TWI630459B - Photosensitive resin element - Google Patents

Abstract

The invention provides a photosensitive resin element, which has a good appearance and a long product life, and reduces defects caused by photoresist chipping in a lamination step when manufacturing a printed circuit board. The present invention provides a photosensitive element, which is a photosensitive resin element including a support layer and a photosensitive resin layer on the support layer, and the photosensitive resin layer contains (a) a carboxyl group content of 100 to 600 in acid equivalent. And a resin for a binder having a weight average molecular weight of 5000 to 500,000, (b) an unsaturated compound capable of photopolymerization, (c) a photopolymerization initiator, and (d) a solvent, and the photosensitive resin layer has the photosensitivity The resin layer contains the (d) solvent in an amount of 0.001% by mass or more and 1% by mass or less based on the mass basis, and the photosensitive resin layer contains one or more compounds selected from the general formulae (I) to (III) as the (b) Unsaturated compounds that can undergo photopolymerization.

Description

Photosensitive resin element

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

The manufacturing method of a photosensitive resin composition for producing a printed circuit usually includes the steps of using a resin for an adhesive, an unsaturated compound capable of photopolymerization, a photopolymerization initiator, and a dye as the main component. Ketones typified by ethyl ethyl ketone, esters typified by ethyl acetate, ethers typified by tetrahydrofuran and the like are uniformly dissolved in a solvent. 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 describes that a photosensitive resin composition can be obtained by uniformly applying such a solution to a polyester film or the like as a support layer using a die coater or the like, and drying and removing the solvent in a drying step. In addition, a polyethylene film or the like as a protective layer may be further laminated to obtain a laminated body having a three-layer structure including a layer containing a photosensitive resin composition. Such laminates are commonly referred to as dry film photoresists (hereinafter referred to as "DF").

[Prior technical literature] [Patent Literature]

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

However, in the conventional manufacturing method using methyl ethyl ketone as a main component of the solvent, the solubility of the resin for the binder and the unsaturated compound capable of photopolymerization, and the dyeing The solubility of additives such as raw materials is not sufficient, and often occurs when the filter is clogged when filtering the blending solution. From the viewpoint of reducing the minute irregularities on the surface of the manufactured DF and reducing the frequency of being observed as unevenness in visual inspection of the appearance, there is still room for improvement in the blending solution.

The inventors have found that if there are many solvents remaining in the photosensitive resin composition after drying, when the DF is formed from the photosensitive resin composition, a photosensitive layer is generated in the DF wound into a roll shape. The phenomenon that the edge exuded from the end surface of the roll melts over time, resulting in a problem that the life of the product is shortened. On the other hand, if the solvent remaining in the dried photosensitive resin composition is too small, the following problems occur: 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. If chips of the photosensitive layer are generated, the chips will re-attach to the substrate and become a cause of failure.

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

The present inventors made repeated efforts in order to solve the above problems, and as a result, they found that a photosensitive resin layer having a specific composition and a residual amount of a solvent within a specific range has a good appearance and a long product life, and can reduce lamination. The defect caused by the photoresist chip in the step has completed the present invention. That is, the present invention is as follows.

[1] A photosensitive element, which is a photosensitive resin element including a support layer and a photosensitive resin layer on the support layer, and the photosensitive resin layer contains (a) a carboxyl group content of 100 to 600 in acid equivalent And a resin for a binder having a weight average molecular weight of 5000 to 500,000, (b) an unsaturated compound capable of photopolymerization, (c) a photopolymerization initiator, and (d) a solvent, and the photosensitive resin layer has the photosensitivity Resin layer based on 0.001% by mass The above (1) mass% or less contains the (d) solvent, and the photosensitive resin layer contains one or more compounds selected from the following general formulae (I) to (III) as the (b) photopolymerizable polymer. Unsaturated compounds.

(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, m ₁ + m ₂ is an integer from 2 to 30, and 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, m ₃ and m ₄ are each independently an integer from 0 to 29,-(AO)-and-(BO)- The arrangement of repeating units can be random or block. In the case of block, either-(AO)-and-(BO)-can be on the biphenyl side)

(In the formula, R ₃ represents a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms, R ₄ , R _5, and R ₆ each independently represent a hydrogen atom or a methyl group, and D represents an alkylene group having 2 to 6 carbon atoms. Base, n ₁ , n ₂ and n ₃ are integers above 0 which satisfy n ₁ + n ₂ + n ₃ = 3 ~ 60, n ₄ is 0 or 1, where plural D in the formula may be the same or Can be different, the repeating structure of-(OD)-can be random or block)

(In the formula, 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 a group of 0 to 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 an integer from 0 to 30,-(OA ₁ )-and- The arrangement of the repeating units of (OB ₁ )-may be random or block. In the case of blocks, any of-(OA ₁ )-and-(OB ₁ )-may be used in aminoformic acid. (Ester side)

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

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

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

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

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

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

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

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

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

The present invention also 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. Furthermore, a method for manufacturing a DF with a three-layer structure by 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 has a good appearance and a long product life, and can reduce defects caused by photoresist chips in a lamination step when a printed wiring board is manufactured. Furthermore, according to a specific aspect of the present invention, a method for producing the above-mentioned photosensitive resin element is provided.

Hereinafter, the exemplified form (hereinafter referred to as "implementation form" State ") for details. The present invention is not limited to the embodiments, and can be implemented with various changes within the scope of the gist thereof.

An embodiment of the present invention is a photosensitive element, which is a photosensitive resin element including a support layer and a photosensitive resin layer on the support layer, and the photosensitive resin layer contains (a) a carboxyl group content in terms of acid equivalent as 100 to 600 binder resins with a weight average molecular weight of 5000 to 500,000, (b) unsaturated compounds capable of photopolymerization, (c) photopolymerization initiators, and (d) solvents. The photosensitive resin layer contains The photosensitive resin layer contains the solvent (d) in an amount of 0.001% by mass or more and 1% by mass or less, and the photosensitive resin layer contains 1 selected from the following general formulae (I) to (III). More than one compound is used as the (b) unsaturated polymerizable compound.

(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 from 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, m ₃ and m ₄ are each independently an integer from 0 to 29,-(AO)-and-(BO) The arrangement of the repeating unit of-may be random or block, and in the case of block, any of-(AO)-and-(BO)-may be on the biphenyl side)

(In the formula, R ₃ represents a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms, R ₄ , R _5, and R ₆ each independently represent a hydrogen atom or a methyl group, and D represents an alkylene group having 2 to 6 carbon atoms. Base, n ₁ , n ₂ and n ₃ are integers above 0 which satisfy n ₁ + n ₂ + n ₃ = 3 ~ 60, n ₄ is 0 or 1, where plural D in the formula may be the same or Can be different, the repeating structure of-(OD)-can be random or block)

(In the formula, 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 a group of 0 to 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 an integer from 0 to 30,-(OA ₁ )-and- The arrangement of the repeating units of (OB ₁ )-may be random or block. In the case of blocks, any of-(OA ₁ )-and-(OB ₁ )-may be used in aminoformic acid. Ester side.)

The photosensitive resin element can be produced, for example, by a method including: (a) a resin for an adhesive having a carboxyl group content of 100 to 600 in terms of acid equivalent and a weight average molecular weight of 5000 to 500,000; and (b) photoluminescence A step of blending the polymerized unsaturated compound, (c) a photopolymerization initiator, (d) a solvent, and (e) other additives as necessary to obtain a blending solution; and applying the blending solution to a support layer, and then A step of drying the blending liquid to form a photosensitive resin layer on the support layer.

In this embodiment, the amount of the solvent remaining in the photosensitive resin layer (for example, obtained after drying and film formation of the blending liquid in the above method) needs to be 0.001% by mass or more and 1% by mass relative to the photosensitive resin layer. the following. If it exceeds 1% by mass, when the photosensitive resin composition is made into DF, the following problem arises: In the DF wound into a roll shape, a problem occurs in which the photosensitive layer melts over time from the edge of the roller end surface. This phenomenon shortens the product life. On the other hand, if it is less than 0.001% by mass, a problem arises in that when the cutter 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 chips will re-adhere to the substrate and 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 even more preferably 0.05% by mass or more. The amount of the solvent remaining in the photosensitive resin layer is preferably 0.7% by mass or less, more preferably 0.5% by mass or less, and even 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 [Example] or a method that the practitioner considers equivalent to this method.

In this embodiment, as a method of controlling the amount of the solvent remaining in the photosensitive resin layer, adjustment of the drying conditions (temperature and time) of the photosensitive resin composition when the photosensitive resin layer is formed can be mentioned. The amount of the solvent remaining in the photosensitive resin layer is determined by the gas phase. Measured by chromatography.

Generally, a photosensitive element refers to a person whose properties are changed by receiving light. The photosensitive element may have various forms such as a film, a plate, a sheet, a roll, and a molded product, and may be, for example, a photosensitive resin element including a photosensitive resin or a composition made of a photosensitive resin. More specifically, a layer containing a photosensitive resin composition is coated with a photosensitive resin composition (referred to as a "photosensitive resin composition" in the present invention) on a supporting layer such as a film. Or a layer obtained by drying the photosensitive resin composition (in the present invention, these are collectively referred to as "photosensitive resin layers") are laminated on a support layer, and the photosensitive resin laminate obtained thereby is used as photosensitive 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. In addition, the photosensitive resin composition may be in any state (for example, a solution, a solid, an emulsion, a suspension, etc.), and is preferably a liquid such as a solution, an emulsion, a suspension (also referred to as a "mixing solution" in the present invention). ). Furthermore, as a photosensitive resin laminate, a protective layer (for example, a protective film, a spacer paper film, etc.) is laminated on a part of the laminated body of the support layer and the photosensitive resin layer that exposes the photosensitive resin layer, and is rolled up. The photosensitive resin roller is more preferably used as a photosensitive resin element, and more preferably in the form of a dry film roller in which the entire photosensitive resin roller or the photosensitive resin layer is partially dried.

The thickness of the photosensitive resin element is preferably 5 μm to 50 μm. Regarding the thickness of the photosensitive resin element, it is preferably adjusted to 5 μm or more from the viewpoint of the accuracy of applying the blending solution to the support layer. On the other hand, from the viewpoint of the drying property in the drying step, Preferably, it is adjusted to 50 μm or less. The thickness of the photosensitive resin element is more preferably 30 μm to 50 μm.

Furthermore, the thinner the photosensitive resin layer is, the higher the resolution is, and the thicker the photosensitive resin layer is, the higher the film strength is. Therefore, the film thickness of the photosensitive resin layer can be appropriately selected according to the application. For example, the film thickness of the photosensitive resin layer may be 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 resin for a binder and (b) photopolymerization A combination of unsaturated compounds, (c) a photopolymerization initiator, and (d) a solvent, and (e) other additives as needed. The photosensitive resin composition is preferably a preparation liquid.

When the photosensitive resin composition is a blending liquid, in the method for manufacturing a photosensitive resin element, the ratio of the total solid content in the blending liquid is preferably 30% by mass to 80% by mass. The ratio of all solid content components in the blending liquid is, for example, the solid content component concentration of the blending liquid obtained by dissolving the components (a) to (c) and (e) in the solvent (d). Regarding the ratio of all solid components, it 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 application speed. In other words, it is preferably 80% by mass or less. The ratio of all solid content components in the preparation liquid is more preferably 40% by mass or more, and more preferably 50% by mass or more. On the other hand, the upper limit is more preferably 70% by mass or less, and still more preferably 60% by mass or less. It is preferable to set the ratio of the total solid content in such a range from the viewpoint of improving the smoothness of the film surface after drying, or reducing uncoated portions such as needle-like pores in the drying step. Viewpoint of obtaining a good coating surface.

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

(a) Resin for adhesive

(a) The carboxyl content of the resin for adhesives is 100 to 600 in terms of acid equivalent, and the weight average molecular weight is 5000 to 500,000, and it is a resin used as an adhesive.

(a) The resin for an adhesive has a carboxyl group in order to impart developability or peelability to an alkaline aqueous solution to a photosensitive resin element. From the viewpoint of developing resistance, resolution, and adhesion, the content of carboxyl group is preferably 100 or more in terms of acid equivalent, and from the viewpoint of developing property and peelability, it is preferably 600 or less. In the present invention, the term "acid equivalent" refers to the mass (g) of a resin having one equivalent of a carboxyl group therein. In the present invention, the acid equivalent is a value measured by a potentiometric titration method (for example, using an Hiranuma automatic titration device (COM-555) manufactured by Hiranuma Industry Co., Ltd. and using 0.1 mol / L sodium hydroxide).

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

The 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, and more preferably 5 or less. In the present invention, 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 containing a carboxyl group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, butenoic acid, itaconic acid, maleic anhydride, and maleic acid half esters. Among these, (meth) acrylic acid is particularly preferred. In this specification, (meth) acrylic acid means acrylic acid or methacrylic acid.

The second monomer is a monomer which 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 n- (meth) acrylate Butyl ester, isobutyl (meth) acrylate, third butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and (meth) acrylic ring Hexyl esters, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, vinyl acetate and other vinyl alcohols; (meth) acrylonitrile, styrene-based monomers (e.g., styrene , And styrene derivatives that can be polymerized). Among them, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, and benzyl (meth) acrylate are preferred, and styrene is particularly preferred from the viewpoint of resolution.

(a) The resin for the binder is preferably synthesized by mixing the first monomer and the second monomer with a solvent such as acetone, methyl ethyl ketone, or isopropanol. An appropriate amount of a radical polymerization initiator, such as benzamidine peroxide or azoisobutyronitrile, is added to the diluted solution and heated and stirred. There is also a case where a part of the mixture is added dropwise to the reaction solution to perform synthesis. After the reaction is completed, a solvent may be further added to the resin for (a) an adhesive to adjust the concentration to a desired concentration. As the synthesis method, in addition to solution polymerization, block polymerization, suspension polymerization, or emulsion polymerization may be used.

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

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

In this embodiment, the content of (a) the resin for the adhesive in the photosensitive resin element (wherein the content is relative to the total solid content of the photosensitive resin element; hereinafter, unless otherwise specified, The content is the same for each of the contained components) is in the range of 20% to 90% by mass, with a preferred lower limit of 25% by mass, a preferred upper limit of 75% by mass, a more preferred lower limit of 40% by mass, and a more preferred upper limit of 65% %. The content is preferably 20% by mass or more from the viewpoint of maintaining alkaline developability. On the other hand, from the viewpoint of fully exhibiting the performance as a photoresist by a photoresist pattern formed by exposure. 90% by mass or less.

(b) Photopolymerizable unsaturated compounds

(b) The unsaturated compound capable of photopolymerization is, for example, a monomer having addition polymerizability due to having an ethylenically unsaturated bond. The ethylenically unsaturated bond is preferably a terminal ethylenically unsaturated group.

(b) Photopolymerizable unsaturated compounds include one or more compounds selected from 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 from 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, m ₃ and m ₄ are each independently an integer from 0 to 29,-(AO)-and-(BO) The arrangement of the repeating unit of-may be random or block, and in the case of block, any of-(AO)-and-(BO)-may be on the biphenyl side)

(In the formula, R ₃ represents a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms, R ₄ , R _5, and R ₆ each independently represent a hydrogen atom or a methyl group, and D represents an alkylene group having 2 to 6 carbon atoms. Base, n ₁ , n ₂ and n ₃ are integers of 0 or more of n ₁ + n ₂ + n ₃ = 3 ~ 60, n ₄ is 0 or 1, where plural D in the formula may be the same or different Different, the repeating structure of-(OD)-can be random or block)

(In the formula, 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 a group of 0 to 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 an integer from 0 to 30,-(OA ₁ )-and- The arrangement of the repeating units of (OB ₁ )-may be random or block. In the case of blocks, any of-(OA ₁ )-and-(OB ₁ )-may be used in aminoformic acid. (Ester side)

In this case, it is effective for improving the resolution or improving the cutting chip. From this viewpoint, it is particularly preferred that (b) the unsaturated compound capable of photopolymerization includes both the compound represented by the general formula (I) and the compound represented by the general formula (II), and the general formula (I Both of the compound represented by) and the compound represented by general formula (III), or both the compound represented by general formula (II) and the compound represented by general formula (III).

In particular, the case where (b) the unsaturated compound capable of photopolymerization contains a large amount of ethylene glycol chain or propylene glycol chain is more effective for improving the chipping property. From this viewpoint, in the general formula (I), m ₁ + m ₂ and m ₃ + m ₄ are each preferably 8 to 30, more preferably 10 to 30, and m ₁ + m ₂ + m. ₃ + m _{4 is} preferably 8 to 60, and more preferably 10 to 60. Further, in the general formula (II), from the viewpoint of chipping properties and resolvability, the number of carbons of D is preferably 2 or 3, more preferably 2, and n ₁ + n ₂ + n ₃ is more It is preferably 3 to 50, more preferably 3 to 35.

Examples of the compound represented by the general formula (I) include a polyethylene glycol dimethacrylate obtained by adding an average of one unit of ethylene oxide to both ends of bisphenol A or bisphenol A Polyethylene glycol dimethacrylate obtained by adding an average of 2 units of ethylene oxide at both ends, and a polymer obtained by adding an average of 5 units of ethylene oxide at both ends of the bisphenol A. Dimethacrylate of ethylene glycol, dimethacrylate of polyethylene glycol obtained by adding an average of 7 units of ethylene oxide to both ends of bisphenol A, respectively at both ends of bisphenol A Addition of an average of 6 units of ethylene oxide and an average of 2 units of propylene oxide to the dimethacrylate of polyalkylene glycol, and an average of 15 units of epoxy were added to both ends of bisphenol A Dimethacrylate of polyalkylene glycol made of ethane and propylene oxide with an average of 2 units.

As the compound represented by the general formula (II), for example, a tri (meth) acrylate obtained by adding 3 units of ethylene oxide to trimethylolpropane on average, and Three (meth) acrylic acid esters obtained by adding 3 units of propylene oxide to an average of methylolpropane, and three (6) ethylene oxide units by adding an average of 6 units to trimethylolpropane (Meth) acrylate, tris (meth) acrylate obtained by adding 9 units of ethylene oxide on average to trimethylolpropane, adding 12 on average by adding trimethylolpropane Tris (meth) acrylates derived from ethylene oxide units, tris (meth) acrylates derived from addition of 21 units of ethylene oxide to trimethylolpropane, and A tri (meth) acrylate obtained by adding methyl propane to an average of 30 units of ethylene oxide in total.

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

(B) As another specific example of the unsaturated compound capable of photopolymerization, for example, from the viewpoints of high resolvability, peelability of the cured film, and flexibility of the cured film, 4-nonylphenyl hepta is preferred. Ethylene glycol dipropylene glycol (meth) acrylate or 4-nonylphenyl octaethylene glycol (meth) acrylate, 4-nonylphenyl tetraethylene glycol (meth) acrylate, 4-octyl Phenylpentapropylene glycol (meth) acrylate and the like.

Specific examples of the other (b) unsaturated compounds that can be photopolymerized include, for example, 2-hydroxy-3-phenoxypropyl acrylate, half-ester compounds of phthalic anhydride and 2-hydroxypropyl acrylate Reactant with propylene oxide, 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 2-bis (p-hydroxyphenyl) propanedi (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, 2 , 2-bis (4-propenyloxypentaethoxyphenyl) propane, glycerol triacrylate, tetraacrylate of diol obtained by adding an average of 4 moles of ethylene oxide to pentaerythritol, and isopropyl alcohol Polyfunctional (meth) acrylates of cyanurate compounds and the like. These can be used alone or in combination of two or more.

The content of the (b) unsaturated polymerizable unsaturated compound in the photosensitive resin element is preferably in a range of 5% to 75% by mass. The content is preferably 5 mass% or more, more preferably 15 mass% or more, and even more preferably 30 mass% or more from the viewpoint of suppressing poor curing and delay in development time. On the other hand, from the viewpoint of suppressing the peeling delay of cold flow and hardened 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 using light. As the (c) photopolymerization initiator, for example, a photopolymerization initiator generally used as a photosensitive resin can be appropriately used. In particular, a hexaarylbiimidazole (hereinafter, also referred to as a 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-methoxyphenyl) ) -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'-tetra (3-methoxyphenyl) -imidazolyl dimer, 2, 2'-bis (2,5-difluorophenyl) -4,4 ', 5,5'-tetra (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis (2 , 6-difluorophenyl) -4,4 ', 5,5'-tetra (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis (2,3,4-tri (Fluorophenyl) -4,4 ', 5,5'-tetra (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis (2,3,5-trifluorophenyl) -4,4 ', 5,5'-Tetra (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis (2,3,6-trifluorophenyl) -4,4', 5, 5'-tetra (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis (2,4,5-trifluorophenyl) -4,4 ', 5,5'-tetra (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis (2,4,6-trifluorophenyl) -4,4 ', 5,5'-tetra (3-methyl Oxyphenyl) -imidazolyl dimer, 2,2'-bis (2,3,4,5-tetrafluorophenyl) -4,4 ', 5,5'-tetra (3-methoxy (Phenyl) -imidazolyl dimer, 2,2'-bis (2,3,4,6-tetrafluorophenyl) -4,4 ', 5,5'-tetra (3-methoxyphenyl ) -Imidazolyl dimer, and 2,2'-bis (2,3,4,5,6-pentafluorophenyl) -4,4 ', 5,5'-tetra (3-methoxybenzene ) -Imidazolyl dimer and the like.

In particular, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer is a photopolymerization initiator having a high effect on the resolution or the strength of the hardened photoresist film, which may be preferred. To use. The triarylimidazolyl dimers listed above may be used alone, or two or more kinds may be used in combination. The triarylimidazolyl dimers listed above can be combined with the following acridine Substances, pyrazoline compounds, and the like are used in combination.

As the (c) photopolymerization initiator, an acridine compound or a pyrazoline compound can be suitably used. Examples of the acridine compound include acridine, 9-phenylacridine, 9- (4-tolyl) acridine, 9- (4-methoxyphenyl) acridine, and 9- (4-hydroxyl Phenyl) acridine, 9-ethylacridine, 9-chloroethylacridine, 9-methoxyacridine, 9-ethoxyacridine, 9- (4-methylphenyl) acridine, 9- (4-ethylphenyl) acridine, 9- (4-n-propylphenyl) acridine, 9- (4-n-butylphenyl) acridine, 9- (4-thirdbutyl Phenyl) acridine, 9- (4-ethoxyphenyl) acridine, 9- (4-acetamidophenyl) acridine, 9- (4-dimethylaminophenyl) acridine, 9- (4-chlorophenyl) acridine, 9- (4-bromophenyl) acridine, 9- (3-methylphenyl) acridine, 9- (3-tert-butylphenyl) acridine Pyridine, 9- (3-ethylaminophenyl) acridine, 9- (3-dimethylaminophenyl) acridine, 9- (3-diethylaminophenyl) acridine, 9- (3-chlorophenyl) acridine, 9- (3-bromophenyl) acridine, 9- (2-pyridyl) acridine, 9- (3-pyridyl) acridine, 9- (4-pyridine Group) acridine and the like. Among them, 9-phenylacridine is preferred.

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

Examples of the (c) photopolymerization initiator include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzoanthraquinone, 2,3-benzoanthraquinone, 2- Phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3 -Dimethylanthraquinone and quinones such as 3-chloro-2-methylanthraquinone, benzophenone, Michelinone [4,4'-bis (dimethylamino) benzophenone] And aromatic ketones such as 4,4'-bis (diethylamino) benzophenone, benzoin, benzoin ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin such as benzoin, benzoin Dimethyl ketal, benzoin diethyl ketal, 9-oxosulfur Combinations of Alkyl and alkylaminobenzoic acid, 1-phenyl-1,2-propanedione-2-O-benzoinoxime, 1-phenyl-1,2-propanedione-2- (O-ethyl Oxycarbonyl) oximes and other oxime esters.

Moreover, as the 9-oxysulfur Combinations of succinic acid and alkylaminobenzoic acid, for example, ethyl-9-oxysulfur Combination with dimethylaminobenzoate, 2-chloro-9-oxysulfur Combination with dimethylaminobenzoate, and isopropyl-9-oxosulfur In combination with dimethylaminobenzoate and the like. Moreover, you may use N-arylamino acid as (c) photoinitiator. Examples of the N-arylamino acid include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, and the like. Among them, N-phenylglycine is particularly preferred.

The content of the (c) photopolymerization initiator in the photosensitive resin element ranges from 0.01% by mass to 30% by mass, with a more preferable lower limit of 0.05% by mass, a further preferable lower limit of 0.1% by mass, and a more preferable upper limit of 15% %, And the more preferable upper limit thereof 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 during photopolymerization by exposure. On the other hand, in the case of photopolymerization, From the viewpoint that sufficient light is transmitted until it reaches the bottom surface of the photosensitive resin element (that is, a portion far from the light source) to obtain good resolution and adhesion, it is preferably 30% by mass or less.

(d) Solvent

As the solvent, solvents such as ketone, alcohol, ether, and ester solvents can be suitably used from the viewpoint of solubility. Examples of the ketone-based solvent include methyl ethyl ketone and acetone. Examples of the alcohol-based 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. Examples of the ether system include tetrahydrofuran and propylene glycol monomethyl ether. Examples of the ester-based solvent include ethyl acetate. In addition, in order to suppress the generation of bubbles in the drying step, toluene or the like may be used in combination as a non-polar solvent.

The blending solution is typically prepared by subjecting the resin (a) for the adhesive, the unsaturated compound (b) that can be photopolymerized, and the (c) photopolymerization initiator in any order or once. It is obtained by dissolving in a solvent (d) and mixing it.

(d) The solvent is preferably a ketone system from the viewpoint of drying properties, and particularly preferably (d) the solvent contains acetone. From the viewpoint of improving the solubility of (b) unsaturated compounds that can be photopolymerized and / or (e) any additives (such as dyes), it is preferable to use acetone and an alcohol-based solvent such as ethanol in combination. . A combination of acetone and ethanol as an alcohol-based solvent is particularly preferred.

In addition, the combined use of acetone and alcohol tends to reduce the viscosity of the preparation liquid, and it is preferable from the viewpoint that the concentration of the solid component in the preparation liquid can be set higher, and the productivity is improved. Further, the combined use of acetone and alcohol is also preferable from the viewpoint of removing the solvent while maintaining the surface of the dried film well in the drying step. That is, the combined use of acetone and alcohol is preferable from the viewpoint that the application speed of the preparation liquid can be increased and the productivity of the photosensitive resin element can be improved. In addition, the term "one side maintains a good dry film surface" herein means that the smoothness of the film surface is high, and there is less unevenness in visual appearance.

In the case where (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, particularly preferably 60% by mass or more. On the other hand, the upper limit is preferably 98% by mass or less, more preferably 90% by mass or less, still more preferably 80% by mass or less, and even more preferably 70% by mass or less. When the ratio of acetone is set in such a range, the viewpoint of improving the smoothness of the film surface after drying, the viewpoint of reducing uncoated portions such as needle-like pores in the drying step, and the viewpoint of obtaining a good coated surface It ’s better.

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

As the viscosity of the blending solution, the viscosity at 25 ° C is preferably 500 Pa‧sec to 4000 mPa‧sec.

(e) Other additives

The blending solution may contain (e) other additives in addition to the components (a) to (d). With Specifically, (e) other additives include coloring substances such as dyes and pigments. As such a coloring substance, a base dye can be used. Examples of the basic dye include basic green 1 [CAS number (the same applies hereinafter): 633-03-4], malachite [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 yellow 2 [2465-27-2] and so on. Among them, basic green 1, peacock greenate, and basic blue 7 are preferred. From the viewpoint of improving hue stability and exposure contrast, basic green 1 and basic blue 7 are particularly preferred.

The content of the coloring substance in the photosensitive resin element is preferably 0.001% by mass to 1% by mass. When the content of the coloring substance is 0.001% by mass or more, it is preferable to improve the workability. On the other hand, when the content is 1% by mass or less, the effect of maintaining storage stability is preferable.

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

Examples of the leuco dye include tris (4-dimethylamino-2-methylphenyl) methane [leuco crystal violet], and tris (4-dimethylamino-2-methylphenyl). ) Methane [occult peacock green], and fluorescent yellow parent dye. Among them, when leuco crystal violet is used, the contrast is good, so it is preferable.

Examples of the halogen compound include bromopentane, bromoisopentane, 1,2-dibromo-2-methylpropane, 1,2-dibromoethane, diphenylbromomethane, dibromotoluene, and Methyl bromide, tribromomethylphenylphosphonium, carbon tetrabromide, tris (2,3-dibromopropyl) phosphate, trichloroacetamide, iodopentane, iodoisopentane, 1,1,1- Trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, trichloride Compounds etc.

The content of the color developer in the photosensitive resin element is independently preferably 0.1% by mass. ~ 10% by mass.

Furthermore, in order to improve the thermal stability and storage stability of the photosensitive resin composition, it is preferred that the blending solution contains a group selected from the group consisting of a radical polymerization inhibitor, benzotriazoles, and carboxybenzotriazoles. At least one of these compounds.

Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tertiary butylcatechol, cuprous chloride, and 2,6-dichlorobenzene. Tributyl-p-cresol, 2,2'-methylenebis (4-methyl-6-third butylphenol), 2,2'-methylenebis (4-ethyl-6-section Tributylphenol), aluminum nitrosophenylhydroxylamine, 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) amino 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, (N, N-dibutyl Amino) carboxybenzotriazole, N- (N, N-di-2-ethylhexyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) Amino methylene carboxybenzotriazole, N- (N, N-di-2-ethylhexyl) amino ethyl carboxybenzobenzotriazole, and the like.

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

If necessary, the blending solution may contain other plasticizers. Examples of such plasticizers include polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, and polyoxyethylene polyoxypropylene monomethyl ether. Diols / esters such as polyoxyethylene monoethyl ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether, polyoxyethylene Sorbitol anhydride derivatives such as sorbitan laurate, polyoxyethylene sorbitan oleate, phthalates such as diethyl phthalate, o-toluenesulfonamide, p-toluenesulfonamide, Tributyl citrate, triethyl citrate, triethyl acetate citrate, tri-n-propyl acetate, and tri-n-butyl acetate are added to each side of bisphenol A. Propylene glycol made from oxypropane, ethylene glycol made by adding ethylene oxide to both sides of bisphenol A, etc.

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

If necessary, the blend solution can also contain other antioxidants. Examples of the antioxidant include triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (monononylphenyl) phosphite, and dinonyl phosphite. Phenyl ester bis (monononylphenyl) ester and the like.

The content of the antioxidant in the photosensitive resin element is preferably in a range of 0.01% by mass to 0.8% by mass, a more preferable lower limit is 0.01% by mass, and a more preferable upper limit is 0.3% by mass. When the content is 0.01% by mass or more, the effect of excellent hue stability of the photosensitive resin composition is well exhibited, and the sensitivity of the photosensitive resin composition upon exposure becomes good, so it is preferable. In the case where the content is 0.8% by mass or less, since the color rendering property is suppressed, the hue stability becomes good and the adhesiveness becomes good, so it is preferable.

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

As the support layer, a transparent support layer that transmits light emitted from the exposure light source is preferred. 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 film. Copolymer film, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film, etc. The support layer is preferably a polyester film from the viewpoints of solvent resistance, heat resistance, and transparency. As these films, an extender can also be used if necessary. 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 and economy, but in terms of maintaining strength, it is preferable to use a thickness of 10 μm to 30 μm, and more preferably 12 μm to 16 μm. A particularly preferred support layer is a polyester film having a thickness of 12 to 16 μm.

From the viewpoint of generation of wrinkles when forming a laminated body, the thermal shrinkage ratio of the polyester film that is peeled from the photosensitive resin element and dried in the TD direction is preferably 3.2% or less. The above-mentioned "dried" means that the volatile components (for example, residual solvents) in the polyester film have been substantially removed. Such a dried state can be obtained, for example, by heating at 200 ° C. for 30 minutes under normal pressure, and then leaving it to stand at normal pressure and room temperature (for example, 20 ° C.) for 30 minutes. The thermal shrinkage rate in the TD direction is a value measured by a method described in the following [Example] or a method considered by a practitioner to be equivalent to this method.

The protective layer preferably has 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 having excellent peelability disclosed in Japanese Patent Laid-Open No. Sho 59-202457 can be used. The thickness of the protective layer is preferably 10 μm to 100 μm, and more preferably 10 μm to 50 μm.

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

The photosensitive resin element manufactured by the above-mentioned manufacturing method is preferably used for precision wiring of metal foils such as printed wiring board manufacturing, lead frame manufacturing for IC chip mounting, and metal mask manufacturing, and ball grid array (BGA, ball grid array). ), Or the manufacture of packages such as chip size packages (CSP), the manufacture of chip-on-film (COF) or tape automated bonding (TAB) tape substrates, Manufacturing of semiconductor bumps, manufacturing of partition walls for flat-panel displays such as indium tin oxide (ITO) electrodes or addressing electrodes, electromagnetic wave shields.

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

[Example]

Hereinafter, the present embodiment will be described more specifically by citing examples and comparative examples. However, the present invention is not limited to the examples as long as it does not exceed the gist thereof.

[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 solution is transported to a die coater by a pump and uniformly coated on a polyethylene terephthalate film as a support layer, and is transported to a drying area to dry and remove the solvent. Thereafter, it was laminated on a polyethylene film as a protective layer to obtain DF having a thickness of the photosensitive resin layer described in Table 1. The film thickness of DF was 40 μm.

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

In addition, the polyethylene terephthalate film used as a support layer uses Teijin stock. GR-16 (thickness: 16μm) manufactured by the company, and the polyethylene film used as the protective layer is GF-18 (thickness: 19μm) manufactured by TAMAPOLY Co., Ltd.

(1) Edge fusion evaluation

Using a mold coater, apply the blending solution to a polyethylene terephthalate film as a support layer and dry remove the solvent to form a photosensitive resin layer, and then laminate the photosensitive resin layer as a protective layer. A polyethylene film is used to obtain a laminated body having a three-layer structure of a support layer, a photosensitive resin layer, and a protective layer. This laminated body was rolled up to form a roll-shaped laminated body (processed to a width of 500 mm and a winding length of 150 m using a slitter), and the roll-shaped laminated body was stored at 20 ° C. The number of days from the start of storage until the bleeding of the photosensitive resin layer from the roller end surface was visually confirmed, and was evaluated based on the following grade.

A: Exudation of the photosensitive resin layer was observed for 50 days or more.

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 within 10 days.

(2) Evaluation of cutting chips

Using a mold coater, apply the blending solution to a polyethylene terephthalate film as a support layer and dry remove the solvent, and then laminate a polyethylene film as a protective layer to support the layer / photosensitive resin layer. A three-layer structure of a protective layer was used to obtain a roll-shaped laminate, and a 10 cm × 10 cm sample was cut out of the laminate. The protective layer was peeled from the sample cut out, and the laminated body was punctured 5 times with an NT cutter (using a new cutter) from the photosensitive resin layer side. The punctured part of the cutter and the surface of the cutter were visually observed, and the occurrence of chipping in the photosensitive resin layer was evaluated based on the following grades.

A: No chipping of the photosensitive resin layer was generated at the punctured portion, and no chipping of the photosensitive resin layer was completely attached to the cutting blade.

B: The cutting edge of the photosensitive resin layer was not adhered to the cutting blade, but a small amount of cutting edge of the photosensitive resin layer was generated at the punctured portion.

C: A small amount of chips of the photosensitive resin layer is generated on the punctured portion, and a small amount of chips of the photosensitive resin layer is also attached to the cutting blade.

D: Chips of the photosensitive resin layer are clearly generated at the punctured portion, and chips of the photosensitive resin layer are also significantly adhered to the cutting blade.

(3) Weight average molecular weight and acid equivalent

The weight average molecular weight (Mw) of the resin was measured by gel permeation chromatography (standard polystyrene conversion). The column used in the measurement was Shodex 805M / 806M, a brand name manufactured by Showa Denko Corporation. The standard monodisperse polystyrene was Shodex STANDARD SM-105, manufactured by Showa Denko Corporation. The developing solvent was N-methyl. -2-Pyrrolidone, the detector uses the brand name Shodex RI-930 manufactured by Showa Denko.

The acid equivalent was measured by a potentiometric titration method (using an Hiranuma automatic titration device (COM-555) manufactured by Hiranuma Industry Co., Ltd. and using 0.1 mol / L sodium hydroxide).

(4) Thermal shrinkage of polyester film in TD direction

Using a mold coater, apply the blending solution to a polyethylene terephthalate film (as a polyester film) as a support layer and dry remove the solvent, and then laminate a polyethylene film as a protective layer to support A three-layer structure of a layer, a photosensitive resin layer, and a protective layer was obtained as a roll-shaped laminate, and the protective layer and the photosensitive resin layer were peeled from the laminate to obtain a polyethylene terephthalate film as a support layer. A test piece with a width of 20 mm and a length of 200 mm was cut out from the polyethylene terephthalate film. Two marks were marked at a distance of 100 mm from the center of the test piece, and the test piece was hung vertically in a hot air circulation type. In a constant temperature bath, heat at 200 ° C for 30 minutes at normal pressure. After heating, it was left at room temperature and normal pressure for 30 minutes, and the distance between the marks was measured to calculate the thermal shrinkage.

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

The quality of the residual solvent was measured by gas chromatography using a photosensitive resin layer obtained by peeling off the protective layer and the support layer from the roll-shaped laminate formed in the same manner as in (4) above. Amount ratio and ratio in residual solvent.

(Comparative Example 4)

The blending solution of the photosensitive resin composition of Comparative Example 1 was uniformly applied to a polyethylene terephthalate film (haze: 1.8) with a thickness of 20 μm, and dried in a hot air retention dryer at 100 ° C. For 10 minutes, a photosensitive film was obtained. The film thickness of the photosensitive resin layer after drying was 25 μm. The solid matter component mass ratio was 43%, and the residual acetone mass ratio was 0%. Various evaluation results of this DF are as follows.

Edge melting evaluation: B, cuttings evaluation: D.

<Symbol Explanation>

P-1: A mixed solution of acetone and ethanol of a terpolymer of 67% by mass of methyl methacrylate, 23% by mass of methacrylic acid, and 10% by mass of butyl acrylate ((solvent mass ratio: acetone / ethanol = 80/20 ), The solid content mass ratio is 34%, the weight average molecular weight is 200,000, the acid equivalent is 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) (Mass ratio of solid content 47%, weight average molecular weight 50,000, acid equivalent 344)

P-3: A mixed solution of methyl ethyl ketone and ethanol in 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 Ketone / ethanol = 75/25), solid content 45% by mass, weight average molecular weight 50,000, acid equivalent 344)

M-1: Diethylene glycol dimethacrylate (BPE-200 manufactured by Shin Nakamura Chemical Co., Ltd.) made by adding an average of 2 moles of ethylene oxide to each end of bisphenol A.

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

M-3: Add an average of 2 moles of propylene oxide and an average of 6 moles at both ends of bisphenol A Polyalkylene glycol dimethacrylate

M-4: Dimethacrylic acid obtained by adding polypropylene glycol with an average of 12 moles of propylene oxide and then adding an average of 3 moles of ethylene oxide at each end ester

M-5: 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-nonylphenyl pentaethylene glycol dipropylene glycol acrylate

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

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

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

D-1: Diamond Green

D-2: leuco crystal violet

A-1: p-toluenesulfonamide

A-2: Benzotriazole

A-3: Addition of aluminum salt with 3 moles 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 Co., Ltd.

A-6: Newcol 3-85 (manufactured by Japan 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 the manufacture of printed wiring boards, the manufacture of lead frames for IC chip mounting, the precision processing of metal foils such as metal mask manufacturing, the manufacture of packages such as BGA or CSP, and the production of tape substrates such as COF or TAB. Manufacturing, manufacturing of semiconductor bumps, manufacturing of partition walls of flat-panel displays such as ITO electrodes or addressing electrodes, and electromagnetic wave shields.

Claims (8)

A photosensitive resin element is a photosensitive resin element including a support layer and a photosensitive resin layer on the support layer, and the photosensitive resin layer includes (a) a carboxyl group content of 100 to 600 in terms of acid equivalent and weight A resin for an adhesive having an average molecular weight of 5,000 to 500,000, (b) an unsaturated compound capable of photopolymerization, (c) a photopolymerization initiator, and (d) a solvent. The photosensitive resin layer includes the photosensitive resin layer. The above-mentioned (d) solvent is included in an amount of 0.001% by mass or more and 1% by mass or less on a mass basis (but excluding the case where the (d) solvent is 0.5% by mass or less), and the photosensitive resin layer includes One or more compounds of the formulae (I) to (III) are the unsaturated compounds that can be photopolymerized in the above (b). The support layer is a polyester film, and the polyester is peeled from the photosensitive resin element and dried. The thermal shrinkage of the film in the TD direction is less than 3.2%. (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 from 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, m ₃ and m ₄ are each independently an integer from 0 to 29,-(AO)-and-(BO) The arrangement of the repeating unit of-may be random or block, and in the case of block, any of-(AO)-and-(BO)-may be on the biphenyl side) (In the formula, R ₃ represents a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms, R ₄ , R _5, and R ₆ each independently represent a hydrogen atom or a methyl group, and D represents an alkylene group having 2 to 6 carbon atoms. Base, n ₁ , n ₂ and n ₃ are integers above 0 which satisfy n ₁ + n ₂ + n ₃ = 3 ~ 60, n ₄ is 0 or 1, where plural D in the formula may be the same or Can be different, the repeating structure of-(OD)-can be random or block) [化 3] (In the formula, 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 a group of 0 to 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 an integer from 0 to 30,-(OA ₁ )-and- The arrangement of the repeating units of (OB ₁ )-may also be random or block. In the case of blocks, any of-(OA ₁ )-and-(OB ₁ )- Acid ester side). The photosensitive resin element according to claim 1, which comprises propylene glycol monomethyl ether as the (d) solvent. The photosensitive resin element according to claim 1, which contains toluene as the above-mentioned (d) solvent. The photosensitive resin element according to claim 1, which contains acetone as the above-mentioned (d) solvent. The photosensitive resin element according to any one of claims 1 to 4, which includes the compound represented by the general formula (I) and the compound represented by the general formula (II) as the non-photopolymerizable component (b). Saturated compounds. The photosensitive resin element according to any one of Claims 1 to 4, which includes the compound represented by the general formula (I) and the compound represented by the general formula (III) as the non-photopolymerizable component (b). Saturated compounds. The photosensitive resin element according to any one of claims 1 to 4, which includes the compound represented by the general formula (II) and the compound represented by the general formula (III) as the non-photopolymerizable component (b). Saturated compounds. The photosensitive resin element according to any one of claims 1 to 4, wherein a film thickness of the polyester film is 12 μm to 16 μm.