Photosensitive resin composition and photosensitive resin laminate

Abstract

To provide a photosensitive resin composition which can improve properties relating to dissolution of peeled chips and plating slipping, and a photosensitive resin laminate using the same, and a resist pattern or semiconductor bump formation method.SOLUTION: There is provided a photosensitive resin laminate in which a photosensitive resin layer containing a photosensitive resin composition containing 10 to 90 mass% of (A) an alkali-soluble polymer, 5 to 70 mass% of (B) a compound having an ethylenically unsaturated bond, and 0.01 to 20 mass% of (C) a photopolymerization initiator is laminated on a support film, wherein (A) the alkali-soluble polymer contains a copolymer having (meth)acrylate having an alkyl group having 3 to 12 carbon atoms as a copolymerization component, 51 to 100 mass% of an acrylate monomer as (B) the compound having the ethylenically unsaturated bond is contained with respect to the total amount of the (B), when film thickness of the photosensitive resin layer is represented by T (μm) and an absorbance at a wavelength of 365 nm is represented by A, T and A satisfy 0<A / T≤0.007, and the film thickness of the photosensitive resin layer is 40 μm or more and 600 μm or less.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a photosensitive resin laminate using the same, a method for forming a resist pattern or a semiconductor bump, and the like.

Background Art

[0002] Conventionally, the manufacture of printed wiring boards, precision machining of metals, etc. have been manufactured by photolithography methods. The photosensitive resin compositions used in photolithography methods are classified into negative-type compositions that dissolve and remove unexposed portions and positive-type compositions that dissolve and remove exposed portions.

[0003] When applying a photosensitive resin composition onto a substrate in a photolithography method, (1) a method of applying a photoresist solution onto a substrate and drying it, and (2) a method of laminating a photosensitive resin layer (hereinafter also referred to as "photosensitive resin layer") including a support and a photosensitive resin composition, and, if necessary, a protective layer, and laminating the photosensitive resin layer onto the substrate using a photosensitive resin laminate in which the layers are sequentially laminated is used. In the manufacture of printed wiring boards, the latter method is often used.

[0004] A method for forming a pattern using the above photosensitive resin laminate will be briefly described below. First, the protective layer is peeled off from the photosensitive resin laminate. Next, using a laminator, the photosensitive resin layer and the support are laminated on a substrate such as a copper-clad laminate or a copper sputtered thin film in the order of the substrate, the photosensitive resin layer, and the support. Next, the photosensitive resin layer is exposed through a photomask having a desired wiring pattern. Next, the support is peeled off from the exposed laminate, and a resist pattern is formed on the substrate by dissolving or dispersing and removing the non-patterned portions with a developer.

[0005] Furthermore, bumps for semiconductors and the like can be formed by subjecting a substrate provided with a resist pattern to plating treatments such as copper plating and solder plating.

[0006] Various photosensitive resin compositions have been investigated for resist pattern or semiconductor bump formation. For example, Patent Documents 1 to 5 describe photosensitive resin compositions containing specific alkali-soluble polymers, monomers, and photopolymerizable initiators. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] International Publication No. 2018 / 164217 [Patent Document 2] Japanese Patent Application Publication No. 5-341532 [Patent Document 3] Japanese Patent Application Publication No. 5-241340 [Patent Document 4] Japanese Patent Application Publication No. 3-200804 [Patent Document 5] International Publication No. 2015 / 178462 [Overview of the project] [Problems that the invention aims to solve]

[0008] In order to cope with the miniaturization and high density of wiring in recent years, the finished line width of conductor lines (e.g., copper lines) after etching is subject to strict requirements. In addition, phenomena such as the dissolution of the hardened resist pattern depending on the type of stripping solution (hereinafter also referred to as "stripping dissolution") and the penetration of plating into the bottom of the posts of the substrate after the hardened resist pattern has been stripped off following the plating process (hereinafter also referred to as "plating penetration") have been reported.

[0009] However, the photosensitive compositions described in Patent Documents 1 to 5 either do not focus on dissolving the peeling material and allowing the plating to penetrate, or there is room for improvement regarding the dissolution of the peeling material and allowing the plating to penetrate.

[0010] Therefore, the present invention aims to provide a photosensitive resin composition that can improve the properties related to the dissolution of peeling fragments and the penetration of plating, a photosensitive resin laminate using the same, and a method for forming a resist pattern or semiconductor bump. [Means for solving the problem]

[0011] The inventors of this invention have diligently conducted research and experiments, and have found that the above problems can be solved by the following technical means, thereby completing the present invention. The present invention illustrates the following embodiments. (1) On the support film (A) Alkali-soluble polymer: 10% to 90% by mass, (B) Compounds having ethylenically unsaturated double bonds: 5% by mass to 70% by mass, (C) Photopolymerization initiator: 0.01% by mass to 20% by mass A photosensitive resin laminate having a photosensitive resin layer containing a photosensitive resin composition containing, The alkali-soluble polymer (A) comprises a copolymer containing a (meth)acrylate having an alkyl group with 3 to 12 carbon atoms as a copolymer component. As the compound having an ethylenically unsaturated double bond (B), the compound contains acrylate monomers in an amount of 51% to 100% by mass relative to the total amount of the compound having an ethylenically unsaturated double bond (B). When the thickness T [μm] of the photosensitive resin layer containing the above photosensitive resin composition is given by the absorbance A at a wavelength of 365 nm, the following equation (I): 0 The relationship expressed by and A photosensitive resin laminate in which the thickness of the photosensitive resin layer containing the aforementioned photosensitive resin composition is 40 μm or more and 600 μm or less. (2) The photosensitive resin laminate according to item (1), wherein the alkali-soluble polymer (A) comprises a copolymer containing 2-ethylhexyl acrylate as a copolymer component. (3) ​The photosensitive resin laminate according to item (1) or (2), wherein the (A) alkali-soluble polymer contains a copolymer containing benzyl (meth)acrylate as a copolymerization component. (4) The (A) alkali-soluble polymer further contains a (meth)acrylate other than the (meth)acrylate having an alkyl group with 3 to 12 carbon atoms and / or a vinyl compound as a copolymerization component, and The photosensitive resin laminate according to any one of items (1) to (3), wherein the (A) alkali-soluble polymer contains 6.0 mass% to 30 mass% of a (meth)acrylate having an alkyl group with 3 to 12 carbon atoms as a copolymerization component. (5) The photosensitive resin laminate according to any one of items (1) to (4), wherein the compound (B) having an ethylenically unsaturated double bond contains a compound having three or more acrylate groups. (6) The photosensitive resin laminate according to item (5), wherein the compound having three or more acrylate groups includes a compound having an acrylate group in any one of the trimethylolpropane, pentaerythritol, or dipentaerythritol skeletons. (7) The photosensitive resin laminate according to item (5) or (6), wherein the compound having three or more acrylate groups includes a compound having an acrylate group in any one of the trimethylolpropane, pentaerythritol, or dipentaerythritol skeletons and is contained at 1 mass% or more based on the total amount of the compound (B) having an ethylenically unsaturated double bond. (8) The photosensitive resin laminate according to any one of items (5) to (7), wherein the compound having three or more acrylate groups includes a compound having an acrylate group in any one of the trimethylolpropane, pentaerythritol, or dipentaerythritol skeletons and is contained at 10 mass% or more based on the total amount of the compound (B) having an ethylenically unsaturated double bond. (9) As the compound having a trifunctional or higher acrylate group, a compound having an acrylate group in any of the trimethylolpropane, pentaerythritol, or dipentaerythritol skeletons is contained at 80% by mass or more based on the total amount of the compound (B) having an ethylenically unsaturated double bond, the photosensitive resin laminate according to any one of items (5) to (8). (10) When the compound (B) having an ethylenically unsaturated double bond contains a compound having an aromatic ring, the compound having an aromatic ring has the following formula (VII):

Chemical formula

[0012] According to the present invention, the properties related to the dissolution of peeled resist patterns and their penetration into the plating can be improved. [Brief explanation of the drawing]

[0013] [Figure 1] This is an SEM image showing an example where the resist edge (a) and plating penetration (b) are small. [Figure 2] This is an SEM image showing an example where the resist hem (a) and plating penetration (b) are large. [Modes for carrying out the invention]

[0014] The following describes in detail embodiments for carrying out the present invention (hereinafter abbreviated as "embodiments"). The present invention is not limited to the following embodiments, and can be implemented in various ways within the scope of its gist.

[0015] <Photosensitive resin composition> One embodiment is, (A) Alkali-soluble polymer: 10% to 90% by mass, (B) Compounds having ethylenically unsaturated double bonds: 5% by mass to 70% by mass, (C) Photopolymerization initiator: 0.01% by mass to 20% by mass A photosensitive resin composition comprising, The (A) alkali-soluble polymer contains a copolymer that includes a (meth)acrylate having an alkyl group with 3 to 12 carbon atoms as a copolymer component. The present invention provides a photosensitive resin composition containing, as the (B) compound having an ethylenically unsaturated double bond, acrylate monomer in an amount of 51% to 100% by mass relative to the total amount of the (B) compound having an ethylenically unsaturated double bond.

[0016] It is understood that by using each of the components (A) to (C) in specific proportions, the photosensitive resin composition of this disclosure can improve the properties related to the dissolution of peeled resist patterns and plating penetration by means such as those exemplified below (but not limited to these). Furthermore, the photosensitive resin composition according to this embodiment may optionally contain, in addition to components (A) to (C), polymers other than component (A), monomers other than component (B), initiators other than component (C), dyes, adhesion aids, plasticizers, etc. The components contained in the photosensitive resin composition of this embodiment will be described in order below.

[0017] <(A) Alkali-soluble polymer> In this embodiment, (A) the alkali-soluble polymer is a polymer that can be dissolved in an alkaline aqueous solution, and can be, for example, a vinyl polymer containing a carboxyl group. In this embodiment, (A) the alkali-soluble polymer includes a copolymer containing (meth)acrylate (A1) having an alkyl group with 3 to 12 carbon atoms as a copolymer component, preferably a copolymer containing (meth)acrylate (A1) as a copolymer component in an amount of 6.0 to 30% by mass relative to the mass of (A) the alkali-soluble polymer, and more preferably a copolymer containing (meth)acrylate (A1) and (meth)acrylate (A2) other than (meth)acrylate (A1) and / or a vinyl compound (A3) as copolymer components. (A) The alkali-soluble polymer can be a copolymer that includes, for example, a (meth)acrylate (A1) having an alkyl group having 3 to 12 carbon atoms, in addition to monomers selected from (meth)acrylic acid, (meth)acrylates having alkyl groups having 2 or fewer carbon atoms and / or 13 or more carbon atoms, (meth)acrylates having aromatic groups, (meth)acrylonitrile, (meth)acrylamide, etc., as copolymer components.

[0018] (A) The alkali-soluble polymer preferably contains carboxyl groups and has an acid equivalent of 100 to 600. Acid equivalent refers to the mass in grams of an alkali-soluble polymer having 1 equivalent of carboxyl groups. An acid equivalent of 100 or more is preferable from the viewpoint of improving development resistance, resolution, and adhesion, while an acid equivalent of 600 or less is preferable from the viewpoint of improving developability and peelability. The acid equivalent can be measured using a titration device (for example, Hiranuma Automatic Titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd.) by potentiometric titration using a 0.1 mol / L aqueous sodium hydroxide solution. (A) The acid equivalent of the alkali-soluble polymer is more preferably 250 to 450, and even more preferably 300 to 440.

[0019] (A) The weight-average molecular weight of the alkali-soluble polymer is preferably 5,000 or more and 500,000 or less. A weight-average molecular weight of 5,000 or more is preferable from the viewpoint of the properties of the developed aggregates and the properties of the unexposed film such as edge fusing and cut-tip properties in the photosensitive resin laminate, while a weight-average molecular weight of 500,000 or less is preferable from the viewpoint of improving solubility in the developer. Edge fusing refers to the property of suppressing the phenomenon in which the photosensitive resin composition layer protrudes from the end face of the roll when the photosensitive resin laminate is wound into a roll shape. Cut-tip properties refer to the property of suppressing the phenomenon in which chips fly off when the unexposed film is cut with a cutter. Poor cut-tip properties can cause problems such as scattered chips adhering to the upper surface of the photosensitive resin laminate, and these chips being transferred to the mask in the subsequent exposure process, causing defects. (A) The weight-average molecular weight of the alkali-soluble polymer is more preferably 5,000 to 300,000, even more preferably 10,000 to 200,000, and even more preferably 25,000 to 120,000.

[0020] (A) The number of carbon atoms in the alkyl group of the (meth)acrylate copolymer component of the alkali-soluble polymer is preferably 4 to 12, and more preferably 5 to 12, from the viewpoint of improving the properties related to the dissolution of peeling pieces and the penetration of plating.

[0021] (A) The (meth)acrylate, which is a copolymer component of the alkali-soluble polymer, is a C3-C12 alkyl group, in a linear or branched configuration. 3~12The alkyl group may have an alkyl group, for example, a propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, etc. Among these, alkyl groups having 4 to 10 carbon atoms are preferred from the viewpoint of development time and the presence, shape, and length of the bottom of the resist pattern, alkyl groups having 5 to 10 carbon atoms are more preferred, alkyl groups having 6 to 8 carbon atoms are even more preferred, and 2-ethylhexyl groups are even more preferred. (A) When the number of carbon atoms of the alkyl group of the (meth)acrylate copolymer component of the alkali-soluble polymer is within the above range, the free volume of the photosensitive resin layer becomes larger, so the developer penetrates relatively easily and it swells easily, which tends to shorten the development time. By using a (meth)acrylate compound having a 2-ethylhexyl group, such as 2-ethylhexyl (meth)acrylate, as part of the monomer used in the synthesis, a copolymer containing 2-ethylhexyl acrylate as a copolymer component can be obtained by introducing a 2-ethylhexyl group into (A) an alkali-soluble polymer.

[0022] (A) The alkali-soluble polymer preferably has an aromatic hydrocarbon group. (A) When alkali-soluble polymers have aromatic hydrocarbon groups, their resolution and adhesion tend to improve, and consequently, their properties related to dissolution of peeling fragments and penetration into plating tend to improve. By using aromatic vinyl compounds, benzyl group-containing (meth)acrylate compounds, such as benzyl (meth)acrylate, as part of the monomers used in synthesis, aromatic hydrocarbon groups can be introduced into (A) alkali-soluble polymers to obtain copolymers containing benzyl (meth)acrylate as a copolymer component.

[0023] Furthermore, (A) alkali-soluble polymers can also be obtained by copolymerizing one or more monomers from the following two types of monomers. The first monomer is a carboxylic acid or acid anhydride having one polymerizable unsaturated group in its molecule. Examples include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid semi-ester. (Meth)acrylic acid is particularly preferred. Here, (meth)acrylic means acrylic or methacrylic.

[0024] (A) The copolymerization ratio of the first monomer in the alkali-soluble polymer can be easily calculated from the desired acid equivalent value in the alkali-soluble polymer. (A) The copolymerization ratio of the first monomer in the alkali-soluble polymer is preferably 10 to 50% by mass, based on the total mass of all monomer components. Setting the copolymerization ratio to 10% by mass or more is preferable from the viewpoint of exhibiting good developability and controlling edge fusing. Setting the copolymerization ratio to 50% by mass or less is preferable from the viewpoint of improving resolution and suppressing the generation of resist tails. From these viewpoints, the copolymerization ratio of the first monomer is more preferably 20 to 40% by mass, and even more preferably 20 to 30% by mass.

[0025] The second monomer is non-acidic and has at least one polymerizable unsaturated group in its molecule. As the second monomer, you may use (meth)acrylate compounds having an alkyl group with 3 to 12 carbon atoms as described above, for example, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc., or (meth)acrylate compounds having an aromatic hydrocarbon group as described above, for example, benzyl (meth)acrylate, etc.

[0026] Furthermore, as the second monomer, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, vinyl alcohol esters; vinyl acetate; (meth)acrylonitrile; aromatic vinyl compounds; and the like can be used.

[0027] Examples of aromatic vinyl compounds include styrene and styrene derivatives. Examples of styrene derivatives include oxystyrene, hydroxystyrene, acetoxystyrene, alkylstyrene, and halogenoalkylstyrene.

[0028] In this embodiment, the amount of (A) alkali-soluble polymer in the photosensitive resin composition is in the range of 10 to 90% by mass, preferably in the range of 40 to 80% by mass, and more preferably in the range of 50 to 70% by mass, when the total solid content mass of the photosensitive resin composition is 100% by mass. Setting the amount to 10% by mass or more is advantageous from the viewpoint of alkali developability, while setting the amount to 90% by mass or less is advantageous from the viewpoint of controlling the development time.

[0029] <(B) Compounds containing ethylenically unsaturated double bonds> In this embodiment, the photosensitive resin composition contains acrylate monomer as (B) a compound having an ethylenically unsaturated double bond in an amount of 51% to 100% by mass relative to the total amount of (B) the compound having an ethylenically unsaturated double bond.

[0030] (B) Compounds having an ethylenically unsaturated double bond tend to improve the properties of dissolving detached resist patterns when 51 to 100% by mass is acrylate monomer compared to when 51 to 100% by mass is methacrylate monomer. From the viewpoint of improving plating resistance in addition to detachment dissolving properties, the acrylate monomer content is preferably 55% or more by mass, 60% or more by mass, 65% or more by mass, 70% or more by mass, 75% or more by mass, 80% or more by mass, 85% or more by mass, or 90% or more by mass, and more preferably 91% or more by mass, relative to the total amount of compound (B).

[0031] The photosensitive resin composition according to this embodiment preferably contains, as (B) a compound having an ethylenically unsaturated double bond, a compound having three or more functional acrylate groups (i.e., three or more acryloyl groups in one molecule). When the photosensitive resin composition contains a compound having three or more functional acrylate groups as compound (B), it tends to improve the properties related to the dissolution of peeled resist patterns and plating penetration, and it is more preferable to use the compound having three or more functional acrylate groups in combination with (A) an alkali-soluble polymer containing the above-described (meth)acrylate (A1), (meth)acrylate (A2), and / or vinyl compound (A3) as copolymer components.

[0032] (B) When 1% by mass or more of the compound having an ethylenically unsaturated double bond is composed of a compound having three or more acrylate groups (three or more acryloyl groups in one molecule), the properties of resist pattern peeling and plating penetration tend to be further improved compared to when more than 0% by mass and less than 1% by mass is composed of a compound having three or more acryloyl groups in one molecule, or when no compound having three or more acryloyl groups in one molecule is included. From this viewpoint, the content of the compound having three or more acrylate groups is preferably 2% by mass or more, 3% by mass or more, 4% by mass or more, 5% by mass or more, 6% by mass or more, 7% by mass or more, 8% by mass or more, 9% by mass or more, or 10% by mass or more, relative to the total amount of compound (B), more preferably 20% by mass or more, 40% by mass or more, 60% by mass or more, or 80% by mass or more, and can be 100% by mass or less.

[0033] Of the compounds having three or more functional acrylate groups described above, compounds having an acrylate group in any of the trimethylolpropane, pentaerythritol, or dipentaerythritol skeletons are preferred from the viewpoint of solubility of peeling fragments and resistance to plating.

[0034] If the photosensitive resin composition contains a compound having an acrylate group in the trimethylolpropane skeleton, the compound having three or more functional acrylate groups is defined by the following general formula (III): [ka] {In the formula, n1, n2, and n3 are each an integer between 1 and 25, where n1 + n2 + n3 is an integer between 3 and 75. It is preferable to include a compound represented by} where R1, R2, and R3 are each independently hydrogen atoms.

[0035] In general formula (V), the value of n1+n2+n3 is preferably between 3 and 50. Setting n1+n2+n3 to 3 or more is preferable from the viewpoint of suppressing the formation of resist edges, imparting flexibility to the cured film, and improving film strength. On the other hand, setting n1+n2+n3 to 50 or less is preferable from the viewpoint of obtaining high resolution and adhesion and good peelability. A more preferable range for n1+n2+n3 is between 6 and 40, and an even more preferable range is between 9 and 30.

[0036] Specific examples of compounds represented by the above general formula (III) include: Triacrylate obtained by adding an average of 3 moles of ethylene oxide to the hydroxyl group terminals of trimethylolpropane. Triacrylate obtained by adding an average of 9 moles of ethylene oxide to the hydroxyl group terminals of trimethylolpropane. Triacrylate obtained by adding an average of 15 moles of ethylene oxide to the hydroxyl group terminals of trimethylolpropane. Triacrylate obtained by adding an average of 30 moles of ethylene oxide to the hydroxyl group terminals of trimethylolpropane. These are some examples.

[0037] If the photosensitive resin composition contains a compound having an acrylate group on a pentaerythritol skeleton, the compound having three or more functional acrylate groups is defined as follows: General formula (IV): [ka] {In the formula, n1, n2, n3, and n4 each independently represent integers from 1 to 25, and n1 + n2 + n3 + n4 are integers from 4 to 100. R1, R2, R3, and R4 each independently represent a hydrogen atom. R5, R6, R7, and R8 each independently represent an alkylene group, and if there are multiple R5, R6, R7, and R8, these multiple R5, R6, R7, and R8 may be the same or different from each other. It is preferable to include a compound represented by}. It is preferable to include a compound represented by .

[0038] In general formula (IV), it is preferable that n1+n2+n3+n4 is between 9 and 60. Setting n1+n2+n3+n4 to 9 or more is preferable from the viewpoint of suppressing the formation of resist edges, improving film strength, and imparting flexibility to the cured film. On the other hand, setting n1+n2+n3+n4 to 60 or less is preferable from the viewpoint of improving resolution and adhesion, obtaining good peelability, and controlling edge fusing. Furthermore, a more preferable range for n1+n2+n3+n4 is between 16 and 60.

[0039] In general formula (IV), R5, R6, R7, and R8 can be 1,2-ethylene, 1,2-propylene, and butylene groups, respectively. From the viewpoint of imparting flexibility to the cured film, improving film strength, suppressing development aggregation, and enhancing the reactivity of ethylenically unsaturated double bonds, 1,2-ethylene groups are preferred. Therefore, as the compound represented by general formula (IV), the following general formula (V) is preferred: [ka] [In the formula, n1, n2, n3, and n4 are each independent integers between 1 and 25, except that n1 + n2 + n3 + n4 is an integer between 4 and 100.] R1, R2, R3, and R4 are each independently hydrogen atoms. The compound is represented as}. The preferred range of n1+n2+n3+n4 is the same as described above.

[0040] Specific examples of compounds represented by the above general formula (IV) include, for example, A tetraacrylate obtained by adding an average of 4 moles of ethylene oxide to the hydroxyl group of pentaerythritol. A tetraacrylate obtained by adding an average of 9 moles of ethylene oxide to the hydroxyl group of pentaerythritol. A tetraacrylate obtained by adding an average of 12 moles of ethylene oxide to the hydroxyl group of pentaerythritol. A tetraacrylate obtained by adding an average of 15 moles of ethylene oxide to the hydroxyl group of pentaerythritol. A tetraacrylate obtained by adding an average of 20 moles of ethylene oxide to the hydroxyl group of pentaerythritol. A tetraacrylate obtained by adding an average of 28 moles of ethylene oxide to the hydroxyl group of pentaerythritol. Tetraacrylate obtained by adding an average of 35 moles of ethylene oxide to the hydroxyl group of pentaerythritol. These are some examples.

[0041] If the photosensitive resin composition contains a compound having an acrylate group on a dipentaerythritol skeleton, the compound having three or more functional acrylate groups is defined by the following general formula (VI): [ka] {In the formula, R represents a hydrogen atom independently, and n is an integer between 0 and 30.} Preferably, it contains a hexaacrylate compound represented by [formula].

[0042] In general formula (VI), n is an integer between 0 and 30, so the presence or absence of the ethylene oxide portion is irrelevant.

[0043] Preferred specific examples of hexaacrylate compounds represented by general formula (VI) include dipentaerythritol hexaacrylate, hexaacrylates in which a total of 1 to 36 moles of ethylene oxide are added to the six terminals of dipentaerythritol, and hexaacrylates in which a total of 1 to 10 moles of ε-caprolactone are added to the six terminals of dipentaerythritol.

[0044] The compound according to this embodiment contains, preferably 1% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, 40% by mass or more, or 60% by mass or more, and particularly preferably 80% by mass or more, of the total amount of compound (B) and the compound having an acrylate group on any of the trimethylolpropane, pentaerythritol, or dipentaerythritol skeletons described above. When the content of the compound having an acrylate group on any of the trimethylolpropane, pentaerythritol, or dipentaerythritol skeletons is 1% by mass or more of the total amount of compound (B), the properties related to the dissolution of peeled resist patterns and plating penetration tend to be further improved. The upper limit of the content of the compound having an acrylate group on any of the trimethylolpropane, pentaerythritol, or dipentaerythritol skeletons may be, for example, 100% by mass or less, or less than 100% by mass, of the total amount of compound (B).

[0045] (B) The compound having an ethylenically unsaturated double bond preferably has an aromatic ring, from the viewpoint of further improving the properties related to the dissolution of peeled resist patterns and plating penetration. From the viewpoint of plating resistance, the compound having an aromatic ring and an ethylenically unsaturated double bond as component (B) is preferably a compound having (meth)acryloyl groups at both ends of alkylene oxide-modified bisphenol A, and from the viewpoint of further improving the properties related to the dissolution of peeled resist patterns and plating penetration, the following formula (VII): [ka] {In the formula, Y independently represents an alkylene group having 2 to 10 carbon atoms, R1 and R2 independently represent a methyl group or a hydrogen atom, and n1 and n2 independently represent an integer from 1 to 100.} It is more preferable to express it as follows:

[0046] In formula (VII), Y is preferably an alkylene group having 2 to 4 carbon atoms, and the (YO) portion may be a random, alternating, or block arrangement of repeating alkylene oxide units with different numbers of carbon atoms. R1 and R2 each independently represent a methyl group or a hydrogen atom, and from the viewpoint of further improving the properties related to dissolution of peeling pieces and penetration of plating, it is preferable that one or both of R1 and R2 are methyl groups. n1 and n2 each independently represent an integer from 1 to 100, and it is preferable that 2 ≤ n1 + n2 ≤ 200.

[0047] The compound represented by formula (VII) may include a di(meth)acrylate compound of ethylene glycol obtained by adding alkylene oxides to both ends of bisphenol A. Such a di(meth)acrylate compound is preferably a diacrylate or dimethacrylate compound, and is preferably a dimethacrylate compound. Specific examples of dimethacrylate compounds include, for example, Dimethacrylate of ethylene glycol, in which an average of 1 mole of ethylene oxide is added to each end of bisphenol A. Dimethacrylate of ethylene glycol, in which an average of 2 moles of ethylene oxide are added to each end of bisphenol A. Dimethacrylate of ethylene glycol, in which an average of 5 moles of ethylene oxide are added to each end of bisphenol A. Dimethacrylate of alkylene glycol, in which an average of 6 moles of ethylene oxide and an average of 2 moles of propylene oxide are attached to each end of bisphenol A. Alkylene glycol dimethacrylate, which is obtained by adding an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide to both ends of bisphenol A. These are some examples.

[0048] In one embodiment, the photosensitive resin composition may use the compounds described above as the compound having an ethylenically unsaturated double bond (B), or it may further contain other (B) compounds. As the other (B) compounds, photopolymerizable ethylenically unsaturated compounds can be used. Examples of such photopolymerizable ethylenically unsaturated compounds include compounds having one ethylenically unsaturated double bond, compounds having two ethylenically unsaturated double bonds, and compounds having three or more ethylenically unsaturated double bonds.

[0049] Examples of compounds having one ethylenic double bond include: A compound obtained by adding (meth)acrylic acid to one end of a polyalkylene oxide; Compounds obtained by adding (meth)acrylic acid to one end of a polyalkylene oxide and alkyl etherifying or allyl etherifying the other end. These are some examples.

[0050] Examples of compounds having two ethylenically unsaturated double bonds in their molecule include: Compounds having (meth)acryloyl groups at both ends of an alkylene oxide chain; Compounds having (meth)acryloyl groups at both ends of an alkylene oxide chain in which ethylene oxide units and propylene oxide units are randomly, alternately, or blockily linked; Examples of alkylene oxide modification include ethylene oxide modification, propylene oxide modification, butylene oxide modification, pentylene oxide modification, and hexylene oxide modification. Compounds having (meth)acryloyl groups at both ends of ethylene oxide-modified bisphenol A are more preferred. Of these, ethylene glycol diacrylate compounds obtained by adding ethylene oxide to both ends of the bisphenol A described above are preferred from the viewpoint of plating resistance.

[0051] Compounds having three or more ethylenically unsaturated double bonds in their molecule include, for example, It is obtained by using a compound having 3 moles or more of a group that can be modified to add an alkylene oxide group within the molecule as the central skeleton, and then adding an alkylene oxide group such as an ethylene oxide group, a propylene oxide group, or a butylene oxide group to the compound to obtain an alcohol, which is then converted into a (meth)acrylate. In this case, as for the other (B) compound, compounds having 3 or more ethylenically unsaturated double bonds within the molecule, examples of compounds that can become the central skeleton include glycerin and compounds having an isocyanurate ring. Among these, a trifunctional glycerin (meth)acrylate that may be modified with alkylene oxide is given by the following formula (VIII): [ka] {In the formula, Y independently represents an alkylene group having 2 to 10 carbon atoms, R independently represents a methyl group or a hydrogen atom, and n independently represents an integer from 0 to 200.} Compounds represented by are preferred. In formula (VIII), each n is an integer between 0 and 200, preferably at least one n is an integer between 1 and 200, and more preferably three n are integers between 1 and 200. Also, -(YO) n The - portion may be a single alkylene oxide repeating unit, or it may contain multiple alkylene oxide units with different numbers of carbon atoms in a random, block, alternating, or other arrangement.

[0052] Other (B) compounds may be used alone or in combination of two or more.

[0053] The amount of (B) compound having an ethylenically unsaturated double bond in the photosensitive resin composition is 5 to 70% by mass, when the total solid content mass of the photosensitive resin composition is 100% by mass. Setting the amount to 5% by mass or more is based on the viewpoint of improving sensitivity, resolution, and adhesion, while setting the amount to 70% by mass or less is based on the viewpoint of suppressing edge fusing and suppressing the delay of peeling of the cured resist. The amount is preferably 10 to 50% by mass, more preferably 20 to 45% by mass.

[0054] <(C) Photopolymerization initiator> In this embodiment, the photosensitive resin composition preferably contains an imidazole compound as (C) a photopolymerization initiator. The imidazole compound contained in the photosensitive resin composition tends to suppress the plating resistance or the formation of a resist edge with respect to the resist pattern.

[0055] Examples of imidazole compounds include, Imidazoles having aliphatic groups, for example, methylimidazole, 2-ethyl-4-methylimidazole, 1-isobutyl-2-methylimidazole, 2-ethyl-4-methylimidazole, ethylimidazole, isopropylimidazole, 2,4-dimethylimidazole, undecylimidazole, heptadecylimidazole, etc.; and Imidazoles having aromatic groups, such as 1-benzyl-2-methylimidazole, phenylimidazole (2-phenylimidazole, etc.), 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, triarylimidazole, or dimers thereof; These include, in particular, imidazoles having aromatic groups are preferred from the viewpoint of plating resistance and suppression of resist hem formation, triarylimidazoles (e.g., rofin) or their dimers are more preferred, and triarylimidazole dimers are even more preferred.

[0056] Examples of triarylimidazole dimers include 2,4,5-triarylimidazole dimers such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0057] The content of the imidazole compound in the (C) photopolymerization initiator is preferably 99% by mass or more and 100% by mass or less of the total amount of the (C) photopolymerization initiator. Adjusting this content to 99-100% by mass of the total amount of the (C) photopolymerization initiator is preferable from the viewpoint of good sensitivity, high resolution, and suppression of aggregation in the developing solution. From these viewpoints, the imidazole compound can constitute 100% by mass of the (C) photopolymerization initiator.

[0058] In this embodiment, the photosensitive resin composition may optionally contain, in addition to the imidazole compound, various substances that can be used as photopolymerization initiators for the photosensitive resin. Examples of photopolymerization initiators other than the imidazole compound include aromatic ketones, acridine compounds, and / or N-aryl-α-amino acid compounds.

[0059] Aromatic ketones are preferred from the viewpoint of improving sensitivity. Examples of aromatic ketones include benzophenone, N,N'-tetramethyl-4,4'-dimethylaminobenzophenone (Michler ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-bis(diethylamino)benzophenone, 2-benzyl-2-dimethylamino-1-(4-monofornophenyl)butanone-1, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1. Among these, 4,4'-bis(diethylamino)benzophenone is preferred.

[0060] Acridine compounds are preferred from the viewpoint of exhibiting high sensitivity and from the viewpoint of achieving both high sensitivity and suppression of resist hem formation. Examples of acridine compounds include 1,7-bis(9,9'-acridinyl)heptane, 9-phenylacridine, 9-methylacridine, 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-tert-butylphenyl)acridine, 9-(4-methoxyphenyl)acridine, 9-(4-ethoxyphenyl)acridine, and 9-(4-acetylphenyl) Examples include acridine, 9-(4-dimethylaminophenyl)acridine, 9-(4-chlorophenyl)acridine, 9-(4-bromophenyl)acridine, 9-(3-methylphenyl)acridine, 9-(3-tert-butylphenyl)acridine, 9-(3-acetylphenyl)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, and 9-(4-pyridyl)acridine. Among these, 1,7-bis(9,9'-acridinyl)heptane or 9-phenylacridine are preferred in terms of sensitivity, resolution, and availability.

[0061] N-aryl-α-amino acid compounds are preferred from the viewpoint of improving sensitivity. Examples of N-aryl-α-amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.

[0062] Furthermore, other examples of photopolymerization initiators besides imidazole compounds include, for example, Quinones such as 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthaquinone, 2-methyl-1,4-naphthoquinone, and 2,3-dimethylanthraquinone; Benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; Benzyl derivatives such as benzyl methyl ketal; Coumarin compounds; Pyrazoline derivatives such as 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, and 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline; These are some examples.

[0063] (C) Photopolymerization initiators may be used individually or in combination of two or more types.

[0064] The amount of (C) photopolymerization initiator in the photosensitive resin composition is 0.01 to 20% by mass, when the total solid content mass of the photosensitive resin composition is 100% by mass. Setting the amount to 0.01% by mass or more is based on the viewpoint of obtaining an exposure pattern with a sufficient residual film rate after development, while setting the amount to 20% by mass or less is based on the viewpoint of sufficiently transmitting light to the bottom surface of the resist to obtain high resolution and suppressing development aggregation in the developer solution. The preferred range for the amount is 0.3 to 10% by mass, and the more preferred range is 1 to 5% by mass.

[0065] <Leuco dyes, fluoran dyes, colorants> The photosensitive resin composition according to the present invention may contain one or more selected from leuco dyes, fluoran dyes, and coloring substances. The inclusion of these components in the photosensitive resin composition causes the exposed area to develop color. Therefore, it is advantageous in terms of visibility. Furthermore, when an inspection machine or the like reads the alignment marker for exposure, the increased contrast between the exposed and unexposed areas makes them easier to recognize, which is also advantageous.

[0066] Examples of leuco dyes include tris(4-dimethylaminophenyl)methane [leucocrystal violet] and bis(4-dimethylaminophenyl)phenylmethane [leucomalachite green]. In particular, from the viewpoint of achieving good contrast, it is preferable to use leucocrystal violet as the leuco dye.

[0067] Examples of fluorane dyes include 2-(dibenzylamino)fluorane, 2-anilino-3-methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-dibutylaminofluorane, 2-anilino-3-methyl-6-N-ethyl-N-isoamylaminofluorane, 2-anilino-3-methyl-6-N-methyl-N-cyclohexylaminofluorane, 2-anilino-3-chlor-6-diethylaminofluorane, and 2-A Examples include nilino-3-methyl-6-N-ethyl-N-isobutylaminofluorane, 2-anilino-6-dibutylaminofluorane, 2-anilino-3-methyl-6-N-ethyl-N-tetrahydrofurfurylaminofluorane, 2-anilino-3-methyl-6-piperidinoaminofluorane, 2-(o-chloroanilino)-6-diethylaminofluorane, and 2-(3,4-dichloroanilino)-6-diethylaminofluorane.

[0068] The content of leuco dye or fluoran dye in the photosensitive resin composition is preferably 0.1 to 10% by mass, when the total solid content mass of the photosensitive resin composition is 100% by mass. A content of 0.1% by mass or more is preferable from the viewpoint of improving the contrast between the exposed and unexposed areas. A content of 0.2% by mass or more is more preferable, and 0.3% by mass or more is even preferable. On the other hand, a content of 10% by mass or less is preferable from the viewpoint of maintaining the storage stability of the photosensitive resin composition and suppressing the generation of aggregates during development. A content of 5% by mass or less is more preferable, and 1% by mass or less is even preferable.

[0069] Examples of coloring substances include fuchsin, phthalocyanine green, auramine base, paramazienta, crystal violet, methyl orange, Nile Blue 2B, malachite green (manufactured by Hodogaya Chemical Co., Ltd., Eisen® MALACHITE GREEN), Basic Blue 7 (e.g., Eisen® Victoria Pure Blue BOH conc.), Basic Blue 20, and Diamond Green (manufactured by Hodogaya Chemical Co., Ltd., Eisen® DIAMOND GREEN GH). The content of the coloring substance in the photosensitive resin composition is preferably 0.001% to 1% by mass, when the total solid content mass of the photosensitive resin composition is taken as 100% by mass. A content of 0.001% by mass or more is preferable from the viewpoint of improving handling, while a content of 1% by mass or less is preferable from the viewpoint of maintaining storage stability.

[0070] <Halogen compounds> In the photosensitive resin composition of this embodiment, using a leuco dye in combination with the following halogen compounds is a preferred embodiment from the viewpoint of adhesion and contrast. Examples of halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, and chlorinated triazine compounds. Tribromomethylphenylsulfone is particularly preferred. Halogen compounds such as tribromomethylphenylsulfone are highly effective when used in combination with acridine compounds and are preferred from the viewpoint of improving resolution, adhesion, sensitivity, contrast, tent film puncture resistance, suppression of resist edging, and etching resistance.

[0071] From the viewpoint of the above, the content of halogen compounds in the photosensitive resin composition is preferably 0.01% by mass when the total solid content mass of the photosensitive resin composition is taken as 100% by mass. More preferably, this content is 0.1% by mass or more, even more preferably 0.3% by mass or more, and particularly preferably 0.5% by mass or more. Furthermore, a content of 3% by mass or less is preferred from the viewpoint of maintaining the storage stability of hue in the photosensitive layer and suppressing the generation of aggregates during development. More preferably, this content is 2% by mass or less, and even more preferably 1.5% by mass or less.

[0072] <Radical polymerization inhibitors, benzotriazoles, carboxybenzotriazoles> In this embodiment, in order to improve the thermal stability and storage stability of the photosensitive resin composition, the photosensitive resin composition may further contain at least one compound selected from the group consisting of radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles.

[0073] Examples of radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, biphenol, 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), and 4,4'-thiobis(6-tert-butyl-m-cresol). Examples include ), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, styrene-phenols (e.g., manufactured by Kawaguchi Chemical Industries, Ltd., trade name "Antage SP"), tripenzylphenol (e.g., manufactured by Kawaguchi Chemical Industries, Ltd., trade name "TBP", phenol compounds having 1 to 3 benzyl groups), and diphenylnitrosamines.

[0074] Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.

[0075] Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole, or mixtures thereof. Among these, a 1:1 mixture of 4-carboxy-1,2,3-benzotriazole and 5-carboxy-1,2,3-benzotriazole is preferred.

[0076] The total content of radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles is preferably 0.01 to 3% by mass, and more preferably 0.05 to 1% by mass, when the total solid content of the photosensitive resin composition is taken as 100% by mass. A content of 0.01% by mass or more is preferable from the viewpoint of imparting storage stability to the photosensitive resin composition, while a content of 3% by mass or less is preferable from the viewpoint of maintaining sensitivity and suppressing dye decolorization.

[0077] <Plasticizer> The photosensitive resin composition of this embodiment may optionally contain a plasticizer. Examples of such plasticizers include glycol esters such as polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxypropylene monoethyl ether, and polyoxyethylene polyoxypropylene monoethyl ether; Phthalates such as diethyl phthalate; o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, triethyl acetyl citrate, tri-n-propyl acetyl citrate, tri-n-butyl acetyl citrate, etc. Propylene glycol, obtained by adding propylene oxide to both ends of bisphenol A; ethylene glycol, obtained by adding ethylene oxide to both ends of bisphenol A; etc. Aluminum salts to which 1-3 moles of nitrosophenylhydroxylamine have been added, etc. These can be used individually or in combination of two or more types. In particular, from the viewpoint of detachment solubility or plating resistance, an aluminum salt to which 3 moles of nitrosophenylhydroxylamine are added is preferred as a plasticizer.

[0078] The plasticizer content in the photosensitive resin composition is preferably 1 to 50% by mass, and more preferably 1 to 30% by mass, when the total solid content mass of the photosensitive resin composition is taken as 100% by mass. A content of 1% by mass or more is preferable from the viewpoint of suppressing delay in development time and imparting flexibility to the cured film, while a content of 50% by mass or less is preferable from the viewpoint of suppressing insufficient curing and edge fusing.

[0079] <Solvent> The photosensitive resin composition can be used as a solution by dissolving it in a solvent. Examples of solvents that can be used include: Ketones, exemplified by methyl ethyl ketone (MEK); Alcohols such as methanol, ethanol, and isopropanol These are some examples. It is preferable to add the solvent to the photosensitive resin composition so that the viscosity of the solution of the photosensitive resin composition to be applied to the support film is 500 to 4,000 mPa·s at 25°C.

[0080] <Properties of photosensitive resin compositions> The photosensitive resin composition of this embodiment is given by the following formula (I): 0 {In the formula, T is the thickness (μm) of the photosensitive resin layer containing the photosensitive resin composition, and A is the absorbance of the photosensitive resin layer containing the photosensitive resin composition at a wavelength of 365 nm.} The relationship expressed by equation (I) is satisfied. A photosensitive resin composition that satisfies the relationship expressed by equation (I) is easier to improve in terms of properties related to the dissolution of peeled resist patterns or plating penetration compared to a photosensitive resin composition with A / T > 0.007. From the viewpoint of further improving the properties related to the dissolution of peeled resist patterns or plating penetration of photosensitive resin compositions, the following equation (II) is obtained: 0 {In the formula, T is the film thickness (μm) of the photosensitive resin layer containing the photosensitive resin composition, and A is the absorbance of the photosensitive resin layer containing the photosensitive resin composition at a wavelength of 365 nm.} ​​It is preferable that the relationship expressed by the formula is satisfied. From a similar viewpoint, the A / T value of the photosensitive resin composition is more preferably greater than 0 and less than 0.005, and even more preferably greater than 0 and 0.004 or less.

[0081] <Photosensitive resin laminate> Another aspect of the present invention allows for the formation of a photosensitive resin laminate using the photosensitive resin composition described above. The photosensitive resin laminate according to this embodiment is preferably a dry film resist. Typically, the photosensitive resin laminate comprises a support film and a layer of the photosensitive resin composition laminated on the support film. The photosensitive resin laminate may optionally have a protective layer on the surface opposite to the support film.

[0082] The photosensitive resin laminate according to this embodiment is given by the following formula (I): 0 {In the formula, T is the film thickness (μm) of the photosensitive resin layer containing the photosensitive resin composition, and A is the absorbance of the photosensitive resin layer containing the photosensitive resin composition at a wavelength of 365 nm.} The relationship expressed by equation (I) is satisfied. Photosensitive resin laminates that satisfy the relationship expressed by equation (I) tend to have improved properties regarding the dissolution of peeled resist patterns or penetration of plating compared to photosensitive resin laminates with A / T > 0.007.

[0083] From the viewpoint of further improving the properties of the photosensitive resin laminate regarding the dissolution of peeled resist patterns or penetration of plating, the following formula (II): 0 {In the formula, T is the film thickness (μm) of the photosensitive resin layer containing the photosensitive resin composition, and A is the absorbance of the photosensitive resin layer containing the photosensitive resin composition at a wavelength of 365 nm.} It is preferable that the relationship expressed by the formula is satisfied. From a similar viewpoint, the A / T value of the photosensitive resin laminate is more preferably greater than 0 and less than 0.005, and even more preferably greater than 0 and 0.004 or less.

[0084] ​​The support film should preferably be transparent and transmit light emitted from the exposure light source. Examples of such support films 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, and cellulose derivative film. These films can also be used in stretched form as needed. The haze of the support film is preferably 5 or less. While a thinner support film is advantageous in terms of image formation and cost-effectiveness, a thickness of 10 to 30 μm is preferable when considering the function of maintaining strength.

[0085] The photosensitive resin composition layer described above may contain the photosensitive resin composition or consist of the photosensitive resin composition. From the viewpoint of a thickness suitable for plating applications, the film thickness of the photosensitive resin composition layer in the photosensitive resin laminate is preferably 40 μm or more and 600 μm or less, more preferably 50 to 400 μm, even more preferably more than 50 μm and 400 μm or less, even more preferably 100 to 400 μm, and particularly preferably 200 to 400 μm.

[0086] An important characteristic of the protective layer used in a photosensitive resin laminate is that it has appropriate adhesion. In other words, it is preferable that the adhesion of the protective layer to the photosensitive resin layer is sufficiently smaller than the adhesion of the support film to the photosensitive resin layer, so that the protective layer can be easily peeled off the photosensitive resin laminate. As the protective layer, for example, polyethylene film, polypropylene film, or a film with excellent peelability as shown in Japanese Patent Publication No. 59-202457 can be used. The thickness of the protective layer is preferably 10 to 100 μm, and more preferably 10 to 50 μm.

[0087] <Method for fabricating photosensitive resin laminates> A photosensitive resin laminate can be manufactured by sequentially laminating a photosensitive resin layer and, if necessary, a protective layer on a support film. Known methods can be used for this process. For example, the photosensitive resin composition to be used for the photosensitive resin layer is mixed with a solvent to dissolve it to form a uniform solution coating liquid. This coating liquid is then applied to the support film using a bar coater or roll coater, and subsequently dried to laminate a photosensitive resin layer made of the photosensitive resin composition onto the support film. A photosensitive resin laminate can then be manufactured by laminating a protective layer onto the photosensitive resin layer if necessary.

[0088] <Method for forming a resist pattern> Another embodiment of the present invention is, The process of laminating the aforementioned photosensitive resin laminate onto a substrate (laminating process), The process of exposing the laminated photosensitive resin laminate to light (exposure process), and A process for developing the exposed photosensitive resin laminate (development process) The present invention provides a method for forming a resist pattern, including the following:

[0089] <Method for forming semiconductor bumps> Another embodiment of the present invention is: A step (plating step) in which a resist pattern is formed on a substrate using the resist pattern formation method described above, by copper plating or solder plating. The present invention provides a semiconductor bump formation method, including the following:

[0090] If desired, the semiconductor bump formation method may further include a step of etching a substrate on which a resist pattern has been formed.

[0091] If desired, the semiconductor bump formation method may include a descam and a pre-plating treatment step before the plating step.

[0092] If desired, the semiconductor bump formation method may further include a peeling step of peeling the resist pattern from the substrate after the above-described series of steps.

[0093] The following describes an example of a method for forming resist patterns and semiconductor bumps using a photosensitive resin laminate and a sputtered copper thin film as a substrate.

[0094] (1) Lamination process The lamination process involves peeling off the protective layer of a photosensitive resin laminate and adhering it to a substrate, such as a sputtered copper thin film, using, for example, a hot roll laminator. The sputtered copper thin film used in the lamination process is preferably a copper sputtered silicon wafer, which has a copper layer formed on a silicon wafer using a sputtering apparatus.

[0095] (2) Exposure process The exposure process is, for example: A step of exposing a photosensitive resin layer of a photosensitive resin laminate laminated on the above substrate to light through a mask film having a desired wiring pattern, while the mask film is in close contact with the photosensitive resin layer. A step of exposing a desired wiring pattern by direct imaging exposure, or The process of exposure using an exposure method that projects the image of a photomask through a lens. It can be.

[0096] (3)Developing process This process involves peeling off the support film from the photosensitive resin layer after the exposure process, and then developing and removing the unexposed areas (in the case of negative type) or exposed areas (in the case of positive type) using an alkaline aqueous developer to form a resist pattern on the substrate.

[0097] As the alkaline aqueous solution, an aqueous solution of Na2CO3 or K2CO3 can be used. The alkaline aqueous solution is appropriately selected according to the characteristics of the photosensitive resin layer, but it is preferable to use an aqueous solution of Na2CO3 with a concentration of about 0.2 to 2% by mass and a temperature of about 20 to 40°C.

[0098] A resist pattern can be obtained through the above steps. In some cases, a heating step may be further performed after these steps at approximately 100°C to 300°C for 1 minute to 5 hours. By performing this heating step, it is possible to further improve the adhesion and chemical resistance of the resulting cured resist pattern. For heating in this case, for example, a heating furnace using hot air, infrared rays, or far infrared rays can be used. Regarding the resulting resist pattern, an example with a small resist tail is shown in Figure 1(a), and an example with a large resist tail is shown in Figure 2(a).

[0099] (Descam and pre-plating treatment) If desired, the substrate on which the resist pattern is formed can be subjected to plasma treatment and / or immersion treatment to perform descamming and pre-plating treatment.

[0100] (4) Plating process A conductive pattern can be manufactured by copper plating or solder plating the substrate surface (for example, the copper surface of a sputtered copper thin film) exposed by development. The plating solution is preferably a copper sulfate plating solution. Figure 1(b) shows an example where the plating penetration is small, and Figure 2(b) shows an example where the plating penetration is large.

[0101] (Etching process) If desired, an etching solution may be sprayed onto the resist pattern formed through the above process to etch the copper surface not covered by the resist pattern and form a circuit pattern. Examples of etching methods include acid etching and alkaline etching, and the method should be suitable for the photosensitive resin laminate being used.

[0102] (Peeling process) Subsequently, the laminate is treated with an aqueous solution having a stronger alkalinity than the developer to remove the resist pattern from the substrate. The stripping solution is preferably at least one selected from the group consisting of an aqueous solution of NaOH or KOH with a concentration of approximately 2-5% by mass and a temperature of approximately 40-70°C; SPR920 (product name); and R-101 (product name). A small amount of water-soluble solvent may be added to the stripping solution.

[0103] The photosensitive resin composition, photosensitive resin laminate, resist pattern, and semiconductor bump described above can be used, for example, in the formation of semiconductor packages. [Examples]

[0104] The embodiments of the present invention will be specifically described below with reference to examples and comparative examples. First, the method for preparing evaluation samples for the examples and comparative examples will be explained, followed by the evaluation method and results for the obtained samples.

[0105] (Examples 1-13 and Comparative Examples 1-4) First, the method for preparing evaluation samples for the examples and comparative examples will be described, followed by the evaluation method and evaluation results for the obtained samples.

[0106] 1. Preparation of evaluation samples The evaluation samples in the examples and comparative examples were prepared as follows.

[0107] <Fabrication of photosensitive resin laminates> A photosensitive resin composition and solvent with the composition shown in Table 1 below (where the numbers for each component indicate the amount (parts by mass) of solids) were thoroughly stirred and mixed to prepare a photosensitive resin composition solution. This solution was uniformly applied to the surface of a 16 μm thick polyethylene terephthalate film (Toray Industries, Inc., FB-40) as a support using a bar coater, and dried in a 95°C dryer for 12 minutes to form a photosensitive resin layer. The thickness (T) of the photosensitive resin layer was 240 μm.

[0108] Next, a 19 μm thick polyethylene film (GF-18, manufactured by Tamapoly Co., Ltd.) was laminated as a protective layer onto the surface of the photosensitive resin layer that did not have a polyethylene terephthalate film laminated on it to obtain a photosensitive resin laminate. Furthermore, the absorbance (A) of the photosensitive resin laminate at a wavelength of 365 nm was measured using a UV-Vis spectrophotometer (U-3010, manufactured by Hitachi High-Technologies Corporation) as follows: The polyethylene film of the photosensitive resin laminate was peeled off, and the absorbance at 365 nm was measured. The obtained value was defined as absorbance (A). Air was used as a blank sample.

[0109] Table 1 below shows the amounts of each component in the photosensitive resin composition solution and the evaluation results, and Table 2 below shows the names of the material components in the photosensitive resin composition solution shown in Table 1.

[0110] 2. Fabrication of semiconductor bumps <Base material> For the fabrication of copper posts, a copper sputtered silicon wafer was used, in which a 2000 angstrom (Å) thick copper layer was formed on a 6-inch silicon wafer using an Anelva sputtering apparatus.

[0111] <Laminate> The polyethylene film of the photosensitive resin laminate was peeled off and laminated onto a silicon wafer preheated to 70°C using a hot roll laminator (Taisei Laminator Co., Ltd., VA-400III) at a roll temperature of 70°C. The air pressure was set to 0.20 MPa and the lamination speed to 0.18 m / min.

[0112] <Exposure> Using a glass chromium mask, 300 mJ / cm² was measured using an Ultratech Prisma ghi stepper (manufactured by Ultratech Co., Ltd.). 2 Exposure was performed. The illuminance measured on the substrate surface was 2400 mW / cm². 2 That was the case.

[0113] <Developing> Developing was performed by spraying a 1% by mass Na2CO3 aqueous solution onto the exposed laminate at a flow rate of 200 mL / min using a spin developer (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.) at 30°C.

[0114] <Descam and pre-plating treatment> The evaluation substrate was plasma-treated using a low-pressure plasma device (EXAM, manufactured by Shinko Seiki Co., Ltd.) under the conditions of 50 Pa, 133 W, 240 mL / min. of O, and 41 mL / min. of CF, and then immersed in pure water for 5 minutes to perform descamming and pre-plating treatment.

[0115] <Copper sulfate plating> The copper posts were fabricated by copper plating as shown below and then stripping the plate as described later. A copper sulfate plating solution was prepared by adding 20 mL of SC-50 R1 (manufactured by MICROFAB®) and 12 mL of SC-50 R2 (manufactured by MICROFAB®) to 968 mL of SC-50 MU MA (manufactured by MICROFAB®). A pre-treated substrate (6 cm × 12.5 cm) for evaluating plating resistance was plated using the prepared copper sulfate plating solution with a Haring cell uniform plating apparatus (manufactured by Yamamoto Plating Testing Equipment Co., Ltd.), adjusting the current value so that copper was deposited at a height of 1 μm per minute. At this time, the thickness of the copper plating film was 100 μm.

[0116] <Peeling> The plated evaluation substrate was stripped by heating it at 65°C for 100 minutes using a stripping solution consisting of 3% NaOH, SPR920 (manufactured by KANTO-PPC), and R-101 (manufactured by Mitsubishi Gas Chemical Co., Ltd.).

[0117] 3. Minimum development time evaluation The shortest time required for the photosensitive resin layer in the unexposed areas to completely dissolve was measured as the "minimum development time" and ranked as follows: S: Minimum development time is 210 seconds or less; A: Minimum development time value is greater than 210 seconds and less than or equal to 220 seconds; B: Minimum development time value is greater than 220 seconds and less than or equal to 230 seconds; C: The minimum development time value is over 230 seconds.

[0118] 4. Resistance evaluation A 150 μm circular hole was patterned onto the substrate, which had been treated with a descam, and the length of the bottom edge of the resist was observed using SEM. The substrates were ranked as follows: S: Hem length 1 μm or less; A: Over 1 μm, 1.5 μm or less; B: greater than 1.5 μm, less than or equal to 2.0 μm; C: More than 2.0 μm.

[0119] 5. Evaluation of plating resistance After copper plating, the bottom of the copper posts on the substrate from which the hardened resist had been removed was observed using SEM and ranked as follows. S: No copper plating; A: Copper plating penetration of 1 μm or less; B: Copper plating penetration between 1 μm and 3 μm; C: Copper plating penetration exceeding 3μm.

[0120] 6. Evaluation of solubility of peeled fragments <Exposure> A photosensitive resin laminate was exposed to light from the support film side to produce a cured resist. An Ultratech Prisma ghi stepper (manufactured by Ultratech Co., Ltd.) was used for exposure. The exposure dose was 300 mJ / cm². 2 It was implemented there.

[0121] <Developing> The support film was peeled off the exposed photosensitive resin laminate, and the laminate was developed by spraying it with a 1% by mass Na2CO3 aqueous solution at 30°C for twice the "minimum development time". After that, the protective layer was peeled off to obtain a cured resist.

[0122] <Evaluation of solubility of peeled fragments 1> Approximately 50 mg of the obtained cured resist was immersed in 20 mL of 3% NaOH stripping solution at 65°C for 75 minutes. The remaining cured film was then filtered, vacuum-dried, and the residual film percentage was determined by dividing the mass of the filtrate by the mass of the cured resist initially immersed. The "strip solubility" was then evaluated. The results were ranked as follows: S: The residual film percentage is 0%; A: The residual film percentage is greater than 0% and less than or equal to 10%; B: The residual film percentage is greater than 10% and less than or equal to 25%; C: The residual film percentage exceeds 25%.

[0123] <Evaluation of detached fragment solubility 2> In the above evaluation 1, SPR920 was used as the stripping solution and the evaluation was performed similarly. S: The residual film percentage is 0%; A: The residual film percentage is greater than 0% and less than or equal to 10%; B: The residual film percentage is greater than 10% and less than or equal to 25%; C: The residual film percentage exceeds 25%.

[0124] <Evaluation of solubility of peeled fragments 3> In the above evaluation 1, R-101 was used as the stripping solution and the evaluation was performed similarly. S: The residual film percentage is 0%; A: The residual film percentage is greater than 0% and less than or equal to 10%; B: The residual film percentage is greater than 10% and less than or equal to 25%; C: The residual film percentage exceeds 25%.

[0125] 7. Evaluation of resist wrinkles during storage A photosensitive resin laminate was wrapped around a 8.5 cm diameter plastic bottle and left for a certain period of time under conditions of 23°C and 50% RH. The degree of wrinkle formation on the resist surface was evaluated and ranked as follows. S: No wrinkles appeared after more than 12 hours; A: Wrinkles appear after more than 6 hours, or within 12 hours; B: Wrinkles appear after more than 3 hours, or within 6 hours; C: Wrinkles appear within 3 hours.

[0126] [Table 1]

[0127] [Table 2]

Claims

1. On the support film (A) Alkali-soluble polymer: 10% to 90% by mass, (B) Compounds having ethylenically unsaturated double bonds: 5% to 70% by mass, (C) Photopolymerization initiator: 0.01% to 20% by mass A photosensitive resin laminate having a photosensitive resin layer containing a photosensitive resin composition containing, The alkali-soluble polymer (A) comprises a copolymer containing a (meth)acrylate having an alkyl group with 3 to 12 carbon atoms as a copolymer component. The compound having an ethylenically unsaturated double bond (B) contains 60% to 100% by mass of a compound having a trifunctional or more acrylate group relative to the total amount of the compound having an ethylenically unsaturated double bond (B). The aforementioned compound having three or more functional acrylate groups includes a compound having an acrylate group on a pentaerythritol skeleton. The (C) photopolymerization initiator comprises an imidazole compound and a photopolymerization initiator other than the imidazole compound. The imidazole compound is a 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer. The photopolymerization initiator other than the imidazole compound is 4,4'-bis(diethylamino)benzophenone. When the thickness of the photosensitive resin layer containing the above photosensitive resin composition is T [μm] and the absorbance at a wavelength of 365 nm is A, then the following equation (I): 0 < A / T ≤ 0.007 Equation (I) The relationship expressed by and A photosensitive resin laminate in which the thickness of the photosensitive resin layer containing the photosensitive resin composition is 40 μm or more and 600 μm or less.

2. The photosensitive resin laminate according to claim 1, wherein the alkali-soluble polymer (A) comprises a copolymer containing 2-ethylhexyl acrylate as a copolymer component.

3. The photosensitive resin laminate according to claim 1 or 2, wherein the alkali-soluble polymer (A) comprises a copolymer containing benzyl (meth)acrylate as a copolymer component.

4. The alkali-soluble polymer (A) further contains (meth)acrylates other than the (meth)acrylates having C3 to C12 alkyl groups, and / or vinyl compounds as copolymer components, and The photosensitive resin laminate according to any one of claims 1 to 3, wherein the alkali-soluble polymer (A) contains 6.0% to 30% by mass of the (meth)acrylate having an alkyl group having 3 to 12 carbon atoms as a copolymer component.

5. The photosensitive resin laminate according to any one of claims 1 to 4, wherein the compound having three or more functional acrylate groups contains 10% by mass or more of a compound having an acrylate group in any of the trimethylolpropane, pentaerythritol, or dipentaerythritol skeletons, relative to the total amount of the compound having an ethylenically unsaturated double bond (B).

6. The photosensitive resin laminate according to any one of claims 1 to 5, wherein the compound having three or more functional acrylate groups contains 80% by mass or more of a compound having an acrylate group in any of the trimethylolpropane, pentaerythritol, or dipentaerythritol skeletons, relative to the total amount of the compound having an ethylenically unsaturated double bond (B).

7. If the compound having an ethylenically unsaturated double bond (B) includes a compound having an aromatic ring, the compound having the aromatic ring is defined by the following formula (VII): 【Chemistry 1】 {In the formula, Y independently represents an alkylene group having 2 to 10 carbon atoms, and R １ and R ２ Each of these independently represents a methyl group or a hydrogen atom, and n １ and n ２ Each of these independently represents an integer between 1 and 100. A photosensitive resin laminate according to any one of claims 1 to 6, represented by [the specified formula].

8. When the thickness of the photosensitive resin layer containing the above photosensitive resin composition is T [μm] and the absorbance at a wavelength of 365 nm is A, then the following equation (II): 0 < A / T ≤ 0.005 Equation (II) A photosensitive resin laminate according to any one of claims 1 to 7, satisfying the relationship represented by [the given formula].

9. The photosensitive resin laminate according to any one of claims 1 to 8, wherein the thickness of the photosensitive resin layer containing the photosensitive resin composition is greater than 50 μm and less than or equal to 400 μm.

10. A photosensitive resin laminate according to any one of claims 1 to 9, wherein the laminate is a dry film resist.

11. A step of laminating a photosensitive resin laminate according to any one of claims 1 to 10 onto a substrate, The process of exposing the laminated photosensitive resin laminate to light, and The process of developing the exposed photosensitive resin laminate. A method for forming a resist pattern that includes [a specific component].

12. A step of laminating a photosensitive resin laminate according to any one of claims 1 to 10 onto a sputtered copper thin film, A step of exposing the laminated photosensitive resin laminate, A step of developing the exposed photosensitive resin laminate, and The process of copper plating or solder plating on the sputtered copper thin film after development. A method for forming semiconductor bumps, including those mentioned above.

Images