JP2006023369A - Photosensitive resin laminate for sand blasting - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin laminate having excellent sensitivity, resolution and adhesion property as a mask material for sand blasting with which a fine pattern can be worked with high yield in a base material to be worked, and to provide a method of sand blast surface working by using the laminate. <P>SOLUTION: Sand blast surface working is carried out by using a photosensitive resin composition comprising a specified polyurethane prepolymer, an alkali-soluble polymer, a photopolymerizable initiator and an ethylenically unsaturated addition polymerizable monomer, or the photosensitive resin laminate prepared by layering the above resin composition on a supporting body. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel photosensitive resin laminate for sandblasting, and more particularly, sensitivity, resolution, adhesion when applied to a substrate to be processed such as glass, low melting point glass, ceramic, etc., particularly a back plate of a plasma display panel. The present invention relates to a photosensitive resin laminate capable of processing a fine pattern on a substrate to be processed with a high yield as a mask material for sand blasting, and a sand blast surface processing method using the same.

In recent years, with the advancement of photolithography technology and sand blasting technology, it has become possible to process glass and ceramic into fine patterns. In particular, a glass substrate such as a low-melting glass is processed by sandblasting to form a partition wall in a lattice shape, a stripe shape, or a waffle shape, and a plasma display panel back plate (hereinafter also simply referred to as a panel). In manufacturing, with the narrowing of the pixel pitch, pattern formation with a pitch of 150 μm or less has recently been required.
In order to produce such a fine barrier rib pattern with a good yield, a photosensitive resin laminate for sandblasting in which a photosensitive resin layer is laminated on a film serving as a support, and further a protective layer is laminated as necessary is used. Yes.

A method of forming the partition wall of the back plate of the plasma display panel using the photosensitive resin laminate for sandblasting will be described. (I) A laminating process in which a photosensitive resin layer laminated on a support is adhered onto a glass substrate (hereinafter simply referred to as a substrate) using a hot roll laminator while peeling off the protective layer of the photosensitive resin laminate. (II) An exposure step in which exposure is performed using an actinic ray source in a state where a photomask having a desired fine pattern is closely attached to the support or in a state where it is separated from several tens to several hundreds of μm, (III) After the support is peeled off, an unexposed portion of the photosensitive resin layer is dissolved and removed using an alkali developer, and a fine resist pattern is formed on the substrate. (IV) A blasting material is formed on the formed resist pattern. Each of the following steps is performed: a sand blasting process in which the substrate is sprayed onto the substrate and the substrate is cut to a desired depth; Te, it is possible to form the barrier ribs of the back plate of a plasma display panel.
Recently, with the rapid expansion of demand for plasma display panels, in order to improve panel productivity, two or three or more panels are simultaneously manufactured on one large substrate, After that, so-called multi-paneling of panels is progressing. At present, there is a place where a large substrate having a width of about 1 m and a length of about 1.5 m is used and three 42-inch panels are chamfered.
When a resist pattern is formed on such a large substrate using the photosensitive resin laminate for sandblasting as described above, there is a big problem in the development process.

The first problem is that, in the central portion and the peripheral portion of a large substrate, the dissolution rate of the unexposed portion of the photosensitive resin layer in the developing solution is slow in the central portion and fast in the peripheral portion. In other words, if an attempt is made to create a panel with a development time such that the resist pattern in the central part is normally formed, development is performed for a longer time than the development time in which the resist pattern is normally formed in the peripheral part of the substrate (over development). Will be. The resist pattern swells as the developing time becomes longer, and the stress due to the swelling acts as a force for peeling the resist pattern from the substrate, so that it is very difficult to ensure adhesion.
As a second issue, demand for lead-free materials has become stronger among recent global environmental efforts. Low melting glass suitably used for the back plate of a plasma display panel usually contains lead, and development is underway to convert it to lead-free low melting glass. As one method for achieving a low melting point without containing lead, it is known to add alkali glass to the constituent components of the low melting point glass.
However, when forming a resist pattern on a low melting point glass substrate containing a large amount of such an alkali component using a conventional photosensitive resin laminate, the resist pattern does not sufficiently adhere to the substrate in the development process. (See Patent Document 1). In particular, when the development time in the development process and the subsequent water washing time increase (excess water washing), the tendency becomes more remarkable.

As described above, when the adhesion of the resist pattern is lowered, the process margin becomes extremely narrow in the mass production of the panel, which is not preferable in terms of productivity and production yield. Therefore, it is required that the resist pattern is normally in close contact with the substrate even when the development time and the washing time are excessive.
So far, many photosensitive resin compositions and photosensitive resin laminates for sandblasting have been disclosed. For example, a photosensitive resin laminate (see Patent Document 2) formed by laminating two photosensitive resin layers, a photosensitive resin laminate (see Patent Document 3) containing a specific structural unit, and the like are disclosed. However, even when these photosensitive resin compositions and photosensitive resin laminates are used, the present situation is that the demands associated with the above-described increase in the size of plasma display panels and lead-free are not sufficiently met.

JP 2002-326839 A JP-A-10-138142 JP 2000-66391 A

  The present invention overcomes the above-described problems and has excellent resist pattern adhesion even when the development is excessive, and has excellent sand blast resistance that can process fine patterns with high yield as a mask material for sand blasting. It is an object of the present invention to provide a photosensitive resin composition, a photosensitive resin laminate using the same, and a surface processing method using the composition or the laminate.

The above object can be achieved by the following configuration of the present invention.
1) Obtained from (i) a polymer or monomer (a) having a hydroxyl group at the end, a polyisocyanate (b), a functional group having active hydrogen and a compound (c) having both ethylenically unsaturated bonds in the molecule. 10 to 70% by mass of a polyurethane prepolymer, (ii) 10 to 70% by mass of an alkali-soluble polymer, (iii) 0.01 to 20% by mass of a photopolymerization initiator, and (iv) ethylenically unsaturated addition polymerization In the photosensitive resin composition composed of 5 to 40% by mass of the monomer, the polymer or the monomer (a) having a hydroxyl group at the terminal comprises 50% by mass or more of the compound represented by the following chemical formula (1) or (2) A photosensitive resin composition for sandblasting, wherein the photosensitive resin composition is one or more kinds of compounds selected from the above.

（上式において、Ｒ₁ はテトラメチレン基、Ｒ₂ はプロピレン基、Ｒ₃ はエチレン基を表す。ｐは２以上１００以下の整数であり、ｑ、及びｒは１００以下の整数である。テトラメチレンオキシド、プロピレンオキシド、及びエチレンオキシドの繰り返し単位からなる構造は、各々ランダムで構成されてもよいし、ブロックで構成されてもよい。）

(In the above formula, R ₁ represents a tetramethylene group, R ₂ represents a propylene group, and R ₃ represents an ethylene group. P is an integer of 2 to 100, and q and r are integers of 100 or less. (The structure consisting of repeating units of methylene oxide, propylene oxide, and ethylene oxide may be composed of random or block).

（上式において、ｍ、ｎ、ｏは１以上１００以下の整数であり、Ｒ₄ 、及びＲ₅ はアルキレン基である。テトラメチレンオキシド、並びにＲ₄ 、及びＲ₅ に基づく繰り返し単位からなる構造はブロックで構成される。）
２）末端に水酸基を有するポリマーまたはモノマー（ａ）の５０質量％以上が、下記化学式（３）〜（９）のいずれかで示される化合物、又は複数の該化合物の混合物である（１）記載のサンドブラスト用感光性樹脂組成物。

(In the above formula, m, n and o are integers of 1 to 100, and R ₄ and R ₅ are alkylene groups. A structure comprising tetramethylene oxide and repeating units based on R ₄ and R _5. Is composed of blocks.)
2) 50% by mass or more of the polymer or monomer (a) having a hydroxyl group at the terminal is a compound represented by any one of the following chemical formulas (3) to (9) or a mixture of a plurality of the compounds (1) Photosensitive resin composition for sandblasting.

（上式において、ｐは２以上１００以下の整数である。）

(In the above formula, p is an integer of 2 to 100.)

（上式において、a 、及びｃは１以上１００以下の整数であり、ｂは２以上１００以下の整数である。テトラメチレンオキシド、及びプロピレンオキシドの繰り返し単位からなる構造は、ブロックで構成される。）

(In the above formula, a and c are integers of 1 or more and 100 or less, and b is an integer of 2 or more and 100 or less. The structure composed of repeating units of tetramethylene oxide and propylene oxide is composed of blocks. .)

（上式において、ｄ、及びｆは１以上１００以下の整数であり、ｅは２以上１００以下の整数である。テトラメチレンオキシド、及びエチレンオキシドの繰り返し単位に基づく構造は、ブロックで構成される。）

(In the above formula, d and f are integers of 1 or more and 100 or less, and e is an integer of 2 or more and 100 or less. The structure based on the repeating units of tetramethylene oxide and ethylene oxide is composed of blocks. )

（上式において、ｇ、ｈ、及びｉは１以上１００以下の整数である。テトラメチレンオキシド、及びプロピレンオキシドの繰り返し単位に基づく構造は、ブロックで構成される。）

(In the above formula, g, h and i are integers of 1 or more and 100 or less. The structure based on the repeating units of tetramethylene oxide and propylene oxide is composed of blocks.)

（上式において、ｊ、ｋ、及びｌは１以上１００以下の整数である。テトラメチレンオキシド、及びエチレンオキシドの繰り返し単位に基づく構造は、ブロックで構成される。）

(In the above formula, j, k, and l are integers of 1 or more and 100 or less. The structure based on tetramethylene oxide and ethylene oxide repeating units is composed of blocks.)

（上式において、ｓは２以上１００以下の整数であり、ｔ、及びｕは０以上１００以下の整数であり、ｔ＋ｕは１以上１００以下の整数である。テトラメチレンオキシド、プロピレンオキシド、及びエチレンオキシドの繰り返し単位に基づく構造はランダムで構成される。）

(In the above formula, s is an integer of 2 to 100, t and u are integers of 0 to 100, and t + u is an integer of 1 to 100. Tetramethylene oxide, propylene oxide, and ethylene oxide The structure based on the repeating unit is randomly formed.)

（上式において、ｓは２以上１００以下の整数であり、ｔ、及びｕは０以上１００以下の整数であり、ｔ＋ｕは１以上１００以下の整数である。Ｒ₆ 、Ｒ₇ は炭素数が２以上１０以下のアルキレン基であり、ｖ、及びｗは１以上１００以下の整数である。[ ] 内のテトラメチレンオキシド、プロピレンオキシド、及びエチレンオキシドの繰り返し単位に基づく構造はランダムで構成される。[ ] 外のアルキレンオキシドの繰り返し単位に基づく構造はブロックで構成される。）
３） 基材フィルムからなる支持体（Ａ）上に、（１）または（２）記載の感光性樹脂組成物からなる感光性樹脂層を積層したサンドブラスト用感光性樹脂積層体。
４） 被加工基材上に（１）若しくは（２）記載の感光性樹脂組成物、または（３）記載の感光性樹脂積層体を用いて感光性樹脂層を形成し、露光工程、現像工程によりレジストパターンを形成した後、サンドブラスト処理を行うことを特徴とする表面加工方法。
５） 被加工基材上に（１）若しくは（２）記載の感光性樹脂組成物、または請求項（３）記載の感光性樹脂積層体を用いて感光性樹脂層を形成し、露光工程、現像工程によりレジストパターンを形成した後、サンドブラスト処理を行う工程を含むプラズマディスプレイパネルの背面板の製造方法。

(In the above formula, s is an integer of 2 to 100, t and u are integers of 0 to 100, and t + u is an integer of 1 to 100. R ₆ and R ₇ have carbon numbers. The alkylene group is 2 or more and 10 or less, and v and w are integers of 1 or more and 100 or less.The structure based on the repeating units of tetramethylene oxide, propylene oxide, and ethylene oxide in [] is randomly formed. [] Structures based on other alkylene oxide repeating units are composed of blocks.)
3) A photosensitive resin laminate for sandblasting, in which a photosensitive resin layer made of the photosensitive resin composition described in (1) or (2) is laminated on a support (A) made of a base film.
4) A photosensitive resin layer is formed on the substrate to be processed using the photosensitive resin composition described in (1) or (2) or the photosensitive resin laminate described in (3), and an exposure process and a development process. A surface processing method comprising performing a sandblast treatment after forming a resist pattern by the method.
5) A photosensitive resin layer is formed on the substrate to be processed using the photosensitive resin composition according to (1) or (2) or the photosensitive resin laminate according to claim (3), an exposure step, A method for producing a back plate of a plasma display panel, comprising a step of performing a sandblast treatment after forming a resist pattern by a development step.

  The photosensitive resin composition for sandblasting of the present invention, the photosensitive resin laminate using the same, and the surface processing method using the composition or the laminate can be used even when the development is excessive. It has excellent pattern adhesion and has an effect that a fine pattern can be processed with high yield as a mask material for sandblasting. A remarkable effect is exhibited when applied to a substrate to be processed such as glass, low-melting glass, or ceramic, or a plasma display panel, particularly a large substrate.

Hereinafter, the present invention will be specifically described.
The polyurethane prepolymer of the component (i) of the composition of the present invention is an active hydrogen with respect to the terminal isocyanate group of the polyurethane obtained by addition polymerization of the polymer or monomer (a) having a terminal hydroxyl group and the polyisocyanate (b). It can be obtained by reacting a functional group having a compound (c) having both an ethylenically unsaturated bond in the molecule.
The polymer or monomer (a) having a hydroxyl group at the terminal used in the present invention must contain at least one compound represented by the following chemical formula (1) or (2).

（上式において、Ｒ₁ はテトラメチレン基、Ｒ₂ はプロピレン基、Ｒ₃ はエチレン基を表す。ｐは２以上１００以下の整数であり、ｑ、及びｒは０以上１００以下の整数である。テトラメチレンオキシド、プロピレンオキシド、及びエチレンオキシドの繰り返し単位からなる構造は、各々ランダムで構成されてもよいし、ブロックで構成されてもよい。）

(In the above formula, R ₁ represents a tetramethylene group, R ₂ represents a propylene group, and R ₃ represents an ethylene group. P is an integer of 2 or more and 100 or less, and q and r are integers of 0 or more and 100 or less. The structure composed of repeating units of tetramethylene oxide, propylene oxide, and ethylene oxide may be composed of random or block.)

（上式において、ｍ、ｎ、ｏは１以上１００以下の整数であり、Ｒ₄ 、及びＲ₅ はアルキレン基である。テトラメチレンオキシド、並びにＲ₄ 、及びＲ₅ に基づく繰り返し単位からなる構造はブロックで構成される。）

(In the above formula, m, n and o are integers of 1 to 100, and R ₄ and R ₅ are alkylene groups. A structure comprising tetramethylene oxide and repeating units based on R ₄ and R _5. Is composed of blocks.)

The compound represented by the chemical formula (1) is a polyalkylene glycol compound having a tetramethylene oxide group as one of repeating units. A preferable structure includes a compound represented by poly (tetramethylene glycol) (PTMG) as represented by the following chemical formula (3). Further, as represented by the following chemical formulas (4) and (5), glycol compounds in which a propylene oxide group or an ethylene oxide group is introduced by block copolymerization using the terminal hydroxyl group of PTMG, and the following chemical formulas (6) and ( Examples thereof include PTMG derivatives such as glycol compounds in which tetramethylene oxide groups are introduced by block copolymerization using terminal hydroxyl groups of polyethylene glycol (PEG) and polypropylene glycol (PPG), as represented by 7). In addition, a glycol compound obtained by random copolymerization of tetrahydrofuran (THF) with ethylene oxide or propylene oxide, represented by the following chemical formula (8), or a chemical formula (9) represented by the following chemical formula (9) The glycol compound which introduce | transduced the ethylene oxide group, the propylene oxide group, and the tetramethylene oxide group further by block copolymerization using the terminal hydroxyl group of the compound of 8) is also mentioned. Among the structures represented by the following chemical formulas (3) to (9), the structure represented by the following chemical formula (3) is preferable.
In the chemical formula (1), p is preferably 4 or more from the viewpoint of improving the adhesion of the resist pattern, and preferably 70 or less from the viewpoint of maintaining developability. More preferably, it is 6 or more and 55 or less. q is preferably 0 or more and 10 or less from the viewpoint of improving the adhesion of the resist pattern. r is preferably 0 or more and 10 or less from the viewpoint of improving the adhesion of the resist pattern.

（上式において、ｐは２以上１００以下の整数である。）

(In the above formula, p is an integer of 2 to 100.)

（上式において、a 、及びｃは１以上１００以下の整数であり、ｂは２以上１００以下の整数である。テトラメチレンオキシド、及びプロピレンオキシドの繰り返し単位からなる構造は、ブロックで構成される。）

(In the above formula, a and c are integers of 1 or more and 100 or less, and b is an integer of 2 or more and 100 or less. The structure composed of repeating units of tetramethylene oxide and propylene oxide is composed of blocks. .)

（上式において、ｄ、及びｆは１以上１００以下の整数であり、ｅは２以上１００以下の整数である。テトラメチレンオキシド、及びエチレンオキシドの繰り返し単位に基づく構造は、ブロックで構成される。）

(In the above formula, d and f are integers of 1 or more and 100 or less, and e is an integer of 2 or more and 100 or less. The structure based on the repeating units of tetramethylene oxide and ethylene oxide is composed of blocks. )

（上式において、ｇ、ｈ、及びｉは１以上１００以下の整数である。テトラメチレンオキシド、及びプロピレンオキシドの繰り返し単位に基づく構造は、ブロックで構成される。）

(In the above formula, g, h and i are integers of 1 or more and 100 or less. The structure based on the repeating units of tetramethylene oxide and propylene oxide is composed of blocks.)

（上式において、ｊ、ｋ、及びｌは１以上１００以下の整数である。テトラメチレンオキシド、及びエチレンオキシドの繰り返し単位に基づく構造は、ブロックで構成される。）

(In the above formula, j, k, and l are integers of 1 or more and 100 or less. The structure based on tetramethylene oxide and ethylene oxide repeating units is composed of blocks.)

（上式において、ｓは２以上１００以下の整数であり、ｔ、及びｕは０以上１００以下の整数であり、ｔ＋ｕは１以上１００以下の整数である。テトラメチレンオキシド、プロピレンオキシド、及びエチレンオキシドの繰り返し単位に基づく構造はランダムで構成される。）

(In the above formula, s is an integer of 2 to 100, t and u are integers of 0 to 100, and t + u is an integer of 1 to 100. Tetramethylene oxide, propylene oxide, and ethylene oxide The structure based on the repeating unit is randomly formed.)

（上式において、ｓは２以上１００以下の整数であり、ｔ、及びｕは０以上１００以下の整数であり、ｔ＋ｕは１以上１００以下の整数である。Ｒ₆ 、Ｒ₇ は炭素数が２以上１０以下のアルキレン基であり、ｖ、及びｗは１以上１００以下の整数である。[ ] 内のテトラメチレンオキシド、プロピレンオキシド、及びエチレンオキシドの繰り返し単位に基づく構造はランダムで構成される。[ ] 外のアルキレンオキシドの繰り返し単位に基づく構造はブロックで構成される。）

(In the above formula, s is an integer of 2 to 100, t and u are integers of 0 to 100, and t + u is an integer of 1 to 100. R ₆ and R ₇ have carbon numbers. The alkylene group is 2 or more and 10 or less, and v and w are integers of 1 or more and 100 or less.The structure based on the repeating units of tetramethylene oxide, propylene oxide, and ethylene oxide in [] is randomly formed. [] Structures based on other alkylene oxide repeating units are composed of blocks.)

The compound represented by the chemical formula (2) is a polyol compound obtained by ring-opening polymerization of a lactone using the terminal hydroxyl group of PTMG. In the chemical formula (2), m is preferably 0 or more, and preferably 10 or less from the viewpoint of improving the adhesion of the resist pattern. n is preferably 4 or more from the viewpoint of improving the adhesion of the resist pattern, and preferably 70 or less from the viewpoint of maintaining developability. o is preferably 0 or more, and preferably 10 or less from the viewpoint of improving the adhesion of the resist pattern.
Among the compounds represented by the chemical formula (1) or (2), the most preferred compound is the compound represented by the chemical formula (3). It is preferable from the viewpoint of improving the adhesion of the resist pattern.
The hydroxyl value of the compound represented by the chemical formula (1) or (2) is preferably 22 to 380 mgKOH / g. 380 mgKOH / g or less is preferable from the viewpoint of improving the adhesion of the resist pattern, and 22 mgKOH / g or more is preferable from the viewpoint of maintaining good developability. More preferably, it is 28-230 mgKOH / g. More preferably, it is 32-115 mgKOH / g. Most preferably, it is 32-78 mgKOH / g.

  The hydroxyl value means the number of milligrams of potassium hydroxide necessary to neutralize acetic acid bound to the acetylated product obtained from 1 g of a sample. The sample is heated with an excess of an acetylating agent such as acetic anhydride, acetylated, and the saponification value of the produced acetylated product is measured, and then calculated according to the following formula. However, A represents the saponification value after acetylation, and B represents the saponification value before acetylation.

水酸基価を測定する方法の一例を下記する。３ｇ程度の試料を精密に秤量し、無水酢酸とピリジンとＮＭＰ（ｎ−メチルピロリドン）をそれぞれ１質量部、４質量部、１５質量部の割合で混合した溶液２０ｍｌに溶解する。得られた溶液を１００℃のオイルバスで５時間攪拌し、更に５ｇ程度の精製水を加え更に１時間１００℃で攪拌する。溶液を室温にまで冷却した後、指示薬としてフェノールフタレインのメタノール溶液を数滴添加し、１／２規定の水酸化カリウム水溶液で中和滴定しアセチル化後のケン化価を測定する。アセチル化前のケン化価は上記において、試料を含有しない溶液について同様の処理と中和滴定を行い求める。 本発明で用いられる、末端に水酸基を有するポリマーまたはモノマー（ａ）には、上記化学式（１）または（２）で示される化合物以外のポリマーまたはモノマーを併用することも可能である。

An example of a method for measuring the hydroxyl value will be described below. A sample of about 3 g is accurately weighed and dissolved in 20 ml of a solution in which acetic anhydride, pyridine and NMP (n-methylpyrrolidone) are mixed at a ratio of 1 part by mass, 4 parts by mass and 15 parts by mass, respectively. The obtained solution is stirred in an oil bath at 100 ° C. for 5 hours, and further about 5 g of purified water is added and further stirred at 100 ° C. for 1 hour. After the solution is cooled to room temperature, a few drops of a phenolphthalein methanol solution is added as an indicator, neutralized with a 1/2 N aqueous potassium hydroxide solution, and the saponification value after acetylation is measured. In the above, the saponification value before acetylation is obtained by performing the same treatment and neutralization titration for a solution containing no sample. The polymer or monomer (a) having a hydroxyl group at the terminal used in the present invention can be used in combination with a polymer or monomer other than the compound represented by the above chemical formula (1) or (2).

Examples of such polymers include polyester polyols such as polyethylene glycol adipate, polypropylene glycol adipate, and poly (1,4-butanediol) adipate, polyether polyols such as polyethylene glycol and polypropylene glycol, polycaprolactone diol, and polyvalerolactone. Examples include lactone diol such as diol, polycarbonate diol, 1,4-polybutadiene having a terminal hydroxyl group, hydrogenated or non-hydrogenated 1,2-polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, and the like. .
Examples of such monomers include glycols such as ethylene glycol, propylene glycol, diethylene glycol, and triethylene glycol. When a carboxylic acid is introduced into the polyurethane prepolymer of the present invention, a diol having a carboxyl group in the molecule, such as dimethylolpropionic acid and dimethylolbutanoic acid, can also be used.

The polymer or monomer (a) having a hydroxyl group at the terminal used in the present invention contains 50% by mass to 100% by mass of the compound represented by the chemical formula (1) or (2). From the viewpoint of improving the properties. More preferably, it is 70 mass% or more and 100 mass% or less. More preferably, it is 90 mass% or more and 100 mass% or less.
The polyisocyanate (b) used in the present invention includes tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate. Isocyanate, α, α′-dimethyl-o-xylylene diisocyanate, α, α′-dimethyl-m-xylylene diisocyanate, α, α′-dimethyl-p-xylylene diisocyanate, α, α, α′-trimethyl- o-xylylene diisocyanate, α, α, α′-trimethyl-m-xylylene diisocyanate, α, α, α′-trimethyl-p-xylylene diisocyanate, α, α, α ′, α′-tetramethyl-o -Xylylene diisocyanate, α, α, α ', α' Tetramethyl -m- xylylene diisocyanate, alpha, alpha, alpha ',. Alpha .'- tetramethyl -p- diisocyanate, cyclohexane diisocyanate. A compound obtained by hydrogenating an aromatic ring of a diisocyanate compound, for example, a hydrogenated product of m-xylylene diisocyanate (Takenate 600 manufactured by Mitsui Takeda Chemical Co., Ltd.) is also included.

  Specific examples of the compound (c) having both a functional group having active hydrogen and an ethylenically unsaturated bond in the molecule used in the present invention include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( (Meth) acrylate, diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, oligoethylene glycol mono (meth) acrylate, oligopropylene glycol (Meth) acrylate, oligotetramethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene Recalls mono (meth) acrylate.

The ethylenically unsaturated bond concentration of the component (i) polyurethane prepolymer is preferably 2 × 10 ⁻⁴ mol / g or more and 10 ⁻² mol / g or less. It is preferably 2 × 10 ⁻⁴ mol / g or more from the viewpoint of sufficient crosslinking to ensure sandblast resistance, and preferably 10 ⁻² mol / g or less from the viewpoint of keeping the cured film soft and ensuring sandblast resistance.
The weight average molecular weight of the component (i) polyurethane prepolymer is preferably from 1,500 to 500. 1,500 or more is preferable from the viewpoint of maintaining the sandblast resistance, and 50,000 or less is preferable from the viewpoint of maintaining developability. More preferably, it is 5,000 or more and 30,000 or less. More preferably, it is 9,000 or more and 25,000 or less. The weight average molecular weight here is GPC method (column: Shodex (trademark) manufactured by Showa Denko KK (KF-807, KF-806M, KF-806M, KF-802.5) in series, moving bed solvent. Is a polystyrene-reduced weight average molecular weight of (tetrahydrofuran) (i) When a carboxylic acid is introduced into the skeleton of the polyurethane prepolymer of the component, the acid value of the polyurethane prepolymer should be 0 to 10 mgKOH / g. It is preferable at the point which improves the adhesiveness of a pattern. More preferably, it is 0-7 mgKOH / g. The acid value refers to the number of milligrams of potassium hydroxide necessary to neutralize free fatty acids contained in 1 g of a sample.

An example of a method for measuring the acid value will be described below. A sample of about 5 g is accurately weighed and dissolved in 20 ml of a solution obtained by mixing 50 parts by mass of acetone and methanol. After adding several drops of a phenolphthalein methanol solution as an indicator, neutralization titration with a 1/10 N aqueous potassium hydroxide solution is performed to determine the number of milligrams of potassium hydroxide required for neutralization.
The content of the polyurethane prepolymer as component (i) is preferably 10% by mass or more and 70% by mass or less, more preferably 20% by mass or more and 65% by mass or less, and further preferably 25% by mass based on the total mass of the photosensitive resin composition. % To 60% by mass. The amount is 10% by mass or more from the viewpoint of securing sufficient sandblast resistance, and 70% by mass or less is preferable from the viewpoint of ensuring developability.
The component (i) polyurethane prepolymer may be used alone or in combination of two or more.

The polyurethane prepolymer of component (i) of the composition of the present invention can be prepared, for example, by the method disclosed in Examples of JP-A-11-188863.
Examples of the alkali-soluble polymer as the component (ii) of the composition of the present invention include carboxylic acid-containing vinyl copolymers and carboxylic acid-containing celluloses.
The carboxylic acid-containing vinyl copolymer is at least one first monomer selected from α, β-unsaturated carboxylic acid, alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, (meth) At least one second monomer selected from acrylamide and a compound in which hydrogen on nitrogen is substituted with an alkyl group or an alkoxy group, styrene and a styrene derivative, (meth) acrylonitrile, and glycidyl (meth) acrylate; It is a compound obtained by vinyl copolymerization. Examples of the first monomer used in the carboxylic acid-containing vinyl copolymer include acrylic acid, methacrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, and maleic acid half ester. You may use and may combine 2 or more types. The proportion of the first monomer in the carboxylic acid-containing vinyl copolymer is preferably 15% by mass or more and 40% by mass or less, more preferably 20% by mass or more and 35% by mass or less. In order to maintain alkali developability, the content is preferably 15% by mass or more, and preferably 40% by mass or less from the viewpoint of the solubility of the carboxylic acid-containing vinyl copolymer.

The second monomer used in the carboxylic acid-containing vinyl copolymer includes methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, cyclohexyl (meth) acrylate, and n-butyl (meth). Acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) ) Acrylate, (meth) acrylamide, N-methylolacrylamide, N-butoxymethylacrylamide, styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, (meth) acrylonitrile Glycidyl (meth) acrylate and the like, may be used alone or used in combination of two or more kinds.
The proportion of the second monomer in the carboxylic acid-containing vinyl copolymer is preferably 60% by mass or more and 85% by mass or less, and more preferably 65% by mass or more and 80% by mass or less.

The weight average molecular weight of the carboxylic acid-containing vinyl copolymer is preferably 20,000 or more and 300,000 or more, more preferably 30,000 or more and 150,000 or less. The weight average molecular weight in this case is a polystyrene-reduced weight average molecular weight by GPC method. In order to maintain the strength of the cured film, it is preferably 20,000 or more, and preferably 300,000 or less from the viewpoint of stability when the photosensitive resin composition is laminated to form the photosensitive resin layer.
Examples of the carboxylic acid-containing cellulose include cellulose acetate phthalate and hydroxyethyl / carboxymethylcellulose.
The content of the alkali-soluble polymer is preferably 10% by mass or more and 70% by mass or less, more preferably 20% by mass or more and 65% by mass or less, still more preferably 25% by mass or more and 60% by mass based on the total mass of the photosensitive resin composition. % Or less. 10 mass% or more is preferable from the point which maintains the dispersibility with respect to an alkali developing solution. 70 mass% or less is preferable from the point of obtaining sufficient sandblast resistance.

  As the photopolymerization initiator of component (iii) of the composition of the present invention, benzyl dimethyl ketal, benzyl diethyl ketal, benzyl dipropyl ketal, benzyl diphenyl ketal, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin phenyl Ether, thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2-fluorothioxanthone, 4-fluorothioxanthone, 2-chlorothioxanthone, 4-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, benzophenone, 4,4'-bis (dimethylamino) benzophenone Michler's ketone], 4,4′-bis (diethylamino) benzophenone, aromatic ketones such as 2,2-dimethoxy-2-phenylacetophenone, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, etc. Acridines such as biimidazole compounds, 9-phenylacridine, α, α-dimethoxy-α-morpholino-methylthiophenylacetophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, phenylglycine, N-phenylglycine and 1-phenyl Oxime esters such as -1,2-propanedione-2-O-benzoyloxime, ethyl 2,3-dioxo-3-phenylpropionate-2- (O-benzoylcarbonyl) -oxime, p-dimethylaminobenzoic acid P-Diethyla Roh benzoic acid and p- diisopropyl-aminobenzoic acid and esters of these alcohols, p- hydroxybenzoic acid esters, triazoles such as 3-mercapto-1,2,4-triazole, tetrazole and the like. Among them, a combination of 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer and Michler's ketone or 4,4 '-(diethylamino) benzophenone is particularly preferable.

  The content of the photopolymerization initiator as the component (iii) is preferably 0.01% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 10% by mass or less, based on the total mass of the photosensitive resin composition. It is. The amount is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity, and is preferably 20% by mass or less in order to sufficiently cure the bottom portion of the photosensitive resin layer.

  Examples of the ethylenically unsaturated addition polymerizable monomer of the component (iv) of the composition of the present invention include 2-hydroxy-3-phenoxypropyl acrylate, β-hydroxypropyl-β ′-(acryloyloxy) propyl phthalate, 1 , 4-tetramethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, octapropylene glycol di (meth) acrylate, glycerol (meth) acrylate 2-di (p-hydroxyphenyl) propane di (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyoxypropyltrimethylolpropane tri (meth) acrylate, poly Oxyethyltrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, bisphenol A diglycidyl ether di (meth) Acrylate, diallyl phthalate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bis (triethylene glycol methacrylate) nonapropylene glycol, bis (tetraethylene glycol methacrylate) polypropylene glycol, bis (triethylene glycol methacrylate) polypropylene Glycol, bis (diethylene glycol acrylate) polypropylene Glycol, and compounds containing both ethylene oxide chain and a propylene oxide chain and the like in the molecule of the bisphenol A-based (meth) acrylic acid ester monomer.

A urethanized compound of a polyvalent isocyanate compound such as hexamethylene diisocyanate or tolylene diisocyanate and a hydroxy acrylate compound such as 2-hydroxypropyl (meth) acrylate can also be used. In this case, the urethanized compound has a polystyrene-reduced number average molecular weight by GPC of less than 1,500. These ethylenically unsaturated addition polymerizable monomers may be used alone or in combination of two or more.
The content of the ethylenically unsaturated addition polymerizable monomer as component (iv) is preferably 5% by mass or more and 40% by mass or less, more preferably 10% by mass or more and 35% by mass or less, based on the total mass of the photosensitive resin composition. is there. 5 mass% or more is preferable in order to fully bridge | crosslink and exhibit sandblasting-proof property. In order to keep the cured film soft and exhibit sandblast resistance, it is preferably 40% by mass or less.

In order to improve the thermal stability and storage stability of the photosensitive resin composition, it is preferable to contain a radical polymerization inhibitor in the photosensitive resin composition of the present invention. Examples of such radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, t-butylcatechol, cuprous chloride, 2,6-di-t-butyl-p-cresol, 2,2 ′. -Methylenebis (4-ethyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol) and the like.
The photosensitive resin composition of the present invention may contain coloring substances such as dyes and pigments. Examples of such coloring substances include fuchsin, phthalocyanine green, auramin base, chalcoxide green S, paramagenta, crystal violet, methyl orange, nile blue 2B, Victoria blue, malachite green, basic blue 20, and diamond green. Can be mentioned.

Further, the photosensitive resin composition of the present invention may contain a coloring dye that develops color when irradiated with light. As such a coloring dye, a combination of a leuco dye and a halogen compound is well known. Examples of the leuco dye include tris (4-dimethylamino-2-methylphenyl) methane [leuco crystal violet] and tris (4-dimethylamino-2-methylphenyl) methane [leucomalachite green]. On the other hand, halogen compounds such as 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 and the like.
Furthermore, you may make the photosensitive resin composition of this invention contain additives, such as a plasticizer, as needed. Examples of such additives include phthalates such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl citrate tri- Examples thereof include n-propyl, tri-n-butyl acetylcitrate, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, and the like.

The ethylenically unsaturated bond concentration of the photosensitive resin composition of the present invention is preferably 5.0 × 10 ⁻⁴ mol / g or more and 3.0 × 10 ⁻³ mol / g or less. From the point of obtaining sufficient resolution, 5.0 × 10 ⁻⁴ mol / g is preferable, and 3.0 × 10 ⁻³ mol / g or less is preferable in order to keep the cured film soft and exhibit sandblast resistance. A more preferable range of the ethylenically unsaturated bond concentration is 8.0 × 10 ⁻⁴ mol / g or more and 2.5 × 10 ⁻³ mol / g or less. The ethylenically unsaturated bond concentration in this case is obtained by dividing the number of unsaturated bonds contained in the ethylenically unsaturated addition polymerizable monomer and the polyurethane prepolymer in the photosensitive resin composition by the total mass of the photosensitive resin composition. Can be calculated. The ethylenically unsaturated bond concentration can also be quantified by the following method. That is, the photosensitive resin composition is dissolved in a solvent, and an excess Wis reagent is added to brominate the ethylenically unsaturated bond. By adding potassium iodide to an unreacted Wis reagent and titrating the liberated iodine with sodium thiosulfate, the ethylenically unsaturated bond concentration can be determined.

  The support (A) of the present invention is a film for supporting the photosensitive resin layer of the present invention, and is preferably made of a transparent substrate film that transmits actinic rays. Examples of such a base film include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate having a thickness of 10 μm to 100 μm. Usually, a base film made of polyethylene terephthalate having moderate flexibility and strength is used. Preferably used. Moreover, in order to improve the peelability from the photosensitive resin layer, it is also possible to use a transparent substrate film that transmits actinic rays and having a release agent formed on one surface or both surfaces. Here, the release agent is a compound having the ability to easily peel the base film from the photosensitive resin layer, and known ones can be used, but examples include silicone-containing release agents and alkyd resins. It is done.

A protective layer (C) is laminated on the photosensitive resin laminate of the present invention as necessary. It is a necessary characteristic for the protective layer that the adhesive force between the photosensitive resin layer and the protective layer is sufficiently smaller than the adhesive force between the photosensitive resin layer and the support in the adhesive force with the photosensitive resin layer. The protective layer can be easily peeled off. Examples of such a film include a polyethylene film, a polypropylene film, and a polyester film.
A method of forming a photosensitive resin laminate by sequentially laminating the support (A), the photosensitive resin layer (B), and the protective layer (C) can be performed by a conventionally known method. For example, the photosensitive resin composition used for the photosensitive resin layer is mixed with a solvent for dissolving them to form a uniform solution. First, a bar coater or roll coater is formed on the surface of the support (A) on which a release agent has been previously formed. The photosensitive resin layer (B) made of the photosensitive resin composition is laminated on the support. Next, the photosensitive resin laminate can be prepared by laminating the protective layer (C) on the photosensitive resin layer (B).

The light transmittance at 365 nm of the photosensitive resin layer (B) of the photosensitive resin laminate is preferably 2% or more and 30% or less. In order to sufficiently cure the bottom portion of the photosensitive resin layer, 2% or more is preferable, and 30% or less is preferable from the viewpoint of obtaining sufficient resolution. A more preferable range of light transmittance is 3% or more and 25% or less. The light transmittance can be controlled by blending a compound having an absorption wavelength at 365 nm, for example, a photopolymerization initiator, a dye, a pigment, a pigment, a UV absorber, and the like, and changing the blending amount. The light transmittance can be easily measured using a visible ultraviolet spectrophotometer.
Next, an example of a method for processing a fine pattern on a substrate to be processed using the photosensitive resin laminate of the present invention will be described. Laminating process in which a protective layer of a photosensitive resin laminate is peeled off while being adhered to a substrate to be processed using a hot roll laminator, a photomask having a desired fine pattern is closely adhered on a support, and exposure is performed using an actinic ray source An exposure process for removing the support, an undeveloped portion of the photosensitive resin layer is dissolved and removed using an alkaline developer, a development process for forming a fine resist pattern on the substrate to be processed, and a formed resist pattern Finely blasted onto the workpiece substrate through a sandblasting process in which blasting material is sprayed from above and the workpiece substrate is cut to the desired depth, and a resist pattern is removed from the workpiece substrate using an alkaline stripping solution. Various patterns can be processed.

Examples of the active light source used in the exposure step include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an ultraviolet fluorescent lamp, a carbon arc lamp, and a xenon lamp.
In order to obtain a finer resist pattern, it is more preferable to use a parallel light source. When it is desired to reduce the influence of dust and foreign matter as much as possible, exposure (proximity exposure) may be performed with the photomask floating several tens to several hundreds of micrometers above the support.
As the alkaline developer used in the development step, a sodium carbonate aqueous solution, a surfactant aqueous solution or the like is usually used.
As the blasting material used in the sandblasting process, known materials are used. For example, fine particles of about 2 to 100 μm such as SiC, SiO ₂ , Al ₂ O ₃ , CaCO ₃ , ZrO, glass, and stainless steel are used.
As the stripper used in the stripping step, an aqueous solution of sodium hydroxide or potassium hydroxide is usually used. It is also possible to provide a step of burning off the resist pattern at a high temperature instead of the peeling step.
As a preferable application example of the method for processing the fine pattern described above, a back plate of a plasma display panel is manufactured by processing a glass substrate such as a low melting glass.
Next, the present invention will be described with reference to examples and reference examples.

Below, the preparation method of the sample for evaluation of an Example and a comparative example, the evaluation method about the obtained sample, and an evaluation result are shown.
1. Production of Evaluation Sample The photosensitive resin laminates in Examples and Comparative Examples were produced as follows.
<Preparation of photosensitive resin laminate>
The photosensitive resin composition having the composition shown in Table 1 is thoroughly stirred and mixed, and the solution of the photosensitive resin composition is uniformly applied to a polyethylene terephthalate film having a thickness of 19 μm using a bar coater, in a dryer at 90 ° C. And dried for 4 minutes to form a photosensitive resin layer having a thickness of 40 μm. Next, a 30 μm thick polyethylene film was laminated on the surface of the photosensitive resin layer to obtain a photosensitive resin laminate.
In addition, the symbol of the composition shown in Table 1 is shown below. Table 2 shows the composition abbreviations and detailed structures of the polyurethane prepolymers U-1 to U-10.
The polyurethane prepolymers U-1 to U-8 are obtained from the compound represented by the above chemical formula (1). The polyurethane prepolymer U-9 is obtained from the compound represented by the above chemical formula (2).
The polyurethane prepolymer U-10 is obtained by reacting a polyester compound of tetramethylene oxide and adipic acid with diisocyanate, and has a structural unit of -O- (CH2) 4-O (CO)-. Is a compound not belonging to the scope of the present invention.

P-1: 35% methyl ethyl ketone solution of a copolymer having a composition of methacrylic acid / methyl methacrylate / n-butyl acrylate (weight ratio 25/65/10) and a weight average molecular weight of 80,000.
M-1: Triethoxytrimethylolpropane triacrylate M-2: Urethane product of hexamethylene diisocyanate and tripropylene glycol monomethacrylate I-1: Benzyldimethyl ketal I-2: Benzophenone I-3: 2- (o- Chlorophenyl) -4,5-diphenylimidazolyl dimer I-4: 4,4 ′-(diethylamino) benzophenone D-1: leucocrystal violet D-2: diamond green

<Preparation of workpiece substrate>
As the substrate to be processed, two types of soda glass having a thickness of 3 mm and soda glass coated with glass paste prepared by the following method were used. A glass paste for plasma display (PLS-3553 manufactured by Nippon Electric Glass Co., Ltd.) is applied on a soda glass having a thickness of 3 mm on the soda glass so that the thickness of the glass paste after drying becomes 150 μm. The soda glass coated with glass paste and dried was prepared.
<Laminate>
While peeling the polyethylene film of the photosensitive resin laminate, the substrate was laminated at 105 ° C. with a hot roll laminator (“AL-70” manufactured by Asahi Kasei Engineering Co., Ltd.). The air pressure was 0.35 MPa, and the laminating speed was 1.0 m / min.
<Exposure>
The photosensitive resin layer was exposed to 200 mJ / cm ² with an ultra high pressure mercury lamp (OMW Seisakusho HMW-801) through the support without a photomask or through a photomask necessary for evaluation.

<Development>
After peeling off the support, a 0.4% sodium carbonate aqueous solution at 30 ° C. was sprayed for a predetermined time to dissolve and remove unexposed portions of the photosensitive resin layer.
<Sandblast>
The resist pattern formed on the substrate to be processed was subjected to sandblasting using an X hyperblasting apparatus HCH-3X7BBART-411M (manufactured by Fuji Seisakusho). S9 # 1200 (Fuji Seisakusho Co., Ltd.) was used as the abrasive, the hose internal pressure was 0.08 MPa, and the gun moving speed was 20 m / min. , Conveyor moving speed 100 mm / min. , Abrasive spraying amount 500 g / min. It was.

2. Evaluation Method (1) Minimum Development Time After performing the above <exposure> operation and peeling off the support, it is necessary to spray a 0.4% aqueous sodium carbonate solution at 30 ° C. to dissolve the unexposed photosensitive resin layer. The time was measured and this was taken as the minimum development time.
(2) Resist line adhesion (normal development)
In the above <exposure>, exposure was performed through a photomask having a line pattern in which the width of the exposed area and the unexposed area was 1: 100. Development was performed at a development time 1.5 times the minimum development time, and the minimum mask width at which a cured resist line was normally formed was defined as the resist line adhesion value. The adhesion was ranked as follows. In Table 1, the value next to the rank is the adhesion value. The same applies to (3) to (4) below.
70 μm or less: ○
More than 70μm and less than 100μm: △
Over 100 μm: ×

(3) Resist line adhesion (over development)
In the above <exposure>, exposure was performed through a photomask having a line pattern in which the width of the exposed area and the unexposed area was 1: 100. Development was performed at a development time 3.0 times the minimum development time, and the minimum mask width in which a cured resist line was normally formed was defined as the resist line adhesion value. The adhesion was ranked as follows.
70 μm or less: ○
More than 70μm and less than 100μm: △
Over 100 μm: ×
(4) Resist line resolution In the above <exposure>, exposure was performed through a photomask having a line pattern in which the width of the exposed area and the unexposed area was 1: 1. Development was performed at a development time 1.5 times the minimum development time, and the minimum mask width at which a cured resist line was normally formed was defined as the resist line adhesion value. The adhesion was ranked as follows.
70 μm or less: ○
More than 70μm and less than 100μm: △
Over 100 μm: ×

(5) Sandblast-resistant adhesion In the above <exposure>, the exposed portion and the unexposed portion are exposed through a photomask having a line pattern with a ratio of 1: 2, and 1.5 times the minimum development time. Developed with development time. Next, sandblasting was performed, and the minimum mask width that was normally formed without the cured resist line being chipped or peeled off was taken as the value of the sandblast resistance. The sandblast resistant adhesion was ranked as follows.
80 μm or less: ○
More than 80μm and less than 100μm: △
Over 100 μm: ×
3. Evaluation Results Table 1 shows the evaluation results of Examples and Comparative Examples.

  The present invention relates to a novel photosensitive resin laminate for sandblasting, and more particularly, sensitivity, resolution, adhesion when applied to a substrate to be processed such as glass, low melting point glass, ceramic, etc., particularly a back plate of a plasma display panel. And a photosensitive resin laminate capable of processing a fine pattern on a substrate to be processed with a high yield as a mask material for sandblasting, and a sandblasting surface processing method using the same.

Claims (5)

(I) A polyurethane prepolymer obtained from a polymer or monomer (a) having a hydroxyl group at the terminal, a polyisocyanate (b), a compound (c) having both a functional group having active hydrogen and an ethylenically unsaturated bond in the molecule. 10 to 70% by mass of a polymer, (ii) 10 to 70% by mass of an alkali-soluble polymer, (iii) 0.01 to 20% by mass of a photopolymerization initiator, and (iv) an ethylenically unsaturated addition polymerizable monomer 5 In the photosensitive resin composition comprising ˜40% by mass, 50% by mass or more of the polymer or monomer (a) having a hydroxyl group at the terminal is selected from the group consisting of compounds represented by the following chemical formula (1) or (2) A photosensitive resin composition for sandblasting, wherein the photosensitive resin composition is one or more kinds of compounds.

(In the above formula, R ₁ represents a tetramethylene group, R ₂ represents a propylene group, and R ₃ represents an ethylene group. P is an integer of 2 or more and 100 or less, and q and r are integers of 0 or more and 100 or less. The structure composed of repeating units of tetramethylene oxide, propylene oxide, and ethylene oxide may be composed of random or block.)

(In the above formula, m, n and o are integers of 1 to 100, and R ₄ and R ₅ are alkylene groups. A structure comprising tetramethylene oxide and repeating units based on R ₄ and R _5. Is composed of blocks.) The sandblast according to claim 1, wherein 50% by mass or more of the polymer or monomer (a) having a hydroxyl group at the terminal is a compound represented by any one of the following chemical formulas (3) to (9), or a mixture of a plurality of the compounds. Photosensitive resin composition.

(In the above formula, p is an integer of 2 to 100.)

(In the above formula, a and c are integers of 1 or more and 100 or less, and b is an integer of 2 or more and 100 or less. The structure composed of repeating units of tetramethylene oxide and propylene oxide is composed of blocks. .)

(In the above formula, d and f are integers of 1 or more and 100 or less, and e is an integer of 2 or more and 100 or less. The structure based on the repeating units of tetramethylene oxide and ethylene oxide is composed of blocks. )

(In the above formula, g, h and i are integers of 1 or more and 100 or less. The structure based on the repeating units of tetramethylene oxide and propylene oxide is composed of blocks.)

(In the above formula, j, k, and l are integers of 1 or more and 100 or less. The structure based on tetramethylene oxide and ethylene oxide repeating units is composed of blocks.)

(In the above formula, s is an integer of 2 to 100, t and u are integers of 0 to 100, and t + u is an integer of 1 to 100. Tetramethylene oxide, propylene oxide, and ethylene oxide The structure based on the repeating unit is randomly formed.)

(In the above formula, s is an integer of 2 to 100, t and u are integers of 0 to 100, and t + u is an integer of 1 to 100. R ₆ and R ₇ have carbon numbers. The alkylene group is 2 or more and 10 or less, and v and w are integers of 1 or more and 100 or less.The structure based on the repeating units of tetramethylene oxide, propylene oxide, and ethylene oxide in [] is randomly formed. [] Structures based on other alkylene oxide repeating units are composed of blocks.)   A photosensitive resin laminate for sandblasting, wherein a photosensitive resin layer comprising a photosensitive resin composition according to claim 1 or 2 is laminated on a support (A) comprising a base film.   A photosensitive resin layer is formed on the substrate to be processed using the photosensitive resin composition according to claim 1 or 2 or the photosensitive resin laminate according to claim 3, and a resist pattern is formed by an exposure step and a development step. A surface processing method characterized by performing a sandblast treatment after the formation. A photosensitive resin layer is formed on the substrate to be processed using the photosensitive resin composition according to claim 1 or 2 or the photosensitive resin laminate according to claim 3, and a resist pattern is formed by an exposure step and a development step. A method for producing a back plate of a plasma display panel, comprising a step of performing a sandblasting treatment after the formation.