ represented by the following general formula (II):

[Chemical Formula 14]

Wherein R ₃ and R ₄ each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , n ₁ , n ₂ , n ₃ and n ₄ are , n ₁ + n ₂ + n ₃ + n ₄ = 2 to 50, and the arrangement of repeating units of - (AO) - and - (BO) - may be random or block, , Any one of - (AO) - and - (BO) - may be a bisphenyl group side.

An alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the following formula:

(b ₃₎ represented by the following general formula (III):

[Chemical Formula 15]

(Wherein R ₅ to R ₇ each independently represent a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, m ₂ , m ₃ and m ₄ each independently represent 0 M ₂ + m ₃ + m ₄ is 0 to 40, and when m ₂ + m ₃ + m ₄ is 2 or more, the plural Xs may be the same or different from each other}

A tri (meth) acrylate compound represented by the following formula

(b ₄₎ the following general formula (IV):

[Chemical Formula 16]

(Wherein R ₈ and R ₉ each independently represent a hydrogen atom or a methyl group, Y represents an alkylene group having 2 to 6 carbon atoms, Z represents a divalent organic group, Each independently, an integer of 0 to 40, and s + t &gt; = 1)

A urethane di (meth) acrylate compound represented by the following formula

(b ₅₎ the following formula (XI):

[Chemical Formula 17]

(Wherein R ₅ to R ₈ each independently represent a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, and m ₂ , m ₃ , m ₄ and m ₅ are each independently M ₂ + m ₃ + m ₄ + m ₅ is an integer of 0 to 50, and when m ₂ + m ₃ + m ₄ + m ₅ is 2 or more, They may be the same or different from each other}

(Meth) acrylate compound represented by the following formula

(b ₆₎ the _{(b 1) ~ (b 5} ) addition polymerizable monomers other than;

And at least one selected from the group consisting of

The ethylenically unsaturated bond-containing compound (B) is preferably a compound containing an ethylene glycol di (meth) acrylate compound represented by the general formula (I) (b ₁ ) from the viewpoint of adjusting the stripping time of the resist pattern and the size of the stripping piece desirable.

In the general formula (I), m ₁ is preferably 2 or more from the viewpoints of the time of peeling and the size of the peeled piece, and is preferably 40 or less from the viewpoints of resolution, tolerance to water and etching resistance. m ₁ is more preferably 4 to 20, and still more preferably 6 to 12.

General formula (I) ethylene glycol di (meth) Specific examples of the acrylate compound, m ₁ = 4 of the tetraethylene glycol di (meth) acrylate, m ₁ = 9 in the na glycol di (meth) acrylate represented by the Or polyethylene glycol di (meth) acrylate of m ₁ = 14 is preferred.

(B) an ethylenically unsaturated bond-containing compounds, from the viewpoint of suppressing the occurrence of agglomeration at the time of development of the photosensitive resin layer made of a photosensitive resin composition, (b ₂₎ alkyl represented by formula (II) alkylene oxide modified bisphenol-A And a di (meth) acrylate compound. B in the general formula (II) may be -CH ₂ CH ₂ CH ₂ - or -CH (CH ₃ ) CH ₂ -.

The hydrogen atom on the aromatic ring in formula (II) may be substituted with a hetero atom and / or a substituent.

Examples of the hetero atom include a halogen atom and the like, and examples of the substituent include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, a phenacyl group, A dialkylamino group having 2 to 20 carbon atoms, a nitro group, a cyano group, a carbonyl group, a mercapto group, an alkylmercapto group having 1 to 10 carbon atoms, an aryl group, a hydroxyl group, a hydroxyalkyl group having 1 to 20 carbon atoms , A carboxyl group, a carboxyalkyl group having 1 to 10 carbon atoms in the alkyl group, an acyl group having 1 to 10 carbon atoms in the alkyl group, an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylcarbonyl group having 2 to 10 carbon atoms , An alkenyl group having 2 to 10 carbon atoms, an N-alkylcarbamoyl group having 2 to 10 carbon atoms, a heterocyclic group, or an aryl group substituted with a substituent of these groups. These substituents may form a condensed ring, or hydrogen atoms in these substituents may be substituted with a hetero atom such as a halogen atom. When the aromatic ring in formula (II) has a plurality of substituents, the plurality of substituents may be the same or different.

R ₃ and R ₄ in the general formula (II) are, each independently, but a hydrogen atom or a methyl contribution, in terms of achieving the contrast to the exposure immediately after the photosensitive resin layer made of a photosensitive resin composition, one of R ₃ and R ₄ Or both of them are preferably hydrogen atoms, and it is more preferable that both of R ₃ and R ₄ are hydrogen atoms.

(b ₂ ) In the alkylene oxide-modified bisphenol A-type di (meth) acrylate compound represented by the general formula (II), a relatively short-chain alkylene oxide is added to improve the resolution and prolong the minimum development time . More specifically, in the general formula (II), n ₁ , n ₂ , n ₃ and n ₄ preferably satisfy a relationship of n ₁ + n ₂ + n ₃ + n ₄ = 0 to 30, More preferably, the relationship of n ₁ + n ₂ + n ₃ + n ₄ = 0 to 25 is satisfied, and more preferably the relationship of n ₁ + n ₂ + n ₃ + n ₄ = 0 to 20 is satisfied, And particularly preferably satisfies a relationship of n ₁ + n ₂ + n ₃ + n ₄ = 0 to 10.

In view of the extension of the sea castle improve the minimum developing time, (B) ethylenically unsaturated bond-containing more than 40% by weight of the compound, preferably, (b ₂₎ the formula (II) as shown alkylene oxide modified bisphenol A More preferably n ₁ , n ₂ , n ₃ and n ₄ in the general formula (II) satisfy the relationship of n ₁ + n ₂ + n ₃ + n ₄ = 0 to 20 (Meth) acrylate compound satisfying the following formula (1). More preferably an alkylene oxide represented by (B) ethylenically to 50% by mass of containing an unsaturated bond compounds, more preferably at least 55 mass% and, most preferably be 60 mass%, (b ₂₎ the formula (II) Modified bisphenol A type di (meth) acrylate compound.

(b ₂ ) Specific preferred examples of the alkylene oxide-modified bisphenol A-type di (meth) acrylate compound represented by the general formula (II) include bisphenol A di (meth) acrylate compounds having an average of 1 unit of ethylene oxide added to both ends of bisphenol A Di (meth) acrylate of polyethylene glycol in which an average of 2 units of ethylene oxide is added to both ends of bisphenol A, di (meth) acrylate of polyethylene glycol in which an average of 5 units of ethylene oxide is added to both ends of bisphenol A, Di (meth) acrylate of polyethylene glycol having an average of 7 units of ethylene oxide added to both ends of bisphenol A, ethylene oxide of 6 units on average and propylene oxide of 2 units on average at both ends of bisphenol A Di (meth) acrylate of the added polyalkylene glycol, bisphenol A, and bis Di (meth) acrylate of a polyalkylene glycol to which ethylene oxide is added in an average of 15 units and an average of 2 units of propylene oxide are added to both ends of bisphenol A, Acrylate, and the like.

In the general formula (II), it is also preferable that n ₁ , n ₂ , n ₃ and n ₄ satisfy the relationship of n ₁ + n ₂ + n ₃ + n ₄ = 2 to 20 from the viewpoint of improvement in resolution And n ₁ + n ₂ + n ₃ + n ₄ = 2 to 10 is particularly preferable.

(B) the ethylenically unsaturated bond-containing compound is a compound which satisfies n ₁ + n ₂ + n ₃ + n ₄ = 2 to 20 in the general formula (II) from the viewpoints of improvement in resolution and prolongation of the minimum development time , A compound in which one or both of R ₃ and R _{4 in} the general formula (II) is a methyl group and a compound satisfying n ₁ + n ₂ + n ₃ + n ₄ = 2 to 16 in the general formula (II) It is particularly preferable that they are contained simultaneously.

(B) an ethylenically unsaturated bond-containing compounds, from the viewpoint of suppressing the occurrence of agglomeration at the time of development of the photosensitive resin layer made of a photosensitive resin composition, (b ₃₎ represents tri (meth) by the general formula (III) acrylate compound . X in the general formula (III) is an alkylene group having 2 to 6 carbon atoms and may be, for example, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH (CH ₃ ) CH ₂ - .

(b ₃₎ the general formula (III) represents a tri (meth) acrylate compound preferably has an alkylene oxide portion at sea viewpoint, relatively short chains. More specifically, in the general formula (III), m ₂ + m ₃ + m ₄ is preferably 8 to 40, and more preferably 9 to 25.

(b _3), examples of preferred embodiments of the indicating tri (meth) acrylate compound with the general formula (III), ethylene oxide (EO) modified trimethylolpropane tri (meth) acrylate (EO average addition mol number: 1 to 40), propylene (PO) -modified trimethylolpropane tri (meth) acrylate (PO average addition mole number: 1 to 40).

The ethylenically unsaturated bond-containing compound (B) preferably contains a urethane di (meth) acrylate compound represented by the general formula (IV) (b ₄ ) from the viewpoint of resolution.

In the general formula (IV), Z represents a divalent organic group and includes, for example, an alkylene group having 1 to 10 carbon atoms, an alkylene oxide group having 2 to 10 carbon atoms, an alkylene oxide group having 3 to 10 carbon atoms Or an alicyclic group or the like.

In the general formula (IV), Y represents an alkylene group having 2 to 6 carbon atoms, for example, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH (CH ₃ ) CH ₂ - Or the like.

(YO) _s - and - (YO) _t - moieties in the general formula (IV) are each independently - (C ₂ H ₅ O) - (C ₃ H ₆ O) ₉ -.

(b ₄₎ of the general formula (IV) examples of the urethane di (meth) acrylate, preferred examples of the compound represented by (meth) acrylic monomers having a hydroxyl group at the β position with isopropyl isophorone diisocyanate, 2,6-toluene diisocyanate, 2 (Meth) acryloxytetraethylene glycol isocyanate), hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, and diisocyanate compounds such as diisocyanate, tetraene diisocyanate and 1,6-hexamethylene diisocyanate, Acrylate, and EO, PO-modified urethane di (meth) acrylate. Further, EO represents ethylene oxide, and the EO-modified compound has a block structure of an ethylene oxide group. In addition, PO represents propylene oxide, and the PO-modified compound has a block structure of propylene oxide group. As the EO-modified urethane di (meth) acrylate, for example, trade name "UA-11" manufactured by Shin-Nakamura Chemical Co., Ltd. and the like can be mentioned. As the EO and PO modified urethane di (meth) acrylate, for example, trade name "UA-13" manufactured by Shin-Nakamura Chemical Co., Ltd. and the like can be mentioned. These may be used singly or in combination of two or more.

(B) an ethylenically unsaturated bond-containing compounds, from the viewpoint of suppressing the occurrence of agglomeration at the time of development of the photosensitive resin layer made of a photosensitive resin composition, (b ₅₎ tetra (meth) acrylate compound represented by the general formula (XI) .

X in the general formula (XI) is an alkylene group having 2 to 6 carbon atoms and may be, for example, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH (CH ₃ ) CH ₂ - .

(b ₅ ) Specific preferred examples of the tetra (meth) acrylate compound represented by the general formula (XI) include pentaerythritol tetra (meth) acrylate, pentaerythritol (poly) alkoxytetra (meth) have.

(B) coupling a compound containing an ethylenically unsaturated is, (b ₆₎ is a _{component, (b 1) ~ (b} 5) may include an addition-polymerizable monomer other than the component.

(b ₆₎ as components, the following:

(b ₃₎ tri (meth) other than the component acrylate, for example, trimethylolpropane tri (meth) acrylate, ethoxylated glycerin tri (meth) acrylate, ethoxy tetroxide SOCCIA press acid tri (meth) acrylate , Pentaerythritol tri (meth) acrylate and the like;

(b ₅₎ acrylate, tetra (meth) other than the component, for example, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate and the like; penta (meth) acrylate, e. For example, dipentaerythritol penta (meth) acrylate and the like;

Hexa (meth) acrylate such as dipentaerythritol hexa (meth) acrylate, hexa (meth) acrylate in which a total of 1 to 24 moles of ethylene oxide is added to six terminals of dipentaerythritol, di Hexa (meth) acrylate in which a total of 1 to 10 moles of? -Caprolactone is added to the six terminals of pentaerythritol;

Acrylate compounds having one (meth) acryloyl group;

A compound obtained by reacting a polyhydric alcohol with an?,? - unsaturated carboxylic acid;

A compound obtained by reacting an?,? - unsaturated carboxylic acid with a glycidyl group-containing compound; and

Phthalic acid compounds such as? -Chloro-2-hydroxypropyl-? '- (meth) acryloyloxylyl-o-phthalate and? -Hydroxyalkyl-?' - (meth) Oxyalkyl-o-phthalate and the like;

.

In the fourth embodiment, the total content of all the ethylenically unsaturated bond-containing compounds (B) in the photosensitive resin composition is preferably 1% by mass to 70% by mass, from the viewpoint of edge fusing property and adhesion property in the photosensitive resin laminate By mass, more preferably from 2% by mass to 60% by mass, and further preferably from 4% by mass to 50% by mass.

[(C) Photopolymerization initiator]

The component (C) is a component that generates a radical capable of initiating polymerization of the component (B) by irradiation of light.

As such component (C), for example, an aromatic ketone compound, a quinone compound, a benzoin ether compound, a benzoin compound, a benzyl compound, a hexaarylbisimidazole compound, an acridine compound and the like can be used. Of these, from the viewpoint of high resolution and good tentability, it is preferable to use at least one selected from a hexaarylbisimidazole compound and an acridine compound. From the viewpoint of the sensitivity of the photosensitive resin composition, the component (C) preferably contains an acridine compound.

Examples of the hexaarylbisimidazole compound include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2,2 ', 5-tris (o-chlorophenyl) -4 - (3,4-dimethoxyphenyl) -4 ', 5'-diphenylimidazolyl dimer, 2,4-bis- (o-chlorophenyl) Diphenylimidazolyl dimer, 2- (o-chlorophenyl) -bis-4,5- (3,4-dichlorophenyl) Dimethoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2-fluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) Dimer, 2,2'-bis- (2,3-difluoromethylphenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) (2,4-difluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,5-difluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'- Difluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3,4-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3- Methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3,5-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) ) -Imidazolyl dimer, 2,2'-bis- (2,3,6-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) (2,4,5-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl 2 (2,4,6-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2 , 2'-bis- (2,3,4,5-tetrafluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, Tetrais- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3,4,6-tetrafluorophenyl) -4,4 ', 5,5'- '- bis- (2,3,4,5,6-pentafluorophenyl) -4,4', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer etc. The can.

As the above-mentioned acridine compound, for example,

Acridine, 9-phenylacridine, 1,6-bis (9-acridinyl) hexane, 1,7-bis (9-acridinyl) heptane, (9-acridinyl) decane, 1,11-bis (9-acridinyl) undecane, 1,12- Bis (9-acridinyl) dodecane, and the like.

The content of the component (C) in the photosensitive resin composition of the fourth embodiment is preferably 0.1% by mass to 2% by mass, more preferably 0.2% by mass to 1.8% by mass, By mass to 1.7% by mass, and particularly preferably 0.4% by mass to 1.6% by mass. Setting the content of the component (C) in such a range is preferable from the viewpoint of obtaining good light sensitivity and peeling property.

The component (C) may further contain a sensitizer in view of improvement in sensitivity and resolution. Examples of such a sensitizer include N-aryl amino acids, organic halogen compounds, and other sensitizers.

As the N-arylamino acid, for example,

N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like;

As the organic halogen compound, for example,

(2,3-dibromopropyl) phosphate, trichloro (2,3-dibromoethyl) phosphate, tributylamine, tributylamine, tributylamine, Amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, chlorinated triazine compounds and the like;

Respectively.

As the other sensitizer, for example,

1,2-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 1, Quinone compounds such as 4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethyl anthraquinone and 3-chloro-2-methyl anthraquinone;

Aromatic ketone compounds such as benzophenone, Michler's ketone [4,4'-bis (dimethylamino) benzophenone] and 4,4'-bis (diethylamino) benzophenone;

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

Benzyldimethyl ketal, benzyldiethyl ketal, 1-phenyl-1,2-propanedione-2-O-benzoin oxime, 1-phenyl-1,2-propanedioyl- 2- (O-ethoxycarbonyl) oxime Oxime ester compounds such as &lt; RTI ID = 0.0 &gt;

And the like.

The content of the sensitizer in the fourth embodiment is preferably 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 3% by mass, from the viewpoints of the light sensitivity of the composition and the peelability of the resist cured film, More preferably 0.1% by mass to 2% by mass.

Further, in the photosensitive resin composition of the fourth embodiment, it is preferable to use an acridine compound and an N-arylamino acid as the component (C), and to use them in combination within the above-mentioned ratio of use, In view of the suppression of the etching rate at the time of etching and the suppression of the vertical and lateral difference of the wiring width.

[(D) Stabilizer]

The photosensitive resin composition may contain a stabilizer as desired. In the fourth embodiment, hindered phenol is preferably used as the stabilizer from the viewpoint of improving the resolution. Generally, hindered phenol refers to a phenol having a large steric hindrance. The photosensitive resin composition is a hindered phenol represented by the following general formula (V):

[Chemical Formula 18]

(Wherein R ⁵¹ represents a linear alkyl group, a branched alkyl group, an aryl group, a cyclohexyl group, a linear alkyl group having a divalent linking group, a branched alkyl group having a divalent linking group, a divalent linking group, And R ⁵² , R ⁵³ and R ⁵⁴ are each independently hydrogen or a linear or branched alkyl group, a branched alkyl group, an aryl group, a cycloalkyl group, a cycloalkyl group, a cycloalkyl group, a cycloalkyl group, A hexyl group, a linear alkyl group having a divalent linking group, a branched alkyl group having a divalent linking group, a cyclohexyl group having a divalent linking group, or an aryl group having a divalent linking group.

The compound represented by the general formula (V) is excellent in terms of improving the resolution of the photosensitive resin composition and suppressing the sensitivity lowering of the photosensitive resin composition. Further, the compound represented by the general formula (V) has no two or more phenolic hydroxyl groups in one aromatic ring and has substituents at only one ortho position among the ortho positions of the phenolic hydroxyl group, It is characterized by the control of the steric hindrance around the sexual hydroxyl group. With such a structure, it is considered that the above excellent performance is expressed.

The compound represented by the general formula (V) is preferably a compound represented by the general formula (V) in which R ⁵¹ , R ⁵² , R ⁵³ and R (R) are the same as or different from each other in terms of improving the resolution of the photosensitive resin composition and suppressing lowering of the sensitivity of the photosensitive resin composition. It is preferable that at least one of the first through fourth layers ⁵⁴ , From the same viewpoint, the hydroxyl group concentration of the hindered phenol is preferably 0.10 mol / 100 g to 0.75 mol / 100 g. From the same viewpoint, it is preferable that at least one of R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ in the general formula (V) is an aryl group via a linear or branched alkyl group or a divalent linking group, Examples of the preferable alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group and a tert- Examples of the linking group include a thioether group, a substituted or unsubstituted alkylene group and the like, and the aryl group may be substituted with a hydroxyl group or an alkyl group.

From the same viewpoint, as the compound represented by the general formula (V), for example, a compound represented by the following general formula (VI):

[Chemical Formula 19]

(Wherein R ⁵⁵ represents a group represented by the general formula (VII):

[Chemical Formula 20]

: Wherein R ⁵⁹ and R ⁶⁰ each independently represent hydrogen or an optionally substituted straight chain alkyl group, branched alkyl group, aryl group or cyclohexyl group; and R ⁵⁶ , R ⁵⁷ and And R &lt; ⁵⁸ &gt; each independently represents hydrogen or the above-described formula (VII), a compound represented by the following formula (VIII)

[Chemical Formula 21]

(Wherein R ⁶¹ and R ⁶⁴ each independently represents a linear or branched alkyl group, and R ⁶² , R ⁶³ , R ⁶⁵ and R ⁶⁶ are each independently hydrogen or a linear or branched alkyl group And X &lt; ¹ &gt; represents a divalent linking group, a compound represented by the following general formula (IX):

[Chemical Formula 22]

Wherein R ⁶⁷ , R ⁷⁰ and R ⁷³ each independently represents a linear or branched alkyl group and R ⁶⁸ , R ⁶⁹ , R ⁷¹ , R ⁷² , R ⁷⁴ and R ⁷⁵ each independently represent a hydrogen atom, Hydrogen, or a linear or branched alkyl group, and Y ¹ represents a trivalent linking group, a compound represented by the following general formula (X):

(23)

Wherein R ⁷⁶ , R ⁷⁹ , R ⁸² and R ⁸⁵ each independently represents a linear or branched alkyl group and R ⁷⁷ , R ⁷⁸ , R ⁸⁰ , R ⁸¹ , R ⁸³ , R ⁸⁴ , R ⁸⁶ And R ⁸⁷ each independently represent hydrogen or a linear or branched alkyl group, and Z ¹ represents a tetravalent linking group. Examples of X ¹ in the general formula (VIII) include a thioether group, a substituted or unsubstituted alkylene group, and the like.

The compound represented by the general formula (V) preferably has a molecular weight of about 130 to about 1,000 from the viewpoints of improving the resolution of the photosensitive resin composition and suppressing the sensitivity lowering of the photosensitive resin composition, More preferably having a molecular weight of about 800, more preferably having a molecular weight of about 300 to about 500, and most preferably having a molecular weight of about 300 to about 400. It is also preferred to have a melting point of about 1.02 to about 1.12 or a melting point of about 155 ° C or more (for example, about 208 ° C or more) or to be insoluble in water and to be soluble in an organic solvent such as methanol, acetone, Or it is preferably a solid (e.g., powder, crystal, etc.) or liquid in use.

Examples of the compound represented by formula (V) include 4,4'-thiobis (6-tert-butyl-m-cresol), 4,4'-butylidenebis -Butylphenol), styrenated phenol (Anteji SP manufactured by Kawaguchi Chemical Industry Co., Ltd.), tribenzylphenol (TBP manufactured by Kawaguchi Chemical Industry Co., Ltd., phenol having 1 to 3 benzyl groups) . Among these, from the viewpoints of improving the resolution and the suppressing the lowering of the sensitivity of the photosensitive resin composition by increasing the content of the compound represented by the general formula (I), 4,4'-thiobis (6-tert- Butyl-m-cresol), and 4,4'-butylidenebis (3-methyl-6-tert-butylphenol) are preferable.

The ratio of the compound represented by the formula (V) to the total mass of the photosensitive resin composition is from 0.001% by mass to 10% by mass. This ratio is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, particularly preferably 0.5% by mass or more from the viewpoint of improvement in resolution By mass, and most preferably 0.7% by mass or more. On the other hand, this ratio is preferably not more than 10% by mass, more preferably not more than 5% by mass, more preferably not more than 3% by mass, further preferably not more than 2% by mass, from the viewpoint of less sensitivity deterioration and improvement in resolution By mass, and particularly preferably not more than 1.5% by mass.

In the fourth embodiment, the hindered phenol may further contain a compound other than the compound represented by the general formula (V). Examples of the compound other than the compound represented by the general formula (V) include 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-amylhydroquinone, (2-hydroxy-3-t-butyl-5-ethylphenyl) methane, triethylene glycol- Bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol- Hydroxyphenyl) propionate], pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- , 3,5-di-t-butyl-4-hydroxybenzylphosphonate-N, Diethyl ester, 1,3,5-trimethyl- (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris- And the like.

In the fourth embodiment, the total content of all hindered phenols in the photosensitive resin composition is preferably 0.001% by mass to 10% by mass with respect to the total mass of the photosensitive resin composition.

In the fourth embodiment, the photosensitive resin composition may contain a stabilizer other than hindered phenol. As stabilizers other than hindered phenol, radical polymerization inhibitors such as p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), di Butyl-5-methyl-4-hydroxyphenylpropionate), and nitrosophenylhydroxyamine aluminum salts; benzotriazoles, such as benzyltriazoles, such as triethyleneglycol-bis For example, there may be mentioned 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene- N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, 1- (2-di-n-octylaminomethyl) -benzotriazole, and bis Methylene-1,2,3-benzotriazole and the like; carboxybenzotriazoles such as 4-carboxy-1,2,3-benzo Carboxy-1,2,3-benzotriazole, 6-carboxy-1,2,3-benzotriazole, 1- (2-di-n-butylaminomethyl) 1: 1 mixture of triazole and 1- (2-di-n-butylaminomethyl) -6-carboxylbenzotriazole, N- (N, N-di- , N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) aminoethylene carboxybenzotriazole and glycidyl For example, neopentyl glycol diglycidyl ether (for example, Epolite 1500NP manufactured by Kyowa Chemical Industry Co., Ltd.), nonaethylene glycol diglycidyl ether (for example, (Epolite 400E manufactured by Eisse Chemical Co., Ltd.), diglycidyl ether of bisphenol A-propylene oxide 2 mol adduct (for example, Epolite 3002 manufactured by Kyowa Chemical Industry Co., Ltd.), hydrogenated bisphenol A diglycidyl ether (for example, Epolite 4000 manufactured by Kyowa Chemical Industry Co., Ltd.), 1,6-hexanediol diglycidyl ether (for example, Epolite manufactured by Kyowa Chemical Industry Co., Ltd.) 1600), and the like.

In the fourth embodiment, the total content of all the stabilizers in the photosensitive resin composition is preferably 0.001 mass% to 3 mass%, more preferably 0.01 mass% to 1 mass%, still more preferably 0.05 mass% 0.7% by mass. The total content of the stabilizer is preferably 0.001% by mass or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, and is preferably 3% by mass or less from the viewpoint of maintaining the sensitivity of the photosensitive resin layer.

[Other components]

The photosensitive resin composition of the fourth embodiment may contain other components in addition to the components (A) to (D) described above. Such other components include, for example, leuco dyes, base dyes, plasticizers, antioxidants, radical polymerization inhibitors, solvents and the like.

[Leuco dye]

The leuco dye can be compounded in the photosensitive resin composition of the fourth embodiment in order to impart desirable coloring property and excellent peeling property to the resist cured film.

Specific examples of the leuco dyes include, for example, leuco crystal violet (tris [4- (dimethylamino) phenyl] methane), 3,3-bis (p-dimethylaminophenyl) (1-ethyl-2-methylindole-3-yl) phthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- 3-methyl-6-dimethylaminofluororan, 3-dibutyl (2-methylbutyl) Amino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3- 2-chloroanilino) -6-dibutylaminofluorane, 3,6-dimethoxyfluoran, 3,6-di-n-butoxyfluororan, 1,2- Methyl-6- (Np-tolyl-N-ethylamino) fluororan, 1,2-benzyl- 2- 2- (3'-trifluoromethylanilino) -6-diethylaminofluororan, 3- (N-phenyl- Chloro-6-cyclohexylaminofluorane, 2-methyl-6-cyclohexylaminofluorane and 3-methoxy-4-dodecoxy-styrinoquinoline. Among them, Loico crystal violet is preferable.

The content of the leuco dye in the photosensitive resin composition of the fourth embodiment is preferably 0.6% by mass to 1.6% by mass, more preferably 0.7% by mass to 1.2% by mass. By setting the usage ratio of the leuco dye within this range, it is possible to realize good coloring property and good releasability.

[Base dye]

Examples of the base dye include Basic Green 1 (CAS No.: 633-03-4) (for example, Aizen Diamond Green GH, trade name, manufactured by Hodogaya Chemical Co., Ltd.), malachite green oxalate (Aizen Malachite Green, trade name, manufactured by Hodogaya Chemical Co., Ltd.), Brilliant Green [633-03-4], fuchsin [632-99-5], methyl violet [603-47- 4], Methyl Violet 2B [8004-87-3], Crystal Violet [548-62-9], Methyl Green [82-94-0], Victoria Blue B [2580-56-5], Basic Blue 7 [2390 -60-5] (for example, Aizen Victoria Pure Blue BOH, a product of Hodogaya Chemical Co., Ltd.), rhodamine B [81-88-9], rhodamine 6G [989-38-8], basic yellow 2 [2465-27-2], diamond green, and the like. Of these, at least one selected from Basic Green 1, Malachite Green Oxalate, Basic Blue 7 and Diamond Green is preferable, and from the viewpoints of color stability and exposure contrast, Basic Green 1 is particularly preferable.

The content of the base dye in the photosensitive resin composition of the fourth embodiment is preferably from 0.001 mass% to 3 mass%, more preferably from 0.01 mass% to 2 mass%, still more preferably from 0.01 Mass% to 1.2 mass%. By setting the ratio in this range, both good color development and high sensitivity can be achieved.

[menstruum]

The photosensitive resin composition of the fourth embodiment may be a mixture of the above components (A) to (C) and optionally other components, or may be a photosensitive resin composition comprising a solvent added to these components It may be used as a combination liquid.

Examples of the solvent used herein include ketone compounds such as methyl ethyl ketone (MEK), and alcohols such as ethanol, ethanol, and isopropyl alcohol.

The ratio of the solvent used is preferably such that the viscosity of the photosensitive resin composition combination solution at 25 캜 is 500 to 4,000 mPa 占 퐏.

<Photosensitive element>

In the fourth embodiment, the photosensitive element is a laminate (photosensitive resin laminate) in which a photosensitive resin layer composed of the above-described photosensitive resin composition is laminated on a support. If necessary, the photosensitive resin layer may have a protective layer on the surface opposite to the support.

[Support]

As the support, a transparent substrate that transmits light emitted from an exposure light source is preferable. Examples of such a support include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film , A polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. As these films, stretched films may be used if necessary.

The haze of the support is preferably 5 or less.

Thickness of the support is advantageous from the viewpoint of image forming property and economical efficiency, but it is necessary to maintain the strength. Considering both of them, a support of 10 占 퐉 to 30 占 퐉 can be preferably used.

[Photosensitive resin layer]

When the photosensitive resin composition used for forming the photosensitive resin layer contains a solvent, the solvent may remain or be removed in the photosensitive resin layer.

The thickness of the photosensitive resin layer is preferably 5 mu m to 100 mu m, more preferably 7 mu m to 60 mu m. The thinner the thickness, the better the resolution, and the thicker the film the better the film strength. Therefore, the thickness of the composition layer can be appropriately selected within the above-described range depending on the application.

[Protective layer]

An important characteristic of the protective layer is that the adhesion strength with the photosensitive resin layer is sufficiently smaller than the adhesion between the support and the photosensitive resin layer and can be easily peeled off. As the protective layer, for example, a polyethylene film, a polypropylene film and the like can be preferably used, and for example, a film having excellent peelability disclosed in Japanese Patent Application Laid-open No. 59-202457 can be used.

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

[Method of producing photosensitive element]

The photosensitive element can be produced by sequentially laminating a support, a photosensitive resin layer and, if necessary, a protective layer. As a method for laminating the support, the photosensitive resin layer, and the protective layer, a known method can be adopted.

For example, a photosensitive resin composition is prepared as a combined solution of the photosensitive resin composition described above, and first, the composition is coated on a support using a bar coater or a roll coater and dried to form a photosensitive resin layer made of a photosensitive resin composition on the support do. Then, if necessary, the photosensitive element can be produced by laminating a protective layer on the formed photosensitive resin layer.

&Lt; Method of forming resist pattern &gt;

A resist pattern can be formed on a substrate using the above-described photosensitive element.

A method of forming a resist pattern includes the following steps:

A lamination step of laminating a photosensitive resin layer of the photosensitive element on a conductive substrate;

An exposure step of exposing the laminated photosensitive resin layer;

A developing step of developing the exposed photosensitive resin layer;

In the order described above.

In the method for forming a resist pattern according to the fourth embodiment, first, a photosensitive resin layer is formed on a substrate by using a laminator in a laminating process. Specifically, when the photosensitive element has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is laminated on the surface of the substrate by heating using a laminator.

As the substrate, a metal plate or an insulating substrate having a metal coating is used. Examples of the material of the metal include copper, stainless steel (SUS), glass, indium tin oxide (ITO), and the like. These substrates may have through-holes corresponding to the multilayer substrate.

Here, the photosensitive resin layer may be laminated only on one side of the substrate surface, and laminated on both sides of the substrate, if necessary. The heating temperature at this time is preferably 40 占 폚 to 160 占 폚. It is preferable to carry out hot pressing twice or more from the viewpoint of further improving the adhesion of the obtained resist pattern to the substrate. In the case of pressing at least two times, a two-stage laminator having two sets of rolls may be used. Alternatively, a laminate of the substrate and the photosensitive resin layer may be repeatedly passed through rolls and pressed.

In the laminating step, the photosensitive resin layer of the photosensitive element can be laminated on the conductive substrate through the wetting agent. This is a preferable lamination method in terms of improvement in trackability and yield. Examples of the wetting agent include at least one selected from pure water, deionized water and electrolytic water and at least one selected from the group consisting of copper chelating agents (for example, imidazole compounds, triazole compounds, pyridine compounds, and pyrazole compounds Compound).

Next, in the exposure step, the photosensitive resin layer is exposed using an exposure machine. This exposure may be carried out through the support without peeling the support, and may be carried out after peeling off the support.

By applying this exposure in the form of a pattern, a resist film (resist pattern) having a desired pattern can be obtained after passing through a developing step described later. Patternwise exposure may be performed by a method of exposure through a photomask, or a maskless exposure method. In the case of exposure through a photomask, the exposure dose is determined by the light source illuminance and the exposure time. The exposure dose may be measured using a photometer.

In maskless exposure, a photomask is not used, and exposure is performed directly on a substrate by a drawing apparatus. As the light source, a semiconductor laser having a wavelength of 350 nm to 410 nm, an ultra-high pressure mercury lamp or the like is used. In maskless exposure, the imaging pattern is controlled by a computer, and the amount of exposure is determined by the illuminance of the exposure light source and the moving speed of the substrate.

Next, in the development step, the exposed photosensitive resin layer is developed. For example, the unexposed portion of the photosensitive resin layer is removed by a developer. If there is a support on the photosensitive resin layer after exposure, it is preferable to remove the support and provide it to the development process.

In the developing step, a developing solution comprising an aqueous alkaline solution is used to develop and remove the unexposed portion to obtain a resist image. As the alkali aqueous solution, for example, an aqueous solution of Na ₂ CO ₃ , K ₂ CO _3, or the like is preferably used. The alkali aqueous solution is selected in accordance with the characteristics of the photosensitive resin layer, but it is preferable to use an aqueous solution of Na ₂ CO _{3 at} a concentration of 0.2 mass% to 2 mass%. A surfactant, a defoaming agent, and a small amount of an organic solvent for promoting the development may be mixed in the aqueous alkali solution.

The temperature of the developing solution in the developing step is preferably maintained at a constant temperature in the range of 20 캜 to 40 캜.

A resist pattern is obtained by the above-described steps. In some cases, a heating step of 100 ° C to 300 ° C may be further performed. This heating step is preferable from the viewpoint of better chemical resistance. For the heating, a heating furnace of an appropriate method such as hot air, infrared ray, and far-infrared ray can be used.

<Method of forming wiring board>

The method for forming a wiring board according to the fourth embodiment is characterized by comprising the steps of:

A lamination step of laminating a photosensitive resin layer of the photosensitive element on a conductive substrate;

An exposure step of exposing the stacked photosensitive resin layer;

A developing step of developing the exposed photosensitive resin layer;

A conductor pattern forming step of etching or plating a conductor substrate on which a resist pattern is formed by development;

A peeling step for peeling the resist pattern,

, Preferably in the order described above.

In the conductor pattern forming step, a conductor pattern can be formed on a substrate surface (for example, a copper surface) exposed by a developing process on a substrate having a resist pattern formed thereon by a known etching method or a plating method.

In the peeling step, the substrate on which the conductor pattern is formed is brought into contact with an appropriate peeling liquid, whereby the resist pattern is peeled off. By this process, a desired wiring board can be obtained.

The peeling liquid used in the peeling step is preferably an aqueous alkali solution. As this alkali aqueous solution, for example, an aqueous NaOH solution or a KOH aqueous solution of 2% by mass to 5% by mass is preferably used. To the release liquid, a small amount of a water-soluble solvent such as an alcohol may be added. The temperature of the peeling liquid in the peeling step is preferably 40 占 폚 to 70 占 폚.

The photosensitive resin composition, the photosensitive element, the method for forming a resist pattern, and the method for manufacturing a wiring board according to the fourth embodiment are very useful for the manufacture of a printed wiring board, a lead frame, a substrate having a concavo- And can be preferably applied.

In addition, the measurement methods of the various parameters described above are measured according to the measurement method in Examples described later, unless otherwise specified.

Example

&Lt; Embodiment and Comparative Example According to First Embodiment &gt;

Hereinafter, the photosensitive resin composition of the first embodiment will be specifically described by way of examples.

(1) Measurement of raw material properties

&Lt; Measurement of weight average molecular weight &gt;

The weight average molecular weight of the polymer was measured by gel permeation chromatography (GPC) (Gulliver, PU-1580 type, column: Shodex (registered trademark) (KF-807, manufactured by Showa Denko K.K.) (Shodex STANDARD SM-105 manufactured by Showa Denko K.K.) using a calibration curve of four series and mobile layer solvents: tetrahydrofuran and polystyrene standard samples (KF-806M, KF-806M, KF-802.5) Polystyrene conversion value.

<Acid equivalent>

In the present specification, an acid equivalent means a mass (gram) of a polymer having one equivalent of carboxyl groups in the molecule. The acid equivalent weight was measured by potentiometric titration using a 0.1 mol / l sodium hydroxide aqueous solution using a Hirunuma automatic titration apparatus (COM-555) manufactured by Hirano Industry Co., Ltd.

(2) Production method and analysis of sample for evaluation

&Lt; Preparation of Photosensitive Element &gt;

Each component shown in Table 1, and each of the following components:

As the coloring material, 0.04 parts by mass of diamond green;

As a leuco dye, 0.6 parts by mass of Loico crystal violet;

0.7 part by mass of trimodbromomethylphenylsulfone as a halogen compound;

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

As the benzotriazoles, 0.05 parts by mass of carboxybenzotriazole;

As the benzotriazoles, 0.15 parts by mass of 1- (2-di-n-octylaminomethyl) -benzotriazole;

0.05 parts by mass of hydrogenated bisphenol A diglycidyl ether (Epolite 4000, manufactured by Kyowa Chemical Industry Co., Ltd.) as an antioxidant, and

As a radical polymerization inhibitor, 0.004 parts by mass of tris (nitrosophenylhydroxyamine) aluminum

And methyl ethyl ketone (MEK) was further added to prepare a photosensitive resin composition having a solid content concentration of 53 mass%. The number of each component column in Table 1 is the amount (parts by mass) of each component provided for preparing the composition.

The obtained photosensitive resin composition was uniformly coated on a polyethylene terephthalate film (R310, manufactured by Mitsubishi Resin Co., Ltd.) having a thickness of 16 탆 and a haze value of 2.1% using a bar coater, and then the temperature was adjusted to 95 캜 Followed by heating and drying in a dryer for 2.5 minutes to form a photosensitive resin composition layer having a thickness of 25 占 퐉 on the support.

Subsequently, a polyethylene film (GF-18, manufactured by Tamapoly Co., Ltd.) having a thickness of 19 占 퐉 as a protective layer was stuck on the surface of the photosensitive resin composition layer opposite to the support to obtain a photosensitive element.

<Substrate Used for Evaluation>

As the substrate for tentability evaluation, a substrate having a through hole having a diameter of 6 mm and having a hole of 1,008 holes was formed on a copper-clad laminate substrate having a thickness of 1.6 mm and a copper foil having a thickness of 35 占 퐉 laminated thereon;

As evaluation substrates other than tentability, a copper-clad laminate substrate having a thickness of 0.4 mm was laminated with copper foils having a thickness of 18 占 퐉;

Respectively.

The substrate for tentability evaluation was provided for evaluation after being faced by surface treatment using a jet scrub grinder.

The substrate for evaluation other than the tentability was subjected to surface treatment using a soft etching agent (CPE-900, manufactured by Ryoko Chemical Co., Ltd.) and surface cleaning with a 10 mass% aqueous H ₂ SO ₄ solution Later ratings were provided.

<Laminate>

(AL-70, manufactured by Asahi Kasei Corporation) at a roll temperature of 105 占 폚, an air pressure of 0.35 MPa, and a pressure of 0.35 MPa while peeling the polyethylene film of the photosensitive element obtained in each Example or Comparative Example, And a lamination speed of 1.5 m / min.

<Exposure>

Using a direct-writeable exposure apparatus (Paragon Ultra 200, manufactured by Nippon Orbotech Co., Ltd., main wavelength: 355 nm).

The exposure pattern will be described later in the section of each evaluation item.

<Development>

After removing the support from the photosensitive resin composition layer after the exposure, a 1% by mass Na ₂ CO ₃ aqueous solution at 30 ° C was sprayed twice with a time of twice the minimum developing time by using an alkaline developing machine (fuji pore making and developing machine for dry film) Thus, the unexposed portion of the photosensitive resin composition layer was dissolved and removed. After development, the substrate was rinsed with pure water for 1.5 times the development time, dehydrated with air knife, and then subjected to hot air drying to obtain a substrate having a cured film for evaluation.

The minimum developing time refers to a minimum time required until the unexposed portion of the photosensitive resin composition layer is completely dissolved and removed.

&Lt; Evaluation of sensitivity &

For evaluation of the sensitivity, a laminate substrate after lapse of 15 minutes after the &lt; laminating &gt;

Ten mask patterns of line / space = 40 占 퐉 / 40 占 퐉 line were directly drawn and exposed to the laminate substrate, and then developed by the method described in the above <Development>. The resist top width of the obtained resist pattern was measured by an optical microscope and the sensitivity was evaluated according to the following criteria.

The exposure amount at which the resist top width became 39.0 m was 28 mJ or less: sensitivity &quot; good (good) &quot;

The exposure amount at which the resist top width becomes 39.0 占 퐉 exceeds 28 mJ: sensitivity "x (poor)"

Here, the measurement point of the resist line was set at a position of about 5 mm from the fifth line from the end of the line having 10 lines and the end in the longitudinal direction, and the average value of three measurements was used as the measurement value. The line width is different due to the diffusion of the developer and wash water at the end of the pattern and the central portion, and the resist line on the end side tends to be thin.

The exposure amount in the evaluation items below was set to an exposure amount such that the resist top width was 39.0 占 퐉 for a mask pattern of line / space = 40 占 퐉 / 40 占 퐉, as described in <Evaluation of Sensitivity>.

&Lt; Evaluation of resolution &gt;

For evaluation of the resolution, a laminate substrate after lapse of 15 minutes after the &lt; laminating &gt;

The laminate substrate was directly exposed to a line / space = 1/1 pattern of various sizes and then developed by the method described in &lt; Development &gt;.

With respect to the obtained pattern, the minimum pattern width formed was observed by an optical microscope, and the resolution was evaluated according to the following criteria.

When the minimum pattern width was 20 占 퐉 or less: Resolution (占 (good))

When the minimum pattern width was more than 20 占 퐉 and not more than 24 占 퐉: the resolution "Δ (a)"

When the minimum pattern width exceeds 24 占 퐉: resolution "× (poor)"

&Lt; Adhesion &gt;

For evaluation of the adhesion, a laminate substrate after lapse of 15 minutes after the &lt; lamination &gt;

The laminate substrate was subjected to a direct drawing and exposure of a pattern of independent lines of various sizes, and then developed by the method described in &lt; Development &gt;.

The obtained pattern was observed by an optical microscope, and the adhesiveness was evaluated according to the following criteria.

When the minimum pattern width formed in the normal direction was 18 占 퐉 or less: adhesion "good (good)"

When the minimum pattern width formed normally was more than 18 μm and not more than 22 μm: adhesion "Δ (a)"

The minimum pattern width formed to the normal exceeds 22 占 퐉: adhesion "× (poor)"

Here, the case where the line pattern is not normally formed refers to a case where the line pattern is collapsed, a case where the line pattern is meandering, or a case where the line pattern does not exist on the substrate.

<Tentability>

The evaluation of the tentability was carried out by observing the laminate substrate after the &lt; lamination &gt; obtained by using the substrate having the through holes.

The number of holes in which the photosensitive resin composition layer (tent film) formed on the through hole was torn was measured, and the ratio (tent film breakage rate) to the entire hole was calculated.

Tent film breakage rate was less than 0.1%: Tentability "◎ (very good)"

Tent film breakage rate was 0.1% or more and less than 2%: Tentability "○ (good)"

Tent film breakage rate was more than 2%: Tentability "× (bad)"

<Etching speed (wiring bottom width)>

The evaluation of the etching rate (wiring bottom width) was carried out by using a laminate substrate after laminating for 15 minutes.

For the laminated substrate, a pattern having 10 lines / line / space = 50 占 퐉 / 30 占 퐉 was directly drawn and exposed. After 15 minutes passed from the exposure, the support was peeled off from the photosensitive resin composition layer, and a 1% by mass Na ₂ CO ₃ aqueous solution at 30 ° C was applied for a minimum developing time And sprayed twice with time to dissolve and remove the unexposed portions of the photosensitive resin composition layer. After development, it was rinsed with pure water for 1.5 times the developing time.

Subsequently, the substrate having the line / space pattern was washed with water and dried in a copper chloride etching apparatus (manufactured by Tokyo Chemical Industry Co., Ltd., NLE-2000) with the line / space direction of the substrate being orthogonal And etched at a line speed of 2.0 m / min for 55 seconds under the conditions of a hydrochloric acid concentration of 3.2 mol / l, a cupric chloride concentration of 2.0 mol / l, an etching spray pressure of 0.2 MPa, and an etchant temperature of 50 캜.

After the etching, the bottom width of the wiring pattern in the MD direction of the copper line obtained by removing the cured film on the substrate at a temperature of 50 占 폚 as an aqueous solution of NaOH at a concentration of 3.0% by mass as a peeling solution was measured by an optical microscope.

Here, the measurement position of the lines of the wiring pattern was set at a position of about 5 mm from the fifth line from the end of the line having 10 lines and the end in the longitudinal direction, and the average value of the measurement for three times was used as the measurement value. The line width of the completed wiring is different and the wiring width at the end side tends to be narrowed because the influence of the developer and the wash water on the resist due to diffusion differs at the end of the pattern and the central portion.

&Lt; Vertical width difference of wiring width &gt;

The evaluation of the vertical and horizontal difference in the wiring width was carried out by using a laminate substrate after laminating for 15 minutes.

10 lines of lines / spaces = 50 占 퐉 / 30 占 퐉 were directly exposed to the laminated substrate in an exposure pattern in which the patterns were arranged in tandem in the MD and TD directions. After 15 minutes passed from the exposure, the support was peeled off from the photosensitive resin composition layer, and a 1% by mass Na ₂ CO ₃ aqueous solution at 30 ° C was applied for a minimum developing time And sprayed twice with time to dissolve and remove the unexposed portions of the photosensitive resin composition layer. After development, it was rinsed with pure water for 1.5 times the developing time.

Subsequently, the substrate after washing with water having the line / space pattern was dried, and the direction of the line / space of the substrate was set to be orthogonal (MD) to the conveying direction. Using a copper chloride vacuum etching apparatus And the number of spray nozzles per one piping is 14 (in the direction of the slit nozzle, the spraying direction is parallel to the TD direction, about the nozzle interval is about 2.6 cm) 14 cm and a distance of about 5 cm from the substrate), no oscillation, a concentration of hydrochloric acid of 2.85 mol / l, a cupric chloride concentration of 2.0 mol / l, an etching spray pressure of 0.3 MPa, a vacuum pressure of 0.15 MPa, Under conditions of a line speed of 2.2 m / min for 71 seconds.

After the etching, for the line patterns of two sets of copper in the MD direction and the TD direction obtained by removing the cured film on the substrate at a temperature of 50 캜 using a 3.0 wt% aqueous solution of NaOH as a peeling solution, It was measured by an optical microscope.

Here, the measurement position of the lines of the wiring pattern was set at a position of about 5 mm from the fifth line from the end of the line having 10 lines and the end in the longitudinal direction, and the average value of the measurement values of 3 times was used as the measurement value. The effect of the developer on the resist due to the diffusion of the developer and the washing water differs in the step of the pattern and the central part, and thus the line width of the completed wiring is different, and the width of the wiring on the end side tends to be narrow.

Then,

Vertical and lateral difference of wiring width (탆) = TD - MD

, The vertical and horizontal differences of the wiring widths were calculated and evaluated according to the following criteria.

When the vertical / horizontal difference of the wiring width was 1 占 퐉 or less: Wiring bottom width vertical / horizontal difference "⊚ (very good)"

When the vertical / horizontal difference of the wiring width is more than 1 占 퐉 and less than 2 占 퐉: wiring bottom width vertical / horizontal difference "good (good)"

When the vertical / horizontal difference of the wiring width was more than 2 占 퐉 and not more than 4 占 퐉: wiring bottom width vertical / horizontal difference "? (A)"

When the vertical / horizontal difference of the wiring width exceeds 4 탆: Wiring bottom width vertical / horizontal difference "× (bad)"

Examples 1 to 23 and Comparative Examples 1 to 8

The compositions of the photosensitive resin compositions used in Examples and Comparative Examples are shown in Table 1,

Details of the respective component names shown in Table 1 are shown in Table 2. The blending amounts of the respective components in Table 1 are all parts by mass in terms of solid content.

The results of evaluations conducted using the respective compositions are summarized in Table 1.

&Lt; Embodiment and Comparative Example According to Second Embodiment &gt;

Hereinafter, the photosensitive resin composition of the second embodiment will be described in detail by way of examples.

(1) Measurement of raw material properties

<Acid equivalent>

The acid equivalent means the mass of an alkali-soluble polymer having one equivalent of carboxyl groups therein. The acid equivalent was measured by a potentiometric titration method using a 0.1 mol / l sodium hydroxide aqueous solution using an automatic titration apparatus (e.g., Hirunuma Automatic Titration Apparatus (COM-555) manufactured by Hiranuma Industrial Co., Ltd.) .

&Lt; Measurement of weight average molecular weight &gt;

The weight average molecular weight of the polymer was measured by gel permeation chromatography (GPC) (Gulliver, PU-1580 type, column: Shodex (registered trademark) (KF-807, manufactured by Showa Denko K.K.) (Shodex STANDARD SM-105 manufactured by Showa Denko K.K.) using a calibration curve of four series and mobile layer solvents: tetrahydrofuran and polystyrene standard samples (KF-806M, KF-806M, KF-802.5) Polystyrene conversion value.

(2) Method for producing sample for evaluation

&Lt; Preparation of Photosensitive Element &gt;

Each component shown in Table 3 was mixed and further methyl ethyl ketone (MEK) was added to prepare a photosensitive resin composition having a solid content concentration of 55% by mass.

The resulting photosensitive resin composition was uniformly coated on a polyethylene terephthalate film (GR-16, manufactured by Teijin DuPont Film Co., Ltd.) having a support chain thickness of 16 占 퐉 using a bar coater, and the temperature was adjusted to 95 占 폚 Followed by heating and drying in a drier for 4 minutes to form a photosensitive resin layer having a thickness of 33 占 퐉 on the support.

Subsequently, a polyethylene film (GF-18, manufactured by Tamapoly Co., Ltd.) having a thickness of 19 占 퐉, which is a protective layer, was applied on the surface opposite to the support of the photosensitive resin layer to obtain a photosensitive element.

<Substrate Used for Evaluation>

As a substrate for evaluation, the surface of a copper clad laminate having a thickness of 1.6 mm, in which 35 탆 rolled copper foil was laminated, was fronted by wet buff roll polishing. Polishing was carried out twice using Scotch Bright (registered trademark) HD # 600 manufactured by Sri Lanka Co., Ltd.

<Laminate>

(AL-70, manufactured by Asahi Chemical Industry Co., Ltd.) while peeling the polyethylene film of the photosensitive element obtained in each Example or Comparative Example on a substrate preliminarily heated to 60 占 폚 at a roll temperature of 105 占 폚, An air pressure of 0.35 MPa, and a lamination speed of 1.5 m / min.

<Exposure>

A stepper 41-step tablet or a predetermined mask pattern for DI exposure was used by a direct imaging exposure apparatus (DE-1DH, Hitachi Biomechanics Co., Ltd., light source: GaN blue-violet diode, main wavelength 405 ± 5 nm) Under conditions of an illuminance of 80 mW / cm &lt; 2 &gt; and an exposure amount corresponding to 14 stages in a stepper 41-step tablet.

<Development>

After removing the support from the photosensitive resin layer after exposure, a 1% by mass Na ₂ CO ₃ aqueous solution at 30 ° C was sprayed for 2 times the minimum developing time by using an alkaline developing machine (fuji pore making and developing machine for dry film) , And the unexposed portion of the photosensitive resin layer was dissolved and removed. After development, the substrate was rinsed with deionized water for 1.5 times the development time, dehydrated by air knife, and then subjected to hot air drying to obtain a substrate having a cured film for evaluation.

The minimum developing time refers to a minimum time required until the unexposed portion of the photosensitive resin layer is completely dissolved and removed.

<Etching>

A copper chloride etching solution (cupric chloride concentration 250 (manufactured by Tokyo Chemical Industry Co., Ltd., salt copper etching equipment)) was applied to an evaluation substrate on which a resist pattern was formed by the development, g / l, HCl concentration: 3 mol / l) was sprayed for 60 seconds to dissolve and remove the copper foil which was not covered by the resist pattern on the copper clad laminate.

<Peeling>

The cured resist was peeled off by spraying an aqueous 3% by mass aqueous solution of sodium hydroxide heated to 50 캜 to the substrate for evaluation after etching.

(3) Evaluation method

(i) Development cohesion test

A photosensitive layer (resist layer) having a thickness of 50 탆 and an area of 0.6 m 2 in the photopolymerizable resin laminate was dissolved in 200 ml of a 1 mass% Na ₂ CO ₃ aqueous solution and sprayed at a spray pressure of 0.1 MPa Spraying was done for 3 hours. Thereafter, the developer was allowed to stand for one day, and the occurrence of aggregates was observed. When a large amount of agglomerates are generated, a powdery or oily matter is observed on the bottom and sides of the spray device. In addition, the aggregate may float in the developer. In the case of a composition having a good developer cohesion property, it is possible to easily wash away such a small amount of aggregate even if it does not occur at all or by washing it with a very small amount. The occurrence state of the agglomerates was classified by visual observation as follows.

◎ (remarkably good): No aggregation occurs at all.

○ (Good): There is no agglomerate on the bottom or side of the sprayer, and a slight amount of agglomerate floating in the developer can be visually observed. However, if it is washed with water, it is simply washed away.

△ (A): Flocculating material is floating in the bottom part or side part of the spray device and developer. It is not possible to rinse out all of the agglomerates even if washed.

× (poor): Agglomerates can be seen throughout the spray device, and the developer is floated with agglomerates. It is impossible to wash out all of the agglomerates even a few times, and most of them remain.

(ii) Sensitivity test

The photosensitive elements obtained in each of the Examples and Comparative Examples were laminated and exposed in accordance with the above method, and the amount of exposure and the number of steps remaining after development corresponded to the application of 14 stages in a stepper 41 step- The exposure amount (mj / cm 2, 14/41 ST exposure amount) was examined and evaluated according to the following criteria.

Sensitivity &quot; Good &quot; (good): When the 14/41 ST exposure amount was 25 mj /

Sensitivity "×" (defective): 14 / 41ST Exceeding the exposure amount of 25 mj / ㎠

(iii) resolution test

Using the photosensitive element obtained in each of the examples and the comparative example, the laminate was subjected to the above-mentioned method. After 15 minutes passed, the sample was used to set the line / space to 1/1, Direct imaging exposure was performed. Subsequently, development was carried out according to the above-mentioned method.

Further, the minimum mask line width in which the cured resist line was normally formed was examined, and evaluation was made based on the following criteria.

Resolution (good): When the minimum line width was less than 25 占 퐉

Resolution &quot; DELTA &quot; (A): When the minimum line width was 25 mu m or more and less than 30 mu m

Resolution &quot; x &quot; (defective): When the minimum line width was 30 탆 or more

(iv) Adhesion test

Using the photosensitive element obtained in each of the examples and the comparative examples, the laminate was subjected to the above-mentioned method, and then the sample subjected to the direct imaging exposure was subjected to the above-described method using the sample after 15 minutes passed. Then, development was carried out according to the above-mentioned method.

Further, when the line / space = X / 200, the minimum mask line width normally formed as X was examined and evaluated according to the following criteria.

Adhesion &quot; Good &quot; (good): When the minimum line width was less than 25 占 퐉

Adhesiveness &quot; DELTA &quot; (A): When the minimum line width was 25 mu m or more and less than 30 mu m

Adhesion &quot; x &quot; (defective): When the minimum line width was 30 mu m or more

Examples 1 to 6 and Comparative Examples 1 to 5

The compositions of the photosensitive resin compositions used in Examples and Comparative Examples are shown in Table 3, and details of each component name in Table 3 are shown in Table 4. [ The blending amounts of each component in Table 4 are all parts by mass in terms of solid content.

Table 4 also shows the evaluation results obtained by using the respective compositions.

&Lt; Embodiment and Comparative Example According to Third Embodiment &gt;

Hereinafter, the photosensitive resin composition of the third embodiment will be described in detail by way of examples.

The measurement of the physical properties of the polymer and the monomer, and the production method of the sample for evaluation in the examples and the comparative examples will be described, and then the evaluation method for the obtained sample and the evaluation result thereof will be shown.

(1) Measurement or calculation of physical properties

&Lt; Measurement of weight average molecular weight or number average molecular weight of polymer &

The weight average molecular weight or the number average molecular weight of the polymer was measured by gel permeation chromatography (GPC) (Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko K.K. (Shodex STANDARD SM-105, manufactured by Showa Denko K.K.) was used as a sample solution for four series and mobile layer solvents: tetrahydrofuran and polystyrene. As polystyrene conversion.

The degree of dispersion of the polymer was calculated as the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight).

<Acid equivalent>

In the present specification, an acid equivalent means a mass (gram) of a polymer having one equivalent of carboxyl groups in the molecule. The acid equivalent weight was measured by a potentiometric titration method using a Hirunuma automatic titrator (COM-555) manufactured by Hirano Industry Co., Ltd. and using an aqueous 0.1 mol / l sodium hydroxide solution.

(2) Method for producing sample for evaluation

The samples for evaluation in Examples 1 to 12 and Comparative Examples 1 to 5 were produced as follows.

&Lt; Preparation of Photosensitive Resin Laminate &gt;

The components shown in the following Table 5 or 6 (note that the number of each component represents the amount (parts by mass) as solid content) and the solvent were sufficiently stirred and mixed to obtain a photosensitive resin composition combination solution. The names of the components indicated by abbreviations in Tables 5 and 6 are shown in Table 7 below. A polyethylene terephthalate film having a thickness of 16 占 퐉 (R310-16B, manufactured by Mitsubishi Plastics, Inc.) was used as a support film, and the surface of the polyethylene terephthalate film was uniformly coated with a bar coater and dried in a dryer at 95 占 폚 And dried for 3 minutes to form a photosensitive resin composition layer. The dry thickness of the photosensitive resin composition layer was 30 mu m.

Then, a polyethylene film (GF-818, manufactured by Tamapoly Co., Ltd.) having a thickness of 19 탆 was bonded as a protective layer on the surface of the photosensitive resin composition layer on which the polyethylene terephthalate film was not laminated Thereby obtaining a photosensitive resin laminate.

<Front surface of substrate>

The 0.4 mm thick copper clad laminate laminated with 35 탆 rolled copper foil was subjected to jet scrub polishing at a spray pressure of 0.2 MPa using an abrasive (Sakuranam R (registered trademark # 220) manufactured by Nippon Carryt Co., Ltd.) To prepare an evaluation substrate.

<Laminate>

The photosensitive resin laminate was heated at a roll temperature of 105 占 폚 by a hot-roll laminator (AL-700, manufactured by Asahi Kasei Corporation) to a copper clad laminate preheated to 60 占 폚 while peeling the polyethylene film of the photosensitive resin laminate. To obtain a test piece. The air pressure was 0.35 MPa and the lamination speed was 1.5 m / min.

<Exposure>

And exposure was carried out at an exposure amount of 15 mJ / cm &lt; 2 &gt; by using a direct-writing-type exposure apparatus (DE-1DH manufactured by Via Mechanics Co., Ltd., main wavelength: 405 nm).

<Development>

After separating the from the photosensitive resin laminate of polyethylene terephthalate film, Ltd. using a Fuji pore manufacturing the developing device, the pool with the nozzle of the cone type, a developer spray pressure 0.15 MPa, 1 wt% Na ₂ CO ₃ in 30 ℃ The aqueous solution was sprayed for a predetermined time and developed to dissolve and remove the unexposed portions of the photosensitive resin layer. At this time, the minimum time required for completely dissolving the photosensitive resin layer of the unexposed portion was measured as the minimum developing time, and the development was performed for twice the minimum developing time to prepare a resist pattern. At that time, the water washing process was carried out with a flat type nozzle at a washing water spray pressure of 0.15 MPa for the same time as the developing process.

(3) Evaluation method of sample

<Tent castle>

A 0.6 mm thick double-sided copper clad laminate having a through hole with a width of 2.0 mm and a length of 15 mm was surface-treated with a jet scrub grinder. Both sides of the laminate were laminated by the method described in the above <Laminate>, and both surfaces of the laminate were exposed to the entire surface by a direct-writeable exposure apparatus (DE-1DH manufactured by VIA MECHANICS CO., LTD., Main wavelength: 405 nm). When developed by the method described in &lt; Development &gt;, the number of tent holes torn was counted, and the breakage rate of the entire tent holes was calculated, and classified by the following criteria.

◎ ◎ (best): The film breakage rate after development is 2% or less.

? (Very good): The film breakage rate after development is more than 2% and not more than 4%.

(Good): The film breakage rate after development is more than 4% and not more than 10%.

X (defective): The film breakage rate after development exceeds 10%.

&Lt; Contact angle (water residual short defect inhibiting property) &gt;

In the evaluation of the contact angle (water residual shade failure suppressing property), lamination was carried out by the method described in the &lt; lamination &gt;, and then the whole surface phenomenon was carried out by the method described in &lt; exposure & The development was carried out by the method described in &lt; RTI ID = 0.0 &gt;

After development, samples were provided for the measurement of contact angle within 30 minutes.

The contact angle was measured in accordance with the static method of JIS R3257 using an optical microscopic contact angle meter "LSE-B100" manufactured by NIKKEI Co., Ltd. under the conditions of a temperature of 23 ° C. and a humidity of 50 RH% , The measurement of the contact angle was started, the value after 120 seconds was adopted, and the results were ranked according to the following criteria. When the value of the contact angle is large, the cured resist shows high hydrophobicity and can suppress the water residual short defects.

⊚ (very good): the contact angle is 35 ° or more.

(Good): The contact angle is 30 DEG or more and less than 35 DEG.

DELTA (Allowable): The contact angle is not less than 25 DEG and less than 30 DEG.

× (poor): The contact angle is less than 25 °.

(4) Evaluation result

The evaluation results of Examples 1 to 12 are shown in Table 5, and the evaluation results of Comparative Examples 1 to 5 are shown in Table 6 below.

&Lt; Examples and Comparative Example According to Fourth Embodiment &gt;

Hereinafter, the photosensitive resin composition of the fourth embodiment will be described in detail by way of examples.

(1) Measurement of raw material properties

&Lt; Measurement of weight average molecular weight &gt;

The weight average molecular weight of the polymer was measured by gel permeation chromatography (GPC) (Gulliver, PU-1580 type, column: Shodex (registered trademark) (KF-807, manufactured by Showa Denko K.K.) (Shodex STANDARD SM-105 manufactured by Showa Denko K.K.) using a calibration curve of four series and mobile layer solvents: tetrahydrofuran and polystyrene standard samples (KF-806M, KF-806M, KF-802.5) Polystyrene conversion value.

<Acid equivalent>

In the present specification, an acid equivalent means a mass (gram) of a polymer having one equivalent of carboxyl groups in the molecule. The acid equivalent weight was measured by potentiometric titration using a 0.1 mol / l sodium hydroxide aqueous solution using a Hirunuma automatic titration apparatus (COM-555) manufactured by Hirano Industry Co., Ltd.

(2) Production method and analysis of sample for evaluation

&Lt; Preparation of Photosensitive Element &gt;

Each component shown in Table 8 was mixed and further methyl ethyl ketone (MEK) was added to prepare a photosensitive resin composition having a solid concentration of 56 mass%. The number of each component column in Table 8 is the amount (parts by mass) of each component provided for preparing the composition.

The resulting photosensitive resin composition was uniformly coated on a polyethylene terephthalate film (GR-16, manufactured by Teijin DuPont Film Co., Ltd., haze value 2.7%) having a support chain thickness of 16 占 퐉 using a bar coater, And dried by heating for 3 minutes and 20 seconds to form a photosensitive resin layer having a thickness of 33 占 퐉 on the support.

Subsequently, a polyethylene film (GF-18, manufactured by Tamapoly Co., Ltd.) having a thickness of 19 占 퐉, which is a protective layer, was applied on the surface opposite to the support of the photosensitive resin layer to obtain a photosensitive element.

<Substrate Used for Evaluation>

As a substrate for evaluation, the surface of a copper clad laminate having a thickness of 1.6 mm, in which 35 탆 rolled copper foil was laminated, was fronted by wet buff roll polishing. Polishing was carried out twice using Scotch Bright (registered trademark) HD # 600 manufactured by Sri Lanka Co., Ltd.

<Laminate>

(AL-70, manufactured by Asahi Kasei Corporation) at a roll temperature of 105 占 폚, an air pressure of 0.35 MPa, and a pressure of 0.35 MPa while peeling the polyethylene film of the photosensitive element obtained in each Example or Comparative Example, And a lamination speed of 1.5 m / min.

<Exposure>

Using a predetermined mask pattern for DI exposure, a predetermined pattern was formed by a direct imaging exposure apparatus (DE-1AH, Hitachi Biomechanics Co., Ltd., light source: GaN blue-violet diode, main wavelength 405 +/- 5 nm) Lt; / RTI &gt;

The exposure pattern and the exposure amount will be described later in the sections of each evaluation item.

<Development>

After the support was peeled from the exposed photosensitive resin layer, a 0.8 mass% Na ₂ CO ₃ aqueous solution at 29 ° C was sprayed for 2 times the minimum developing time by using an alkaline developing machine (Fuji Pore Manufacturing Co., a dry film developing machine) , And the unexposed portion of the photosensitive resin layer was dissolved and removed. After development, the substrate was rinsed with pure water for the same time as the developing time, and the substrate was naturally dried without being subjected to hot air drying treatment after the rinsing, thereby obtaining a substrate having a cured film for evaluation.

The minimum developing time refers to a minimum time required until the unexposed portion of the photosensitive resin layer is completely dissolved and removed and depends on the concentration or temperature of the developing solution, the direction or spray amount of the spray, the pressure, Change.

Here, the minimum developing time was ranked as follows:

○: Minimum development time exceeds 30 seconds.

×: Minimum development time is 30 seconds or less.

&Lt; Evaluation of sensitivity &

For evaluation of the sensitivity, a laminate substrate after lapse of 15 minutes after the &lt; laminating &gt;

Ten mask patterns of line / space = 40 占 퐉 / 40 占 퐉 line were directly drawn and exposed to the laminate substrate, and then developed by the method described in the above <Development>. The resist top width of the obtained resist pattern was measured by an optical microscope, and the exposure amount at which the resist top width became 39 占 퐉 was evaluated as the sensitivity.

Here, the measurement point of the resist line was set at a position of about 5 mm from the fifth line from the end of the line having 10 lines and the end in the longitudinal direction, and the average value of three measurements was used as the measurement value. It is important to specify the measurement position because the line width is different due to the diffusion of developer and wash water and the resist line at the end side tends to be thin at the end and central part of the pattern.

The amount of exposure in the evaluation items below was set to an exposure amount such that the resist top width became 39 占 퐉 with respect to the mask pattern of line / space = 40 占 퐉 / 40 占 퐉, as described in <Evaluation of Sensitivity>. Here, the sensitivity was ranked according to the exposure amount as follows:

?: The exposure amount at which the line width was 39 占 퐉 was 28 mJ / cm2 or less.

X: Exposure amount exceeding 28 mJ / cm &lt; 2 &gt;

&Lt; Evaluation of resolution &gt;

For evaluation of the resolution, a laminate substrate after lapse of 15 minutes after the &lt; laminating &gt;

The laminate substrate was directly exposed to a line / space = 1/1 pattern of various sizes and then developed by the method described in &lt; Development &gt;.

With respect to the obtained pattern, the minimum pattern width formed was observed by an optical microscope, and the resolution was evaluated according to the following criteria.

?: The minimum pattern width formed was 28 占 퐉 or less.

X: The minimum pattern width formed exceeds 28 占 퐉.

&Lt; Evaluation of adhesion &

For evaluation of the adhesion, a laminate substrate after lapse of 15 minutes after the &lt; lamination &gt;

The laminate substrate was subjected to a direct drawing and exposure of a pattern of independent lines of various sizes, and then developed by the method described in &lt; Development &gt;.

The obtained pattern was observed by an optical microscope, and the adhesiveness was evaluated according to the following criteria.

Here, the case where the line pattern is not normally formed refers to a case where the line pattern is collapsed, a case where the line pattern is meandering, or a case where the line pattern does not exist on the substrate.

?: The minimum pattern width formed was 28 占 퐉 or less.

X: The minimum pattern width formed exceeds 28 占 퐉.

&Lt; Evaluation of cohesiveness &gt;

A photosensitive layer (resist layer) having a thickness of 50 탆 and an area of 0.6 m 2 in the photopolymerizable resin laminate was dissolved in 200 ml of a 1 mass% Na ₂ CO ₃ aqueous solution and sprayed at a spray pressure of 0.1 MPa Spraying was done for 3 hours. Thereafter, the developer was allowed to stand for one day, and the occurrence of aggregates was observed. When a large amount of agglomerates are generated, a powdery or oily matter is observed on the bottom and sides of the spray device. In the case of a composition having a good developing solution cohesiveness, no such aggregate is generated. The cohesiveness was ranked according to the occurrence state of the aggregates as follows:

○: No aggregation occurs at all.

?: Aggregates are seen on the bottom part or side part of the spray device.

X: Aggregates are seen throughout the spray device.

&Lt; Evaluation of peelability &

A rectangular pattern of 4 cm x 6 cm was directly drawn and exposed to the laminate substrate using the substrate 15 minutes after the treatment described in the &lt; lamination &gt;, and then developed by the method described in the & .

The cured resist on the obtained substrate was immersed in 3% by mass of NaOH at 50 占 폚, and the time from when the resist completely peeled off from the substrate was measured to be the peeling time.

Here, the peelability was ranked as follows:

○: Time to completely peel off is 40 seconds or less.

X: Time to completely peel off exceeds 40 seconds.

Examples 1 to 7 and Comparative Examples 1 to 4

The compositions of the photosensitive resin compositions used in Examples and Comparative Examples are shown in Table 8, and details of each component name in Table 8 are shown in Table 9. The blending amounts of the respective components in Table 8 are all parts by mass in terms of solid content.

Table 8 shows the evaluation results of each composition.

Claims (17)

Each of the following components (A) to (C)
(A) Component: alkali-soluble polymer,
(B): a compound having an ethylenic double bond, and
(C): Photopolymerization initiator
Wherein the photosensitive resin composition comprises
A photosensitive resin layer composed of the above photosensitive resin composition was laminated to a thickness of 25 mu m on a copper clad laminate in which copper foils having a thickness of 18 mu m were laminated and subjected to light irradiation and development processing in a pattern of line / space = 50 mu m / 30 mu m And the bottom width of the copper line pattern obtained by removing the cured resist pattern after performing the copper etching treatment at 50 占 폚 for 55 seconds is 38 占 퐉 or more. The method according to claim 1,
Wherein the component (A) is a copolymer having a (meth) acrylic acid unit content of 10% by mass or more and 24% by mass or less. 3. The method according to claim 1 or 2,
Wherein the content of the styrene unit in the component (A) is 32% by mass or more and 60% by mass or less. 4. The method according to any one of claims 1 to 3,
Wherein the component (C) contains an acridine compound. 5. The method according to any one of claims 1 to 4,
Wherein the component (B) contains a pentaerythritol compound. 6. The method according to any one of claims 1 to 5,
Wherein the component (B) contains a trimethylolpropane compound. 7. The method according to any one of claims 1 to 6,
Wherein the component (B) contains a bisphenol A compound. Each of the following components (A) to (C)
(A) Component: alkali-soluble polymer,
(B): a compound having an ethylenic double bond, and
(C): Photopolymerization initiator
Wherein the photosensitive resin composition comprises
The component (A) comprises a copolymer having a content of (meth) acrylic acid units of 10 mass% or more and 24 mass% or less and a content of styrene units of 32 mass% or more,
Wherein the component (C) comprises an acridine compound. 9. The method of claim 8,
Wherein the content of the (meth) acrylic acid unit in the component (A) is 10 mass% or more and 24 mass% or less, and the content of the styrene unit is 32 mass% or more and 60 mass% or less. 10. The method according to claim 8 or 9,
Wherein the component (B) contains a pentaerythritol compound. 11. The method according to any one of claims 8 to 10,
Wherein the component (B) contains a trimethylolpropane compound. The method according to any one of claims 8 to 11,
Wherein the component (B) contains a bisphenol A compound. 13. A photosensitive element in which a photosensitive resin layer comprising the photosensitive resin composition according to any one of claims 1 to 12 is laminated on a support. A lamination process for laminating a photosensitive resin layer of the photosensitive element according to claim 13 on a conductor substrate,
An exposure step of exposing the laminated photosensitive resin composition layer, and
A developing step of removing the unexposed portion after the exposure with a developer,
And forming a resist pattern on the resist pattern. 15. The method of claim 14,
Wherein the lamination step is a step of laminating a photosensitive resin layer of a photosensitive element on a conductive substrate through a wetting agent. A lamination step of laminating the photosensitive resin composition layer of the photosensitive element according to claim 13 onto a conductor substrate,
An exposure step of exposing the laminated photosensitive resin composition layer,
A developing step of removing the unexposed portion after the exposure with a developer,
A conductor pattern forming step of etching or plating a conductor substrate on which a resist pattern is formed by the above phenomenon, and
A peeling step of peeling the resist pattern,
And a step of forming the wiring pattern. 17. The method of claim 16,
Wherein the lamination step is a step of laminating a photosensitive resin layer of a photosensitive element on a conductive substrate through a wetting agent.