JPWO2015080257A1 - Photosensitive resin element - Google Patents

Abstract

Provided is a photosensitive resin element that has a good appearance, has a long product life, and reduces defects caused by a resist chip in a laminating process when a printed circuit board is produced. The present disclosure is a photosensitive resin element including a support layer and a photosensitive resin layer on the support layer, wherein the photosensitive resin layer has (a) a carboxyl group content of 100 to 600 in terms of acid equivalent. A binder resin having a weight average molecular weight of 5,000 to 500,000, (b) a photopolymerizable unsaturated compound, (c) a photopolymerization initiator, and (d) a solvent, the photosensitive resin layer comprising: The solvent (d) is contained in an amount of 0.001% by mass or more and 1% by mass or less based on the mass of the photosensitive resin layer, and the photosensitive resin layer is used as the photopolymerizable unsaturated compound (b). Provided is a photosensitive element comprising one or more compounds selected from general formulas (I) to (III).

Description

  The present invention relates to a photosensitive resin element and the like.

  The manufacturing method of the photosensitive resin composition for producing a printed circuit is a resin for a binder, a photopolymerizable unsaturated compound, a photopolymerization initiator, a dye, etc., a ketone represented by methyl ethyl ketone, and a representative of ethyl acetate. In general, the method includes a step of uniformly stirring and dissolving in a solvent mainly composed of esters such as tetrahydrofuran and ethers typified by tetrahydrofuran. For example, Patent Document 1 describes a solution prepared by using a mixed solvent of methyl ethyl ketone / 1-methoxy-2-propanol = 2/1 (weight ratio). In Patent Document 1, such a solution is uniformly applied on a polyester film or the like as a support layer using a die coater or the like, and the solvent is dried in a drying step to have a layer of a photosensitive resin composition. It is described that a laminate can be obtained, and further, a polyethylene film or the like as a protective layer can be further laminated to obtain a laminate having a three-layer structure having a layer made of a photosensitive resin composition. These laminates are generally called dry film photoresists (hereinafter abbreviated as “DF”).

JP 11-143069 A

  However, in the conventional production method using methyl ethyl ketone as the main component of the solvent, the solubility of the binder resin and the photopolymerizable unsaturated compound and the solubility of additives such as dyes are insufficient, and the preparation liquid is filtered. When doing so, the filter was often clogged. In addition, the preparation liquid still has room for improvement from the viewpoint of reducing minute irregularities on the surface of the manufactured DF and reducing the frequency observed as unevenness by visual inspection of the appearance.

  When the DF is formed from the photosensitive resin composition when the solvent remaining in the photosensitive resin composition is large after drying, the inventors of the present invention exposed the photosensitive resin composition from the roll end face over time. The phenomenon of edge fuse that the layer oozes out occurs, thereby causing a problem that the product life is shortened.On the other hand, if too little solvent remains in the photosensitive resin composition after drying, the photosensitive layer It has been found that there is a problem that a chip of the photosensitive layer is generated when a cutter blade is inserted. The cutter blade is used in the laminating process, and when a chip of the photosensitive layer is generated, the chip is reattached to the substrate and causes a defect.

  Accordingly, an object of the present invention is to provide a photosensitive resin element that has a good appearance, has a long product life, and reduces defects due to a resist chip in a laminating process when a printed circuit board is produced.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have a good appearance and a good product according to the photosensitive resin layer having a specific composition and the residual amount of solvent being controlled within a specific range. It has been found that the life is long and defects due to the resist chip in the laminating process can be reduced, and the present invention has been completed. That is, the present invention is as follows.

（式中、Ｒ₁及びＲ₂はそれぞれ独立に水素原子又はメチル基を表し、ＡはＣ₂Ｈ₄基を表し、ＢはＣＨ₂ＣＨ（ＣＨ₃）基を表し、ｍ₁＋ｍ₂は２〜３０の整数であり、ｍ₃＋ｍ₄は０〜３０の整数であり、ｍ₁及びｍ₂はそれぞれ独立に１〜２９の整数であり、ｍ₃及びｍ₄はそれぞれ独立に０〜２９の整数であり、−（Ａ−Ｏ）−及び−（Ｂ−Ｏ）−の繰り返し単位の配列は、ランダムであってもブロックであってもよく、ブロックの場合、−（Ａ−Ｏ）−及び−（Ｂ−Ｏ）−の何れがビスフェニル基側であってもよい。）

（式中、Ｒ₃は水素原子又は炭素数が１〜８である一価の有機基を表し、Ｒ₄、Ｒ₅及びＲ₆はそれぞれ独立に水素原子又はメチル基を表し、Ｄは炭素数２〜６のアルキレン基を表し、ｎ₁、ｎ₂及びｎ₃はｎ₁＋ｎ₂＋ｎ₃＝３〜６０を満たす０以上の整数であり、ｎ₄は０又は１であり、但し式中複数存在するＤはそれぞれ同一でも異なっていてもよく、−（Ｏ−Ｄ）−の繰り返し構造はランダムであってもブロックであってもよい。）

（式中、Ｒ₇〜Ｒ₁₁はそれぞれ独立に水素原子又はメチル基を表し、Ａ₁はＣ₂Ｈ₄基を表し、Ｂ₁はＣＨ₂ＣＨ（ＣＨ₃）基を表し、ｎ₅＋ｎ₆は０〜３０の整数であり、ｎ₇＋ｎ₈は０〜３０の整数であり、ｎ₅及びｎ₆はそれぞれ独立に０〜３０の整数であり、ｎ₇及びｎ₈はそれぞれ独立に０〜３０の整数であり、−（Ｏ−Ａ₁）−及び−（Ｏ−Ｂ₁）−の繰り返し単位の配列は、ランダムであってもブロックであってもよく、ブロックの場合、−（Ｏ−Ａ₁）−及び−（Ｏ−Ｂ₁）−の何れがウレタン基側であってもよい。）
［２］ 該（ｄ）溶媒としてプロピレングリコールモノメチルエーテルを含む、上記態様１に記載の感光性樹脂エレメント。
［３］ 該（ｄ）溶媒としてトルエンを含む、上記態様１に記載の感光性樹脂エレメント。
［４］ 該（ｄ）溶媒としてアセトンを含む、上記態様１に記載の感光性樹脂エレメント。
［５］ 該（ｂ）光重合可能な不飽和化合物として該一般式（Ｉ）で表される化合物及び該一般式（ＩＩ）で表される化合物を含む、上記態様１〜４のいずれかに記載の感光性樹脂エレメント。
［６］ 該（ｂ）光重合可能な不飽和化合物として該一般式（Ｉ）で表される化合物及び該一般式（ＩＩＩ）で表される化合物を含む、上記態様１〜４のいずれかに記載の感光性樹脂エレメント。
［７］ 該（ｂ）光重合可能な不飽和化合物として該一般式（ＩＩ）で表される化合物及び該一般式（ＩＩＩ）で表される化合物を含む、上記態様１〜４のいずれかに記載の感光性樹脂エレメント。
［８］ 該支持層がポリエステルフィルムである、上記態様１〜７のいずれかに記載の感光性樹脂エレメント。
［９］ 該感光性樹脂エレメントから剥離及び乾燥された該ポリエステルフィルムのＴＤ方向の熱収縮率が３．２％以下である、上記態様８に記載の感光性樹脂エレメント。
［１０］ 該ポリエステルフィルムの膜厚が１２μｍ〜１６μｍである、上記態様８又は９に記載の感光性樹脂エレメント。[1] A photosensitive resin element comprising a support layer and a photosensitive resin layer on the support layer,
The photosensitive resin layer is
(A) Resin for binders having a carboxyl group content of 100 to 600 in terms of acid equivalent and a weight average molecular weight of 5,000 to 500,000, (b) a photopolymerizable unsaturated compound, (c) a photopolymerization initiator, And (d) includes a solvent,
The photosensitive resin layer contains the solvent (d) in an amount of 0.001% by mass to 1% by mass based on the mass of the photosensitive resin layer,
The photosensitive resin layer comprises (b) one or more compounds selected from the following general formulas (I) to (III) as a photopolymerizable unsaturated compound.

(Wherein R ₁ and R ₂ each independently represents a hydrogen atom or a methyl group, A represents a C ₂ H ₄ group, B represents a CH ₂ CH (CH ₃ ) group, and m ₁ + m ₂ represents 2) M ₃ + m ₄ is an integer from 0 to 30, m ₁ and m ₂ are each independently an integer from 1 to 29, and m ₃ and m ₄ are each independently from 0 to 29. It is an integer, and the arrangement of repeating units of-(AO)-and-(B-O)-may be random or block, and in the case of a block,-(AO)-and Any of-(B-O)-may be on the bisphenyl group side.)

(In the formula, R ₃ represents a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms, R ₄ , R ₅ and R ₆ each independently represents a hydrogen atom or a methyl group, and D represents the number of carbon atoms. Represents an alkylene group of 2 to 6, n ₁ , n ₂ and n ₃ are integers of 0 or more satisfying n ₁ + n ₂ + n ₃ = 3 to 60, n ₄ is 0 or 1, provided that D may be the same or different, and the repeating structure of-(OD)-may be random or block.)

(Wherein R _{7 to} R ₁₁ each independently represents a hydrogen atom or a methyl group, A ₁ represents a C ₂ H ₄ group, B ₁ represents a CH ₂ CH (CH ₃ ) group, and n ₅ + n ₆ Is an integer of 0 to 30, n ₇ + n ₈ is an integer of 0 to 30, n ₅ and n ₆ are each independently an integer of 0 to 30, and n ₇ and n ₈ are each independently 0 to 30. The arrangement of repeating units of-(O-A ₁ )-and-(O-B ₁ )-may be random or block, and in the case of a block,-(O- Any of A ₁ )-and-(OB ₁ )-may be on the urethane group side.)
[2] The photosensitive resin element according to the above aspect 1, which includes propylene glycol monomethyl ether as the solvent (d).
[3] The photosensitive resin element according to the above aspect 1, wherein the solvent (d) includes toluene.
[4] The photosensitive resin element according to the above aspect 1, which includes acetone as the solvent (d).
[5] In any one of the above embodiments 1 to 4, the compound (b) includes the compound represented by the general formula (I) and the compound represented by the general formula (II) as the photopolymerizable unsaturated compound. The photosensitive resin element as described.
[6] In any one of the above embodiments 1 to 4, the compound (b) includes the compound represented by the general formula (I) and the compound represented by the general formula (III) as the photopolymerizable unsaturated compound. The photosensitive resin element as described.
[7] In any one of the above embodiments 1 to 4, the compound (b) includes the compound represented by the general formula (II) and the compound represented by the general formula (III) as the photopolymerizable unsaturated compound. The photosensitive resin element as described.
[8] The photosensitive resin element according to any one of the above aspects 1 to 7, wherein the support layer is a polyester film.
[9] The photosensitive resin element according to the above aspect 8, wherein the polyester film peeled and dried from the photosensitive resin element has a thermal shrinkage rate in the TD direction of 3.2% or less.
[10] The photosensitive resin element according to the aspect 8 or 9, wherein the thickness of the polyester film is 12 μm to 16 μm.

  The present invention also provides a DF by coating a photosensitive resin composition containing the above components (a) to (d) on a support layer and drying the composition to form a photosensitive resin layer. And a method for producing a DF having a three-layer structure by further forming a protective layer on the surface of the photosensitive resin layer formed on the support layer.

  ADVANTAGE OF THE INVENTION According to this invention, the external appearance is favorable, the product life is long, and the photosensitive resin element which can reduce the malfunction by the resist chip in the lamination process at the time of printed wiring board preparation is provided. Moreover, according to the specific aspect of this invention, the manufacturing method of the said photosensitive resin element is provided.

  Hereinafter, exemplary modes for carrying out the present invention (hereinafter abbreviated as “embodiments”) will be described in detail. In addition, this invention is not limited to embodiment, It can implement by changing variously within the range of the summary.

（式中、Ｒ₁及びＲ₂はそれぞれ独立に水素原子又はメチル基を表し、ＡはＣ₂Ｈ₄基を表し、ＢはＣＨ₂ＣＨ（ＣＨ₃）基を表し、ｍ₁＋ｍ₂は２〜３０の整数であり、ｍ₃＋ｍ₄は０〜３０の整数であり、ｍ₁及びｍ₂はそれぞれ独立に１〜２９の整数であり、ｍ₃及びｍ₄はそれぞれ独立に０〜２９の整数であり、−（Ａ−Ｏ）−及び−（Ｂ−Ｏ）−の繰り返し単位の配列は、ランダムであってもブロックであってもよく、ブロックの場合、−（Ａ−Ｏ）−及び−（Ｂ−Ｏ）−の何れがビスフェニル基側であってもよい。）

（式中、Ｒ₃は水素原子又は炭素数が１〜８である一価の有機基を表し、Ｒ₄、Ｒ₅及びＲ₆はそれぞれ独立に水素原子又はメチル基を表し、Ｄは炭素数２〜６のアルキレン基を表し、ｎ₁、ｎ₂及びｎ₃はｎ₁＋ｎ₂＋ｎ₃＝３〜６０を満たす０以上の整数であり、ｎ₄は０又は１であり、但し式中複数存在するＤはそれぞれ同一でも異なっていてもよく、−（Ｏ−Ｄ）−の繰り返し構造はランダムであってもブロックであってもよい。）

（式中、Ｒ₇〜Ｒ₁₁はそれぞれ独立に水素原子又はメチル基を表し、Ａ₁はＣ₂Ｈ₄基を表し、Ｂ₁はＣＨ₂ＣＨ（ＣＨ₃）基を表し、ｎ₅＋ｎ₆は０〜３０の整数であり、ｎ₇＋ｎ₈は０〜３０の整数であり、ｎ₅及びｎ₆はそれぞれ独立に０〜３０の整数であり、ｎ₇及びｎ₈はそれぞれ独立に０〜３０の整数であり、−（Ｏ−Ａ₁）−及び−（Ｏ−Ｂ₁）−の繰り返し単位の配列は、ランダムであってもブロックであってもよく、ブロックの場合、−（Ｏ−Ａ₁）−及び−（Ｏ−Ｂ₁）−の何れがウレタン基側であってもよい。Embodiments of the present invention
A photosensitive resin element comprising a support layer and a photosensitive resin layer on the support layer,
The photosensitive resin layer is
(A) Resin for binders having a carboxyl group content of 100 to 600 in terms of acid equivalent and a weight average molecular weight of 5000 to 500000, (b) a photopolymerizable unsaturated compound, and (c) a photopolymerization initiator. And (d) a solvent,
The photosensitive resin layer contains the solvent (d) in an amount of 0.001% by mass to 1% by mass based on the mass of the photosensitive resin layer,
The photosensitive resin layer is a photosensitive element containing (b) one or more compounds selected from the following general formulas (I) to (III) as the photopolymerizable unsaturated compound.

(Wherein R ₁ and R ₂ each independently represents a hydrogen atom or a methyl group, A represents a C ₂ H ₄ group, B represents a CH ₂ CH (CH ₃ ) group, and m ₁ + m ₂ represents 2) M ₃ + m ₄ is an integer from 0 to 30, m ₁ and m ₂ are each independently an integer from 1 to 29, and m ₃ and m ₄ are each independently from 0 to 29. It is an integer, and the arrangement of repeating units of-(AO)-and-(B-O)-may be random or block, and in the case of a block,-(AO)-and Any of-(B-O)-may be on the bisphenyl group side.)

(In the formula, R ₃ represents a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms, R ₄ , R ₅ and R ₆ each independently represents a hydrogen atom or a methyl group, and D represents the number of carbon atoms. Represents an alkylene group of 2 to 6, n ₁ , n ₂ and n ₃ are integers of 0 or more satisfying n ₁ + n ₂ + n ₃ = 3 to 60, n ₄ is 0 or 1, provided that D may be the same or different, and the repeating structure of-(OD)-may be random or block.)

(Wherein R _{7 to} R ₁₁ each independently represents a hydrogen atom or a methyl group, A ₁ represents a C ₂ H ₄ group, B ₁ represents a CH ₂ CH (CH ₃ ) group, and n ₅ + n ₆ Is an integer of 0 to 30, n ₇ + n ₈ is an integer of 0 to 30, n ₅ and n ₆ are each independently an integer of 0 to 30, and n ₇ and n ₈ are each independently 0 to 30. The arrangement of repeating units of-(O-A ₁ )-and-(O-B ₁ )-may be random or block, and in the case of a block,-(O- Any of A ₁ ) — and — (O—B ₁ ) — may be on the urethane group side.

For example, the photosensitive resin element includes the following steps:
(A) a binder resin having a carboxyl group content of 100 to 600 in terms of acid equivalent and a weight average molecular weight of 5000 to 500,000, (b) a photopolymerizable unsaturated compound, and (c) photopolymerization. Formulating an initiator, (d) a solvent, and optionally (e) other additives to obtain a formulation; and applying the formulation on a support layer, then drying the formulation; Forming a photosensitive resin layer on the support layer.

  In the present embodiment, the amount of the solvent remaining in the photosensitive resin layer (for example, obtained after drying of the preparation liquid and film formation in the above-described method) is 0.001% by mass or more based on the photosensitive resin layer. It is necessary to be 1% by mass or less. When the amount exceeds 1% by mass, when the photosensitive resin composition is DF, in the DF wound up in a roll shape, a phenomenon called edge fuse in which the photosensitive layer exudes from the end surface of the roll with time occurs, and the product life is shortened. A problem occurs. On the other hand, when the content is less than 0.001% by mass, there is a problem that a chip of the photosensitive resin layer is generated when a cutter blade is inserted into the photosensitive resin layer. The cutter blade is used in the laminating process, and when a chip of the photosensitive resin layer is generated, the chip is reattached to the substrate and causes a defect. The amount of the solvent remaining in the photosensitive resin layer is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and particularly preferably 0.05% by mass or more. The amount of the solvent remaining in the photosensitive resin layer is preferably 0.7% by mass or less, more preferably 0.5% by mass or less, and particularly preferably 0.2% by mass or less. The amount and type of the solvent remaining in the photosensitive resin layer are values measured by a method described in the section of [Examples] described later or a method understood by those skilled in the art to be equivalent thereto.

  In the present embodiment, as a means for controlling the amount of the solvent remaining in the photosensitive resin layer, adjustment of drying conditions (temperature and time) of the photosensitive resin composition when forming the photosensitive resin layer can be mentioned. It is done. The amount of the solvent remaining in the photosensitive resin layer is a value measured by gas chromatography.

  In general, a photosensitive element refers to a substance that changes its properties by receiving light. The photosensitive element may be in various forms such as a film, a plate, a sheet, a roll, and a molded article, for example, a photosensitive resin element that includes or is made of a photosensitive resin. Good. More specifically, a layer comprising a photosensitive resin composition by applying a composition containing a photosensitive resin (referred to as a “photosensitive resin composition” in the present disclosure) on a support layer such as a film, or A photosensitive resin laminate obtained by laminating a layer obtained by drying a photosensitive resin composition (in the present disclosure, these are collectively referred to as “photosensitive resin layer”) on a support layer is a photosensitive resin element. As preferred. The present invention provides a photosensitive resin element which is a laminate having such a photosensitive resin layer and a support layer. The photosensitive resin composition may be in any state (for example, a solution, solid, emulsion, suspension, etc.), but may be a liquid such as a solution, emulsion, suspension, etc. It is preferable that Furthermore, it is obtained by further laminating and winding a protective layer (for example, a protective film, a slip sheet film, etc.) on the exposed portion of the photosensitive resin layer of the laminate of the support layer and the photosensitive resin layer, A photosensitive resin roll as the photosensitive resin laminate is more preferable as the photosensitive resin element, and a dry film roll in which the entire photosensitive resin roll or the photosensitive resin layer portion is dried is particularly preferable.

The thickness of the photosensitive resin element is preferably 5 μm to 50 μm. The thickness of the photosensitive resin element is preferably adjusted to 5 μm or more from the viewpoint of the accuracy with which the preparation liquid is applied to the support layer, and on the other hand, adjusted to 50 μm or less from the viewpoint of drying properties in the drying process. Is preferred. The thickness of the photosensitive resin element is more preferably 30 μm to 50 μm.
Note that the resolution is improved as the photosensitive resin layer is thinner, and the film strength is improved as the photosensitive resin layer is thicker. Therefore, the film thickness of the photosensitive resin layer can be appropriately selected according to the application. For example, the film thickness of the photosensitive resin layer can be 15 μm to 50 μm, such as 15 μm to 30 μm, or 30 μm to 40 μm, or 40 μm to 50 μm.

<Photosensitive resin composition>
The photosensitive resin composition comprises (a) a binder resin, (b) a photopolymerizable unsaturated compound, (c) a photopolymerization initiator, and (d) a solvent, and optionally (e) other additives. It is preferable to contain. The photosensitive resin composition is preferably a preparation liquid.

When the photosensitive resin composition is a preparation liquid, in the method for producing a photosensitive resin element, the ratio of the total solid content in the preparation liquid is preferably 30% by mass to 80% by mass. The ratio of the total solid content in the preparation liquid is, for example, the solid content concentration of the preparation liquid obtained by dissolving the components (a) to (c) and (e) in the solvent (d). In order to obtain the effect of improving the coating speed, the ratio of the total solid content is preferably 30% by mass or more from the viewpoint of controlling the amount of solvent to be dried / evaporated. From the viewpoint, it is preferably 80% by mass or less. The ratio of the total solid content in the preparation liquid is more preferably 40% by mass or more, further preferably 50% by mass or more, while the upper limit is more preferably 70% by mass or less, and further preferably 60% by mass or less. . Setting the ratio of the total solid content in such a range is to improve the smoothness of the film surface after drying, to reduce uncoated parts such as pinholes in the drying process, and good coating This is preferable from the viewpoint of obtaining a surface.
Hereinafter, components (a) to (e) will be described in detail.

(A) Resin for binder (a) Resin for binder is resin used as a binder whose carboxyl group content is 100-600 in an acid equivalent, and whose weight average molecular weight is 5000-500,000. is there.

  (A) The binder resin has a carboxyl group in order to give the photosensitive resin element developability or releasability to an alkaline aqueous solution. The content of the carboxyl group is an acid equivalent, and is preferably 100 or more from the viewpoint of development resistance, resolution and adhesion, while 600 or less is preferable from the viewpoint of developability and peelability. In the present disclosure, the acid equivalent refers to the mass (gram) of the resin having 1 equivalent of a carboxyl group therein. In the present disclosure, the acid equivalent is a value measured by a potentiometric titration method (for example, using Hiranuma Automatic Titration Device (COM-555) manufactured by Hiranuma Sangyo Co., Ltd. and using 0.1 mol / L sodium hydroxide). is there.

  The weight average molecular weight of the (a) binder resin is 5,000 or more, preferably 20,000 or more, from the viewpoint of maintaining the DF thickness uniform and obtaining resistance to the developer. On the other hand, the weight average molecular weight is 500,000 or less, preferably 300,000 or less, from the viewpoint of maintaining developability.

  Moreover, a preferable molecular weight distribution (ratio of weight average molecular weight / number average molecular weight) is 1.5 or more, more preferably 2 or more. On the other hand, the molecular weight distribution is preferably 7 or less, more preferably 5 or less. In the present disclosure, the molecular weight and the molecular weight distribution are values measured in terms of standard polystyrene using gel permeation chromatography.

  Typically, (a) the binder resin is a thermoplastic copolymer containing at least a carboxyl group-containing monomer as a copolymerization component. The thermoplastic copolymer is preferably obtained by copolymerizing at least one first monomer described below and at least one second monomer described below.

  The first monomer is a monomer containing a carboxyl group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Among these, (meth) acrylic acid is particularly preferable. In this specification, (meth) acryl indicates acrylic or methacrylic.

  The second monomer is a monomer that is non-acidic and has 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) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , Tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, vinyl acetate, etc. And (meth) acrylonitrile, styrenic monomers (for example, styrene and polymerizable styrene derivatives), and the like. Among them, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, and benzyl (meth) acrylate are preferable, and styrene is particularly preferable from the viewpoint of resolution.

  (A) A binder resin is prepared by mixing a first monomer and a second monomer and diluting with a solvent such as acetone, methyl ethyl ketone, or isopropanol, into a radical polymerization initiator such as benzoyl peroxide or azoiso It is preferable to synthesize by adding an appropriate amount of butyronitrile and stirring with heating. In some cases, the synthesis is performed while a part of the mixture is dropped into the reaction solution. After completion of the reaction, a solvent may be further added to the (a) binder resin to adjust to a desired concentration. As synthesis means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

  (A) In the binder resin, the preferred copolymerization ratio of the first monomer and the second monomer is such that the first monomer is 10% by mass to 60% by mass and the second monomer The mass is 40% by mass to 90% by mass. More preferably, the first monomer is 15% by mass to 35% by mass, and the second monomer is 65% by mass to 85% by mass.

  (A) More specific examples of the binder resin include, for example, a polymer containing methyl methacrylate, methacrylic acid, and styrene as a copolymerization component, methyl methacrylate, methacrylic acid, and n-butyl acrylate as a copolymerization component. And a polymer containing benzyl methacrylate, methyl methacrylate and 2-ethylhexyl acrylate as a copolymerization component.

  In the present embodiment, the content of (a) binder resin in the photosensitive resin element (however, based on the total solid content of the photosensitive resin element. Unless otherwise specified, each The same is true for the contained components.) Is in the range of 20% by mass to 90% by mass, the preferred lower limit is 25% by mass, the preferred upper limit is 75% by mass, the more preferred lower limit is 40% by mass, and the more preferred upper limit is 65% by mass. %. This content is preferably 20% by mass or more from the viewpoint of maintaining alkali developability, and on the other hand, 90% by mass from the viewpoint that the resist pattern formed by exposure sufficiently exhibits the performance as a resist. The following is preferable.

（式中、Ｒ₁及びＲ₂はそれぞれ独立に水素原子又はメチル基を表し、ＡはＣ₂Ｈ₄基を表し、ＢはＣＨ₂ＣＨ（ＣＨ₃）基を表し、ｍ₁＋ｍ₂は２〜３０の整数であり、ｍ₃＋ｍ₄は０〜３０の整数であり、ｍ₁及びｍ₂はそれぞれ独立に１〜２９の整数であり、ｍ₃及びｍ₄はそれぞれ独立に０〜２９の整数であり、−（Ａ−Ｏ）−及び−（Ｂ−Ｏ）−の繰り返し単位の配列は、ランダムであってもブロックであってもよく、ブロックの場合、−（Ａ−Ｏ）−及び−（Ｂ−Ｏ）−の何れがビスフェニル基側であってもよい。）

（式中、Ｒ₃は水素原子又は炭素数が１〜８である一価の有機基を表し、Ｒ₄、Ｒ₅及びＲ₆はそれぞれ独立に水素原子又はメチル基を表し、Ｄは炭素数２〜６のアルキレン基を表し、ｎ₁、ｎ₂及びｎ₃はｎ₁＋ｎ₂＋ｎ₃＝３〜６０を満たす０以上の整数であり、ｎ₄は０又は１であり、但し式中複数存在するＤはそれぞれ同一でも異なっていてもよく、−（Ｏ−Ｄ）−の繰り返し構造はランダムであってもブロックであってもよい。）

（式中、Ｒ₇〜Ｒ₁₁はそれぞれ独立に水素原子又はメチル基を表し、Ａ₁はＣ₂Ｈ₄基を表し、Ｂ₁はＣＨ₂ＣＨ（ＣＨ₃）基を表し、ｎ₅＋ｎ₆は０〜３０の整数であり、ｎ₇＋ｎ₈は０〜３０の整数であり、ｎ₅及びｎ₆はそれぞれ独立に０〜３０の整数であり、ｎ₇及びｎ₈はそれぞれ独立に０〜３０の整数であり、−（Ｏ−Ａ₁）−及び−（Ｏ−Ｂ₁）−の繰り返し単位の配列は、ランダムであってもブロックであってもよく、ブロックの場合、−（Ｏ−Ａ₁）−及び−（Ｏ−Ｂ₁）−の何れがウレタン基側であってもよい。）
を含む場合、解像性向上やカットチップ性向上に有効である。またこの観点で特に、（ｂ）光重合可能な不飽和化合物が一般式（Ｉ）で表される化合物及び一般式（ＩＩ）で表される化合物の両者、一般式（Ｉ）で表される化合物及び一般式（ＩＩＩ）で表される化合物の両者、又は一般式（ＩＩ）で表される化合物及び一般式（ＩＩＩ）で表される化合物の両者を含むことが好ましい。(B) Photopolymerizable unsaturated compound (b) The photopolymerizable unsaturated compound is, for example, a monomer having an addition polymerization property by having an ethylenically unsaturated bond. The ethylenically unsaturated bond is preferably a terminal ethylenically unsaturated group.
(B) One or more compounds wherein the photopolymerizable unsaturated compound is selected from the following general formulas (I) to (III):

(Wherein R ₁ and R ₂ each independently represents a hydrogen atom or a methyl group, A represents a C ₂ H ₄ group, B represents a CH ₂ CH (CH ₃ ) group, and m ₁ + m ₂ represents 2) M ₃ + m ₄ is an integer from 0 to 30, m ₁ and m ₂ are each independently an integer from 1 to 29, and m ₃ and m ₄ are each independently from 0 to 29. It is an integer, and the arrangement of repeating units of-(AO)-and-(B-O)-may be random or block, and in the case of a block,-(AO)-and Any of-(B-O)-may be on the bisphenyl group side.)

(In the formula, R ₃ represents a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms, R ₄ , R ₅ and R ₆ each independently represents a hydrogen atom or a methyl group, and D represents the number of carbon atoms. Represents an alkylene group of 2 to 6, n ₁ , n ₂ and n ₃ are integers of 0 or more satisfying n ₁ + n ₂ + n ₃ = 3 to 60, n ₄ is 0 or 1, provided that D may be the same or different, and the repeating structure of-(OD)-may be random or block.)

(Wherein R _{7 to} R ₁₁ each independently represents a hydrogen atom or a methyl group, A ₁ represents a C ₂ H ₄ group, B ₁ represents a CH ₂ CH (CH ₃ ) group, and n ₅ + n ₆ Is an integer of 0 to 30, n ₇ + n ₈ is an integer of 0 to 30, n ₅ and n ₆ are each independently an integer of 0 to 30, and n ₇ and n ₈ are each independently 0 to 30. The arrangement of repeating units of-(O-A ₁ )-and-(O-B ₁ )-may be random or block, and in the case of a block,-(O- Any of A ₁ )-and-(OB ₁ )-may be on the urethane group side.)
When it contains, it is effective for improving the resolution and cutting chip properties. In this respect, in particular, (b) the photopolymerizable unsaturated compound is represented by the general formula (I), both the compound represented by the general formula (I) and the compound represented by the general formula (II). It is preferable that both the compound and the compound represented by the general formula (III), or both the compound represented by the general formula (II) and the compound represented by the general formula (III) are included.

In particular, it is more effective to improve the cut chip property that (b) the photopolymerizable unsaturated compound contains a large amount of ethylene glycol chains or propylene glycol chains. From this viewpoint, in the general formula (I), m ₁ + m ₂ and m ₃ + m ₄ are each preferably 8 to 30, more preferably 10 to 30, and m ₁ + m ₂ + m ₃ + m ₄ is , Preferably 8-60, more preferably 10-60. In general formula (II), from the viewpoint of cut-chip properties and resolution, the carbon number of D is preferably 2 or 3, more preferably 2, and n ₁ + n ₂ + n ₃ is Preferably it is 3-50, More preferably, it is 3-35.

  Examples of the compound represented by the general formula (I) include polyethylene glycol dimethacrylate obtained by adding an average of 1 unit of ethylene oxide to both ends of bisphenol A or polyethylene having an average of 2 units of ethylene oxide added to both ends of bisphenol A, respectively. Of diglycol of glycol, polyethylene glycol dimethacrylate with an average of 5 units of ethylene oxide added to both ends of bisphenol A, polyethylene glycol dimethacrylate with an average of 7 units of ethylene oxide added to both ends of bisphenol A, and bisphenol A Polyalkylene glycol dimethacrylate, bisphenol A, with an average of 6 units of ethylene oxide and 2 units of propylene oxide added to each end Ends there dimethacrylate polyalkylene glycol and that each adding propylene oxide ethylene oxide and average 2 units of the average 15 units.

  Examples of the compound represented by the general formula (II) include tri (meth) acrylate obtained by adding an average of 3 units of ethylene oxide to trimethylolpropane and trimethylolpropane added by an average of 3 units of propylene oxide. Tri (meth) acrylate obtained by adding an average of 6 units of ethylene oxide to (meth) acrylate and trimethylolpropane, and tri (meth) acrylate and trimethylolpropane obtained by adding an average of 9 units of ethylene oxide to trimethylolpropane Tri (meth) acrylate added with a total of 12 units of ethylene oxide on average, and tri (meth) acrylate added with a total of 21 units of ethylene oxide on average to trimethylolpropane, and a total of 30 units on average to trimethylolpropane. Tri (meth) acrylate obtained by adding ethylene oxide are preferably exemplified.

Examples of the compound represented by the general formula (III) include urethane (meth) acrylate obtained by adding propylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate or a compound containing both to both ends of isophorone diisocyanate. .

  (B) Other specific examples of the photopolymerizable unsaturated compound include, for example, 4-nonylphenylheptaethylene glycol dipropylene glycol, from the viewpoint of high resolution, cured film peeling performance, and cured film flexibility. (Meth) acrylate, 4-nonylphenyl octaethylene glycol (meth) acrylate, 4-nonylphenyltetraethylene glycol (meth) acrylate, 4-octylphenylpentapropylene glycol (meth) acrylate, and the like are preferable.

  Specific examples of the other (b) photopolymerizable unsaturated compound include, for example, reaction of 2-hydroxy-3-phenoxypropyl acrylate, a half ester compound of phthalic anhydride and 2-hydroxypropyl acrylate, and propylene oxide. 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 2-di (p-hydroxyphenyl) propane di (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, 2,2-bis (4-methacryloxypentaethoxyphenyl) propane, glycerol triacryl Over DOO, tetraacrylate glycol obtained by adding an average of 4 moles of ethylene oxide to pentaerythritol, and polyfunctional (meth) acrylate of isocyanuric acid ester compounds. These may be used alone or in combination of two or more.

  The content of (b) the photopolymerizable unsaturated compound in the photosensitive resin element is preferably in the range of 5% by mass to 75% by mass. This content is preferably 5% by mass or more, more preferably 15% by mass or more, and further preferably 30% by mass or more from the viewpoint of suppressing poor curing and delay in development time. On the other hand, it is preferably 75% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less from the viewpoint of suppressing cold flow and delay of peeling of the cured resist.

(C) Photopolymerization initiator (c) The photopolymerization initiator is a compound that polymerizes a monomer by light. As the (c) photopolymerization initiator, for example, those usually used as photopolymerization initiators for photosensitive resins can be used as appropriate. In particular, hexaarylbisimidazole (hereinafter also referred to as triarylimidazolyl dimer). Is preferably used.

  Examples of the triarylimidazolyl dimer include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer (hereinafter referred to as “2,2′-bis (2-chlorophenyl) -4,4 ′, 5”). , 5′-tetraphenyl-1,1′-bisimidazole ”), 2,2 ′, 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ′, 5 '-Diphenylimidazolyl dimer, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylimidazolyl dimer,

  2,4,5-tris- (o-chlorophenyl) -diphenylimidazolyl dimer, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -imidazolyl dimer, 2, 2′-bis- (2-fluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,3-difluoromethyl) Phenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (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′-bis- (2, 6-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) -imidazolyl dimer, 2,2′-bis- (2,4,5-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (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, 2,2′- Bis- (2,3,4,6-tetrafluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, and 2,2′-bis- (2 , 3,4,5,6-pentafluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer and the like.

  In particular, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer is a photopolymerization initiator having a high effect on resolution or the strength of a cured resist film, and is preferably used. The triarylimidazolyl dimers listed above may be used alone or in combination of two or more. The triarylimidazolyl dimers listed above can be used in combination with the following acridine compounds, pyrazoline compounds and the like.

  (C) As the photopolymerization initiator, an acridine compound or a pyrazoline compound is preferably used. Examples of the acridine compound include acridine, 9-phenylacridine, 9- (4-tolyl) acridine, 9- (4-methoxyphenyl) acridine, 9- (4-hydroxyphenyl) acridine, 9-ethylacridine, 9- Chloroethyl acridine, 9-methoxyacridine, 9-ethoxyacridine,

  9- (4-methylphenyl) acridine, 9- (4-ethylphenyl) acridine, 9- (4-n-propylphenyl) acridine, 9- (4-n-butylphenyl) acridine, 9- (4-tert -Butylphenyl) acridine, 9- (4-ethoxyphenyl) acridine, 9- (4-acetylphenyl) acridine, 9- (4-dimethylaminophenyl) acridine, 9- (4-chlorophenyl) acridine,

  9- (4-bromophenyl) acridine, 9- (3-methylphenyl) acridine, 9- (3-tert-butylphenyl) acridine, 9- (3-acetylphenyl) acridine, 9- (3-dimethylaminophenyl) ) Acridine, 9- (3-diethylaminophenyl) acridine, 9- (3-chlorophenyl) acridine, 9- (3-bromophenyl) acridine, 9- (2-pyridyl) acridine, 9- (3-pyridyl) acridine, Examples include 9- (4-pyridyl) acridine. Of these, 9-phenylacridine is preferable.

  Examples of the pyrazoline compound include 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzoxazol-2-yl) Phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl- Phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline and the like.

  Examples of (c) photopolymerization initiator other than the above include, for example, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, Quinones such as 1-chloroanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone Benzophenone, Michler's ketone [4,4′-bis (dimethylamino) benzophenone], and aromatic ketones such as 4,4′-bis (diethylamino) benzophenone, benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, and Echi Benzoin ethers such as benzoin, benzyl dimethyl ketal, benzyl diethyl ketal, combinations of thioxanthones and alkylaminobenzoic acid, 1-phenyl-1,2-propanedione-2-O-benzoin oxime, 1-phenyl-1,2 -Oxime esters such as propanedione-2- (O-ethoxycarbonyl) oxime.

  Examples of the combination of the above thioxanthones and alkylaminobenzoic acid include, for example, a combination of ethylthioxanthone and ethyl dimethylaminobenzoate, a combination of 2-chlorothioxanthone and ethyl dimethylaminobenzoate, and isopropylthioxanthone and dimethylamino. A combination with ethyl benzoate and the like can be mentioned. Moreover, you may use N-arylamino acid as (c) photoinitiator. Examples of N-aryl amino acids include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like. Among these, N-phenylglycine is particularly preferable.

  The content of the photopolymerization initiator (c) in the photosensitive resin element is in the range of 0.01% by mass to 30% by mass, a more preferable lower limit is 0.05% by mass, and a further preferable lower limit is 0.00. 1 mass%, a more preferred upper limit is 15 mass%, and a more preferred upper limit is 10 mass%. (C) The content of the photopolymerization initiator is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity during photopolymerization by exposure, while the bottom surface of the photosensitive resin element ( That is, it is preferably 30% by mass or less from the viewpoint of sufficiently transmitting light to a portion far from the light source and obtaining good resolution and adhesion.

(D) Solvent As the solvent, a ketone-based, alcohol-based, ether-based or ester-based solvent is preferably used from the viewpoint of solubility. Examples of ketone solvents include methyl ethyl ketone and acetone. Examples of the alcohol solvent include methanol, ethanol, isopropyl alcohol, normal propyl alcohol, and normal butanol. In particular, ethanol is preferable from the viewpoints of solubility and coating film appearance. As the ether type, tetrahydrofuran, propylene glycol monomethyl ether, or the like is used. Examples of the ester solvent include ethyl acetate. Moreover, toluene etc. may be added and used together as a nonpolar solvent for the purpose of suppressing bubble generation in the drying process.

  The preparation liquid typically contains the (a) binder resin, the (b) photopolymerizable unsaturated compound, and the (c) photopolymerization initiator in any order or in a lump ( d) It is obtained by dissolving in a solvent and mixing.

  (D) It is preferable that a solvent is a ketone type from a dryness viewpoint, and it is preferable that (d) solvent contains acetone especially. In addition, using acetone and an alcohol solvent typified by ethanol improves the solubility of (b) a photopolymerizable unsaturated compound and / or (e) an optional additive (for example, a dye). From the viewpoint of making it. In particular, a combined system of acetone and ethanol as an alcohol solvent is preferable.

  Further, the combined use of acetone and alcohol tends to decrease the viscosity of the preparation liquid, so that the solid content concentration in the preparation liquid can be set higher, which is preferable from the viewpoint of improving productivity. The combined use of acetone and alcohol is also preferable from the viewpoint of removing the solvent while maintaining a good dry film surface in the drying step. That is, the combined use of acetone and alcohol is preferable from the viewpoint of increasing the coating speed of the preparation liquid and improving the productivity of the photosensitive resin element. Here, “while maintaining the dry film surface satisfactorily” means that the film surface has high smoothness and little visual unevenness.

  (D) When the solvent contains acetone, the ratio of the mass of acetone to the total mass of the solvent is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, and particularly preferably 60% by mass. % Or more. On the other hand, the upper limit is preferably 98% by mass or less, more preferably 90% by mass or less, still more preferably 80% by mass or less, and particularly preferably 70% by mass or less. Setting the ratio of acetone within these ranges is to improve the smoothness of the film surface after drying, to reduce uncoated parts such as pinholes in the drying process, and to provide a good coated surface. From the viewpoint of obtaining.

The alcohol solvent contains ethanol as a main component (preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and may be 100% by mass). It is preferable to do.
The viscosity of the preparation liquid is preferably 500 Pa · sec to 4000 mPa · sec as a viscosity at 25 ° C.

(E) Other additives In addition to components (a) to (d), (e) other additives can be contained in the preparation liquid. Specifically, (e) other additives include, for example, coloring substances such as dyes and pigments. A base dye can be used as such a coloring substance. Examples of the base dye include basic green 1 [CAS number (hereinafter the same): 633-03-4], malachite green oxalate [2437-29-8], brilliant green [633-03-4], and 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], Rhodamine B [81-88-9], Rhodamine 6G [989-38-8], Basic Yellow 2 [2465-27-2 ] Etc. are mentioned. Of these, basic green 1, malachite green oxalate, and basic blue 7 are preferable, and basic green 1 and basic blue 7 are particularly preferable from the viewpoint of improving hue stability and exposure contrast.

  The content of the coloring substance in the photosensitive resin element is preferably 0.001% by mass to 1% by mass. When the content of the coloring material is 0.001% by mass or more, it is preferable because of the effect of improving the handleability. On the other hand, when it is 1% by mass or less, the storage stability is maintained. Therefore, it is preferable.

  Further, a color former such as a color developing dye may be contained in the preparation liquid so that a visible image can be provided by exposure. Examples of such coloring dyes include leuco dyes or combinations of fluorane dyes and halogen compounds.

  Examples of the leuco dye include tris (4-dimethylamino-2-methylphenyl) methane [leuco crystal violet], tris (4-dimethylamino-2-methylphenyl) methane [leucomalachite green], and fluorane dye. Etc. Among these, when leuco crystal violet is used, the contrast is good and preferable.

  Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2 , 3-Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, chlorinated triazine compounds and the like. .

  The content of the color former in the photosensitive resin element is preferably independently from 0.1% by mass to 10% by mass.

  Furthermore, in order to improve the thermal stability and storage stability of the photosensitive resin composition, a radical polymerization inhibitor or at least one compound selected from the group consisting of benzotriazoles and carboxybenzotriazoles is prepared. It is preferable to make it contain.

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

  Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, Bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole and the like can be mentioned.

  Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, (N, N-dibutylamino) carboxybenzotriazole, N- ( N, N-di-2-ethylhexyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-ethylhexyl) amino And ethylene carboxybenzotriazole.

  The total content of radical polymerization inhibitors, benzotriazoles, and / or carboxybenzotriazoles in the photosensitive resin element is preferably 0.001% by mass to 3% by mass, and a more preferable lower limit is 0.05% by mass. The upper limit is more preferably 1% by mass. The total content is preferably 0.001% by mass or more from the viewpoint of imparting storage stability to the photosensitive resin composition, and preferably 3% by mass or less from the viewpoint of maintaining sensitivity.

  The preparation liquid may contain other plasticizers as necessary. Examples of such plasticizers include polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, and polyoxyethylene monoethyl. Glycols and esters such as ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether, sorbitan derivatives such as polyoxyethylene sorbitan laurate and polyoxyethylene sorbitan oleate, and phthalates such as diethyl phthalate , O-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, citrate Ethylene, triethyl acetylcitrate, tri-n-propyl acetylcitrate, tri-n-butyl acetylcitrate, propylene glycol with propylene oxide added to both sides of bisphenol A, ethylene oxide added to both sides of bisphenol A Ethylene glycol and the like.

  The content of the plasticizer in the photosensitive resin element is preferably 0.1% by mass to 50% by mass, a more preferable lower limit is 1% by mass, and a more preferable upper limit is 30% by mass. This content is preferably 0.1% by mass or more from the viewpoint of suppressing development time delay and imparting flexibility to the cured film. On the other hand, the edge is insufficiently cured and the photosensitive layer exudes from the end face of the roll. It is preferable that it is 50 mass% or less from a viewpoint of suppressing a fuse.

  You may contain other antioxidant in a liquid preparation as needed. Examples of the antioxidant include triphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (monononylphenyl) phosphite, and bis (monononylphenyl) -dinonylphenyl phosphite. Fight etc. are mentioned.

  The content of the antioxidant in the photosensitive resin element is preferably in the range of 0.01% by mass to 0.8% by mass, the more preferable lower limit is 0.01% by mass, and the more preferable upper limit is 0.00. 3% by mass. When the content is 0.01% by mass or more, the effect of excellent hue stability of the photosensitive resin composition is favorably expressed, and the sensitivity at the time of exposure of the photosensitive resin composition is preferable. In the case where the content is 0.8% by mass or less, color developability is suppressed, so that hue stability is improved and adhesion is also improved.

  The support layer supports the photosensitive resin layer formed thereon. Moreover, the manufacturing method of the photosensitive resin element may include the process of forming a protective layer on the opposite side to the support layer side of the photosensitive resin layer if desired.

  The support layer is preferably a transparent support layer that transmits light emitted from the exposure light source. As such a support layer, for example, 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, Examples thereof include a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. The support layer is preferably a polyester film from the viewpoint of solvent resistance, heat resistance, transparency, and the like. As these films, stretched films can be used as necessary. The haze of the support layer is preferably 5 or less. A thinner support layer is advantageous in terms of image forming property and economic efficiency, but preferably 10 μm to 30 μm, more preferably 12 μm to 16 μm, in order to maintain strength. A particularly preferable support layer is a polyester film having a thickness of 12 to 16 μm.

  From the viewpoint of generation of wrinkles when the laminate is formed, the thermal shrinkage rate in the TD direction of the polyester film peeled and dried from the photosensitive resin element is preferably 3.2% or less. The above-mentioned “dried” means that volatile components (for example, residual solvent) in the polyester film are substantially removed. Such a dry state can be obtained, for example, by heating at normal pressure and 200 ° C. for 30 minutes, and then standing at normal pressure and room temperature (for example, 20 ° C.) for 30 minutes. The thermal contraction rate in the TD direction is a value measured by a method described in the section of [Example] described later or a method understood by those skilled in the art to be equivalent to this.

  It is preferable that the protective layer has a property that the protective layer is sufficiently smaller than the support layer and can be easily peeled with respect to the adhesive strength with the photosensitive resin layer. For example, a polyethylene film and a polypropylene film can be preferably used as the protective layer. As the protective layer, for example, a film having excellent releasability disclosed in JP-A-59-202457 can be used. The thickness of the protective layer is preferably 10 μm to 100 μm, and more preferably 10 μm to 50 μm.

  In the method for producing a photosensitive resin element, the step of applying the preparation liquid on the support layer and drying to form the photosensitive resin element on the support layer may be performed by a coating means and, optionally, a drying means. it can. As the coating means, for example, a spin coater, a die coater, a spray coater, dipping, printing, a blade coater, a roll coating, or the like can be used. As a drying means, for example, air drying, hot air drying, light irradiation, a hot plate, an inert oven, a temperature rising oven capable of setting a temperature program, or the like can be used. Moreover, the preparation of a plurality of components contained in the preparation liquid and the application and drying of the preparation liquid can be performed in an atmosphere of air or an inert gas such as nitrogen or argon. At this time, the residual solvent amount in the photosensitive resin element can be controlled within a desired range by controlling the temperature and the drying time.

The photosensitive resin element manufactured by the above-described manufacturing method is used for the manufacture of printed wiring boards, the manufacture of lead frames for IC chip mounting, the manufacture of metal foils such as the manufacture of metal masks, ball grid arrays (BGA), Manufacturing of packages such as size packages (CSP), manufacturing of tape substrates such as chip-on-film (COF) or tape automated bonding (TAB), manufacturing of semiconductor bumps, indium tin oxide (ITO) electrodes or address electrodes It is preferably used for manufacturing a partition wall of a flat panel display such as an electromagnetic wave shield.
According to the photosensitive resin element of this embodiment, the appearance of the DF formed from the photosensitive resin element useful for forming a printed circuit can be improved satisfactorily.

  Hereinafter, the present embodiment will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the examples as long as the gist thereof is not exceeded.

[Examples 1 to 14 and Comparative Examples 1 to 4]
The components of the photosensitive resin composition shown in Table 1 were prepared, stirred and dissolved in a dissolution tank, and the prepared solution was filtered through a filter. Next, the prepared solution was sent to a die coater with a pump and uniformly applied onto a polyethylene terephthalate film as a support layer, and the solvent was sent to a drying zone to dry the solvent. Then, it laminated with the polyethylene film which is a protective layer, and obtained DF which has the thickness of the photosensitive resin layer described in Table 1. The film thickness of DF was 40 μm.
In the above process, edge fuse evaluation and cut chip evaluation were performed by the following methods. Moreover, the weight average molecular weight of resin was measured by the method shown below. The results will be described later.

  In addition, as a polyethylene terephthalate film as a support layer, GR-16 (16 μm thickness) manufactured by Teijin Limited is used, and as a polyethylene film as a protective layer, GF-18 (19 μm thickness) manufactured by Tamapoly Co., Ltd. is used. It was used.

(1) Edge fuse evaluation After using a die coater to apply the prepared solution onto a polyethylene terephthalate film as a support layer and drying the solvent to form a photosensitive resin layer, the polyethylene film as a protective layer is used as the photosensitive resin. Further laminated on the layer, a laminate having a three-layer structure of support layer / photosensitive resin layer / protective layer was obtained. This laminated body was wound up to form a roll-shaped laminated body (processed to a width of 500 mm and a winding length of 150 m using a slitter) and stored at 20 ° C. The number of days from the start of storage until the seepage of the photosensitive resin layer from the end face of the roll was visually confirmed was measured and evaluated according to the following rank.
A: The photosensitive resin layer oozes out after 50 days or more.
B: Exudation of the photosensitive resin layer is observed in 30 days or more and less than 50 days.
C: Exudation of the photosensitive resin layer is observed in 10 days or more and less than 30 days.
D: The photosensitive resin layer oozes out in less than 10 days.

(2) Cut chip evaluation After applying the prepared solution on a polyethylene terephthalate film as a support layer using a die coater and drying the solvent, a polyethylene film as a protective layer is further laminated, and the support layer / photosensitive resin layer / protection A sample of 10 cm × 10 cm was cut out from a roll-shaped laminate obtained with a three-layer structure. The protective layer was peeled off from the cut sample, and the laminate was pierced 5 times with an NT cutter (using a new cutter blade) from the photosensitive resin layer surface side. The portion where the cutter was pierced and the surface of the cutter blade were visually observed, and the occurrence of the photosensitive resin layer chip was evaluated in the following rank.
A: No chip of the photosensitive resin layer was generated at the pierced portion, and no chip of the photosensitive resin layer was attached to the cutter blade.
B: Although the chip | tip of the photosensitive resin layer did not adhere to a cutter blade, the very small amount of photosensitive resin layer chip | tips generate | occur | produced in the pierced part.
C: A small amount of a chip of the photosensitive resin layer was generated at the pierced portion, and a small amount of the chip of the photosensitive resin layer adhered to the cutter blade.
D: The chip | tip of the photosensitive resin layer generate | occur | produced remarkably in the pierced part, and the chip | tip of the photosensitive resin layer adhered also to the cutter blade.

(3) Weight average molecular weight and acid equivalent The weight average molecular weight (Mw) of the resin was measured by gel permeation chromatography (standard polystyrene conversion). The column used for the measurement was a trade name Shodex 805M / 806M series manufactured by Showa Denko KK, the standard monodisperse polystyrene was Shodex STANDARD SM-105 manufactured by Showa Denko KK, and the developing solvent was N-methyl-2- It was pyrrolidone, and the detector used was a trade name Shodex RI-930 manufactured by Showa Denko.
The acid equivalent was measured by potentiometric titration (using Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd., using 0.1 mol / L sodium hydroxide).

(4) Thermal shrinkage in the TD direction of the polyester film After applying the prepared solution on a polyethylene terephthalate film (as a polyester film) as a support layer using a die coater and drying the solvent, a polyethylene film as a protective layer is further laminated. Then, the protective layer and the photosensitive resin layer were peeled off from the roll-shaped laminate obtained with a three-layer structure of support layer / photosensitive resin layer / protective layer to obtain a polyethylene terephthalate film as a support layer. Cut out a test piece having a width of 20 mm and a length of 200 mm from the polyethylene terephthalate film, attaching two marks at a distance of 100 mm at the center of the test piece, and hanging the test piece vertically in a hot air circulating thermostat, Heated at 200 ° C. for 30 minutes at normal pressure. After heating, it was left at room temperature for 30 minutes at normal pressure, and then the distance between the gauge points was measured to calculate the heat shrinkage rate.

(5) Mass ratio of residual solvent in photosensitive resin layer By gas chromatography measurement of the photosensitive resin layer obtained by peeling off the protective layer and the support layer from the roll-shaped laminate formed in the same manner as (4) above, A mass ratio of the residual solvent was obtained.

(Comparative Example 4)
The preparation liquid of the photosensitive resin composition of Comparative Example 1 was uniformly applied onto a 20 μm thick polyethylene terephthalate film (haze: 1.8), and dried for 10 minutes with a hot air retention type dryer at 100 ° C. for photosensitive film. Got. The film thickness after drying of the photosensitive resin layer was 25 μm. The solid content mass ratio was 43%, and the residual acetone mass ratio was 0%. The various evaluation results for this DF are as follows.
Edge fuse evaluation: B, cut chip evaluation: D.

<Symbol explanation>
P-1: A mixed solution of acetone and ethanol of a terpolymer of 67% by mass of methyl methacrylate, 23% by mass of methacrylic acid and 10% by mass of butyl acrylate (solvent mass ratio: acetone / ethanol = 80/20), solid 34% mass ratio, weight average molecular weight 200,000, acid equivalent 374)
P-2: A mixture of acetone and ethanol of a terpolymer of 50% by mass of methyl methacrylate, 25% by mass of methacrylic acid, and 25% by mass of styrene (solvent mass ratio: acetone / ethanol = 75/25), mass of solid content Ratio 47%, weight average molecular weight 50,000, acid equivalent 344)
P-3: Methyl ethyl ketone and ethanol mixed solution of 50% by mass of methyl methacrylate, 25% by mass of methacrylic acid, and 25% by mass of styrene (solvent mass ratio: methyl ethyl ketone / ethanol = 75/25), solid mass Ratio 45%, weight average molecular weight 50,000, acid equivalent 344)
M-1: Polyethylene glycol dimethacrylate (BPE-200 manufactured by Shin-Nakamura Chemical Co., Ltd.) obtained by adding an average of 2 moles of ethylene oxide to both ends of bisphenol A.
M-2: Polyethylene glycol dimethacrylate (BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.) having an average of 5 moles of ethylene oxide added to both ends of bisphenol A.
M-3: Polyalkylene glycol dimethacrylate having an average of 2 mol of propylene oxide and an average of 6 mol of ethylene oxide added to both ends of bisphenol A, respectively. M-4: An average of 12 mol of propylene oxide was added. Polyalkylene glycol dimethacrylate M-5 with an average of 3 moles of ethylene oxide added to each end of polypropylene glycol M5: acrylate with an average of 3 moles of ethylene oxide added to trimethylolpropane (manufactured by Shin-Nakamura Chemical Co., Ltd.) A-TMPT-3EO)
M-6: 4-nonylphenylheptaethylene glycol dipropylene glycol acrylate M-7: urethane acrylate compound obtained by adding polypropylene glycol acrylate to both ends of isophorone diisocyanate (in formula III, R ₇ = R ₈ = H, R _9, R _10, R ₁₁ = CH _3, n ₅ = n ₆ = 0, n ₇ = n ₈ = 12)
I-1: 4,4′-bis (diethylamino) benzophenone I-2: 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer D-1: Diamond Green D-2: Leuco Crystal Violet A- 1: p-Toluenesulfonamide A-2: Benzotriazole A-3: Aluminum salt with 3 moles of nitrosophenylhydroxylamine A-4: Polypropylene glycol A with 2 moles of propylene oxide added to each end of bisphenol A -5: IRGANOX245 manufactured by Ciba Specialty Chemicals Co., Ltd.
A-6: New Coal 3-85 (manufactured by Nippon Emulsifier Co., Ltd.)
S-1: Ethanol S-2: Propylene glycol monomethyl ether S-3: Toluene

  The photosensitive resin element according to the present invention is a printed wiring board, a lead frame for mounting an IC chip, a metal foil precision processing such as a metal mask, a package such as BGA or CSP, a tape such as COF or TAB. It can be used for the production of substrates, the production of semiconductor bumps, the production of partition walls for flat panel displays such as ITO electrodes or address electrodes, and electromagnetic wave shields.

Claims (10)

A photosensitive resin element comprising a support layer and a photosensitive resin layer on the support layer,
The photosensitive resin layer is
(A) Resin for binders having a carboxyl group content of 100 to 600 in terms of acid equivalent and a weight average molecular weight of 5,000 to 500,000, (b) a photopolymerizable unsaturated compound, (c) a photopolymerization initiator, And (d) includes a solvent,
The photosensitive resin layer contains the solvent (d) in an amount of 0.001% by mass or more and 1% by mass or less based on the mass of the photosensitive resin layer.
The photosensitive resin layer is a photosensitive element containing at least one compound selected from the following general formulas (I) to (III) as the photopolymerizable unsaturated compound (b).

(Wherein R ₁ and R ₂ each independently represents a hydrogen atom or a methyl group, A represents a C ₂ H ₄ group, B represents a CH ₂ CH (CH ₃ ) group, and m ₁ + m ₂ represents 2) M ₃ + m ₄ is an integer from 0 to 30, m ₁ and m ₂ are each independently an integer from 1 to 29, and m ₃ and m ₄ are each independently from 0 to 29. It is an integer, and the arrangement of repeating units of-(AO)-and-(B-O)-may be random or block, and in the case of a block,-(AO)-and Any of-(B-O)-may be on the bisphenyl group side.)

(In the formula, R ₃ represents a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms, R ₄ , R ₅ and R ₆ each independently represents a hydrogen atom or a methyl group, and D represents the number of carbon atoms. Represents an alkylene group of 2 to 6, n ₁ , n ₂ and n ₃ are integers of 0 or more satisfying n ₁ + n ₂ + n ₃ = 3 to 60, n ₄ is 0 or 1, provided that D may be the same or different, and the repeating structure of-(OD)-may be random or block.)

(Wherein R _{7 to} R ₁₁ each independently represents a hydrogen atom or a methyl group, A ₁ represents a C ₂ H ₄ group, B ₁ represents a CH ₂ CH (CH ₃ ) group, and n ₅ + n ₆ Is an integer of 0 to 30, n ₇ + n ₈ is an integer of 0 to 30, n ₅ and n ₆ are each independently an integer of 0 to 30, and n ₇ and n ₈ are each independently 0 to 30. The arrangement of repeating units of-(O-A ₁ )-and-(O-B ₁ )-may be random or block, and in the case of a block,-(O- Any of A ₁ )-and-(OB ₁ )-may be on the urethane group side.)   The photosensitive resin element of Claim 1 which contains propylene glycol monomethyl ether as said (d) solvent.   The photosensitive resin element of Claim 1 which contains toluene as said (d) solvent.   The photosensitive resin element of Claim 1 containing acetone as said (d) solvent.   The compound represented by the general formula (I) and the compound represented by the general formula (II) are included as the (b) photopolymerizable unsaturated compound according to any one of claims 1 to 4. Photosensitive resin element.    The compound represented by the said general formula (I) and the compound represented by the said general formula (III) as said (b) photopolymerizable unsaturated compound are as described in any one of Claims 1-4. Photosensitive resin element.    The compound represented by the general formula (II) and the compound represented by the general formula (III) are included as the photopolymerizable unsaturated compound (b) according to any one of claims 1 to 4. Photosensitive resin element.   The photosensitive resin element as described in any one of Claims 1-7 whose said support layer is a polyester film.   The photosensitive resin element of Claim 8 whose heat shrinkage rate of the TD direction of the said polyester film peeled and dried from the said photosensitive resin element is 3.2% or less.   The photosensitive resin element of Claim 8 or 9 whose film thickness of the said polyester film is 12 micrometers-16 micrometers.