TW201525615A - Photosensitive resin element - Google Patents

Abstract

Provided is a photosensitive element which has an aesthetic appearance, long product life, and which reduces defects caused by resist chips in the lamination step when fabricating printed circuit boards. This photosensitive resin element contains a support layer and a photosensitive resin layer on top of said support layer. The photosensitive resin layer contains: (a) a binder resin having a carboxyl group content of 100-600 (acid equivalent), and a weight-average molecular weight of 5,000-500,000; (b) a photopolymerizable unsaturated compound; (c) a photopolymerization initiator; and (d) a solvent. The photosensitive resin layer contains 0.001 mass % to 1 mass % of the solvent (d) with reference to the mass of the photosensitive resin layer, and the photosensitive resin layer contains at least one compound selected from general formulae (I) to (III) as (b) the polymerizable unsaturated compound.

Description

Photosensitive resin element

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

The method for producing a photosensitive resin composition for producing a printed circuit generally comprises the steps of: a resin for a binder, an unsaturated compound capable of photopolymerization, a photopolymerization initiator, a dye, etc. The base ketone is a solvent which is represented by a ketone, an ester represented by ethyl acetate, and an ether represented by tetrahydrofuran, and the mixture is uniformly stirred and dissolved. For example, Patent Document 1 describes a solution prepared by using a mixed solvent of methyl ethyl ketone / 1-methoxy-2-propanol = 2 / 1 (weight ratio). Patent Document 1 discloses that such a solution is uniformly applied onto a polyester film or the like as a support layer by using a die coater or the like, and the solvent is dried and removed in a drying step to obtain a photosensitive resin composition. Further, a laminate having a three-layer structure including a layer of the photosensitive resin composition may be obtained by laminating a polyethylene film or the like as a protective layer. These laminates are generally referred to as dry film photoresists (hereinafter abbreviated as "DF").

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 11-143069

However, in the prior manufacturing method in which methyl ethyl ketone is used as a main component of the solvent, the solubility of the resin for the binder and the unsaturated compound which can be photopolymerized, and dyeing The solubility of additives such as materials is insufficient, and it often occurs when the filter is clogged with the filter solution. Moreover, there is still room for improvement in the blending liquid from the viewpoint of reducing the minute irregularities on the surface of the produced DF and reducing the frequency of observation as unevenness in the visual inspection of the appearance.

The inventors of the present invention have found that when a large amount of a solvent remains in the photosensitive resin composition after drying, when a DF is formed from the photosensitive resin composition, a photosensitive layer is produced in the DF wound into a roll. The phenomenon that the edge oozing out from the end surface of the roll melts over time, thereby causing a problem that the life of the product is shortened. On the other hand, if the solvent remaining in the photosensitive resin composition after drying is too small, the following problem occurs: When the photosensitive layer is cut into the cutting blade, chips of the photosensitive layer are generated. The dicing blade is used in the laminating step, and if the chips of the photosensitive layer are generated, the swarf may adhere to the substrate again and cause a defect.

Therefore, the problem of the present invention is to provide a photosensitive resin element which is excellent in appearance, long in product life, and which reduces defects caused by photoresist chips in the laminating step in the production of a printed circuit board.

In order to solve the above problems, the inventors of the present invention have conducted intensive studies, and as a result, it has been found that a photosensitive resin layer having a specific composition and a residual amount of a solvent is controlled to a specific range, and the appearance is good and the life of the product is long, and lamination can be reduced. The present invention has been accomplished in the step due to defects caused by the photoresist chips. That is, the present invention is as follows.

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

(wherein R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, A represents C ₂ H ₄ , B represents a CH ₂ CH(CH ₃ ) group, and m ₁ + m ₂ is an integer of 2 to 30, m ₃ + m ₄ is an integer from 0 to 30, m ₁ and m ₂ are each independently an integer from 1 to 29, and m ₃ and m ₄ are each independently an integer from 0 to 29, -(AO)- and -(BO)- The arrangement of the repeating units may be random or block, and in the case of a block, any of -(AO)- and -(BO)- may be on the biphenyl side) [Chemical 2]

(wherein R ₃ represents a hydrogen atom or a one-valent 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 a hydrocarbon having 2 to 6 carbon atoms; The base, 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, wherein a plurality of Ds in the formula may be the same Differently, the repeating structure of -(OD)- can be random or block)

(wherein R ₇ to R ₁₁ each independently represent a hydrogen atom or a methyl group, A ₁ represents a C ₂ H ₄ group, B ₁ represents a CH ₂ CH(CH ₃ ) group, and n ₅ + n ₆ is 0 to 30 Integer, n ₇ + n ₈ is an integer from 0 to 30, n ₅ and n ₆ are each an integer of 0 to 30, and n ₇ and n ₈ are each independently an integer of 0 to 30, -(OA ₁ )-and- The arrangement of the repeating units of (OB ₁ )- may be random or block, and in the case of a block, any of -(OA ₁ )- and -(OB ₁ )- may be used in the urethane. Ester side)

[2] The photosensitive resin element according to the above aspect 1, which comprises propylene glycol monomethyl ether as the solvent (d).

[3] The photosensitive resin element according to the above aspect 1, which comprises toluene as the solvent (d).

[4] The photosensitive resin element according to the above aspect 1, which comprises acetone as the solvent (d).

[5] The photosensitive resin element according to any one of the above aspects 1 to 4, which comprises the compound represented by the formula (I) and the compound represented by the formula (II) as the (b) Photopolymerized unsaturated compounds.

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

[7] The photosensitive resin element according to any one of the above aspects 1 to 4, which comprises the compound represented by the formula (II) and the compound represented by the formula (III) as the (b) Photopolymerized unsaturated compounds.

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

[9] The photosensitive resin element according to the above aspect 8, wherein a heat shrinkage ratio in a TD (Transverse Direction) direction of the polyester film peeled off from the photosensitive resin element and dried is 3.2% or less.

[10] The photosensitive resin element according to the above aspect 8 or 9, wherein the polyester film has a film thickness of from 12 μm to 16 μm.

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

According to the present invention, there is provided a photosensitive resin element which is excellent in appearance, long in product life, and which can reduce defects caused by photoresist chips in a laminating step in producing a printed wiring board. Moreover, according to a specific aspect of the present invention, a method of producing the above-mentioned photosensitive resin element is provided.

Hereinafter, an exemplary embodiment (hereinafter, simply referred to as "embodiment") for carrying out the invention will be described in detail. The present invention is not limited to the embodiment, and various modifications can be made without departing from the spirit and scope of the invention.

The embodiment of the present invention is a photosensitive element comprising a support layer and a photosensitive resin element of a photosensitive resin layer on the support layer, and the photosensitive resin layer contains (a) a carboxyl group content in terms of acid equivalent a resin for a binder having a weight average molecular weight of from 5,000 to 500,000, (b) a photopolymerizable unsaturated compound, (c) a photopolymerization initiator, and (d) a solvent, wherein the photosensitive resin layer is 100 to 600 The (d) solvent is contained in an amount of 0.001% by mass or more and 1% by mass or less based on the mass of the photosensitive resin layer, and the photosensitive resin layer contains one selected from the following general formulae (I) to (III). The above compounds are used as the (a) photopolymerizable unsaturated compound.

[Chemical 4]

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

(wherein R ₃ represents a hydrogen atom or a one-valent 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 a hydrocarbon having 2 to 6 carbon atoms; The base, 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, wherein a plurality of Ds in the formula may be the same Differently, the repeating structure of -(OD)- can be random or block)

(wherein R ₇ to R ₁₁ each independently represent a hydrogen atom or a methyl group, A ₁ represents a C ₂ H ₄ group, B ₁ represents a CH ₂ CH(CH ₃ ) group, and n ₅ + n ₆ is 0 to 30 Integer, n ₇ + n ₈ is an integer from 0 to 30, n ₅ and n ₆ are each an integer of 0 to 30, and n ₇ and n ₈ are each independently an integer of 0 to 30, -(OA ₁ )-and- The arrangement of the repeating units of (OB ₁ )- may be random or block, and in the case of a block, any of -(OA ₁ )- and -(OB ₁ )- may be used in the urethane. Ester side.)

The photosensitive resin element can be produced, for example, by a method comprising the steps of: (a) a binder resin having a carboxyl group content of from 100 to 600 in terms of acid equivalent weight and a weight average molecular weight of from 5,000 to 500,000, and (b) light-receiving a step of obtaining a blending solution by polymerizing an unsaturated compound, (c) a photopolymerization initiator, (d) a solvent, and optionally (e) other additives, and applying the blending solution to the support layer, and then applying the blending solution to the support layer, and then The step of drying the preparation liquid to form a photosensitive resin layer on the support layer.

In the present embodiment, the amount of the solvent remaining in the photosensitive resin layer (for example, the drying of the preparation liquid in the above-mentioned method and the film formation) is 0.001% by mass or more and 1% by mass based on the photosensitive resin layer. the following. If it exceeds 1% by mass, the photosensitive resin is used. When the composition is made into DF, there is a problem that in the DF wound into a roll shape, a phenomenon in which the edge of the photosensitive layer oozes from the end face of the roll is melted over time, and the life of the product is shortened. On the other hand, if it is less than 0.001% by mass, there is a problem in that when the dicing blade is inserted into the photosensitive resin layer, chips of the photosensitive resin layer are generated. The dicing blade is used in the laminating step, and if chips of the photosensitive resin layer are generated, the swarf may adhere to the substrate again, which may cause a defect. The amount of the solvent remaining in the photosensitive resin layer is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and still more preferably 0.05% by mass or more. Moreover, the amount of the solvent remaining in the photosensitive resin layer is preferably 0.7% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0.2% by mass or less. The amount and type of the solvent remaining in the photosensitive resin layer are values measured by the method described in the following [Examples] or the method considered by the practitioner to be equivalent to the method.

In the present embodiment, as a method of controlling the amount of the solvent remaining in the photosensitive resin layer, the drying conditions (temperature and time) of the photosensitive resin composition when the photosensitive resin layer is formed are adjusted. 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 person who changes properties due to receiving light. The photosensitive element may be, for example, a film, a plate, a sheet, a roll, a molded article, or the like, and may be, for example, a photosensitive resin element including a photosensitive resin or a photosensitive resin. More specifically, a composition containing a photosensitive resin (referred to as "photosensitive resin composition" in the present invention) is applied onto a support layer such as a film to form a layer containing the photosensitive resin composition. The layer obtained by drying the photosensitive resin composition (in the present invention, collectively referred to as "photosensitive resin layer") is laminated on the support layer, whereby the photosensitive resin laminate obtained as a photosensitive property A resin element is preferred. The present invention provides such a photosensitive resin element as a laminate having a photosensitive resin layer and a support layer. Further, the photosensitive resin composition may be in any state (for example, a solution, a solid, an emulsion, a suspension, etc.), preferably a solution, an emulsion, a suspension, or the like (also referred to as "blending liquid" in the present invention). ). Further, borrow A photosensitive resin as a photosensitive resin laminate obtained by laminating a protective layer (for example, a protective film, a spacer film, or the like) by laminating a portion of the photosensitive resin layer between the support layer and the photosensitive resin layer The roller is more preferably a photosensitive resin element, and is preferably in the form of a dry film roll in which the entire photosensitive resin roll or the photosensitive resin layer is partially dried.

The thickness of the photosensitive resin element is preferably 5 μm to 50 μm. The thickness of the photosensitive resin element is preferably adjusted to 5 μm or more from the viewpoint of the accuracy of applying the preparation liquid onto the support layer, and on the other hand, from the viewpoint of the drying property in the drying step, The optimum is adjusted to 50 μm or less. The thickness of the photosensitive resin element is more preferably from 30 μm to 50 μm.

In addition, the thinner the photosensitive resin layer is, the higher the resolution is, and the thicker the photosensitive resin layer is, the larger the film strength is. Therefore, the film thickness of the photosensitive resin layer can be appropriately selected depending on the application. For example, the photosensitive resin layer may have a film thickness of 15 μm to 50 μm, for example, 15 μm to 30 μm, or 30 μm to 40 μm, or 40 μm to 50 μm.

<Photosensitive Resin Composition>

The photosensitive resin composition preferably contains (a) a binder resin, (b) a photopolymerizable unsaturated compound, (c) a photopolymerization initiator, and (d) a solvent, and optionally (e) ) other additives. The photosensitive resin composition is preferably a blending liquid.

In the case where the photosensitive resin composition is a preparation liquid, in the method for producing a photosensitive resin element, the ratio of all the solid content in the preparation liquid is preferably 30% by mass to 80% by mass. The ratio of all the solid content components in the preparation liquid is, for example, the solid content concentration of the preparation liquid obtained by dissolving the components (a) to (c) and (e) in the solvent (d). The ratio of all the solid content components is preferably 30% by mass or more from the viewpoint of controlling the amount of the solvent to be dried and evaporated to obtain an effect of increasing the coating speed, and on the other hand, from the viewpoint of the uniformity of the preparation liquid. In other words, it is preferably 80% by mass or less. The ratio of all the solid content in the preparation liquid is more preferably 40% by mass or more, further preferably 50% by mass or more, and more preferably 70% by mass or less, and still more preferably 60% by mass or less. It is preferable to set the ratio of all the solid components to such a range from the viewpoint of improving, that is, increasing From the viewpoint of the smoothness of the surface of the film after drying, or the viewpoint of reducing the uncoated portion such as needle-like pores in the drying step, and obtaining a favorable coated surface.

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

(a) Resin for resin

(a) The resin for the binder is a resin having a carboxyl group content of from 100 to 600 in terms of acid equivalent weight and a weight average molecular weight of from 5,000 to 500,000, and is used as a binder.

(a) The binder resin has a carboxyl group in order to impart developability or releasability to an alkaline aqueous solution to the photosensitive resin element. The content of the carboxyl group is preferably 100 or more in terms of acid resistance, and is preferably 600 or less from the viewpoint of developability and peelability from the viewpoint of the development resistance, the resolution, and the adhesion. In the present invention, the acid equivalent means a mass (gram) of a resin having 1 equivalent of a carboxyl group. In the present invention, the acid equivalent is measured by a potentiometric titration method (for example, using a flat-automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd., and using 0.1 mol/L of sodium hydroxide).

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

Further, a preferred 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, more preferably 5 or less. In the present invention, the molecular weight and molecular weight distribution are values measured by gel permeation chromatography and converted by standard polystyrene.

Typically, (a) the resin for a binder 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 following first monomers and at least one of the following second monomers.

The first monomer is a monomer having a carboxyl group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, and norbutene. Diacid anhydride, maleic acid half ester, and the like. Among them, (meth)acrylic acid is particularly preferred. In the present specification, the term "(meth)acrylic acid" means acrylic acid or methacrylic acid.

The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and (meth)acrylic acid. Butyl ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid ring An ester of vinyl alcohol such as hexyl ester, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate or vinyl acetate; (meth)acrylonitrile, styrene monomer (for example, styrene) And a styrene derivative which can be polymerized) and the like. Among them, methyl (meth)acrylate, n-butyl (meth)acrylate, styrene, and benzyl (meth)acrylate are preferred, and styrene is particularly preferably used from the viewpoint of resolution.

(a) The binder resin is preferably synthesized by mixing the first monomer and the second monomer and diluting with a solvent such as acetone, methyl ethyl ketone or isopropyl alcohol. A suitable amount of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile is added to the resulting solution and stirred under heating. There is also a case where a part of the mixture is added dropwise to the reaction liquid for synthesis. After the completion of the reaction, the solvent is added to the (a) binder resin to adjust the concentration to a desired concentration. As the synthesis method, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

In (a) the resin for a binder, a 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% by mass to 35% by mass, and the second monomer is 65% by mass to 85% by mass.

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

In the present embodiment, the content of the (a) binder resin in the photosensitive resin element (wherein the content is based on the total amount of the solid content of the photosensitive resin element; unless otherwise specified) The same is true for each component contained) in the range of 20% by mass to 90% by mass, preferably the lower limit is 25% by mass, preferably the upper limit is 75% by mass, the lower limit is more preferably 40% by mass, and the upper limit is more preferably 65% by mass. %. The content is preferably 20% by mass or more from the viewpoint of maintaining alkali developability. On the other hand, it is preferable that the photoresist pattern formed by exposure sufficiently exhibits performance as a photoresist. 90% by mass or less.

(b) Photopolymerizable unsaturated compounds

(b) The photopolymerizable unsaturated compound is, for example, a monomer having an addition polymerizable property due to an ethylenically unsaturated bond. The ethylenically unsaturated bond is preferably a terminal ethylenically unsaturated group.

(b) The photopolymerizable unsaturated compound contains one or more compounds selected from the group consisting of the following general formulae (I) to (III):

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

(wherein R ₃ represents a hydrogen atom or a one-valent 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 a hydrocarbon having 2 to 6 carbon atoms; The bases, n ₁ , n ₂ and n ₃ are integers of 0 or more of n ₁ + n ₂ + n ₃ = 3 to 60, and n ₄ is 0 or 1, wherein a plurality of Ds in the formula may be the same Different, -(OD)- the repeating structure may be random or block) [Chemical 9]

(wherein R ₇ to R ₁₁ each independently represent a hydrogen atom or a methyl group, A ₁ represents a C ₂ H ₄ group, B ₁ represents a CH ₂ CH(CH ₃ ) group, and n ₅ + n ₆ is 0 to 30 Integer, n ₇ + n ₈ is an integer from 0 to 30, n ₅ and n ₆ are each an integer of 0 to 30, and n ₇ and n ₈ are each independently an integer of 0 to 30, -(OA ₁ )-and- The arrangement of the repeating units of (OB ₁ )- may be random or block, and in the case of a block, any of -(OA ₁ )- and -(OB ₁ )- may be used in the urethane. Ester side)

In the case of the case, it is effective for improving the resolution or improving the chipping property. Further, from this point of view, it is particularly preferred that (b) the photopolymerizable unsaturated compound comprises both the compound represented by the formula (I) and the compound represented by the formula (II), and the formula (I). And a compound represented by the formula (III), and a compound represented by the formula (III) and a compound represented by the formula (III).

In particular, (b) the case where the photopolymerizable unsaturated compound contains a large amount of an ethylene glycol chain or a propylene glycol chain is more effective for improving chip cutting property. From this point of view, in the general formula (I), m ₁ + m ₂ and m ₃ + m ₄ are each preferably 8 to 30, more preferably 10 to 30, and further, m ₁ + m ₂ + m. ₃ + m _{4 is} preferably 8 to 60, more preferably 10 to 60. Further, in the general formula (II), the carbon number of D is preferably 2 or 3, more preferably 2, and more preferably n ₁ + n ₂ + n _{3 from} the viewpoint of chipping property and resolution. Good for 3~50, better for 3~35.

The compound represented by the formula (I) is, for example, a dimethacrylate of polyethylene glycol or an bisphenol A obtained by adding an average of one unit of ethylene oxide to both ends of bisphenol A. The two ends are respectively added with an average of two units of ethylene oxide to form a polyethylene glycol dimethacrylate, and an average of five units of ethylene oxide is added to both ends of the bisphenol A to form a poly Ethylene glycol dimethacrylate, dimethyl acrylate of ethylene glycol formed by adding an average of 7 units of ethylene oxide to both ends of bisphenol A, respectively, at the two ends of bisphenol A Adding an average of 6 units of ethylene oxide and an average of 2 units of propylene oxide to a polyalkylene glycol dimethacrylate, adding an average of 15 units of epoxy to both ends of bisphenol A Ethane and an average of two units of propylene oxide, such as dialkyl diol diol dimethacrylate.

The compound represented by the formula (II) is, for example, preferably a tri(meth)acrylate obtained by adding 3 units of ethylene oxide to an average of trimethylolpropane. Hydroxymethylpropane is added to a total of three units of propylene oxide to form a tri(meth) acrylate, and trimethylolpropane is added in an average of 6 units of ethylene oxide. (Meth) acrylate, trimethylolpropane addition to a total of 9 units of ethylene oxide to a total of 9 (meth) acrylate, trimethylolpropane addition to average 12 a unit of ethylene oxide to a tris(meth)acrylate, a trimethylolpropane addition to an average of 21 units of ethylene oxide to a tris(meth)acrylate, p-trihydroxyl Methylpropane is added to a total of 30 units of ethylene oxide to form a tris(meth)acrylate.

As the compound represented by the formula (III), for example, propylene glycol (meth) acrylate or polyethylene glycol (meth) acrylate or a compound containing the two is added to both ends of the isophorone diisocyanate. Amino methacrylate (meth) acrylate.

Other examples of the (b) photopolymerizable unsaturated compound are, for example, 4-mercaptophenyl 7 from the viewpoint of high resolution, peeling property of the cured film, and softness of the cured film. Ethylene glycol dipropylene glycol (meth) acrylate or 4-mercaptophenyl octaethylene glycol (meth) acrylate, 4-mercaptophenyltetraethylene glycol (meth) acrylate, 4-octyl Phenyl pentapropylene glycol (meth) acrylate, and the like.

Specific examples of the other (b) photopolymerizable unsaturated compound, for example, A reaction of 2-hydroxy-3-phenoxypropyl acrylate, a half ester of phthalic anhydride with 2-hydroxypropyl acrylate and propylene oxide, 1,6-hexanediol di(methyl Acrylate, 1,4-cyclohexanediol di(meth)acrylate, 2-bis(p-hydroxyphenyl)propane di(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol (Meth) acrylate, dipentaerythritol hexa(meth) acrylate, trimethylolpropane tri(meth) acrylate, 2,2-bis(4-propenyl methoxypentaethoxyphenyl)propane A glycerol triacrylate, a tetraacrylate of a diol having an average of 4 moles of ethylene oxide added to pentaerythritol, and a polyfunctional (meth) acrylate of an isomeric cyanurate compound. These may be used alone or in combination of two or more.

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

(c) Photopolymerization initiator

(c) A photopolymerization initiator is a compound which polymerizes a monomer by light. As the (c) photopolymerization initiator, for example, a photopolymerization initiator which is generally used as a photosensitive resin can be suitably used, and in particular, hexaarylbiimidazole (hereinafter, also referred to as triarylimidazolyl) can be preferably used. Polymer).

Examples of the triarylimidazolyl dimer include 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer (hereinafter, also referred to as "2,2'-bis(2- Chlorophenyl)-4,4',5,5'-tetraphenyl-1,1'-biimidazole", 2,2',5-tris(o-chlorophenyl)-4-(3,4 -dimethoxyphenyl)-4',5'-diphenylimidazolyl dimer, 2,4-bis(o-chlorophenyl)-5-(3,4-dimethoxyphenyl) -diphenylimidazolyl dimer, 2,4,5-tris(o-chlorophenyl)-diphenylimidazolyl dimer, 2-(o-chlorophenyl)-bis-4,5- (3,4-dimethoxyphenyl)-imidazolyl dimer, 2,2'-bis(2-fluorophenyl)-4,4',5,5'-tetrakis(3-methoxy Phenyl)-imidazolyl dimer, 2,2'-bis(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)- Imidazolyl dimer, 2,2'-bis(2,4-difluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-imidazolyl dimer, 2,2'-bis(2,5-difluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-imidazolyl dimer, 2,2'-double (2,6-difluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-imidazolyl dimer, 2,2'-bis (2,3,4 -trifluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-imidazolyl dimer, 2,2'-bis(2,3,5-trifluorobenzene -4,4',5,5'-tetrakis(3-methoxyphenyl)-imidazolyl dimer, 2,2'-bis(2,3,6-trifluorophenyl)-4 , 4',5,5'-tetrakis(3-methoxyphenyl)-imidazolyl dimer, 2,2'-bis(2,4,5-trifluorophenyl)-4,4', 5,5'-tetrakis(3-methoxyphenyl)-imidazolyl dimer, 2,2'-bis(2,4,6-trifluorophenyl)-4,4',5,5' -tetrakis(3-methoxyphenyl)-imidazolyl dimer, 2,2'-bis(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-four (3-methoxyphenyl)-imidazolyl dimer, 2,2'-bis(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetra (3 - Oxyphenyl)-imidazolyl dimer, and 2,2'-bis(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetra (3- Methoxyphenyl)-imidazolyl dimer, and the like.

In particular, the 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer is preferably a photopolymerization initiator having a high effect on the strength of the resolution or cured photoresist film. Use. The triaryl imidazolyl dimers listed above may be used singly or in combination of two or more. Further, the above-mentioned triaryl imidazolyl dimer can be used in combination with the following acridine compound, pyrazoline compound or the like.

As the (c) photopolymerization initiator, an acridine compound or a pyrazoline compound can be suitably used. Examples of the acridine compound include acridine, 9-phenyl acridine, 9-(4-methylphenyl)acridine, 9-(4-methoxyphenyl)acridine, and 9-(4-hydroxyl group. Phenyl) acridine, 9-ethyl acridine, 9-chloroethyl acridine, 9-methoxyacridine, 9-ethoxy acridine, 9-(4-methylphenyl)acridine, 9-(4-ethylphenyl)acridine, 9-(4-n-propylphenyl)anthracene Pyridine, 9-(4-n-butylphenyl)acridine, 9-(4-t-butylphenyl)acridine, 9-(4-ethoxyphenyl)acridine, 9-(4- Ethyl phenyl) acridine, 9-(4-dimethylaminophenyl) acridine, 9-(4-chlorophenyl)acridine, 9-(4-bromophenyl)acridine, 9 -(3-methylphenyl)acridine, 9-(3-tert-butylphenyl)acridine, 9-(3-acetamidophenyl)acridine, 9-(3-dimethylamine Phenyl) acridine, 9-(3-diethylaminophenyl) acridine, 9-(3-chlorophenyl)acridine, 9-(3-bromophenyl)acridine, 9-( 2-pyridyl) acridine, 9-(3-pyridyl)acridine, 9-(4-pyridyl)acridine, and the like. Among them, 9-phenyl acridine is preferred.

As the pyrazoline compound, for example, 1-phenyl-3-(4-t-butyl-styryl)-5-(4-t-butyl-phenyl)-pyrazoline, 1- (4-(benzoxyl) Zin-2-yl)phenyl)-3-(4-t-butyl-styryl)-5-(4-t-butyl-phenyl)-pyrazoline, 1-phenyl-3- (4-biphenyl)-5-(4-t-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-t-octyl- Phenyl)-pyrazoline and the like.

Examples of the photopolymerization initiator other than the above (c) include 2-ethyl hydrazine, octaethyl hydrazine, 1,2-benzopyrene, 2,3-benzopyrene, and 2- Phenylhydrazine, 2,3-diphenylfluorene, 1-chloroindole, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3 - dimethyl hydrazine, and chloroquinones such as 3-chloro-2-methyl hydrazine, benzophenone, and miscene [4,4'-bis(dimethylamino)benzophenone] And aromatic ketones such as 4,4'-bis(diethylamino)benzophenone, benzoin ethers such as benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin, benzoin Dimethyl ketal, benzoin diethyl ketal, 9-oxygen sulphide Combination with alkylaminobenzoic acid, 1-phenyl-1,2-propanedione-2-O-benzoin, 1-phenyl-1,2-propanedione-2-(O-B An oxoester such as oxycarbonyl)anthracene.

Furthermore, as the above 9-oxygen sulfur A combination of a class and an alkylaminobenzoic acid, for example, ethyl-9-oxygen sulfide Combination with ethyl dimethylaminobenzoate, 2-chloro-9-oxosulfur Combination with ethyl dimethylaminobenzoate and isopropyl-9-oxosulfur Combination with ethyl dimethylaminobenzoate and the like. Further, an N-arylamino acid can also be used as the (c) photopolymerization initiator. Examples of the N-arylamino acid include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Among them, N-phenylglycine is particularly preferred.

The content of the (c) photopolymerization initiator in the photosensitive resin element is in the range of 0.01% by mass to 30% by mass, more preferably 0.05% by mass, and further preferably 0.1% by mass, more preferably 15% by mass. %, and further preferably, the upper limit is 10% by mass. The content of the (c) photopolymerization initiator is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity in photopolymerization by exposure, and on the other hand, in photopolymerization. The light is sufficiently transmitted until it reaches the bottom surface of the photosensitive resin element (that is, a portion farther from the light source), and is preferably 30% by mass or less from the viewpoint of obtaining good resolution and adhesion.

(d) solvent

As a solvent, a solvent such as a ketone system, an alcohol system, an ether system or an ester system can be suitably used from the viewpoint of solubility. Examples of the ketone solvent include methyl ethyl ketone or acetone. Examples of the alcohol solvent include methanol, ethanol, isopropanol, n-propanol, and n-butanol. From the viewpoint of solubility and appearance of the coating film, ethanol is particularly preferred. As the ether system, tetrahydrofuran, propylene glycol monomethyl ether or the like can be used. Examples of the ester solvent include ethyl acetate and the like. Further, in order to suppress the generation of bubbles in the drying step, toluene or the like is added as a non-polar solvent.

The blending liquid is typically dissolved in an arbitrary order or in a single pass by the above-mentioned (a) binder resin, the above (b) photopolymerizable unsaturated compound, and the above (c) photopolymerization initiator. (d) Obtained in a solvent and mixed.

(d) The solvent is preferably a ketone system from the viewpoint of drying property, and particularly preferably (d) the solvent contains acetone. Further, from the viewpoint of improving (b) the photopolymerizable unsaturated compound and/or (e) the solubility of any additive (for example, a dye or the like), it is preferred to use acetone and an alcohol solvent represented by ethanol in combination. . It is especially preferred to use acetone in combination with ethanol as an alcohol solvent.

Moreover, the combination of acetone and alcohol is a tendency to lower the viscosity of the preparation liquid, and it is possible to It is preferable from the viewpoint of setting the concentration of the solid content in the blending liquid to be higher and improving the productivity. Further, the combination of acetone and alcohol is also preferable from the viewpoint of maintaining the surface of the dried film while removing the solvent while maintaining the surface of the dried film well. In other words, the combination of acetone and alcohol is preferable from the viewpoint of improving the coating speed of the preparation liquid and improving the productivity of the photosensitive resin element. In addition, the term "maintaining a dry film surface while maintaining good" means that the surface of the film has high smoothness, and the visually uneven appearance is small.

When (d) the solvent contains acetone, the ratio of the mass of acetone to the total mass of the solvent is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, and particularly preferably 60% by mass or more. On the other hand, the upper limit is preferably 98% by mass or less, more preferably 90% by mass or less, further preferably 80% by mass or less, and particularly preferably 70% by mass or less. When the ratio of the acetone is set to such a range, the viewpoint of improving the smoothness of the surface of the film after drying, or the viewpoint of reducing the uncoated portion such as needle-like pores in the drying step, and obtaining a good coated surface are obtained. It is better.

In addition, as the alcohol solvent, ethanol is preferably contained as a main component (preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, or 100% by mass). .

Moreover, as the viscosity of the above-mentioned mixing liquid, the viscosity at 25 ° C is preferably 500 Pa. Sec~4000mPa. Sec.

(e) Other additives

In the blending solution, in addition to the components (a) to (d), (e) other additives may be contained. Specifically, (e) other additives include, for example, a coloring matter such as a dye or a pigment. As such a coloring substance, a base dye can be used. Examples of the base dye include basic green 1 [CAS number (the same applies hereinafter): 633-03-4], peacock green grass salt [2437-29-8], bright green [633-03-4], Magenta [632-99-5], methyl violet [603-47-4], methyl violet 2B [8004-87-3], crystal violet [548-62-9], methyl green [82-94] -0], Victoria Blue B [2580-56-5], Basic Blue 7 [2390-60-5], Rose Red B [81-88-9], Rose Red 6G [989-38-8], alkali Sex Huang 2 [2465-27-2] and so on. Among them, alkaline green 1, peacock green grass, and basic blue 7 are preferable, and alkali green 1 and basic blue 7 are particularly preferable from the viewpoint of improving hue stability and exposure contrast.

The content of the coloring matter in the photosensitive resin element is preferably 0.001% by mass to 1% by mass. When the content of the coloring matter is 0.001% by mass or more, the effect of improving workability is improved. Therefore, when the content is 1% by mass or less, the effect of maintaining storage stability is preferable.

Further, in order to provide a visible image by exposure, a coloring agent such as a chromogenic dye or the like may be contained in the preparation liquid. Examples of such a color-developing dye include a leuco dye, a combination of a fluorescent yellow mother dye and a halogen compound, and the like.

As the leuco dye, for example, tris(4-dimethylamino-2-methylphenyl)methane [leuco crystal violet], tris(4-dimethylamino-2-methylphenyl) Methane [hidden malachite green], and fluorescent yellow mother dye. Among them, in the case of using leuco crystal violet, the contrast is good, so that it is preferable.

Examples of the halogen compound include bromopentane, bromoisopentane, 1,2-dibromo-2-methylpropane, 1,2-dibromoethane, diphenylbromomethane, dibrominated toluene, and the like. Methyl bromide, tribromomethylphenyl hydrazine, carbon tetrabromide, tris(2,3-dibromopropyl) phosphate, trichloroacetamide, iodopentane, iodine isopentane, 1,1,1- Trichloro-2,2-bis(p-chlorophenyl)ethane, hexachloroethane, chlorinated three Compounds, etc.

The content of the color developing agent in the photosensitive resin element is preferably from 0.1% by mass to 10% by mass, respectively.

Further, in order to improve the thermal stability and storage stability of the photosensitive resin composition, it is preferred that the preparation liquid contains a group selected from the group consisting of a radical polymerization inhibitor, or a benzotriazole and a carboxybenzotriazole. At least one or more compounds.

Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butyl catechol, cuprous chloride, and 2,6-di Sanding Base-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-third Phenol), nitrosophenylhydroxylamine aluminum salt, N-nitrosodiphenylamine, and the like.

Examples of the benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, and bis(N-2-ethylhexyl)aminone. Methyl-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, bis(N-2-hydroxyethyl) Aminomethylene-1,2,3-benzotriazole and the like.

Examples of the carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and (N,N-dibutyl). Amino)carboxybenzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl) Aminomethylenecarboxybenzotriazole, N-(N,N-di-2-ethylhexyl)amine-based ethylcarboxybenzotriazole, and the like.

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

The blending solution may also contain other plasticizers as needed. Examples of such a plasticizer include polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, and polyoxyethylene polyoxypropylene monomethyl ether. , diol/ester such as polyoxyethylene monoethyl ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether, sorbitol such as polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan oleate Anhydride derivative, phthalic acid ester such as diethyl phthalate, o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, triethyl citrate , acetonitrile tri-n-propyl citrate, and tri-n-butyl citrate, propylene glycol formed by adding propylene oxide to both sides of bisphenol A, and epoxy added to both sides of bisphenol A Ethylene glycol and the like.

The content of the plasticizer in the photosensitive resin element is preferably from 0.1% by mass to 50% by mass. A lower limit is preferably 1% by mass, and a more preferred upper limit is 30% by mass. With respect to the content, the retardation of the development time is suppressed, and from the viewpoint of imparting flexibility to the cured film, it is preferably 0.1% by mass or more. On the other hand, the viewpoint of suppressing insufficient hardening and melting of the edge of the photosensitive layer from the roll end surface is suppressed. Therefore, it is preferably 50% by mass or less.

The blending solution may also contain other antioxidants as needed. Examples of the antioxidant include triphenyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, tris(monodecylphenyl) phosphite, and dinonyl phosphite. Phenyl ester bis(monodecylphenyl) ester 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, the coloring stability of the photosensitive resin composition is excellent, and the sensitivity of the photosensitive resin composition at the time of exposure is good, and therefore, it is preferable. When the content is 0.8% by mass or less, the coloring property is suppressed, so that the hue stability is good and the adhesion is also good, which is preferable.

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

As the support layer, a transparent support layer that transmits light emitted from the exposure light source is preferable. Examples of such a support layer include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, and a vinylidene chloride copolymer film. A polymethyl methacrylate copolymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, a cellulose derivative film, or the like. The support layer is preferably a polyester film from the viewpoints of solvent resistance, heat resistance, transparency, and the like. As such films, an extender can also be used as needed. The haze of the support layer is preferably 5 or less. When the thickness of the support layer is thin, it is advantageous in terms of image formation property and economy. However, in order to maintain the strength, it is preferably used in a thickness of 10 μm to 30 μm, more preferably 12 μm to 16 μm. You Jia's support A polyester film having a layer thickness of 12 to 16 μm.

The heat shrinkage ratio of the polyester film peeled off from the photosensitive resin element and dried in the TD direction is preferably 3.2% or less from the viewpoint of occurrence of wrinkles in the case of producing a laminate. The above-mentioned "drying" means that the volatile component (for example, a residual solvent) in the polyester film has been substantially removed. Such a dry state can be obtained, for example, by heating at normal pressure, heating at 200 ° C for 30 minutes, and then standing at normal pressure at room temperature (for example, 20 ° C) for 30 minutes. The heat shrinkage ratio in the TD direction is a value measured by the method described in the following [Examples] or the method considered by the practitioner to be equivalent to the method.

The protective layer preferably has such a property that the adhesion between the protective layer and the photosensitive resin layer is sufficiently smaller than the adhesion between the support layer and the photosensitive resin layer, so that the protective layer can be easily peeled off. For example, a polyethylene film, a polypropylene film, or the like can be preferably used as the protective layer. As the protective layer, for example, a film excellent in peelability as disclosed in JP-A-59-202457 can be used. The thickness of the protective layer is preferably from 10 μm to 100 μm, more preferably from 10 μm to 50 μm.

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

The photosensitive resin element manufactured by the above-described production method is preferably used for manufacturing a printed wiring board, manufacturing a lead frame for IC chip mounting, metal foil manufacturing, and the like, and ball grid array (BGA). ), or wafer level package (CSP, chip Manufacturing of package such as size package), fabrication of strip substrate such as chip-on-film (COF) or tape automated bonding (TAB), fabrication of semiconductor bumps, indium tin oxide ( Manufacture of partition walls of flat panel displays such as ITO electrodes or address electrodes, electromagnetic wave masks, etc.

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

[Examples]

Hereinafter, the present embodiment will be more specifically described by way of examples and comparative examples, but the present invention is not limited to the examples as long as the scope of the invention is not exceeded.

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

The components of the photosensitive resin composition shown in Table 1 were prepared, stirred and dissolved in a dissolution tank, and the mixture was filtered through a filter. Then, the blending liquid was transferred by a pump to a die coater to be uniformly applied onto a polyethylene terephthalate film as a support layer, and sent to a drying zone to dry the solvent. Thereafter, it was laminated on 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 μm.

In the above steps, edge melting evaluation and chip cutting evaluation were performed by the method shown below. Further, the weight average molecular weight of the resin was measured by the method shown below. The results are shown below.

Further, the polyethylene terephthalate film as the support layer was GR-16 (thickness: 16 μm) manufactured by Teijin Co., Ltd., and the polyethylene film used as the protective layer was GF-manufactured by TAMAPOLY Co., Ltd. 18 (thickness 19 μm).

(1) Edge melting assessment

The preparation liquid is applied onto a polyethylene terephthalate film as a support layer by a die coater, and the solvent is dried and removed to form a photosensitive resin layer, and then a layer is laminated on the photosensitive resin layer as a protective layer. Polyethylene film to obtain support layer / photosensitive resin layer / A layered structure of a three-layer structure of a protective layer. This laminated body was taken up to form a roll-shaped laminated body (processed into a width of 500 mm and a winding length of 150 m using a slitter), and the roll-shaped laminated body was stored at 20 °C. The number of days from the start of storage to the visual observation of the bleeding of the photosensitive resin layer from the end surface of the roll was measured, and the evaluation was performed based on the following grade.

A: Exudation of the photosensitive resin layer was observed over 50 days.

B: Exudation of the photosensitive resin layer was observed for 30 days or more and less than 50 days.

C: Exudation of the photosensitive resin layer was observed for 10 days or more and less than 30 days.

D: Exudation of the photosensitive resin layer was observed in less than 10 days.

(2) Cutting chip evaluation

The coating liquid is applied onto a polyethylene terephthalate film as a support layer by a die coater, and the solvent is dried and removed, and then a polyethylene film as a protective layer is laminated to support the layer/photosensitive resin layer. The three-layer structure of the protective layer was obtained as a roll-like laminated body, and a sample of 10 cm × 10 cm was cut out from the laminated body. The self-cut sample was peeled off from the protective layer, and the laminate was punctured 5 times from the photosensitive resin layer side using an NT cutter (using a new cutter). The portion where the cutter was punctured and the surface of the dicing blade were visually observed, and the generation of chips of the photosensitive resin layer was evaluated based on the following grades.

A: The chips of the photosensitive resin layer were not generated at all in the punctured portion, and the chips of the photosensitive resin layer were not attached to the dicing blade at all.

B: The chips of the photosensitive resin layer were not attached to the dicing blade, but a very small amount of the photosensitive resin layer chips were generated in the punctured portion.

C: A small amount of chips of the photosensitive resin layer are generated in the punctured portion, and a small amount of chips of the photosensitive resin layer are also adhered to the dicing blade.

D: The chips of the photosensitive resin layer were apparently produced in the punctured portion, and the chips of the photosensitive resin layer were also clearly adhered to the dicing blade.

(3) Weight average molecular weight and acid equivalent

Determination of the weight average of the resin by gel permeation chromatography (standard polystyrene conversion) Molecular weight (Mw). The column used for the measurement was serially sold under the trade name Shodex 805M/806M manufactured by Showa Denko Co., Ltd., and the standard monodisperse polystyrene was selected from Shodex STANDARD SM-105 manufactured by Showa Denko Co., Ltd., and the solvent was N-methyl. -2-pyrrolidone, the detector was sold under the trade name Shodex RI-930 by Showa Denko.

Further, the acid equivalent was measured by a potentiometric titration method (using a homogenate automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd. and using 0.1 mol/L of sodium hydroxide).

(4) Thermal shrinkage of polyester film in TD direction

The coating liquid is applied onto a polyethylene terephthalate film (as a polyester film) as a support layer using a die coater, and the solvent is dried and removed, and then a polyethylene film as a protective layer is laminated to support In the three-layer structure of the layer/photosensitive resin layer/protective layer, a roll-shaped laminate is obtained, and the protective layer and the photosensitive resin layer are peeled off from the laminate to obtain a polyethylene terephthalate film as a support 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 marks were placed at a distance of 100 mm from the center of the test piece, and the test piece was vertically suspended in a hot air circulation type. In a constant temperature bath, it was heated at 200 ° C for 30 minutes under normal pressure. After heating, the mixture was allowed to stand at room temperature under normal pressure for 30 minutes, and the distance between the marks was measured to calculate the heat shrinkage ratio.

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

By measuring the photosensitive resin layer obtained by peeling the protective layer and the support layer from the roll-like laminated body formed in the same manner as in the above (4), the mass ratio of the residual solvent and the residual solvent are obtained. The ratio in the middle.

(Comparative Example 4)

The preparation liquid of the photosensitive resin composition of Comparative Example 1 was uniformly applied onto a polyethylene terephthalate film (haze: 1.8) having a thickness of 20 μm, and dried in a hot air retention type dryer at 100 ° C. 10 minutes to obtain a photosensitive film. The film thickness of the photosensitive resin layer after drying was 25 μm. The mass ratio of solid components is 43%, and the mass ratio of residual acetone is 0%. The various evaluation results of the DF are as follows.

Edge melt evaluation: B, chip removal evaluation: D.

<Symbol description>

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

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

P-3: a mixed solution of methyl ethyl ketone and ethanol of a terpolymer of 50% by mass of methyl methacrylate, 25% by mass of methacrylic acid and 25% by mass of styrene ((solvent mass ratio: methyl ethyl group) Ketone/ethanol = 75/25), solid content ratio 45%, weight average molecular weight 50,000, acid equivalent 344)

M-1: a polyethylene glycol dimethacrylate obtained by adding an average of 2 moles of ethylene oxide to both ends of bisphenol A (BPE-200 manufactured by Shin-Nakamura Chemical Co., Ltd.)

M-2: Diethylene glycol dimethacrylate (each BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.) obtained by adding an average of 5 moles of ethylene oxide to both ends of bisphenol A.

M-3: Dimethyl methacrylate of a polyalkylene glycol formed by adding an average of 2 moles of propylene oxide and an average of 6 moles of ethylene oxide to both ends of bisphenol A

M-4: a dialkyl diol obtained by adding a polypropylene propylene glycol having an average of 12 moles of propylene oxide and further adding an average of 3 moles of ethylene oxide to both ends. ester

M-5: an acrylate obtained by adding an average of 3 moles of ethylene oxide to trimethylolpropane (A-TMPT-3EO manufactured by Shin-Nakamura Chemical Co., Ltd.)

M-6: 4-mercaptophenylpentaethylene glycol dipropylene glycol acrylate

M-7: an urethane urethane compound obtained by adding polypropylene glycol acrylate to both ends of isophorone diisocyanate (in the formula III, R ₇ = R ₈ = H, R ₉ , R ₁₀ , R ₁₁ =CH ₃ ,n ₅ =n ₆ =0,n ₇ =n ₈ =12)

I-1: 4,4'-bis(diethylamino)benzophenone

I-2: 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer

D-1: Diamond Green

D-2: leuco crystal violet

A-1: p-toluenesulfonamide

A-2: benzotriazole

A-3: Addition of 3 moles of aluminum salt of nitrosophenylhydroxylamine

A-4: Polypropylene glycol obtained by adding an average of 2 moles of propylene oxide to both ends of bisphenol A

A-5: IRGANOX 245 manufactured by Ciba Specialty Chemicals, Inc.

A-6: Newcol 3-85 (manufactured by Nippon Emulsifier Co., Ltd.)

S-1: ethanol

S-2: propylene glycol monomethyl ether

S-3: toluene

[Industrial availability]

The photosensitive resin element of the present invention can be used for manufacturing a printed wiring board, manufacturing a lead frame for IC chip mounting, metal foil precision processing such as metal mask manufacturing, manufacturing of a package such as BGA or CSP, or a strip substrate such as COF or TAB. Fabrication of manufacturing, fabrication of semiconductor bumps, spacers for flat panel displays such as ITO electrodes or address electrodes, and electromagnetic wave masks.

Claims (10)

A photosensitive resin element comprising a support layer and a photosensitive resin element of the photosensitive resin layer on the support layer, wherein the photosensitive resin layer contains (a) a carboxyl group content of from 100 to 600 in terms of acid equivalent weight a resin for a binder having an average molecular weight of 5,000 to 500,000, (b) a photopolymerizable unsaturated compound, (c) a photopolymerization initiator, and (d) a solvent, wherein the photosensitive resin layer is a photosensitive resin layer The (d) solvent is contained in an amount of 0.001% by mass or more and 1% by mass or less, and the photosensitive resin layer contains one or more compounds selected from the following general formulae (I) to (III) as the above-mentioned (b) an unsaturated compound which is photopolymerizable, (wherein R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, A represents a C ₂ H ₄ group, B represents a CH ₂ CH(CH ₃ ) group, and m ₁ + m ₂ is an integer of 2 to 30, m ₃ + m ₄ is an integer from 0 to 30, m ₁ and m ₂ are each independently an integer from 1 to 29, and m ₃ and m ₄ are each independently an integer from 0 to 29, -(AO)- and -(BO). - the arrangement of the repeating units may be random or block, and in the case of a block, any of -(AO)- and -(BO)- may be on the biphenyl side) (wherein R ₃ represents a hydrogen atom or a one-valent 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 a hydrocarbon having 2 to 6 carbon atoms; The base, 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, wherein a plurality of Ds in the formula may be the same Differently, the repeating structure of -(OD)- can be random or block) (wherein R ₇ to R ₁₁ each independently represent a hydrogen atom or a methyl group, A ₁ represents a C ₂ H ₄ group, B ₁ represents a CH ₂ CH(CH ₃ ) group, and n ₅ + n ₆ is 0 to 30 Integer, n ₇ + n ₈ is an integer from 0 to 30, n ₅ and n ₆ are each an integer of 0 to 30, and n ₇ and n ₈ are each independently an integer of 0 to 30, -(OA ₁ )-and- The arrangement of the repeating units of (OB ₁ )- may also be random or block, and in the case of a block, any of -(OA ₁ )- and -(OB ₁ )- may be used in the amine group. Acid ester side). The photosensitive resin element of claim 1, which comprises propylene glycol monomethyl ether as the above (d) solvent. The photosensitive resin element of claim 1, which contains toluene as the above (d) solvent. The photosensitive resin element of claim 1, which comprises acetone as the above (d) solvent. The photosensitive resin element according to any one of claims 1 to 4, which comprises the compound represented by the above formula (I) and the compound represented by the above formula (II) as the above (b) photopolymerizable Saturated compound. The photosensitive resin element according to any one of claims 1 to 4, which comprises the compound represented by the above formula (I) and the compound represented by the above formula (III) as the above (b) photopolymerizable Saturated compound. The photosensitive resin element according to any one of claims 1 to 4, which comprises the compound represented by the above formula (II) and the compound represented by the above formula (III) as the above (b) photopolymerizable Saturated compound. The photosensitive resin member according to any one of claims 1 to 7, wherein the support layer is a polyester film. The photosensitive resin element of claim 8, wherein the polyester film peeled off from the photosensitive resin element and dried in the TD direction has a heat shrinkage ratio of 3.2% or less. The photosensitive resin element according to claim 8 or 9, wherein the polyester film has a film thickness of from 12 μm to 16 μm.