JP5905773B2 - Photopolymerizable resin composition - Google Patents

Description

  The present invention relates to a photopolymerizable resin composition and its use. More specifically, a photopolymerizable resin composition suitable for forming a conductive pattern for manufacturing a printed wiring board including a rigid substrate or a flexible substrate, a lead frame, and the like, a photopolymerizable resin laminate formed by the same, The present invention also relates to a resist pattern forming method, a circuit board manufacturing method, a lead frame manufacturing method, and a semiconductor package manufacturing method using the resist pattern.

  For electronic devices such as personal computers and mobile phones, printed wiring boards for mounting components and semiconductors are used. As a resist for producing a printed wiring board or the like, a so-called dry film resist in which a support, a photopolymerizable resin layer, and a protective layer as necessary is further laminated is conventionally used. The dry film resist is generally formed by laminating a photopolymerizable resin layer on a support, and further laminating a protective layer on the photopolymerizable resin layer as necessary. As the photopolymerizable resin layer, an alkali developing type is generally used, and a weak alkaline aqueous solution is used as a developing solution.

  To produce a printed wiring board or the like using a dry film resist, first remove the protective layer (if it has a protective layer), then place a laminator or the like on a permanent circuit production substrate such as a copper-clad laminate or a flexible substrate. The dry film resist used is laminated, the support is peeled off as necessary, and the photopolymerizable resin layer is exposed through a wiring pattern mask film or the like. Next, if a support is present, the support is peeled off, and the photopolymerizable resin layer in the unexposed portion is dissolved or dispersed with a developer to form a resist pattern on the substrate.

  After forming the resist pattern, the process for forming a circuit is roughly divided into two methods. The first method is a method in which after removing a copper surface such as a copper clad laminate not covered with a resist pattern by etching, the resist pattern portion is removed with an alkaline aqueous solution stronger than the developer. In this case, for simplicity of the process, a method (tenting method) in which a through hole (through hole) is covered with a cured film and then etched is frequently used. The second method is to remove the resist pattern after etching the copper surface with copper, solder, nickel, tin, etc., and then etch the copper surface of the copper-clad laminate that appears (plating) Law). In any case, cupric chloride, ferric chloride, a copper ammonia complex solution or the like is used for etching.

  Responding to the recent miniaturization of printed wiring boards mounted on personal computers and the like, high resolution and high adhesion of resists are required. Higher resolution of the resist is generally achieved by improving the crosslink density of the photopolymerizable resin composition. However, if the crosslink density is increased, the cured resist film becomes harder, resulting in delayed peeling time or stripped pieces. There is a problem that the resist becomes difficult to break and the peelability of the resist deteriorates. In particular, in the resist pattern peeling step, when the peeled piece size of the resist cured film is large, the entanglement of the peeling layer with the ring roll may become a problem. Further, when plating is performed, the plating often overhangs. In this case, if the peeling piece is large, a peeling failure may occur and the resist film may remain on the substrate. Therefore, there is a demand for a technique that achieves both high resolution of the resist and resist peelability. A technique for reducing the size of the peeled piece by using a low molecular weight thermoplastic polymer has been proposed (for example, Patent Document 1), but only by adding a small amount of a more general-purpose general-purpose plasticizer or monomer. If the strip effect of the peeled piece can be exhibited while maintaining other resist performances, the technology can be expected to be widely applied in the design of the photopolymerizable resin composition.

JP-A-11-327138

  The present invention relates to a photopolymerizable resin composition having good resolution after development and good resist releasability, and a photopolymerizable resin having a photopolymerizable resin layer comprising the photopolymerizable resin composition It is an object of the present invention to provide a laminate, a method of forming a resist pattern using the photopolymerizable resin composition, and a method of manufacturing a circuit board, a lead frame, and a semiconductor package.

  As a result of investigations to solve the above problems, the present inventor can provide a specific photopolymerizable resin composition with good resolution and resist peelability and a good conductor pattern. As a result, they have reached the present invention.

｛式中、Ｒ^１は水素原子又はメチル基を表す。｝
で表される化合物：０．０５〜０．５質量％
を含む、光重合性樹脂組成物。
［２］ 前記（Ａ）バインダー用樹脂の重量平均分子量が、４０，０００〜１３０，０００である、［１］に記載の光重合性樹脂組成物。
［３］ 前記（Ａ）バインダー用樹脂のモノマー成分は、下記一般式（ＩＩ）：

｛式中、Ｒ^２は、水素原子又はメチル基であり、そしてＲ^３は、水素原子、ハロゲン原子、ヒドロキシル基、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、カルボキシル基、又は炭素数１〜１２のハロアルキル基である。｝で表される化合物を含む、［１］又は［２］に記載の光重合性樹脂組成物。
［４］ 前記（Ｂ）光重合性不飽和化合物は、下記一般式（ＩＩＩ）：

｛式中、Ｒ^４及びＲ^５は、各々独立に、水素原子またはメチル基であり、Ａ^１及びＢ^１は、各々独立に、エチレン基又はプロピレン基であり、それぞれ同一であっても異なっていてもよく、異なっている場合、−（Ａ^１−Ｏ）−及び−（Ｂ^１−Ｏ）−の繰り返し単位は、ブロック構造でもランダム構造でもよく、−（Ａ^１−Ｏ）−と−（Ｂ^１−Ｏ）−は、いずれがエステル側であってもよく、そしてｍ_１、ｍ_２、ｍ_３、及びｍ_４は、０又は正の整数であり、ｍ_１＋ｍ_２＋ｍ_３＋ｍ_４は、２〜４０である。｝
で表される化合物を含む、［１］〜［３］のいずれか一つに記載の光重合性樹脂組成物。
［５］ ［１］〜［４］のいずれか一つに記載の光重合性樹脂組成物を、支持体上に積層してなる、光重合性樹脂積層体。
［６］ ［１］〜［４］のいずれか一つに記載の光重合性樹脂組成物を、基板上に積層する積層工程；該光重合性樹脂組成物を露光する露光工程；及び該光重合性樹脂組成物の未露光部を除去することによってレジストパターンを形成する現像工程を含む、レジストパターンの形成方法。
［７］ ［１］〜［４］のいずれか一つに記載の光重合性樹脂組成物を、基板上に積層する積層工程；該光重合性樹脂組成物を露光する露光工程；該光重合性樹脂組成物の未露光部を除去することによってレジストパターンを形成する現像工程；該レジストパターンが形成された該基板をエッチング又はめっきする配線パターン形成工程；及び該配線パターン形成工程後の基板からレジストパターンを剥離する剥離工程を含む、回路基板の製造方法。
［８］ ［１］〜［４］のいずれか一つに記載の光重合性樹脂組成物を、金属板である基板上に積層する工程；該光重合性樹脂組成物を露光する露光工程；該光重合性樹脂組成物の未露光部を除去することによってレジストパターンを形成する現像工程；該レジストパターンが形成された該基板をエッチングする導体パターン形成工程；及び該導体パターン形成工程後の基板からレジストパターンを剥離する剥離工程を含む、リードフレームの製造方法。
［９］ ［１］〜［４］のいずれか一項に記載の光重合性樹脂組成物を、ＬＳＩとしての回路形成が終了したウェハに積層する積層工程；該光重合性樹脂組成物を露光する露光工程；該光重合性樹脂組成物の未露光部を除去することによってレジストパターンを形成する現像工程；該レジストパターンが形成された該ウェハをめっきするめっき工程；及び該めっき工程後のウェハからレジストパターンを剥離する剥離工程を含む、半導体パッケージの製造方法。 That is, the present invention is as follows.
[1] (A) Resin for binders having a carboxyl group content of 100 to 600 in terms of acid equivalent and a weight average molecular weight of 5,000 to 500,000: 10 to 90% by mass;
(B) Photopolymerizable unsaturated compound: 5 to 70% by mass;
(C) Photopolymerization initiator: 0.01 to 20% by mass; and (D) The following general formula (I):

{In the formula, R ¹ represents a hydrogen atom or a methyl group. }
Compound represented by: 0.05 to 0.5% by mass
A photopolymerizable resin composition comprising:
[2] The photopolymerizable resin composition according to [1], wherein the (A) binder resin has a weight average molecular weight of 40,000 to 130,000.
[3] The monomer component of the (A) binder resin has the following general formula (II):

{Wherein R ² is a hydrogen atom or a methyl group, and R ³ is a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a carboxyl group. Or a haloalkyl group having 1 to 12 carbon atoms. } The photopolymerizable resin composition as described in [1] or [2] containing the compound represented by this.
[4] The photopolymerizable unsaturated compound (B) is represented by the following general formula (III):

{In the formula, R ⁴ and R ⁵ are each independently a hydrogen atom or a methyl group; A ¹ and B ¹ are each independently an ethylene group or a propylene group, and each is the same or different. If they are different, the repeating unit of-(A ¹ -O)-and-(B ¹ -O)-may be a block structure or a random structure, and-(A ¹ -O)-and-( B ¹ —O) — may be any ester side, and m ₁ , m ₂ , m ₃ , and m ₄ are 0 or a positive integer, and m ₁ + m ₂ + m ₃ + m ₄ is 2-40. }
The photopolymerizable resin composition according to any one of [1] to [3], comprising a compound represented by:
[5] A photopolymerizable resin laminate obtained by laminating the photopolymerizable resin composition according to any one of [1] to [4] on a support.
[6] A lamination step of laminating the photopolymerizable resin composition according to any one of [1] to [4] on a substrate; an exposure step of exposing the photopolymerizable resin composition; and the light A method for forming a resist pattern, comprising a development step of forming a resist pattern by removing an unexposed portion of the polymerizable resin composition.
[7] Lamination step of laminating the photopolymerizable resin composition according to any one of [1] to [4] on a substrate; an exposure step of exposing the photopolymerizable resin composition; A development step of forming a resist pattern by removing an unexposed portion of the conductive resin composition; a wiring pattern formation step of etching or plating the substrate on which the resist pattern is formed; and a substrate after the wiring pattern formation step A method for manufacturing a circuit board, comprising a peeling step for peeling a resist pattern.
[8] A step of laminating the photopolymerizable resin composition according to any one of [1] to [4] on a substrate that is a metal plate; an exposure step of exposing the photopolymerizable resin composition; A development step of forming a resist pattern by removing an unexposed portion of the photopolymerizable resin composition; a conductor pattern formation step of etching the substrate on which the resist pattern is formed; and a substrate after the conductor pattern formation step A method for producing a lead frame, comprising a peeling step of peeling the resist pattern from the substrate.
[9] A laminating step of laminating the photopolymerizable resin composition according to any one of [1] to [4] on a wafer on which circuit formation as an LSI has been completed; exposing the photopolymerizable resin composition An exposure step; a development step of forming a resist pattern by removing unexposed portions of the photopolymerizable resin composition; a plating step of plating the wafer on which the resist pattern is formed; and a wafer after the plating step A method for manufacturing a semiconductor package, comprising a peeling step of peeling a resist pattern from the substrate.

  The photopolymerizable resin composition of the present invention and the photopolymerizable resin laminate formed therewith have good resolution and resist peelability after development. In particular, with respect to resist peelability, it is possible to make strips small while suppressing a delay in stripping time, and it is possible to realize the manufacture of a stable circuit board, lead frame, and semiconductor package.

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

｛式中、Ｒ^１は水素原子又はメチル基を表す。｝
で表される化合物：０．０５〜０．５質量％を含む、光重合性樹脂組成物を提供する。 <Photopolymerizable resin composition>
In one embodiment, (A) Resin for binders having a carboxyl group content of 100 to 600 in terms of acid equivalent and a weight average molecular weight of 5,000 to 500,000: 10 to 90% by mass, (B) Photopolymerizable unsaturated compound: 5-70% by mass, (C) Photopolymerization initiator: 0.01-20% by mass, and (D) the following general formula (I):

{In the formula, R ¹ represents a hydrogen atom or a methyl group. }
The photopolymerizable resin composition containing 0.05-0.5 mass% of compounds represented by these is provided.

  (D) The compound represented by the general formula (I) may be added at the time of preparing the photopolymerizable resin composition. As described later, the compound of the binder resin or the photopolymerizable unsaturated compound may be added. You may leave as an unreacted component at the time of a synthesis | combination. (D) Addition of the compound represented by the general formula (I) and introduction of a carboxyl group into the crosslinked network at the time of curing increases the swelling of the cured film in an alkaline aqueous solution and makes the peeled piece finer Can be made. The addition amount is preferably 0.05% by mass or more from the viewpoint of increasing the swelling of the cured film, more preferably 0.2% by mass or more, and further preferably 0.3% by mass or more. On the other hand, the upper limit is preferably 0.5% by mass or less from the viewpoint of maintaining the resist resolution after development and preventing the delay of the peeling time.

[(A) Resin for binder]
(A) The binder resin has a carboxyl group content of 100 to 600, preferably 250 to 450, as an acid equivalent. (A) When the binder resin is composed of two or more kinds of polymers, the acid equivalent of the average of all polymers may be within the above range. Preferably, (A) the acid equivalent is in the above range for all polymers constituting the binder resin. An acid equivalent means the mass (gram) of the polymer which has a 1 equivalent carboxyl group in it. (A) The carboxyl group in the binder resin is useful for imparting developability and releasability to an alkaline aqueous solution of a photopolymerizable resin composition containing the carboxyl group. The acid equivalent is 100 or more from the viewpoint of development resistance, resolution, and adhesion to a support and the like, and is 600 or less from the viewpoint of developability and peelability. The acid equivalent is measured by potentiometric titration using an automatic titrator (for example, Hiranuma Auto titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd.) and using 0.1 mol / L sodium hydroxide aqueous solution. .

(A) The weight average molecular weight of the binder resin can be 5,000 to 500,000. (A) The weight average molecular weight of the binder resin can be 500,000 or less from the viewpoint of resolution, and can be 5,000 or more from the viewpoint of edge fuse. In order to exhibit the above-described effect more satisfactorily, the weight average molecular weight of the (A) binder resin is preferably 5,000 to 200,000, more preferably 5,000 to 150,000, and still more preferably. Is 40,000-130,000, most preferably 40,000-90,000. Here, the weight average molecular weight is determined by gel permeation chromatography (for example, gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: GullIver, PU-1580 type, column: Shodex manufactured by Showa Denko KK). Trademarks) (KF-807, KF-806M, KF-806M, KF-802.5) in series, moving bed solvent: tetrahydrofuran, polystyrene standard sample (Showex STANDARD SM-105 Polystyrene) calibration The weight average molecular weight (in terms of polystyrene) is obtained by using a line)). (A) The dispersion degree of the molecular weight of the binder resin (sometimes referred to as molecular weight distribution) is typically 1 to 6, for example, and preferably 1 to 4. The degree of dispersion is represented by the ratio between the weight average molecular weight and the number average molecular weight as shown in the following formula.
(Dispersity) = (weight average molecular weight) / (number average molecular weight)
(A) When the binder resin is composed of two or more polymers, the weight average molecular weight and the degree of dispersion of all the polymers may be within the above ranges. However, preferably, the weight average molecular weight and the dispersity are within the above ranges for all the polymers constituting the (A) binder resin.

｛式中、Ｒ^２は、水素原子又はメチル基であり、そしてＲ^３は水素原子、ハロゲン原子、ヒドロキシル基、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、カルボキシル基、又は炭素数１〜１２のハロアルキル基である。｝
で表される化合物であることが好ましい。 In one embodiment, as the first monomer, (A) the monomer component of the binder resin is represented by the following general formula (II):

{Wherein R ² is a hydrogen atom or a methyl group, and R ³ is a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a carboxyl group, Or it is a C1-C12 haloalkyl group. }
It is preferable that it is a compound represented by these.

  From the viewpoint of resolution after development, the first monomer is preferably included, and the proportion thereof is preferably in the range of 5 to 60% by mass, more preferably 20 to 55% by mass of the total monomer components. It is a range.

The monomer component preferably contains, in addition to the first monomer, a second monomer that is a carboxylic acid or acid anhydride having one polymerizable unsaturated group as a copolymerization component. The monomer content of (A) is determined by the desired acid equivalent of the binder resin (A), and the proportion thereof is preferably in the range of 5 to 90% by mass in the monomer component from the viewpoint of alkali developability, more preferably. It is in the range of 10 to 55% by mass.
More specifically, when MAA is used, for example, it is preferably in the range of 14 to 86% by mass in the monomer component, and more preferably in the range of 14 to 50% by mass from the viewpoint of resolution / adhesion. is there.

  Examples of the second monomer include (meth) acrylic acid (the above general formula (I)), fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester, and the like. In one embodiment, the compound represented by the above general formula (I) is preferable from the viewpoint of the reactivity of the monomer, and at the time of synthesis, the compound is added in an amount of 0.05 to 0.5 mass in the photopolymerizable resin composition. % May be left as an unreacted component at an arbitrary ratio.

  In addition, the monomer component may further contain, as a copolymerization component, a third monomer that is a non-acidic compound having one polymerizable unsaturated group in the molecule. The third monomer includes developability of the photopolymerizable resin composition, resistance to etching and / or plating, peelability, and flexibility of a cured film obtained by curing the photopolymerizable resin composition. It is chosen to retain various properties.

  Examples of the third monomer include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth). Aryl (meth) such as acrylate, (meth) acrylonitrile, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl (meth) acrylate, cresyl (meth) acrylate, naphthyl (meth) acrylate, etc. ) Acrylate, and substituted structures such as alkoxy groups, halogen atoms, alkyl groups on the aromatic ring of benzyl (meth) acrylate such as methoxybenzyl (meth) acrylate and chlorobenzyl (meth) acrylate A compound having the like.

  (A) The binder resin is a radical polymerization such as benzoyl peroxide or azoisobutyronitrile in a solution obtained by diluting at least one of the first to third monomers with a solvent such as acetone, methyl ethyl ketone, or isopropanol. It is preferable to polymerize the monomer component by adding an appropriate amount of an initiator and stirring with heating. Polymerization may be performed while dropping a part of the monomer component mixture into the reaction solution. After completion of the polymerization reaction, a solvent may be further added to adjust the solution to a desired concentration. As the polymerization means, in addition to solution polymerization as described above, bulk polymerization, suspension polymerization, or emulsion polymerization may be used.

  (A) The content rate with respect to the total amount of the photopolymerizable resin composition of resin for binders can be made into a suitable content rate as a photopolymerizable resin composition of this invention. Specifically, the resist pattern formed by exposure and development has a characteristic as a resist, for example, in the range of 10 to 90% by mass from the viewpoint of having sufficient resistance in tenting, etching and various plating processes. Yes, preferably 20 to 90 mass%, more preferably 30 to 70 mass%.

｛式中、Ｒ^４及びＲ^５は、各々独立に、水素原子またはメチル基であり、Ａ^１及びＢ^１は、各々独立に、エチレン基又はプロピレン基であり、それぞれ同一であっても異なっていてもよく、異なっている場合、−（Ａ^１−Ｏ）−及び−（Ｂ^１−Ｏ）−の繰り返し単位は、ブロック構造でもランダム構造でもよく、−（Ａ^１−Ｏ）−と−（Ｂ^１−Ｏ）−は、いずれがエステル側であってもよく、そしてｍ_１、ｍ_２、ｍ_３、及びｍ_４は、０又は正の整数であり、ｍ_１＋ｍ_２＋ｍ_３＋ｍ_４は、２〜４０である。｝
で表される群から選ばれる少なくとも１種の化合物を含有することが好ましい。 [(B) Photopolymerizable unsaturated compound]
(B) The photopolymerizable unsaturated compound should just be a compound which has a photopolymerizable unsaturated bond, and is a compound which has an ethylenically unsaturated bond typically. Further, when the reactive group of the photopolymerizable unsaturated compound is a (meth) acrylic group, the photopolymerizable unsaturated compound is obtained by reacting the precursor represented by the general formula (I) with various alcohols. A compound is obtained, but in this reaction, any ratio such that the unreacted compound represented by the general formula (I) is 0.05 to 0.5% by mass in the photopolymerizable resin composition Thus, the compound represented by the general formula (I) may be intentionally left. (B) The photopolymerizable unsaturated compound is represented by the following general formula (III) from the viewpoint of resolution:

{In the formula, R ⁴ and R ⁵ are each independently a hydrogen atom or a methyl group; A ¹ and B ¹ are each independently an ethylene group or a propylene group, and each is the same or different. If they are different, the repeating unit of-(A ¹ -O)-and-(B ¹ -O)-may be a block structure or a random structure, and-(A ¹ -O)-and-( B ¹ —O) — may be any ester side, and m ₁ , m ₂ , m ₃ , and m ₄ are 0 or a positive integer, and m ₁ + m ₂ + m ₃ + m ₄ is 2-40. }
It is preferable to contain at least one compound selected from the group represented by:

  Specific examples of at least one compound selected from the group represented by the general formula (III) include 2,2-bis {(4-acryloxypolyethyleneoxy) phenyl} propane, 2,2-bis {(4 -Methacryloxypolyethyleneoxy) phenyl} propane, 2,2-bis {(4-acryloxypolypropyleneoxy) phenyl} propane, 2,2-bis {(4-methacryloxypolypropyleneoxy) phenyl} propane and the like. The polyethyleneoxy group of the compound is a group consisting of a monoethyleneoxy group, a diethyleneoxy group, a triethyleneoxy group, a tetraethyleneoxy group, a pentaethyleneoxy group, a hexaethyleneoxy group, a heptaethyleneoxy group, and an octaethyleneoxy group. A compound having any group selected from the group consisting of bisphenol A and a diglycolate of polyethylene glycol in which 2 moles of ethylene oxide is added to both ends of bisphenol A (Shin Nakamura Chemical Co., Ltd.) is preferable. NK ester BPE-200 manufactured by Kogyo Co., Ltd., and dimethacrylate of polyethylene glycol (NK ester BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.) and bisphenol A each having an average of 5 moles of ethylene oxide added to both ends of bisphenol A On both ends There are dimethacrylate polyalkylene glycols respectively obtained by adding propylene oxide by an average of 2 moles of ethylene oxide by an average of 6 moles.

  The content ratio of the compound represented by the general formula (III) is preferably 5 to 80% by mass and more preferably 10 to 80% by mass in 100% by mass of the photopolymerizable unsaturated compound (B). The content is preferably 5% by mass or more from the viewpoint of resolution after development, and preferably 80% by mass or less from the viewpoint of developability.

  In the photopolymerizable resin composition of the present embodiment, (B) as a photopolymerizable unsaturated compound, in addition to or in place of the photopolymerizable monomer represented by the general formula (III), The compound shown by can be used. Specifically, for example, 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate 2-di (p-hydroxyphenyl) propane di (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyoxypropyltrimethylolpropane tri (meth) acrylate, polyoxyethyltrimethylol- Propanetriacrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, vinyl Phenolic A diglycidyl ether terdi (meth) acrylate, β-hydroxypropyl-β ′-(acryloyloxy) propyl phthalate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyalkylene glycol (Meth) acrylate, polypropylene glycol mono (meth) acrylate, 2,2-bis {(4- (meth) acryloxypolyethoxy) cyclohexyl} propane, poly (ethylene oxide) added to both ends of polypropylene glycol with propylene oxide added Alkylene glycol dimethacrylates, polyfunctional (meth) acrylates containing urethane groups, eg hexamethylene diisocyanate and penta B urethane compound and propylene glycol monomethacrylate, and the like.

  (B) The content rate with respect to the total amount of a photopolymerizable resin composition of a photopolymerizable unsaturated compound can be made into a content rate suitable as a photopolymerizable resin composition of this invention. Specifically, it is the range of 5-70 mass%, Preferably it is 10-60 mass%. This amount is 5% by mass or more from the viewpoint of improving sensitivity, resolution, and adhesion, and is 70% by mass or less from the viewpoint of suppressing cold flow and delay in peeling of the cured resist.

[(C) Photopolymerization initiator]
(C) As the photopolymerization initiator, a photopolymerization initiator generally known as a compound that is activated by actinic rays (for example, ultraviolet rays or the like) to initiate a polymerization reaction can be used. From the viewpoint of sensitivity, resolution, and adhesion, the (C) photopolymerization initiator preferably contains a 2,4,5-triarylimidazole dimer, and 2,4,5-triarylimidazole dimer. A combined system of the isomer and p-aminophenyl ketone is more preferred.

  Examples of the 2,4,5-triarylimidazole dimer include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis. -(M-methoxyphenyl) imidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, etc. are mentioned, and in particular, 2- (o-chlorophenyl) A -4,5-diphenylimidazole dimer is preferred.

  Examples of p-aminophenyl ketone include p-aminobenzophenone, p-butylaminoacetophenone, p-dimethylaminoacetophenone, p-dimethylaminobenzophenone, p, p'-bis (ethylamino) benzophenone, p, p'- Examples thereof include bis (dimethylamino) benzophenone [Michler's ketone], p, p′-bis (diethylamino) benzophenone, p, p′-bis (dibutylamino) benzophenone, and the like.

  Also, 2,4,5-triarylimidazole dimer and / or p-aminophenyl ketone and 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) ) -Pyrazolin and other pyrazoline compounds are also preferred.

  Furthermore, examples of the photopolymerization initiator that can be used include quinones such as 2-ethylanthraquinone and 2-tert-butylanthraquinone, aromatic ketones such as benzophenone, and benzoin ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether. And acridine compounds such as 9-phenylacridine, and ketals such as benzyldimethylketal and benzyldiethylketal.

  Moreover, for example, combinations of thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, and 2-chlorothioxanthone and tertiary amine compounds such as dimethylaminobenzoic acid alkyl ester compounds are also included.

  Furthermore, oxime esters such as 1-phenyl-1,2-propanedione-2-O-benzoyloxime and 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime are also exemplified. . In addition, N-aryl-α-amino acid compounds can be used, and among these, N-phenylglycine is particularly preferable.

  (C) The content rate with respect to the total amount of a photopolymerizable resin composition of a photoinitiator can be made into a suitable content rate as a photopolymerizable resin composition of this invention. Specifically, it is the range of 0.01-20 mass%, and a preferable range is 0.05-10 mass%. The above content ratio is 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity, and the active light is sufficiently transmitted to the bottom surface of the resist made of the photopolymerizable resin composition, and good resolution is achieved. Is 20% by mass or less from the viewpoint of obtaining.

[Additive]
In addition to the above components, the photopolymerizable resin composition can contain various additives such as coloring substances, coloring dyes, stabilizers, and plasticizers.

  As coloring substances, dyes, pigments and the like can be used. For example, fuchsin, phthalocyanine green, auramin base, chalcoxide green S, paramadienta, crystal violet, methyl orange, Nile Blue 2B, Victoria Blue, Malachite Green (Hodogaya Chemical Co., Ltd.) Eisen (registered trademark) MALACHITE GREEN), Basic Bull-20, Diamond Green (Eizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.), and the like.

  The photopolymerizable resin composition can also contain a coloring dye that develops color when irradiated with light. Examples of the coloring dye used include a combination of a leuco dye or a fluorane dye and a halogen compound. Examples of the leuco dye include tris (4-dimethylamino-2-methylphenyl) methane [leuco crystal violet], tris (4-dimethylamino-2-methylphenyl) methane [leucomalachite green], and the like. .

  Halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2,3 -Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, triazine compounds and the like. Examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine and the like.

  Among such coloring dyes, combinations of tribromomethylphenylsulfone and leuco dyes, and combinations of triazine compounds and leuco dyes are useful.

  The content of the coloring substance and / or the coloring dye (when used) is preferably 0.01 to 10% by mass in 100% by mass of the photopolymerizable resin composition. The content is preferably 0.01% by mass or more from the viewpoint that sufficient coloring property (in the case of a coloring substance) and coloring property (in the case of a coloring dye) can be recognized, and has a contrast between an exposed portion and an unexposed portion. From the standpoint of maintaining the storage stability, 10% by mass or less is preferable.

  Stabilizers that can be added to improve the thermal stability and storage stability of the photopolymerizable resin composition include, for example, p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), And diphenylnitrosamine. Further, as stabilizers, a compound in which propylene oxide is further added to both sides of polypropylene glycol in which an average of 1 mol of propylene oxide is added to both sides of bisphenol A, benzotriazole, carboxybenzotriazole, 1- (2-dialkylamino) carboxybenzo And triazole, pentaerythritol 3,5-di-t-butyl-4-hydroxyphenylpropionic acid tetraester, and the like. A radical polymerization inhibitor can also be used as a stabilizer. Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di- -Tert-butyl-p-cresol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), nitrosophenylhydroxyamine aluminum Examples thereof include a salt, diphenylnitrosamine, and a condensate obtained by reacting 2 mol of 3-[(3-tert-butyl) -5-methyl-4-hydroxyphenyl] propanoic acid with 1 mol of triethylene glycol.

  The content of the stabilizer (when used) is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass, out of 100% by mass of the photopolymerizable resin composition. The total content is preferably 0.01% by mass or more from the viewpoint of imparting good storage stability to the photopolymerizable resin composition, and more preferably 3% by mass or less from the viewpoint of maintaining good sensitivity. preferable.

  Furthermore, you may make a photopolymerizable resin composition contain a plasticizer as needed. Examples of the plasticizer include phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, and acetyl tricitrate tri-n-propyl. Acetyl citrate tri-n-butyl, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, and the like.

  The content of the plasticizer (when used) is preferably 5 to 50% by mass, more preferably 5 to 30% by mass, out of 100% by mass of the photopolymerizable resin composition. The content is preferably 5% by mass or more from the viewpoint of suppressing delay in development time and imparting flexibility to the cured film, and is preferably 50% by mass or less from the viewpoint of suppressing insufficient curing and cold flow. preferable.

  In addition, when using a photopolymerizable resin composition for various uses, the photopolymerizable resin composition solution obtained by mixing the solvent which is mentioned later with a photopolymerizable resin composition can be used preferably, for example.

<Photopolymerizable resin laminate>
Another aspect of the embodiment provides a photopolymerizable resin laminate obtained by laminating the above-described photopolymerizable resin composition on a support. The photopolymerizable resin laminate typically comprises a photopolymerizable resin layer made of a photopolymerizable resin composition and a support that supports the layer. If necessary, a support for the photopolymerizable resin layer is used. You may have a protective layer on the surface on the opposite side. As a support used here, a transparent one that transmits an actinic ray emitted from an exposure light source is desirable. Examples of such a support include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film. , Polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film and the like. As these films, those stretched as necessary can be used. The haze of the support (particularly the film) is preferably 5 or less. The thinner the support (especially the film) is, the more advantageous in terms of image formation and economy, but 10 to 30 μm is preferable from the viewpoint of maintaining the strength.

  In addition, an important characteristic of the protective layer used in the photopolymerizable resin laminate is that the protective layer is sufficiently smaller than the support in terms of adhesion to the photopolymerizable resin layer, and the protective layer is a photopolymerizable resin layer. It can be easily peeled off. For example, a polyethylene film or a polypropylene film can be preferably used as the protective layer. Further, for example, a film having excellent peelability disclosed in JP-A-59-202457 can be used.

  The thickness of the protective layer is preferably 10 to 100 μm, and more preferably 10 to 50 μm.

  The thickness of the photopolymerizable resin layer in the photopolymerizable resin laminate varies depending on the use, but is preferably 3 to 100 μm, more preferably 3 to 50 μm. The thinner the resolution, the better the film strength. improves.

  As a method for preparing a photopolymerizable resin laminate by sequentially laminating a support, a photopolymerizable resin layer, and, if necessary, a protective layer, a conventionally known method can be employed. For example, the photopolymerizable resin composition used to form the photopolymerizable resin layer is mixed with a solvent that dissolves the photopolymerizable resin composition to form a uniform solution, and is first coated on the support using a bar coater or a roll coater. And dried, and a photopolymerizable resin layer made of a photopolymerizable resin composition is laminated on the support. Next, if necessary, a protective layer is laminated on the photopolymerizable resin layer. As described above, a photopolymerizable resin laminate can be produced.

  Examples of the solvent include ketones represented by methyl ethyl ketone (MEK), and alcohols represented by methanol, ethanol, and isopropanol. The solvent is preferably added to the photopolymerizable resin composition so that the viscosity of the solution of the photopolymerizable resin composition applied on the support is 500 to 4000 mPa at 25 ° C.

  Hereinafter, various embodiments in which the above-described photopolymerizable resin composition is used as a negative photosensitive resin composition will be further described.

<Resist pattern formation method>
Another aspect of the embodiment includes a lamination step of laminating the above-described photopolymerizable resin composition on a substrate, an exposure step of exposing the photopolymerizable resin composition, and an unexposed portion of the photopolymerizable resin composition. There is provided a method for forming a resist pattern, which includes a developing step of forming a resist pattern by removing the resist pattern. An example of a specific method for forming a resist pattern will be described.

[Lamination process]
First, in a lamination process, a photopolymerizable resin composition is laminated on a substrate using a laminator, for example. The photopolymerizable resin composition can typically be formed on a substrate as a photopolymerizable resin layer in the form of the photopolymerizable resin laminate described above combined with a support and optionally a protective layer. Specifically, for example, when the photopolymerizable resin laminate has a protective layer, the protective layer is peeled off, and then the photopolymerizable resin layer is heat-pressed and laminated on the substrate surface with a laminator. In this case, the photopolymerizable resin layer may be laminated only on one side of the substrate surface, or may be laminated on both sides. The heating temperature at this time is generally 40 to 160 ° C. In addition, adhesion and chemical resistance are improved by performing the thermocompression bonding twice or more. At this time, a two-stage laminator equipped with two rolls may be used for crimping, or the substrate and the photopolymerizable resin laminate are stacked several times and passed through the roll to crimp both. Also good.

[Exposure process]
Next, in the exposure step, the photopolymerizable resin composition is exposed using an exposure machine. If necessary, the support is peeled off and exposed to active light through a photomask. The exposure amount is determined from the light source illuminance and the exposure time, and may be measured using a light meter.

  In the exposure process, a maskless exposure method may be used. In maskless exposure, exposure is performed by directly drawing on a substrate without using a photomask. As the light source, a semiconductor laser having a wavelength of 350 to 410 nm, an ultrahigh pressure mercury lamp, or the like is used. The drawing pattern is controlled by a computer, and the exposure amount in this case is determined by the light source illuminance and the moving speed of the substrate.

[Development process]
Next, in the developing step, the unexposed portion of the photopolymerizable resin composition is removed using a developing device. After the exposure, when there is a support on the photopolymerizable resin layer, the support is removed as necessary, and then the unexposed portion is removed using a developing solution of an alkaline aqueous solution to obtain a resist pattern. As the alkaline aqueous solution, an aqueous solution such as Na ₂ CO ₃ or K ₂ CO ₃ can be used. These are selected according to the characteristics of the photopolymerizable resin layer, and a Na ₂ CO ₃ aqueous solution having a concentration of 0.2 to 2% by mass and 20 to 40 ° C. is generally used. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed.

  Although a resist pattern is obtained by the above-mentioned process, depending on the case, a 60-300 degreeC heating process and / or a UV curing process can also be performed. By performing this heating step and / or UV curing step, it is possible to further improve the chemical resistance of the resist pattern. A heating furnace of a hot air, infrared ray, far infrared ray, or the like can be used for heating, and a light irradiation device such as an ultrahigh pressure mercury lamp or a metal halide lamp can be used for UV curing.

<Circuit board manufacturing method>
Another embodiment includes a circuit pattern forming step for etching or plating a substrate on which a resist pattern is formed, and a peeling step for removing the resist pattern from the substrate, in addition to the steps of the resist pattern forming method described above. A manufacturing method is provided. That is, the manufacturing method of a circuit board (specifically, a printed wiring board) is carried out by using, for example, a copper-clad laminate or a flexible substrate as a substrate, followed by the following steps following the above-described resist pattern formation method. it can.

[Wiring pattern formation process]
A wiring pattern is formed by performing etching or plating by a known plating method on the surface (for example, a copper surface) of the substrate exposed by forming a resist pattern by development. Although there is no restriction | limiting in particular as a plating method, The plating method using copper, solder, tin, nickel, palladium, gold | metal | money, silver, etc. is mentioned. The plating method may be electrolytic plating or electroless plating.

[Peeling process]
After the wiring pattern forming step, the resist pattern is peeled from the substrate with an aqueous solution having alkalinity stronger than that of the developer, for example, to obtain a desired circuit board (printed wiring board). There is no particular limitation on the alkaline aqueous solution for stripping (hereinafter also referred to as “stripping solution”), but an aqueous solution of NaOH, KOH or an organic amine compound at a concentration of 2 to 5 mass% and 40 to 70 ° C. is common. Used for. It is possible to add a small amount of a water-soluble solvent to the stripping solution.

<Lead frame manufacturing method>
Another aspect of the embodiment includes a lead frame including a conductor pattern forming step of etching the substrate on which the resist pattern is formed and a peeling step of peeling the resist pattern from the substrate in addition to the steps of the resist pattern forming method described above. A manufacturing method is provided.

  That is, the lead frame manufacturing method can be carried out by using the following steps following the above-described resist pattern forming method using a metal plate such as copper, copper alloy, iron-based alloy or the like as a substrate. First, in the conductor pattern forming step, the exposed substrate with the resist pattern formed by development is etched by the same method as the etching in the above-described wiring pattern step to form a conductor pattern. Thereafter, in the peeling process, the resist pattern is peeled by the same method as the above-described circuit board manufacturing method to obtain a desired lead frame.

<Semiconductor package manufacturing method>
According to another aspect of the embodiment, the above-described photopolymerizable resin composition is used to form a resist pattern by the above-described resist pattern forming method using a wafer on which circuit formation as LSI has been completed as a substrate, and the resist pattern Provided is a method for manufacturing a semiconductor package, in which a plating process for plating a wafer substrate on which a resist pattern is formed and a peeling process for peeling a resist pattern from the wafer substrate after the plating process are provided. In other words, the semiconductor package manufacturing method can be performed by using the wafer on which the circuit formation as an LSI has been completed as a substrate and performing the following steps following the above-described resist pattern forming method.

  A resist pattern is formed by development, and the opening of the exposed substrate is subjected to columnar plating such as copper or solder to form a conductor pattern. Thereafter, the resist pattern is peeled off by the same method as the above-described method for manufacturing a circuit board (printed wiring board), and a thin metal layer other than the columnar plating is typically removed by etching to obtain a desired pattern. A semiconductor package is obtained.

<Substrate having an uneven pattern>
A photopolymerizable resin composition is typically used as a dry film resist in the form of a photopolymerizable resin laminate, and a substrate having a concavo-convex pattern can be formed by processing the substrate by a sandblasting method. . In this case, the photopolymerizable resin laminate is laminated on the substrate by the same method as the resist pattern forming method described above, and exposure and development are performed. Furthermore, the substrate is subjected to a sandblasting process in which a blast material is sprayed from the formed resist pattern and cut to a desired depth, and a resin part remaining on the substrate is removed from the substrate with an alkali stripping solution or the like. A fine pattern can be processed on the material. A known material is used as the blasting material used in the sandblasting process, and for example, fine particles having a particle diameter of about 2 to 100 μm such as SiC, SiO ₂ , Al ₂ O ₃ , CaCO ₃ , ZrO, glass, and stainless steel are used.

  Hereinafter, examples of the present embodiment will be described in more detail with reference to examples and comparative examples.

1. Production of Evaluation Samples Photopolymerizable resin laminates in Examples and Comparative Examples were produced as follows.

<Preparation of photopolymerizable resin composition>
The compounds shown in Table 1 were prepared, and photopolymerizable resin compositions were prepared at the composition ratios shown in Table 2. In Table 1, “polymerization ratio” is a mass ratio, and “%” is mass%. In addition, the mass parts of A-1 to A-3 in Table 2 are values of only the resin component not containing methyl ethyl ketone.

<Production of photopolymerizable resin laminate>
The above photopolymerizable resin composition was thoroughly stirred and mixed, and uniformly applied to the surface of a 16 μm thick polyethylene terephthalate film (GR-16, manufactured by Teijin Films Ltd.) as a support using a bar coater. A photopolymerizable resin layer was formed by drying for 4 minutes in a dryer at 0 ° C. The thickness of the photopolymerizable resin layer was 40 μm.

  Next, a 20 μm thick polyethylene film (manufactured by Tamapoly Co., Ltd., GF-18) is laminated as a protective layer on the surface of the photopolymerizable resin layer on which the polyethylene terephthalate film is not laminated, and the photopolymerizable resin laminate. Got.

[Lamination process]
As a substrate for evaluation of the following (1), a 1.6 mm thick copper clad laminate in which 35 μm thick rolled copper foil is laminated, and the surface is wet buffol polishing (manufactured by 3M Co., Ltd., Scotch Bright (registered trademark)). HD # 600, 2 times).

  The substrates for evaluation of (1) and (2) below were obtained by jet scrubbing the surface with a spray pressure of 0.20 MPa (made by Nippon Carlit Co., Ltd., using Sac Random R (registered trademark) # 220). .

  While peeling off the polyethylene film of the photopolymerizable resin laminate, it was laminated at a roll temperature of 105 ° C. using a copper-clad laminate pre-heated to 60 ° C. and a hot roll laminator (manufactured by Asahi Kasei Co., Ltd., AL-700). . The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.

[Exposure process]
A mask film necessary for evaluation is placed on a polyethylene terephthalate film as a support, and an exposure amount at which a 21-step tablet made by Stöffer becomes 8 steps by using an ultra-high pressure mercury lamp (manufactured by Oak Manufacturing Co., Ltd., HMW-801). Then, the photopolymerizable resin layer was exposed.

[Development process]
After the polyethylene terephthalate film is peeled off, a 1% by weight Na ₂ CO ₃ aqueous solution at 30 ° C. is sprayed for a predetermined time using an alkali developing machine (manufactured by Fuji Kiko Co., Ltd., a dry film developing machine) to unexpose the photopolymerizable resin layer. The portion was dissolved and removed in a time twice the minimum image time. At this time, the minimum development time was defined as the minimum time required for the photopolymerizable resin layer in the unexposed portion to completely dissolve.

[Peeling process]
The cured resist was peeled off by spraying a 3% by mass aqueous sodium hydroxide solution heated to 50 ° C. onto the evaluation substrate after plating.

2. Evaluation Method (1) Resolution Evaluation A substrate for resolution evaluation that had passed 15 minutes after lamination was exposed with a line pattern in which the width of the exposed area and the unexposed area was 1: 1. Development was performed with a development time twice as long as the minimum development time, and the minimum mask width in which a cured resist line was normally formed was defined as a resolution value, and the resolution was ranked as follows.
◎: Resolution value of 20 μm or less ○: Resolution value of more than 20 μm, 24 μm or less Δ: Resolution value of more than 24 μm, 28 μm or less ×: Resolution value of more than 28 μm

(2) Evaluation of resist peelability A substrate for peelability evaluation that had passed 15 minutes after lamination was exposed through a 4 cm x 5 cm solid pattern mask and developed. The substrate on which the solid pattern was formed was immersed in a 3% aqueous sodium hydroxide solution at 50 ° C., and the time until the solid pattern resist was completely removed from the substrate was measured. The rank was classified as follows according to the peeling time.
A: Peeling time 44 seconds or less O: Peeling time over 44 seconds and 47 seconds or less Δ: Peeling time over 47 seconds and 50 seconds or less X: Peeling time over 50 seconds and 53 seconds or less
XX: peeling time exceeds 53 seconds

(3) Shape of peeled piece Similarly, it was immersed in a 3% aqueous sodium hydroxide solution at 50 ° C., and the peeled solid pattern resist piece was showered with washing water with a slit nozzle of 0.1 MPa for 10 seconds to form the peeled piece shape. Was observed. Ranking was performed as follows according to the shape of the peeled piece.
◎: The peeled piece is broken, and the piece is about 1 mm square. ○: The peeled piece is broken, and the piece is about 5 mm square. Δ: The peeled piece is broken, and the piece is about 10 mm square. ×: The peeled piece can only be broken into several pieces

  The photopolymerizable resin composition of the present invention and the photopolymerizable resin laminate formed therewith have good resolution after development and resist releasability, stable circuit boards, lead frames and A semiconductor package can be manufactured.

Claims (8)

(A) Resin for binders having a carboxyl group content of 100 to 600 in terms of acid equivalent and a weight average molecular weight of 40,000 to 130,000 : 10 to 90% by mass;
(B) Photopolymerizable unsaturated compound: 5 to 70% by mass;
(C) Photopolymerization initiator: 0.01 to 20% by mass; and (D) The following general formula (I):

{In the formula, R ¹ represents a hydrogen atom or a methyl group. }
Compound represented by: 0.05 to 0.5% by mass
A photopolymerizable resin composition comprising: The monomer component of the (A) binder resin has the following general formula (II):

{Wherein R ² is a hydrogen atom or a methyl group, and R ³ is a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a carboxyl group. Or a haloalkyl group having 1 to 12 carbon atoms. Comprising a compound represented by}, photopolymerizable resin composition according to claim 1. The (B) photopolymerizable unsaturated compound has the following general formula (III):

{In the formula, R ⁴ and R ⁵ are each independently a hydrogen atom or a methyl group; A ¹ and B ¹ are each independently an ethylene group or a propylene group, and each is the same or different. If they are different, the repeating unit of-(A ¹ -O)-and-(B ¹ -O)-may be a block structure or a random structure, and-(A ¹ -O)-and-( B ¹ —O) — may be any ester side, and m ₁ , m ₂ , m ₃ , and m ₄ are 0 or a positive integer, and m ₁ + m ₂ + m ₃ + m ₄ is 2-40. }
The photopolymerizable resin composition of Claim 1 or 2 containing the compound represented by these. The photopolymerizable resin laminated body formed by laminating | stacking the photopolymerizable resin composition as described in any one of Claims 1-3 on a support body. A lamination step of laminating the photopolymerizable resin composition according to any one of claims 1 to 3 on a substrate; an exposure step of exposing the photopolymerizable resin composition; and the photopolymerizable resin composition A method for forming a resist pattern, comprising a developing step of forming a resist pattern by removing an unexposed portion of the substrate. A lamination step of laminating the photopolymerizable resin composition according to any one of claims 1 to 3 on a substrate; an exposure step of exposing the photopolymerizable resin composition; of the photopolymerizable resin composition A developing process for forming a resist pattern by removing unexposed portions; a wiring pattern forming process for etching or plating the substrate on which the resist pattern is formed; and a resist pattern is peeled from the substrate after the wiring pattern forming process A method for manufacturing a circuit board, comprising a peeling step. A step of laminating the photopolymerizable resin composition according to any one of claims 1 to 3 on a substrate which is a metal plate; an exposure step of exposing the photopolymerizable resin composition; the photopolymerizable resin A development step of forming a resist pattern by removing an unexposed portion of the composition; a conductor pattern forming step of etching the substrate on which the resist pattern is formed; and peeling the resist pattern from the substrate after the conductor pattern forming step A method for manufacturing a lead frame, comprising a peeling step. A laminating step of laminating the photopolymerizable resin composition according to any one of claims 1 to 3 on a wafer on which circuit formation as LSI has been completed; an exposure step of exposing the photopolymerizable resin composition; A development process for forming a resist pattern by removing an unexposed portion of the photopolymerizable resin composition; a plating process for plating the wafer on which the resist pattern is formed; and peeling the resist pattern from the wafer after the plating process A method for manufacturing a semiconductor package, comprising a peeling step.