KR20180040739A - Photosensitive resin element - Google Patents

Abstract

Provided is a photosensitive resin element which has good appearance, has a long product life, and can reduce defects caused by a resist chip in a lamination process at the time of manufacturing a printed circuit board. The present disclosure relates to a photosensitive resin element comprising 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 an acid equivalent and a weight average molecular weight of 5000 to 500000 (C) a photopolymerization initiator, and (d) a solvent, wherein the photosensitive resin layer contains (d) a solvent in an amount of 0.001 Wherein the photosensitive resin layer contains the photosensitive element in an amount of not less than 1 mass% and not more than 1 mass%, and the photosensitive resin layer is a photopolymerizable unsaturated compound (b) Lt; / RTI >

Description

[0001] PHOTOSENSITIVE RESIN ELEMENT [0002]

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

A method for producing a photosensitive resin composition for producing a printed circuit is a method for producing a photosensitive resin composition which comprises mixing a resin for a binder, a photopolymerizable unsaturated compound, a photopolymerization initiator, a dye and the like with a ketone represented by methyl ethyl ketone, an ester represented by ethyl acetate, And a step of homogeneously stirring and dissolving them in a solvent containing as a main component an ether represented by furan. For example, Patent Document 1 discloses a solution prepared by using a mixed solvent of methyl ethyl ketone / 1-methoxy-2-propanol = 2/1 (weight ratio). Patent Document 1 discloses that a layered product having a layer of a photosensitive resin composition can be obtained by uniformly applying such a solution onto a polyester film or the like as a support layer using a die coater or the like and drying the solvent in a drying process, And a laminate of a three-layer structure having a layer made of a photosensitive resin composition can be obtained by further laminating a polyethylene film or the like as a protective layer. These laminated bodies are generally referred to as dry film photoresists (hereinafter abbreviated as " DF ").

Japanese Patent Application Laid-Open No. 11-143069

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 the additive such as a dye are insufficient and the filter is clogged There were often cases. From the viewpoint of reducing the minute irregularities on the surface of the produced DF and reducing the frequency observed as unevenness in the visual inspection of the appearance, there was still room for improvement in the combination solution.

The inventors of the present invention have found out that when the solvent remaining in the photosensitive resin composition after drying is large, when DF is formed from the photosensitive resin composition, an edge fuse in which the photosensitive layer seeps from the end surface of the roll over time in DF wound in roll form If the amount of the solvent remaining in the photosensitive resin composition after drying is too small, chips of the photosensitive layer are generated when the cutter blade is put in the photosensitive layer. I found out there was a problem. The cutter blade is used in a laminating process, and when a chip of the photosensitive layer is generated, the chip is reattached to the substrate, causing a defect.

Accordingly, an object of the present invention is to provide a photosensitive resin element which is excellent in appearance, has a long product life, and can reduce defects caused by a resist chip in a lamination process at the time of manufacturing a printed circuit board.

The inventors of the present invention have conducted intensive investigations to solve the above problems. As a result, the inventors have found that a photosensitive resin layer having a specific composition and a solvent remaining in a specific range has a good appearance, a long product life, It is possible to reduce defects caused by the resist chips in the resist pattern. Thus, the present invention has been accomplished. That is, the present invention is as follows.

[1] A photosensitive resin element comprising a support layer and a photosensitive resin layer on the support layer,

The photosensitive resin layer,

(b) a photopolymerizable unsaturated compound, (c) a photopolymerization initiator, and (d) a solvent, wherein the content of the carboxyl group is 100 to 600 in terms of an acid equivalent and the weight average molecular weight is 5,000 to 500,000. and,

The photosensitive resin layer contains (d) a solvent in an amount of 0.001 mass% or more and 1 mass% or less based on the mass of the photosensitive resin layer,

The photosensitive resin layer contains (b) at least one compound selected from the following formulas (I) to (III) as a photopolymerizable unsaturated compound.

[Chemical Formula 1]

(Wherein, R ₁ and R ₂ each independently represents a hydrogen atom or a methyl group, A is C ₂ H ₄ represents a group, B represents a group _{CH 2 CH (CH 3),} m 1 + m 2 is 2 to 30 of an integer, m ₃ + m ₄ is an integer from 0 to 30, and m ₁ and m ₂ are each independently an integer of 1 ~ 29, m ₃ and m ₄ are each independently an integer from 0 to 29, - (AO) - and - (BO) - may be random or block, and in the case of a block, any of - (AO) - and - (BO) - may be a bisphenyl group side.

(2)

(Wherein 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 represent a hydrogen atom or a methyl group, and D represents an alkylene group having 2 to 6 carbon atoms N ₁ , n ₂ and n ₃ are integers of 0 or more satisfying n ₁ + n ₂ + n ₃ = 3 to 60 and n ₄ is 0 or 1, provided that a plurality of D in the formulas May be the same or different, and the repeating structure of - (OD) - may be random or may be a block)

(3)

(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 represents 0 ~ a 30 integer, n ₇ + n ₈ is an integer from 0 to 30, n ₅ and n ₆ are each independently an integer from 0 to 30, n ₇ and n ₈ are each independently from 0 to 30, integer , - (OA ₁₎ -, and - (OB ₁₎ - repeatedly arranged in a unit is may be either be a random and block, in the case of the block, - (OA ₁₎ -, and - (OB ₁₎ - of which one urethane gicheuk Or the like)

[2] The photosensitive resin element according to the above-mentioned mode 1, wherein (d) contains propylene glycol monomethyl ether as a solvent.

[3] The photosensitive resin element according to the above-mentioned mode 1, which contains (d) toluene as a solvent.

[4] The photosensitive resin element according to the above-mentioned mode 1, wherein (d) acetone is contained as a solvent.

[5] The photosensitive resin element according to any one of the above-mentioned aspects 1 to 4, which contains, as the photopolymerizable unsaturated compound (b), a compound represented by the general formula (I) and a compound represented by the general formula (II).

[6] The photosensitive resin element according to any one of the above-mentioned aspects 1 to 4, which contains as the photopolymerizable unsaturated compound (b) the compound represented by the general formula (I) and the compound represented by the general formula (III).

[7] The photosensitive resin element according to any one of the above-mentioned aspects 1 to 4, which contains, as the photopolymerizable unsaturated compound (b), a compound represented by the general formula (II) and a compound represented by the general formula (III).

[8] The photosensitive resin element according to any one of the above-mentioned aspects 1 to 7, wherein the support layer is a polyester film.

[9] The photosensitive resin element according to the above-mentioned mode 8, wherein the polyester film peeled and dried from the photosensitive resin element has a heat shrinkage ratio in the TD direction of 3.2% or less.

[10] The photosensitive resin element according to the above-mentioned mode 8 or 9, wherein the polyester film has a thickness of 12 탆 to 16 탆.

The present invention also provides a method for producing DF by applying a photosensitive resin composition containing the above components (a) to (d) onto a support layer and drying the composition to form a photosensitive resin layer, Further, a method of producing a three-layered DF by further forming a protective layer on the surface of the photosensitive resin layer formed on the support layer is also provided.

According to the present invention, there is provided a photosensitive resin element which is excellent in appearance, has a long product life, and can reduce a problem caused by a resist chip in a lamination process at the time of manufacturing a printed wiring board. According to a particular aspect of the present invention, there is provided a method of manufacturing the photosensitive resin element.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, exemplary embodiments (hereinafter abbreviated as "embodiments") for carrying out the present invention will be described in detail. The present invention is not limited to the embodiments, and various modifications may be made within the scope of the present invention.

According to an embodiment of the present invention,

1. A photosensitive resin element comprising a support layer and a photosensitive resin layer on the support layer,

The photosensitive resin layer,

(b) a photopolymerizable unsaturated compound, (c) a photopolymerization initiator, and (d) a solvent, wherein the content of the carboxyl group is 100 to 600 in terms of an acid equivalent and the weight average molecular weight is 5,000 to 500,000. and,

The photosensitive resin layer contains (d) a solvent in an amount of 0.001 mass% or more and 1 mass% or less based on the mass of the photosensitive resin layer,

The photosensitive resin layer contains (b) at least one compound selected from the following formulas (I) to (III) as a photopolymerizable unsaturated compound.

[Chemical Formula 4]

(Wherein, R ₁ and R ₂ each independently represents a hydrogen atom or a methyl group, A is C ₂ H ₄ represents a group, B represents a group _{CH 2 CH (CH 3),} m 1 + m 2 is 2 to 30 of an integer, m ₃ + m ₄ is an integer from 0 to 30, and m ₁ and m ₂ are each independently an integer of 1 ~ 29, m ₃ and m ₄ are each independently an integer from 0 to 29, - (AO) - and - (BO) - may be random or block, and in the case of a block, any of - (AO) - and - (BO) - may be a bisphenyl group side.

[Chemical Formula 5]

(Wherein 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 represent a hydrogen atom or a methyl group, and D represents an alkylene group having 2 to 6 carbon atoms N ₁ , n ₂ and n ₃ are integers of 0 or more satisfying n ₁ + n ₂ + n ₃ = 3 to 60 and n ₄ is 0 or 1, provided that a plurality of D in the formulas May be the same or different, and the repeating structure of - (OD) - may be random or may be a block)

[Chemical Formula 6]

(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 represents 0 ~ a 30 integer, n ₇ + n ₈ is an integer from 0 to 30, n ₅ and n ₆ are each independently an integer from 0 to 30, n ₇ and n ₈ are each independently from 0 to 30, integer , - (OA ₁₎ -, and - (OB ₁₎ - repeatedly arranged in a unit is may be either be a random and block, in the case of the block, - (OA ₁₎ -, and - (OB ₁₎ - of which one urethane gicheuk .

The photosensitive resin element may be produced, for example, by the following steps:

(b) a photopolymerizable unsaturated compound, (c) a photopolymerization initiator, (d) a solvent, and (c) a polymerizable unsaturated compound having a carboxyl group content of 100 to 600 and a weight average molecular weight of 5,000 to 500,000, (E) combining other additives to obtain a combination solution; Applying the combination liquid onto the support layer, and then drying the combination liquid to form a photosensitive resin layer on the support layer; . ≪ / RTI >

In the present embodiment, the amount of the solvent remaining in the photosensitive resin layer (for example, one obtained by drying the combination liquid in the above-described method or obtained after film formation) is preferably 0.001% by mass or more and 1% by mass or less with respect to the photosensitive resin layer need. On the other hand, when the photosensitive resin composition is used as DF, a phenomenon called edge fuse in which the photosensitive layer seeps out from the end face of the roll in the DF wound in roll form over time, shortening the life of the product Occurs. On the other hand, if it is less than 0.001% by mass, there arises a problem that a chip of a photosensitive resin layer is generated by inserting a cutter blade into the photosensitive resin layer. The cutter blade is used in a laminating process, and when a chip of the photosensitive resin layer is generated, the chip is reattached to the substrate, causing a defect. The amount of the solvent remaining in the photosensitive resin layer is preferably 0.005 mass% or more, more preferably 0.01 mass% or more, and particularly preferably 0.05 mass% or more. The amount of the solvent remaining in the photosensitive resin layer is preferably 0.7 mass% or less, more preferably 0.5 mass% or less, and particularly preferably 0.2 mass% or less. The amount and kind of the solvent remaining in the photosensitive resin layer is a value measured by a method described in the section of [Examples] to be described later or a method understood by those skilled in the art that is equivalent thereto.

In the present embodiment, the means for controlling the amount of the solvent remaining in the photosensitive resin layer includes adjustment of the drying condition (temperature and time) of the photosensitive resin composition at the time of forming the photosensitive resin layer. The amount of the solvent remaining in the photosensitive resin layer is a value measured by gas chromatography.

Generally, a photosensitive element refers to a change in properties by receiving light. The photosensitive element may be in various forms such as, for example, a film, a plate, a sheet, a roll, a molded product and the like, and may be, for example, a photosensitive resin element containing a photosensitive resin or a photosensitive resin element made of a photosensitive resin. More specifically, by applying a composition containing a photosensitive resin (referred to as a " photosensitive resin composition " in this disclosure) to a supporting layer such as a film, a layer comprising a photosensitive resin composition or a layer obtained by drying a photosensitive resin composition A photosensitive resin laminate obtained by laminating a photosensitive resin layer ") on a support layer is preferably used as the photosensitive resin element. The present invention provides a photosensitive resin element as 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, a solid, an emulsion, a suspension or the like), but a liquid such as a solution, an emulsion or a suspension desirable. Further, a protective layer (for example, a protective film, a laminated film, or the like) is further laminated on a portion of the laminate of the support layer and the photosensitive resin layer where the photosensitive resin layer is exposed, and the laminate is taken up to form a photosensitive resin laminate This photosensitive resin element is more preferable, and the form of the 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 from 5 탆 to 50 탆. The thickness of the photosensitive resin element is preferably adjusted to 5 占 퐉 or more from the viewpoint of accuracy of applying the combination liquid to the support layer, and is preferably adjusted to 50 占 퐉 or less from the viewpoint of drying property in the drying step. It is more preferable that the thickness of the photosensitive resin element is 30 mu m to 50 mu m.

The thinner the photosensitive resin layer, the higher the resolution. The thicker the photosensitive resin layer, the better the film strength. Therefore, the film thickness of the photosensitive resin layer can be appropriately selected depending on the application. For example, the thickness of the photosensitive resin layer may be from 15 탆 to 50 탆, for example, from 15 탆 to 30 탆, or from 30 탆 to 40 탆, or from 40 탆 to 50 탆.

<Photosensitive resin composition>

The photosensitive resin composition preferably contains (e) a binder resin, (b) a photopolymerizable unsaturated compound, (c) a photopolymerization initiator, and (d) Do. The photosensitive resin composition is preferably a combination liquid.

When the photosensitive resin composition is a combination solution, it is preferable that the ratio of the total solid content in the combination solution in the production method of the photosensitive resin element is 30% by mass to 80% by mass. The ratio of the total solid content in the combination liquid is, for example, the solid content concentration of the combination liquid obtained by dissolving the components (a) to (c) and (e) in the solvent (d). From the viewpoint of controlling the amount of the solvent to be dried and evaporated, the proportion of the total solid content is preferably 30% by mass or more from the viewpoint of obtaining the effect of improving the application speed, and is preferably 80% by mass or less Do. The ratio of the total solid content in the combination liquid is more preferably 40 mass% or more, and still more preferably 50 mass% or more, and the upper limit is more preferably 70 mass% or less, further preferably 60 mass% or less . Setting the ratio of the total solid content within these ranges is preferable from the viewpoint of improving the smoothness of the film surface after drying, from the viewpoint of reducing the uncoated portions such as pinholes in the drying step, and from the viewpoint of obtaining a good coated surface.

Hereinafter, the components (a) to (e) will be described in detail.

(a) Resin for binder

The resin for the binder (a) is a resin having a carboxyl group content of 100 to 600 in terms of acid equivalent, a weight average molecular weight of 5000 to 500,000, and a binder.

(a) The binder resin has a carboxyl group in order to impart developability or peelability to the photosensitive resin element in an aqueous alkaline solution. The content of the carboxyl group is an acid equivalent, preferably 100 or more from the viewpoint of developing resistance, resolution and adhesion, and is preferably 600 or less from the viewpoint of developability and releasability. In the present disclosure, the acid equivalent means the mass (gram) of the resin having one equivalent of carboxyl groups therein. In the present disclosure, the acid equivalent is a value measured by a potentiometric titration method (for example, using a Hirunuma automatic titrator (COM-555 manufactured by Hiranuma Industry Co., Ltd.) and using 0.1 mol / l of sodium hydroxide) to be.

The weight average molecular weight of the resin for the binder (a) is 5,000 or more, preferably 20,000 or more, from the viewpoint of uniformly maintaining the thickness of DF and obtaining resistance to a developer. On the other hand, the weight average molecular weight is not more than 500,000, preferably not more than 300,000 from the viewpoint of maintaining developability.

Further, a preferable molecular weight distribution (ratio of weight average molecular weight / number average molecular weight) is 1.5 or more, and more preferably 2 or more. On the other hand, the molecular weight distribution is preferably 7 or less, and more preferably 5 or less. In the present disclosure, molecular weight and 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 of the 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 them, (meth) acrylic acid is particularly preferable. In the present specification, (meth) acryl represents acryl or methacryl.

The second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl Esters of vinyl alcohols such as hexyl (meth) acrylate, benzyl (meth) acrylate and vinyl acetate; (Meth) acrylonitrile, styrene-based 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 use of styrene from the viewpoint of resolution is particularly preferable.

The resin for the binder (a) is obtained by mixing the first and second monomers and adding a radical polymerization initiator, for example, benzoyl peroxide or azo peroxide, to a solution diluted with a solvent such as acetone, methyl ethyl ketone or isopropanol It is preferable to add an appropriate amount of isobutyronitrile and stir by heating. The synthesis may be carried out while dropping a part of the mixture into the reaction solution. After the completion of the reaction, the solvent may be further added to the resin for binder (a) to adjust the concentration to a desired level. As the synthesizing means, besides solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may be used.

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

More specific examples of the resin for the binder (a) include, for example, a polymer containing methyl methacrylate, methacrylic acid and styrene as copolymer components, methyl methacrylate, methacrylic acid and n- , And polymers containing benzyl methacrylate, methyl methacrylate, and 2-ethylhexyl acrylate as copolymerizable components.

In the present embodiment, the content of the resin for the binder (a) in the photosensitive resin element (with respect to the total amount of the solid components of the photosensitive resin element) is 20 mass% % To 90% by mass, and the lower limit is preferably 25% by mass and the upper limit is preferably 75% by mass, more preferably 40% by mass, and still more preferably 65% by mass. This content is preferably 20% by mass or more from the viewpoint of maintaining alkali developability, and is preferably 90% by mass or less from the viewpoint that the resist pattern formed by exposure sufficiently exhibits the performance as a resist.

(b) a photopolymerizable unsaturated compound

(b) Photopolymerizable unsaturated compounds are, for example, monomers having addition polymerizability by having an ethylenic unsaturated bond. The ethylenically unsaturated bond is preferably a terminal ethylenic unsaturated group.

(b) at least one compound wherein the photopolymerizable unsaturated compound is selected from the following general formulas (I) to (III):

(7)

(Wherein, R ₁ and R ₂ each independently represents a hydrogen atom or a methyl group, A is C ₂ H ₄ represents a group, B represents a group _{CH 2 CH (CH 3),} m 1 + m 2 is 2 to 30 of an integer, m ₃ + m ₄ is an integer from 0 to 30, and m ₁ and m ₂ are each independently an integer of 1 ~ 29, m ₃ and m ₄ are each independently an integer from 0 to 29, - (AO) - and - (BO) - may be random or block, and in the case of a block, any of - (AO) - and - (BO) - may be a bisphenyl group side.

[Chemical Formula 8]

(Wherein 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 represent a hydrogen atom or a methyl group, and D represents an alkylene group having 2 to 6 carbon atoms N ₁ , n ₂ and n ₃ are integers of 0 or more satisfying n ₁ + n ₂ + n ₃ = 3 to 60 and n ₄ is 0 or 1, provided that a plurality of D in the formulas May be the same or different, and the repeating structure of - (OD) - may be random or may be a block)

[Chemical Formula 9]

(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 represents 0 ~ a 30 integer, n ₇ + n ₈ is an integer from 0 to 30, n ₅ and n ₆ are each independently an integer from 0 to 30, n ₇ and n ₈ are each independently from 0 to 30, integer , - (OA ₁₎ -, and - (OB ₁₎ - repeatedly arranged in a unit is may be either be a random and block, in the case of the block, - (OA ₁₎ -, and - (OB ₁₎ - of which one urethane gicheuk Or the like)

It is effective for improvement in resolution and cut-off property. In this respect, in particular, it is preferable that the photopolymerizable unsaturated compound (b) is both a compound represented by the general formula (I) and a compound represented by the general formula (II), a compound represented by the general formula (I) , The compound represented by the formula (II) and the compound represented by the formula (III).

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

As the compound represented by the general formula (I), for example, an average of 2 units of ethylene oxide is added to both ends of dimethacrylate or bisphenol A of polyethylene glycol to which an average of 1 unit of ethylene oxide is added to both ends of bisphenol A Dimethacrylate of a polyethylene glycol, dimethacrylate of polyethylene glycol to which an average of 5 units of ethylene oxide is added at both ends of bisphenol A, polyethylene glycol of an average of 7 units of ethylene oxide added to both ends of bisphenol A Dimethacrylate of dimethacrylate, dimethacrylate of polyalkylene glycol having an average of 6 units of ethylene oxide and an average of 2 units of propylene oxide added to both ends of bisphenol A, and ethylene oxide of 15 units on average at both ends of bisphenol A Of an average of 2 units of propylene oxide-added polyalkylene glycol Dimethacrylate, and the like.

Examples of the compound represented by the general formula (II) include tri (meth) acrylate in which ethylene oxide in a total of 3 units is added to trimethylol propane in an average, trimethylolpropane, and propylene oxide in an average of 3 units in total Tri (meth) acrylate, tri (meth) acrylate in which ethylene oxide is added in an average of 6 units to trimethylol propane, tri (meth) acrylate in which trimethylene oxide is added in an average of 9 units to trimethylolpropane, , Tri (meth) acrylates in which a total of 12 units of ethylene oxide are added to trimethylolpropane in an average, tri (meth) acrylates in which trimethylolpropane is augmented with ethylene oxide in an average of 21 units in total, tri Tri (meth) acrylate in which a total of 30 units of ethylene oxide is added. There.

Examples of the compound represented by the general formula (III) include urethane (meth) acrylate in which propylene glycol (meth) acrylate or polyethylene glycol (meth) acrylate or a compound containing both thereof is added to both terminals of isophorone diisocyanate, Acrylate.

Other examples of the photopolymerizable unsaturated compound (b) include 4-nonylphenylheptaethylene glycol dipropylene glycol (meth) acrylate (meth) acrylate Or 4-nonylphenyloctaethylene glycol (meth) acrylate, 4-nonylphenyltetraethylene glycol (meth) acrylate, and 4-octylphenylpentapropylene glycol (meth) acrylate.

Specific examples of other photopolymerizable unsaturated compounds (b) include, for example, 2-hydroxy-3-phenoxypropyl acrylate, half ester compounds of phthalic anhydride and 2-hydroxypropyl acrylate, and propylene oxide (P-hydroxyphenyl) propane di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylol propane tri (meth) acrylate, 2,2- Glycerol triacrylate, tetraacrylate of glycol having an average of 4 moles of ethylene oxide added to pentaerythritol, and polyfunctional (meth) acrylate of isocyanuric acid ester compound It can be given. These may be used alone or in combination of two or more.

The content of the photopolymerizable unsaturated compound (b) in the photosensitive resin element is preferably in the range of 5% by mass to 75% by mass. This content is preferably not less than 5% by mass, more preferably not less than 15% by mass, further preferably not less than 30% by mass from the viewpoint of suppressing the curing failure and the delay of the developing time. On the other hand, it is preferably not more than 75% by mass, more preferably not more than 60% by mass, further preferably not more than 50% by mass from the viewpoint of suppressing the delamination delay of the cold flow and the curing resist.

(c) a photopolymerization initiator

(c) The photopolymerization initiator is a compound that polymerizes monomers by light. As the photopolymerization initiator (c), for example, those conventionally used as a photopolymerization initiator for a photosensitive resin can be suitably used, but hexaaryl bisimidazole (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- Dimethoxyphenyl) -4 ', 5'-diphenylimidazolyl dimer, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) &Lt; / RTI &

2,4,5-tris- (o-chlorophenyl) -diphenylimidazolyl dimer, 2- (o-chlorophenyl) -bis-4,5- (3,4- dimethoxyphenyl) (2-fluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'- - (2, 3-difluoromethylphenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'- , 4-difluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer,

(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'- (3,4-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'- -Trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer,

(2,3,6-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis 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,

Tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2, 2'-bis- (2,3,4,5-tetrafluorophenyl) -4,4 ' , 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 etc. .

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

As the photopolymerization initiator (c), 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) Hydroxyphenyl) acridine, 9-ethylacridine, 9-chloroethylacridine, 9-methoxyacridine, 9-ethoxyacridine,

9- (4-methylphenyl) acridine, 9- (4-ethylphenyl) acridine, 9- , 9- (4-tert-butylphenyl) acridine, 9- (4-ethoxyphenyl) acridine, 9- Pyridine, 9- (4-chlorophenyl) acridine,

9- (3-tert-butylphenyl) acridine, 9- (3-methylphenyl) acridine, 9- 9- (3-bromophenyl) acridine, 9- (3-dimethylaminophenyl) acridine, 9- Pyridine) acridine, 9- (2-pyridyl) acridine, 9- (3-pyridyl) acridine, and 9- (4-pyridyl) acridine. Among them, 9-phenylacridine is preferable.

Examples of the pyrazoline compound include 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert- butylphenyl) Phenyl-3- (4-tert-butyl-styryl) -5- (4-tert- butylphenyl) 5- (4-tert-butyl-phenyl) -pyrazoline and 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline.

Examples of the photopolymerization initiator (c) other than the above include, for example, 2-ethyl anthraquinone, octaethyl anthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, , 3-diphenylanthraquinone, 1-chloroanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3- And quinones such as 3-chloro-2-methyl anthraquinone, quinones such as benzophenone, Michler's ketone [4,4'-bis (dimethylamino) benzophenone], and 4,4'-bis (diethylamino) And benzoin ethers such as benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin, benzyl dimethyl ketal, benzyl diethyl ketal, thioacetic acid and alkyl aminobenzoic acid Oxime esters such as 1-phenyl-1,2-propanedione-2-O-benzoin oxime and 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) .

Examples of combinations of the thioxantho acids described above with alkylaminobenzoic acid include a combination of ethylthioxanthone and ethyl dimethylaminobenzoate, a combination of 2-chlorothioxanthone and ethyl dimethylaminobenzoate, and a combination of iso A combination of propyl thioxanthone and ethyl dimethyl aminobenzoate, and the like. As the photo polymerization initiator (c), an N-aryl amino acid may be used. Examples of the N-aryl amino acid include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like. Among them, N-phenylglycine is particularly preferable.

The content of the photopolymerization initiator (c) in the photosensitive resin element is in the range of 0.01 mass% to 30 mass%, more preferably 0.05 mass%, still more preferably 0.1 mass%, still more preferably 15 mass% , And a more preferred upper limit is 10 mass%. The content of the photopolymerization initiator (c) is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity at the time of photopolymerization by exposure. On the other hand, at the time of photopolymerization, ) From the viewpoint of satisfactory light transmittance and good resolution and adhesiveness.

(d) solvent

As the solvent, a solvent such as a ketone solvent, an alcohol solvent, an ether solvent or an ester solvent is preferably used from the viewpoint of solubility. Examples of the ketone solvent include methyl ethyl ketone and acetone. Examples of the alcoholic solvent include methanol, ethanol, isopropyl alcohol, normal propyl alcohol and normal butanol. Particularly, ethanol is preferable from the viewpoints of solubility and coating film appearance. As the ethers, tetrahydrofuran, propylene glycol monomethyl ether and the like are used. Examples of the ester-based solvent include ethyl acetate and the like. As a nonpolar solvent, toluene or the like may be added in combination with the purpose of suppressing the generation of bubbles in the drying step.

Typically, the combination liquid is prepared by dissolving the resin for the binder (a), the photopolymerizable unsaturated compound (b), and the photopolymerization initiator (c) in an arbitrary order or in a batch (d) , And mixing.

The solvent (d) is preferably a ketone-based solvent in view of drying property, and it is particularly preferable that the solvent (d) contains acetone. In addition, the use of acetone in combination with an alcoholic solvent represented by ethanol is preferable from the viewpoint of improving the solubility of (b) a photopolymerizable unsaturated compound and / or (e) an optional additive (for example, a dye or the like) . Particularly, a combination system of acetone and ethanol as an alcohol-based solvent is preferable.

Further, the combined use of acetone and alcohol tends to decrease the viscosity of the combined solution, so that the solid content concentration in the combined solution can be set higher, and further, from the viewpoint of improving the productivity. The combination of acetone and alcohol is also preferable from the viewpoint of removing the solvent while keeping the surface of the dried film well in the drying step. That is, the combination of acetone and alcohol is preferable from the viewpoint of improving the productivity of the photosensitive resin element by increasing the application speed of the combination liquid. Here, &quot; keeping the surface of the dried film well &quot; means that the surface smoothness of the film surface is high and the appearance unevenness due to the naked eye is small.

(d) When the solvent contains acetone, the ratio of the mass of acetone to the total mass of the solvent is preferably 30 mass% or more, more preferably 40 mass% or more, further preferably 50 mass% or more, Particularly preferably not less than 60% by mass. On the other hand, the upper limit is preferably 98 mass% or less, more preferably 90 mass% or less, further preferably 80 mass% or less, particularly preferably 70 mass% or less. Setting the ratio of acetone to the same range as above is preferable from the viewpoint of improving the smoothness of the film surface after drying, from the viewpoint of reducing the uncoated portion such as pinholes in the drying step, and from the viewpoint of obtaining a good coated surface.

The alcohol-based solvent preferably contains ethanol as a main component (preferably 50 mass% or more, more preferably 70 mass% or more, further preferably 90 mass% or more and 100 mass% or less) desirable.

The viscosity of the combined liquid is preferably 500 Pa · sec to 4000 mPa · sec at 25 ° C.

(e) Other additives

The combination liquid may contain, in addition to the components (a) to (d), (e) other additives. Concretely, (e) Other additives include coloring materials such as dyes and pigments. As the same coloring material, a base dye may be used. Examples of the base dye include Basic Green 1 (CAS No.: 633-03-4), Malachite Green Oxalate [2437-29-8], Brilliant Green [633-03-4] , 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]. Of these, Basic Green 1, Malachite Green Oxalate, and Basic Blue 7 are preferred, and Basic Green 1 and Basic Blue 7 are particularly preferred from the viewpoint of improving color stability and exposure contrast.

The content of the coloring material in the photosensitive resin element is preferably 0.001 mass% to 1 mass%. When the content of the coloring material is 0.001% by mass or more, it is preferable because it has an effect of improving handling properties. On the other hand, when the content is 1% by mass or less, the effect of maintaining storage stability is preferable.

In addition, a coloring agent such as a coloring dye or the like may be contained in the combination liquid so that a visible image can be given by exposure. Examples of such a coloring dye include a leuco dye or a combination of a fluoro dye and a halogen compound.

Examples of the leuco dyes include tris (4-dimethylamino-2-methylphenyl) methane [leuco crystal violet], tris (4-dimethylamino-2-methylphenyl) methane [leuco malachite green] . Among them, leuco crystal violet is preferable because contrast is good.

Examples of the halogen compound include amides such as amyl bromide, isoamyl bromide, isobutyl bromide, ethylene bromide, diphenylmethyl bromide, benzene bromide, methylene bromide, tribromomethylphenylsulfone, tris (2,3 (Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p- chlorophenyl) ethane, hexachloroethane, Compounds and the like.

The content of the coloring agent in the photosensitive resin element is preferably independently 0.1% by mass to 10% by mass.

In order to improve the thermal stability and the storage stability of the photosensitive resin composition, it is preferable to incorporate at least one compound selected from the group consisting of radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles into the combination liquid .

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

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

Carboxybenzotriazoles include, for example, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, (N, N- dibutylamino) Triazole, N- (N, N-di-2-ethylhexyl) aminomethylene carboxybenzotriazole, N- (N, N-di- 2- hydroxyethyl) aminomethylene carboxybenzotriazole, N- , N-di-2-ethylhexyl) aminoethylene carboxybenzotriazole, and the like.

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

Other plasticizers may be added to the combination liquid, if necessary. Such plasticizers include, for example, polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, poly Sorbitan derivatives such as polyoxyethylene sorbitan laurate and polyoxyethylene sorbitan oleate; glycol esters such as polyoxyethylene monoethyl ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether and the like; Phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, triethyl acetylcitrate, tri-n-propyl acetylcitrate, , Propylene oxide is added to both sides of bisphenol A Propylene glycol, ethylene glycol by adding an ethylene oxide to each of both sides of the bisphenol A and the like.

The content of the plasticizer in the photosensitive resin element is preferably 0.1% by mass to 50% by mass, more preferably 1% by mass, and still more preferably 30% by mass. This content is preferably 0.1% by mass or more from the viewpoint of suppressing the delay in developing time and imparting flexibility to the cured film. On the other hand, from the viewpoint of suppressing the curing and the edge fuse from which the photosensitive layer seeps out from the roll cross section, By mass or less.

The combination solution may contain other antioxidant, if necessary. Examples of the antioxidant include triphenylphosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (monononylphenyl) phosphite, and bis (monononylphenyl) Phosphite, and the like.

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, more preferably 0.01% by mass, and still more preferably 0.3% by mass. When the content is 0.01% by mass or more, it is preferable that the effect of excellent color stability of the photosensitive resin composition is satisfactorily exhibited and the sensitivity of the photosensitive resin composition upon exposure is favorable. On the other hand, when the content is less than 0.8% By weight, the coloring property is suppressed, so that the color stability is improved and the adhesion is also improved, which is preferable.

The support layer supports the photosensitive resin layer formed thereon. The manufacturing method of the photosensitive resin element may include a step of forming a protective layer on the opposite side of the support layer side of the photosensitive resin layer as desired.

The support layer is preferably a transparent support layer that transmits light emitted from the exposure light source. Examples of the support layer include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer Film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. The support layer is preferably a polyester film from the viewpoints of solvent resistance, heat resistance, transparency and the like. As these films, stretched films can be used if necessary. The haze of the support layer is preferably 5 or less. The thickness of the support layer is preferably from 10 탆 to 30 탆, more preferably from 12 탆 to 16 탆 in order to maintain the strength, while being thin is advantageous from the viewpoints of image forming property and economical efficiency. A particularly preferable support layer is a polyester film having a thickness of 12 to 16 탆.

From the viewpoint of the occurrence of wrinkles in the laminate, the heat shrinkage rate in the TD direction of the polyester film peeled and dried from the photosensitive resin element is preferably 3.2% or less. By &quot; dried &quot; is meant that the volatile components (e.g., residual solvent) in the polyester film are substantially removed. Such a drying state can be obtained, for example, by heating at normal pressure, at 200 占 폚 for 30 minutes, then at normal pressure, and at room temperature (for example, 20 占 폚) for 30 minutes. The heat shrinkage ratio in the TD direction is a value measured by a method described in the section of [Examples] to be described later or a method understood by those skilled in the art that is equivalent thereto.

It is preferable that the protective layer has a property that the protective layer side is sufficiently smaller than the support layer and can easily peel off from the support layer in adhesion to the photosensitive resin layer. For example, a polyethylene film, a polypropylene film and the like can be preferably used as a protective layer. As the protective layer, for example, a film having excellent peelability as disclosed in JP-A-59-202457 can be used. The thickness of the protective layer is preferably 10 mu m to 100 mu m, more preferably 10 mu m to 50 mu m.

In the method for producing a photosensitive resin element, the step of applying the combination solution onto the support layer, drying the solution, and forming the photosensitive resin element on the support layer may be carried out by the application means and the drying means as desired. As the application means, for example, a spin coater, a die coater, a spray coater, an immersion, a printing, a blade coater, a roll coating and the like can be used. As the drying means, there can be used, for example, air drying, hot air drying, light irradiation, hot plate, inert oven, heating oven capable of setting a temperature program, and the like. The combination of a plurality of components contained in the combination liquid and the application of the combination liquid and drying can be carried out in an atmosphere of air or an inert gas such as nitrogen or argon. At this time, by controlling the temperature and the drying time, the amount of the residual solvent in the photosensitive resin element can be controlled in a desired range.

The photosensitive resin element produced by the above-described manufacturing method can be used for various purposes such as manufacturing of a printed wiring board, manufacture of a lead frame for mounting an IC chip, precision processing of a metal foil such as a metal mask, a ball grid array (BGA) Manufacture of a package such as a package (CSP), manufacture of a tape substrate such as chip on film (COF) or tape automated bonding (TAB), manufacture of semiconductor bumps, indium tin oxide It is desirable to use it for the production of barrier ribs of flat panel displays such as shields.

According to the photosensitive resin element of the present embodiment, the appearance of the DF formed from the photosensitive resin element useful for forming a printed circuit can be satisfactorily improved.

Example

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to the examples unless it goes beyond the gist of the present invention.

[Examples 1 to 14 and Comparative Examples 1 to 4]

The components of the photosensitive resin composition shown in Table 1 were combined, dissolved in a dissolution tank with stirring, passed through a filter, and the combined solution was filtered. Subsequently, the combined solution was sent to a die coater by a pump, uniformly applied on a polyethylene terephthalate film as a support layer, and sent to a drying zone to dry the solvent. Thereafter, the laminate was laminated with a polyethylene film as a protective layer to obtain DF having the thickness of the photosensitive resin layer described in Table 1. [ The film thickness of DF was 40 탆.

In this process, edge fuse evaluation and cut chip evaluation were carried out by the following methods. The weight average molecular weight of the resin was measured by the following method. The results are described below.

GR-16 (16 占 퐉 thickness) manufactured by Teijin Co., Ltd. was used as the polyethylene terephthalate film as the support layer, and GF-18 (19 占 퐉 Thickness) was used.

(1) Evaluation of edge fuse

A combination liquid is applied on a polyethylene terephthalate film as a support layer using a die coater and the solvent is dried to form a photosensitive resin layer and then a polyethylene film as a protective layer is further laminated on the photosensitive resin layer to form a support layer / To obtain a laminate having a three-layer structure of a layer / protective layer. This laminate was wound up to form a roll laminate (which was processed to a width of 500 mm and a winding length of 150 m using a slitter), and this was stored at 20 占 폚. From the start of storage, the number of days until the penetration of the photosensitive resin layer from the end face of the roll was visually confirmed was measured and evaluated by the following rank.

A: The permeation of the photosensitive resin layer can be seen in over 50 days.

B: From 30 days to less than 50 days, the permeation of the photosensitive resin layer can be seen.

C: The permeation of the photosensitive resin layer can be seen from 10 days to less than 30 days.

D: Less than 10 days, the permeation of the photosensitive resin layer can be seen.

(2) Cut-chip evaluation

A combination liquid was applied on a polyethylene terephthalate film as a support layer using a die coater, the solvent was dried, and then a polyethylene film as a protective layer was further laminated to obtain a roll surface obtained by a three-layer structure of a support layer / photosensitive resin layer / A sample of 10 cm x 10 cm was cut out from the laminate. The protective layer was peeled off from the cut sample, and the laminate was punched five times from the photosensitive resin layer side with an NT cutter (using a new cutter blade). The portion where the cutter was inserted and the surface of the cutter blade were visually observed to evaluate the occurrence status of the photosensitive resin layer chip as the following rank.

A: There was no chip of the photosensitive resin layer at the stuck portion, and no chips of the photosensitive resin layer adhered to the cutter blade at all.

B: The chip of the photosensitive resin layer was not attached to the cutter blade, but a very small amount of the photosensitive resin layer chip was generated at the stuck portion.

C: A small amount of chips of the photosensitive resin layer was formed at the stuck portion, and a small amount of chips of the photosensitive resin layer was attached to the cutter edge.

D: A chip of the photosensitive resin layer was remarkably generated at the stuck portion, and a chip of the photosensitive resin layer was remarkably attached 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 (in terms of standard polystyrene). The column used for the measurement was Shodex 805M / 806M series manufactured by Showa Denko KK. Standard monodisperse polystyrene was Shodex STANDARD SM-105 manufactured by Showa Denko K.K., and the developing solvent was N-methyl-2- Pyrrolidone, and the detector used was Shodex RI-930 manufactured by Showa Denko.

The acid equivalent was measured by a potentiometric titration method (Hirunuma Automatic Titration Apparatus (COM-555) manufactured by Hiranuma Industrial Co., Ltd., using 0.1 mol / l of sodium hydroxide).

(4) Heat shrinkage ratio of the polyester film in the TD direction

A combination liquid was applied on a polyethylene terephthalate film (as a polyester film) as a support layer using a die coater, and the solvent was dried, and then a polyethylene film as a protective layer was further laminated to obtain a support layer / photosensitive resin layer / protective layer 3 The protective layer and the photosensitive resin layer were peeled off from the roll-like laminate obtained in the layer structure to obtain a polyethylene terephthalate film as a supporting layer. A test piece having a width of 20 mm and a length of 200 mm was cut out from the polyethylene terephthalate film and two test points were placed at the center of the test piece at a distance of 100 mm and the test piece was vertically suspended in a hot air circulating type thermostat, Lt; 0 &gt; C for 30 minutes. After heating, it was allowed to stand at room temperature for 30 minutes at room temperature, and the distance between the gauges was measured to calculate the heat shrinkage rate.

(5) The mass ratio of the residual solvent in the photosensitive resin layer

The mass ratio of the residual solvent was obtained by gas chromatography measurement of the photosensitive resin layer obtained by peeling the protective layer and the support layer from the roll-like laminate formed in the same manner as in the above (4).

(Comparative Example 4)

The combined solution of the photosensitive resin composition of Comparative Example 1 was uniformly coated on a polyethylene terephthalate film (haze: 1.8) having a thickness of 20 占 퐉 and dried with a hot air blow dryer at 100 占 폚 for 10 minutes to obtain a photosensitive film. The thickness of the photosensitive resin layer after drying was 25 占 퐉. The solid mass ratio was 43%, and the residual acetone mass ratio was 0%. The evaluation results of the DF are as follows.

Edge fuse evaluation: B, cut chip evaluation: D.

<Symbol description>

P-1: acetone / ethanol mixed solution (solvent mass ratio: acetone / ethanol = 80/20) of a ternary copolymer of methyl methacrylate of 67 mass%, methacrylic acid of 23 mass% and butyl acrylate of 10 mass% Mass ratio 34%, weight average molecular weight 200,000, acid equivalent 374)

P-2: acetone / ethanol mixed solution (solvent mass ratio: acetone / ethanol = 75/25) of a ternary copolymer of 50 mass% of methyl methacrylate, 25 mass% of methacrylic acid and 25 mass% of styrene, Ratio 47%, weight average molecular weight 50,000, acid equivalent 344)

P-3: A mixed solution of methyl ethyl ketone and ethanol (solvent mass ratio: methyl ethyl ketone / ethanol = 75/25) of a ternary copolymer of 50 mass% of methyl methacrylate, 25 mass% of methacrylic acid and 25 mass% ), A solid mass ratio of 45%, a weight average molecular weight of 50,000, an acid equivalent of 344)

M-1: Dimethacrylate of polyethylene glycol (BPE-200 manufactured by Shin Nakamura Chemical Co., Ltd.) to which 2 mols of ethylene oxide was added to both ends of bisphenol A on average,

M-2: Dimethacrylate of polyethylene glycol (BPE-500 manufactured by Shin Nakamura Chemical Co., Ltd.) to which an average of 5 moles of ethylene oxide was added to both ends of bisphenol A,

M-3: Dimethacrylates of polyalkylene glycols to which an average of 2 moles of propylene oxide and an average of 6 moles of ethylene oxide were added to both ends of bisphenol A

M-4: A polyalkylene glycol dimethacrylate having an average of 3 moles of ethylene oxide added to both ends of a polypropylene glycol to which an average of 12 moles of propylene oxide was added,

M-5: acrylate (A-TMPT-3EO manufactured by Shin-Nakamura Chemical Co., Ltd.) to which trimethylolpropane had been added with 3 moles of ethylene oxide on average,

M-6: 4-nonylphenylheptaethylene glycol dipropylene glycol acrylate

M-7: Urethane acrylate compound in which polypropylene glycol acrylate is added at both terminals to isophorone diisocyanate (R ₇ = R ₈ = H, R ₉ , R ₁₀ , R ₁₁ = CH ₃ , n _{5 = n 6 = 0, n} 7 = n 8 = 12 in the compound)

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 added

A-4: Polypropylene glycol having an average of 2 moles of propylene oxide added to both ends of bisphenol A

A-5: IRGANOX245 manufactured by Ciba Specialty Chemicals Co., Ltd.

A-6: Nyukol 3-85 (manufactured by Nippon Petrochemical Co., Ltd.)

S-1: Ethanol

S-2: Propylene glycol monomethyl ether

S-3: Toluene

Industrial availability

The photosensitive resin element according to the present invention can be used for manufacturing a printed wiring board, manufacturing a lead frame for mounting an IC chip, a metal foil precision processing such as a metal mask production, a package such as BGA or CSP, , The manufacture of semiconductor bumps, the fabrication of barrier ribs for flat panel displays such as ITO electrodes or address electrodes, electromagnetic shields and the like.

Claims (10)

A photosensitive resin element comprising a support layer and a photosensitive resin layer on the support layer,
The above-
(b) a photopolymerizable unsaturated compound, (c) a photopolymerization initiator, and (d) a solvent, wherein the content of the carboxyl group is 100 to 600 in terms of an acid equivalent and the weight average molecular weight is 5,000 to 500,000. and,
The photosensitive resin layer contains the solvent (d) in an amount of 0.001 mass% or more and 1 mass% or less based on the mass of the photosensitive resin layer,
Wherein the photosensitive resin layer contains at least one compound selected from the following formulas (I) to (III) as the (b) photopolymerizable unsaturated compound.
[Chemical Formula 1]

(Wherein, R ₁ and R ₂ each independently represents a hydrogen atom or a methyl group, A is C ₂ H ₄ represents a group, B represents a group _{CH 2 CH (CH 3),} m 1 + m 2 is 2 to 30 of an integer, m ₃ + m ₄ is an integer from 0 to 30, and m ₁ and m ₂ are each independently an integer of 1 ~ 29, m ₃ and m ₄ are each independently an integer from 0 to 29, - (AO) - and - (BO) - may be random or block, and in the case of a block, any of - (AO) - and - (BO) - may be a bisphenyl group side.
(2)

(Wherein 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 represent a hydrogen atom or a methyl group, and D represents an alkylene group having 2 to 6 carbon atoms N ₁ , n ₂ and n ₃ are integers of 0 or more satisfying n ₁ + n ₂ + n ₃ = 3 to 60 and n ₄ is 0 or 1, provided that a plurality of D in the formulas May be the same or different, and the repeating structure of - (OD) - may be random or may be a block)
(3)

(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 represents 0 ~ a 30 integer, n ₇ + n ₈ is an integer from 0 to 30, n ₅ and n ₆ are each independently an integer from 0 to 30, n ₇ and n ₈ are each independently from 0 to 30, integer , - (OA ₁₎ -, and - (OB ₁₎ - repeatedly arranged in a unit is may be either be a random and block, in the case of the block, - (OA ₁₎ -, and - (OB ₁₎ - of which one urethane gicheuk Or the like) The method according to claim 1,
(D) a photosensitive resin element containing propylene glycol monomethyl ether as a solvent. The method according to claim 1,
(D) a photosensitive resin element containing toluene as a solvent. The method according to claim 1,
(D) a photosensitive resin element containing acetone as a solvent. 5. The method according to any one of claims 1 to 4,
The photosensitive resin element containing the compound represented by the general formula (I) and the compound represented by the general formula (II) as the photopolymerizable unsaturated compound (b). 5. The method according to any one of claims 1 to 4,
The photosensitive resin element containing as the photopolymerizable unsaturated compound (b) the compound represented by the general formula (I) and the compound represented by the general formula (III). 5. The method according to any one of claims 1 to 4,
The photosensitive resin element containing as the photopolymerizable unsaturated compound (b) the compound represented by the general formula (II) and the compound represented by the general formula (III). 8. The method according to any one of claims 1 to 7,
Wherein the support layer is a polyester film. 9. The method of claim 8,
And the heat shrinkage rate in the TD direction of the polyester film peeled and dried from the photosensitive resin element is 3.2% or less. 10. The method according to claim 8 or 9,
Wherein the polyester film has a thickness of 12 탆 to 16 탆.