Negative photosensitive resin composition

Abstract

To provide a negative photosensitive composition or the like that can give a cured product having excellent marginal resolution, little decrease in film thickness during development, a low thermal expansion coefficient, a high elongation, a reduced warpage, and excellent dielectric properties.SOLUTION: A negative photosensitive resin composition has (A) a polyimide resin having a hydroxy carbonyl group in each molecule, (B) a photoradical generator, and (C) a compound having two or more ethylenically unsaturated bonds.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a negative photosensitive resin composition. Further, the present invention relates to a semiconductor package substrate, a semiconductor device, and a method for manufacturing a semiconductor package substrate obtained by using the negative photosensitive resin composition.

Background Art

[0002] Conventionally, polyimide resins having excellent heat resistance, insulating properties, mechanical properties, etc. have been used for surface protective films and interlayer insulating films of semiconductor elements. For example, Patent Document 1 describes a method of introducing an ester bond into a polyimide precursor, a soluble polyimide having a photopolymerizable olefin, a self-sensitizing polyimide having a benzophenone skeleton and an alkyl group at the ortho position of an aromatic ring to which a nitrogen atom is bonded, and the like.

[0003] Also, recently, a positive photosensitive resin that can be developed with an alkaline aqueous solution has been proposed. As such a resin, for example, Patent Document 2 describes a soluble polybenzoxazole precursor in the positive type, and Patent Document 3 describes a method of mixing a naphthoquinone diazide compound with a hydroxyphenyl group-substituted imide, a method of introducing a naphthoquinone diazide through an ester bond into a soluble polyimide, and the like.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0005] In recent years, with the increasing speed and capacity of communication in communication devices, excellent dielectric properties such as low dielectric constant and low dielectric loss of the cured product have been required for the photosensitive resin composition used in the semiconductor package substrate of communication devices. In addition, since the number of layers used for the redistribution of the package is required to be stacked in large numbers from 2 layers to 4 layers and 5 layers, the coefficient of thermal expansion (CTE) of the cured product of the photosensitive resin composition for suppressing the warpage of the multilayer substrate is lowered, and furthermore, high tensile strength (elongation rate) and high elastic modulus for increasing the mechanical strength, reliability, and impact resistance of the package itself are required.

[0006] The photosensitive resin compositions described in Patent Documents 1 to 3 cannot satisfy the characteristics of low dielectric constant and low dielectric loss required for 5G communication applications, and furthermore, warpage may occur in the substrate due to stress generated during the manufacture of the multilayer film of the package or due to heat or impact.

[0007] In addition, in the negative-type photosensitive polyimide of Patent Document 1, it is necessary to use an organic solvent in the developer, which has a large environmental load during the manufacture of semiconductor packages. Moreover, since the photosensitive composition resin is a polyimide precursor, a curing temperature of 250°C or higher is required for imidization, and the resulting mechanical properties and dielectric properties are also not sufficient in terms of the performance of the cured film due to incomplete imidization.

[0008] Patent Documents 2 and 3 need to introduce a hydroxyphenyl group to ensure the development performance in an alkaline aqueous solution, but this inevitably causes deterioration of dielectric properties and mechanical properties. In addition, the resolution, pattern shape, and film thickness reduction during development peculiar to the positive type during the formation of the insulating layer pattern are also not satisfactory.

[0009] The present invention has been made in view of the above problems, and by alkali aqueous solution development, it is possible to form an insulating layer in an appropriate pattern shape, that is, it is excellent in limiting resolution and residual film properties during development, has a low coefficient of thermal expansion, a high elongation rate, the amount of warpage is suppressed, and furthermore, a cured product excellent in dielectric properties can be obtained. An object of the present invention is to provide a negative photosensitive resin composition, a semiconductor package substrate, a semiconductor device, and a method for manufacturing a semiconductor package substrate obtained by using the negative photosensitive resin composition.

Means for Solving the Problems

[0010] As a result of intensive studies by the present inventors, it has been found that the above problems can be achieved by including a specific polyimide resin, a photo radical generator, and a compound having two or more ethylenically unsaturated bonds in a negative photosensitive resin composition, and the present invention has been completed.

[0011] That is, the present invention includes the following content. [1] A negative photosensitive resin composition containing (A) a polyimide resin having a hydroxycarbonyl group in the molecule, (B) a photo radical generator, and (C) a compound having two or more ethylenically unsaturated bonds. [2] The negative photosensitive resin composition according to [1], containing (D) a sensitizer. [3] The negative photosensitive resin composition according to [1] or [2], wherein the component (C) is a compound represented by the following general formula (C-1). [Chemical formula] (In the formula (C-1), R 1Each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, Z each independently represents a linear or branched alkylene group having 1 to 20 carbon atoms which may contain an oxygen atom, an arylene group which may contain an oxygen atom, or a propenylene group, and A represents a linear, cyclic or branched nc-valent hydrocarbon group having 1 to 10 carbon atoms, an nc-valent group derived from bisphenol, an nc-valent group derived from fluorene, an nc-valent group derived from tricyclodecane, or an nc-valent group derived from an isocyanuric group. nc represents a positive integer of 2 to 6.) [4] The negative photosensitive resin composition according to any one of [1] to [3], wherein the component (C) is a compound represented by the following general formula (C-2). [Chemical formula] (In formula (C-2), R 12 each independently represents a hydrogen atom or a methyl group.) [5] The negative photosensitive resin composition according to any one of [1] to [4], which contains an (E) adhesion promoter. [6] The negative photosensitive resin composition according to any one of [1] to [5], which contains a compound having two or more epoxy groups. [7] The negative photosensitive resin composition according to any one of [1] to [6], wherein the component (A) contains a polyimide resin having a structural unit represented by the following general formula (A-1) and a structural unit represented by the following general formula (A-2). [Chemical formula] (In formula (A-1) and formula (A-2), X each independently represents a single bond, an oxygen atom, a sulfur atom, an ester bond, an alkylene group having 1 to 20 carbon atoms, an arylene group having 7 to 20 carbon atoms, or a divalent group composed of a combination thereof, and Y 1 , Y 2 each independently represents a hydrogen atom, a halogen atom, a trimethylsilyl group, a trifluoromethyl group, a trimethylsilyloxy group, or a hydroxy group. m and n are any positive integers whose sum is 90 to 100.) [8] The component (A) contains a copolymer including a structural unit represented by the general formula (A-1) and a structural unit represented by the general formula (A-2), and the copolymerization ratio of the structural unit represented by the general formula (A-1) and the structural unit represented by the general formula (A-2) (structural unit m represented by the general formula (A-1) / structural unit n represented by the general formula (A-2)) is 5 / 95 or more and 50 / 50 or less. The negative photosensitive resin composition according to [7]. [9] The negative photosensitive resin composition according to any one of [1] to [8], wherein the component (A) contains a polyimide resin having a structural unit represented by the following general formula (A-3) and a structural unit represented by the following general formula (A-4). [Chemical formula] (In formulas (A-3) and (A-4), m1 and n1 are any positive integers whose sum is 90 to 100.)

[10] The component (A) contains a copolymer including a structural unit represented by the general formula (A-3) and a structural unit represented by the general formula (A-4), and the copolymerization ratio of the structural unit represented by the general formula (A-3) and the structural unit represented by the general formula (A-4) (structural unit m1 represented by the general formula (A-3) / structural unit n1 represented by the general formula (A-4)) is 5 / 95 or more and 50 / 50 or less. The negative photosensitive resin composition according to [9].

[11] A semiconductor package substrate including an insulating layer formed by a cured product of the negative photosensitive resin composition according to any one of [1] to

[10] .

[12] A semiconductor device including the semiconductor package substrate according to

[11] .

[13] A step of forming a photosensitive resin composition layer including the negative photosensitive resin composition according to any one of [1] to

[10] on a circuit board; A step of irradiating the photosensitive resin composition layer with actinic rays; A step of developing the photosensitive resin composition layer. A method for manufacturing a semiconductor package substrate including these steps. [Advantages of the Invention]

[0012] According to the present invention, a negative photosensitive resin composition capable of obtaining a cured product having excellent ultimate resolution, little film thickness reduction during development, a low coefficient of thermal expansion, a high elongation rate, suppressed warpage amount, and further excellent dielectric properties, a semiconductor package substrate, a semiconductor device, and a method for manufacturing a semiconductor package substrate obtained by using the negative photosensitive resin composition can be provided.

Embodiments for Carrying Out the Invention

[0013] Hereinafter, the negative photosensitive resin composition of the present invention, a semiconductor package substrate, a semiconductor device, and a method for manufacturing a semiconductor package substrate obtained by using the negative photosensitive resin composition will be described in detail.

[0014] [Negative Photosensitive Resin Composition] The negative photosensitive resin composition contains (A) a polyimide resin having a hydroxycarbonyl group in the molecule, (B) a photo radical generator, and (C) a compound having two or more ethylenically unsaturated bonds. By combining the components (A) to (C) and containing them in the negative photosensitive resin composition, it is possible to obtain a cured product that achieves a well-balanced reduction in the coefficient of thermal expansion to suppress warpage and an improvement in the elongation rate to improve mechanical strength. In addition, a cured product having excellent dielectric properties can also be obtained. Furthermore, this negative photosensitive resin composition has excellent ultimate resolution and little film thickness reduction during development.

[0015] The negative photosensitive resin composition may further contain an arbitrary component in combination with the components (A) to (C). Examples of the arbitrary component include (D) a sensitizer, (E) an adhesion aid, (F) a compound having two or more epoxy groups, (G) a solvent, and (H) other additives. Hereinafter, each component contained in the negative photosensitive resin composition will be described in detail.

[0016] <(A) Polyimide Resin Having a Hydroxycarbonyl Group in the Molecule> The negative photosensitive resin composition contains, as component (A), a polyimide resin having a hydroxycarbonyl group in the molecule. By including component (A) in the negative photosensitive resin composition, a cured product can be obtained that is excellent in ultimate resolution, has a low coefficient of thermal expansion, a high elongation rate, a suppressed warpage amount, and furthermore excellent dielectric properties. Component (A) may be used alone or in combination of two or more.

[0017] As component (A), a resin having a hydroxycarbonyl group and a plurality of imide structures can be used. From the viewpoint of significantly obtaining the effects of the present invention, it is preferable that there is one or more hydroxycarbonyl groups per molecule of component (A), and more preferably two or more. Also, as the upper limit, it is preferably four or less. The hydroxycarbonyl group is preferably bonded to an aromatic ring contained in the molecule of component (A). Further, the hydroxycarbonyl group may be present at the terminal of component (A).

[0018] From the viewpoint of significantly obtaining the effects of the present invention, component (A) preferably has the following structural unit (1). [Chemical formula] (In the formula, A 1 and A 3 each independently represent a trivalent hydrocarbon group, and A 2 and A 4 each independently represent a divalent group composed of an alkylene group, an arylene group, a carbonyl group, an oxygen atom, or a combination thereof.)

[0019] A 1 and A 3each independently represents a trivalent hydrocarbon group. The trivalent hydrocarbon group may be linear, branched, cyclic, or a combination thereof. From the viewpoint of significantly obtaining the effects of the present invention, the number of carbon atoms of the trivalent hydrocarbon group is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and preferably 15 or less, more preferably 10 or less, still more preferably 8 or less. Examples of the trivalent hydrocarbon group include a trivalent aliphatic hydrocarbon group, a trivalent aromatic hydrocarbon group, and a trivalent alicyclic hydrocarbon group. Examples of the trivalent hydrocarbon group include groups represented by the following structures. [Chemical formula] In the formula, * represents a bond.

[0020] A 2 and A 4 each independently represents a divalent group composed of an alkylene group, an arylene group, a carbonyl group, an oxygen atom, or a combination thereof. The number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 3. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, etc. The number of carbon atoms of the arylene group is preferably 6 to 20, more preferably 6 to 15, still more preferably 6 to 10. Examples of the arylene group include a phenylene group, a naphthylene group, an anthracenylene group, a biphenylene group (-C6H4-C6H4-), etc., and among them, the phenylene group is preferable.

[0021] As the divalent group composed of these combinations, a group composed of a combination of an arylene group, a carbonyl group, and an oxygen atom is preferable. Examples of such a divalent group include divalent groups represented by the following structures. [Chemical formula] * represents a bond.

[0022] A 1 and A 3 the trivalent hydrocarbon group represented, and A2 The divalent group consisting of an alkylene group, an arylene group and combinations thereof represented by may have a substituent. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom; a halogen atom-substituted alkyl group such as a hydroxy group, a trifluoromethyl group and the like. The above-mentioned substituents may further have a substituent (hereinafter sometimes referred to as a "secondary substituent"). The substituents may be included alone or in combination of two or more.

[0023] (A) component preferably contains a polyimide resin having a structural unit represented by the following general formula (A-1) and a structural unit represented by the following general formula (A-2) from the viewpoint of significantly obtaining the effects of the present invention.

Chemical formula

[0024] X each independently represents a single bond, an oxygen atom, a sulfur atom, an ester bond, an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a divalent group composed of a combination thereof.

[0025] The number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 3. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group and the like.

[0026] The number of carbon atoms in the arylene group is preferably 6 to 15, more preferably 6 to 10, and still more preferably 6. Examples of the arylene group include a phenylene group, a naphthylene group, an anthracenylene group, a biphenylene group (-C6H4-C6H4-), and the like.

[0027] Examples of the divalent group composed of these combinations include a divalent group composed of a combination of an ester bond and an alkylene group having 1 to 20 carbon atoms, a divalent group composed of a combination of an ester bond and an arylene group having 6 to 20 carbon atoms, and the like. Examples of such a group include a carbonyloxymethylene group, a carbonyloxyethylene group, a carbonyloxypropylene group, a carbonyloxyphenylene group, a carbonyloxynaphthylene group, a carbonyloxybiphenylene group, and the like.

[0028] Among these, X preferably represents a single bond.

[0029] Y 1 、Y 2 Each independently represents a hydrogen atom, a halogen atom, a trimethyl group, a trifluoromethyl group, a trimethyloxy group, or a hydroxy group, and a trifluoromethyl group is preferred.

[0030] m and n are any positive integers whose sum is 90 to 100. m is preferably 5 or more, more preferably 10 or more, still more preferably 20 or more, preferably 60 or less, more preferably 50 or less, and still more preferably 40 or less. n is preferably 40 or more, more preferably 50 or more, still more preferably 60 or more, preferably 100 or less, more preferably 90 or less, and still more preferably 80 or less.

[0031] Component (A) preferably contains a copolymer containing a structural unit represented by (A-1) and a structural unit represented by (A-2) from the viewpoint of significantly obtaining the effects of the present invention. The copolymerization ratio of the structural unit represented by the general formula (A-1) and the structural unit represented by the general formula (A-2) (structural unit m represented by the general formula (A-1) / structural unit n represented by the general formula (A-2)) is preferably 5 / 95 or more, more preferably 10 / 90 or more, still more preferably 15 / 85 or more, and preferably 50 / 50 or less, still more preferably 40 / 60 or less, and more preferably 30 / 70 or less.

[0032] From the viewpoint of significantly obtaining the effects of the present invention, component (A) preferably contains a polyimide resin having a structural unit represented by the following general formula (A-3) and a structural unit represented by the following general formula (A-4). [Chemical formula] In formulas (A-3) and (A-4), m1 and n1 are any positive integers whose sum is from 90 to 100.

[0033] m1 is the same as m in formula (A-1). Also, n1 is the same as n in formula (A-2).

[0034] From the viewpoint of significantly obtaining the effects of the present invention, component (A) preferably contains a copolymer containing a structural unit represented by (A-3) and a structural unit represented by (A-4). The copolymerization ratio of the structural unit represented by the general formula (A-3) and the structural unit represented by the general formula (A-4) (structural unit m1 represented by the general formula (A-3) / structural unit n1 represented by the general formula (A-4)) is preferably 5 / 95 or more, more preferably 10 / 90 or more, still more preferably 15 / 85 or more, and preferably 50 / 50 or less, still more preferably 40 / 60 or less, and more preferably 30 / 70 or less.

[0035] The weight average molecular weight of component (A) is preferably 10,000 or more, more preferably 30,000 or more, still more preferably 40,000 or more, and preferably 500,000 or less, more preferably 200,000 or less, still more preferably 100,000 or less, from the viewpoints of developer solubility and physical properties of the cured film. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0036] Component (A) can be synthesized, for example, by synthesizing a polyimide from an amic acid by an imidization reaction and copolymerizing the polyimide with a compound having a hydroxycarbonyl group such as a carboxylic acid.

[0037] The content of component (A) is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, 80% by mass or more, and preferably 98% by mass or less, more preferably 95% by mass or less, still more preferably 93% by mass or less, based on 100% by mass of the non-volatile components of the negative photosensitive resin composition, from the viewpoints of ultimate resolution and physical properties of the cured film. In the present invention, the content of each component in the negative photosensitive resin composition is a value based on 100% by mass of the non-volatile components in the negative photosensitive resin composition unless otherwise specified.

[0038] <(B) Photo radical generator> The negative photosensitive resin composition contains a photo radical generator as component (B). Component (B) generates radicals upon irradiation with actinic rays, and in the negative photosensitive resin composition, the portions where crosslinking reactions by radicals etc. occur are insoluble in an alkaline solution. Therefore, during development, it becomes possible to selectively remove the photosensitive resin composition except for the portions where the crosslinking reaction has proceeded, and a negative pattern can be advantageously formed. Component (B) may be used alone or in combination of two or more.

[0039] (B) components include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone; benzyl derivatives such as benzyl, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin, benzoin methyl ether; oximes such as 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime; N-aryl glycines such as N-phenylglycine; peroxides such as benzoyl perchloride; aromatic biimidazoles; titanocenes; α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide; etc. Among them, as the (B) component, oximes are preferred from the viewpoint of photosensitivity.

[0040] Regarding the content of the (B) component, from the viewpoint of improving photosensitivity or patterning property and improving the physical properties of the photosensitive resin composition layer after curing of the negative photosensitive resin composition, it is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, still more preferably 1 part by mass or more, and preferably 20 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, based on 100 parts by mass of the (A) component.

[0041] As the content of component (B), from the viewpoint of improving photosensitivity or patterning property and improving the physical properties of the photosensitive resin composition layer after curing of the negative photosensitive resin composition, when the non-volatile components of the negative photosensitive resin composition are 100% by mass, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less.

[0042] When the non-volatile components of the negative photosensitive resin composition are 100% by mass, when the content of component (B) is b1 and the content of component (A) is a1, as a1 / b1, from the viewpoint of significantly obtaining the effects of the present invention, it is preferably 10 or more, more preferably 20 or more, still more preferably 30 or more, and preferably 60 or less, more preferably 50 or less, still more preferably 45 or less.

[0043] <Compound having two or more ethylenically unsaturated bonds (C)> The negative photosensitive resin composition contains, as component (C), a compound having two or more ethylenically unsaturated bonds. When radicals are generated from a photoinitiator upon irradiation with actinic rays, a crosslinking reaction or the like of component (C) occurs and it becomes insoluble in an alkaline solution. Therefore, during development, it becomes possible to selectively remove the photosensitive resin composition except for the portions where the crosslinking reaction has proceeded, and a negative pattern can be advantageously formed. Component (C) may be used alone or in combination of two or more.

[0044] (C) component can use a compound having an ethylenically unsaturated bond. The ethylenically unsaturated bond has a carbon-carbon double bond. For example, vinyl group, allyl group, propargyl group, butenyl group, ethynyl group, phenylethynyl group, maleimide group, nadimide group, (meth)acryloyl group can be mentioned. From the viewpoint of the reactivity of photoradical polymerization, (meth)acryloyl group is preferred. The “(meth)acryloyl group” includes a methacryloyl group, an acryloyl group, and combinations thereof. Since the (C) component contains an ethylenically unsaturated group, photoradical polymerization is possible. The number of ethylenically unsaturated groups per molecule of the (C) component is preferably 1 or more, more preferably 2 or more. When the (C) component contains 2 or more ethylenically unsaturated groups per molecule, these ethylenically unsaturated groups may be the same or different.

[0045] (C) component is not particularly limited as long as it has an ethylenically unsaturated bond, but a compound represented by the following general formula (C-1) is preferred.

Chemical formula

[0046] R 1Each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. Examples of the linear or branched alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a 1-butyl group, an s-butyl group, a t-butyl group, and the like. Among them, R 1 is preferably a hydrogen atom or a methyl group.

[0047] Z each independently represents a linear or branched alkylene group having 1 to 20 carbon atoms which may contain an oxygen atom, an arylene group which may contain an oxygen atom, or a propenylene group. As the linear or branched alkylene group having 1 to 20 carbon atoms, a linear or branched alkylene group having 1 to 10 carbon atoms is preferable, and a linear or branched alkylene group having 1 to 6 carbon atoms is more preferable. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and the like. The alkylene group may also be an oxyalkylene group containing an oxygen atom, and specific examples of such a group include those shown below. In the formula, "*" represents a bond, and a represents an integer of 1 to 23.

Chemical formula

[0048] As the arylene group which may contain an oxygen atom, an arylene group having 6 to 20 carbon atoms is preferable, an arylene group having 6 to 15 carbon atoms is more preferable, and an arylene group having 6 to 10 carbon atoms is even more preferable. Examples of such an arylene group include a phenylene group, a naphthylene group, and the like. The arylene group may also contain an oxygen atom, and specific examples of such a group include those shown below. In the formula, "*" represents a bond, and a represents an integer of 1 to 23.

Chemical formula

[0049] Among them, as Z, a linear or branched alkylene group having 1 to 20 carbon atoms which may contain an oxygen atom is preferable, and an oxyalkylene group is more preferable.

[0050] A represents a linear, cyclic or branched nc-valent hydrocarbon group having 1 to 10 carbon atoms, an nc-valent group derived from bisphenol, an nc-valent group derived from fluorene, an nc-valent group derived from tricyclodecane, or an nc-valent group derived from an isocyanuric group. The nc-valent hydrocarbon group includes an nc-valent aliphatic hydrocarbon group and an nc-valent aromatic hydrocarbon group, and the nc-valent aliphatic hydrocarbon group is preferable. For example, when nc is 2, an alkylene group is preferable. Specific examples of the group represented by A include, for example, those shown below. In the formula, “*” represents a bond.

Chemical formula

[0051] nc represents a positive integer of 2 to 6, preferably a positive integer of 2 to 5, more preferably a positive integer of 2 to 4, and even more preferably 2 or 3.

[0052] As the component (C), a compound represented by the following general formula (C-2) is preferable.

Chemical formula

[0053] R 12 represents a hydrogen atom or a methyl group, and a methyl group is preferable.

[0054] Specific examples of the component (C) include the following compounds (CL-1) to (CL-10).

Chemical formula

Chemical formula

[0055] (C) component can use commercially available products. Examples of commercially available products include NK esters - 4G, 9G, 14G, 23G, DCP, etc. manufactured by Shin-Nakamura Chemical Co., Ltd.

[0056] From the viewpoint of significantly obtaining the effects of the present invention, the content of (C) component is preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, and preferably 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less, based on 100 parts by mass of (A) component.

[0057] From the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile components of the negative photosensitive resin composition are 100% by mass, the content of (C) component is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less.

[0058] When the non-volatile components of the negative photosensitive resin composition are 100% by mass, when the content of (C) component is c1 and the content of (A) component is a1, from the viewpoint of significantly obtaining the effects of the present invention, a1 / c1 is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, and preferably 25 or less, more preferably 20 or less, still more preferably 15 or less.

[0059] <(D) Sensitizer> The negative photosensitive resin composition may contain (D) sensitizer as an optional component. By containing (D) sensitizer, it becomes possible to improve the photosensitivity of the negative photosensitive resin composition. (D) component may be used alone or in combination of two or more.

[0060] (D) component can use a compound capable of improving the photosensitivity of the negative photosensitive resin composition. Examples of such compounds include benzophenones such as Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 4-morpholinobenzophenone; cyclic alkanes such as 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone; chalcones such as 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone; indanones such as p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone; thiazoles such as 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole; acetones such as 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone; coumarins such as 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin; amines such as N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate; heterocyclics such as 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 1-phenyl-5-mercaptotetrazole, 1-p-hydroxyphenyl-5-mercaptotetrazole; styrenes such as 2-(p-dimethylaminobenzoyl)styrene.

[0061] Among them, as the component (D), from the viewpoint of remarkably obtaining the effects of the present invention, heterocyclics are preferable, and a compound represented by the following general formula (D-1) is more preferable.

Chemical formula

[0062] R 2 represents a hydrogen atom, a linear or branched alkyl group having 1 to 7 carbon atoms, a halogen atom, a hydroxy group, a methoxy group, or a t-butoxy group. Examples of the linear or branched alkyl group having 1 to 7 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, and the like. Among them, R 2 preferably represents a hydroxy group, a methoxy group, or a t-butoxy group having an oxygen atom, more preferably a hydrogen atom or a hydroxy group, and even more preferably a hydrogen atom.

[0063] R 2 The bonding position of R may be any of the ortho position, meta position, and para position with respect to the site of the phenylene group bonded to the nitrogen atom of mercaptotetrazole. From the viewpoint of remarkably obtaining the effects of the present invention, the para position is preferable.

[0064] The compound represented by (D-1) is preferably either the compound represented by the following (D-2) or the compound represented by the following (D-3).

Chemical formula

[0065] The content of the (D) component is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 5% by mass or less, when the non-volatile components of the negative photosensitive resin composition are taken as 100% by mass, from the viewpoint of remarkably obtaining the effects of the present invention.

[0066] <(E) Adhesion promoter> The negative photosensitive resin composition may contain an (E) adhesion promoter as an optional component. By incorporating the (E) adhesion promoter into the negative photosensitive resin composition, the adhesion strength between the substrate and the cured product of the negative photosensitive resin composition can be improved. The (E) component may be used alone or in combination of two or more.

[0067] (E) As the adhesion promoter, a compound that improves the adhesion strength between the substrate and the film formed using the negative photosensitive resin composition can be used. Examples of such compounds include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalic acid, benzophenone-3,3’-bis(N-[3-triethoxysilyl]propylamide)-4,4’-dicarboxylic acid, benzene-1,4-bis(N-3-triethoxysilyl]propylamide)-2,Silane coupling agents such as 5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-(trialkoxysilyl)propyl succinic anhydride, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethylmethyldimethoxysilane, 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyl dimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N-(3-triethoxysilylpropyl)urea, N-(3-trimethoxysilylpropyl)urea, and compounds having an aminotriazine ring and an ethoxysilyl group; Aluminum-based adhesion aids such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and aluminum diisopropylate ethylacetoacetate. Among them, (E) as an adhesion aid, from the viewpoint of significantly obtaining the effects of the present invention, a silane coupling agent is preferred.,

[0068] (E) The adhesion promoter can be a commercially available product. Examples of commercially available products include "KBM403" (3-glycidoxypropyltriethoxysilane), "KBM803" (3-mercaptopropyltrimethoxysilane), "LS1375" (3-mercaptopropylmethyldimethoxysilane), "LS3610" (N-(3-triethoxysilylpropyl)urea) manufactured by Shin-Etsu Chemical Co., Ltd.; "Silace S810" (3-mercaptopropyltrimethoxysilane) manufactured by Chisso Corporation; "SIM6475.0" (3-mercaptopropyltriethoxysilane), "SIM6474.0" (3-mercaptopropylmethyldimethoxysilane), "SIM6473.5C" (mercaptomethyltrimethoxysilane), "SIM6473.0" (mercaptomethylmethyldimethoxysilane), "SIU9055.0" (N-(3-triethoxysilylpropyl)urea), "SIU9058.0" (N-(3-trimethoxysilylpropyl)urea) manufactured by Azmax Co., Ltd.; "VD-5" (a compound having an aminotriazine ring and an ethoxysilyl group) manufactured by Shikoku Kasei Co., Ltd., etc.

[0069] (E) From the viewpoints of substrate adhesion and mechanical strength, when the non-volatile components of the negative photosensitive resin composition are 100% by mass, the content of component (E) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less.

[0070] <Compound having two or more epoxy groups> The negative photosensitive resin composition may contain, as an optional component, a compound having two or more epoxy groups (F). By including a compound having two or more epoxy groups (F) in the negative photosensitive resin composition, the strength of the cured product of the negative photosensitive resin composition can be improved. Component (F) may be used alone or in combination of two or more.

[0071] (F) The number of epoxy groups contained in the component 1 molecule is 2 or more, preferably 10 or less, more preferably 8 or less, and still more preferably 4 or less, from the viewpoints of the limit resolution of the negative photosensitive resin composition and the mechanical strength of the cured product of the negative photosensitive resin composition.

[0072] Examples of the component (F) include aromatic epoxy compounds such as bixylenol type epoxy compounds, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, bisphenol AF type epoxy compounds, trisphenol type epoxy compounds, naphthol novolak type epoxy compounds, phenol novolak type epoxy compounds, tert-butyl-catechol type epoxy compounds, naphthalene type epoxy compounds, naphthol type epoxy compounds, anthracene type epoxy compounds, cresol novolak type epoxy compounds, biphenyl type epoxy compounds, naphthylene ether type epoxy compounds; aliphatic epoxy compounds such as epoxy compounds having a butadiene structure, cyclohexane type epoxy compounds, cyclohexanedimethanol type epoxy compounds, trimethylol type epoxy compounds, tetraphenylethane type epoxy compounds; alicyclic epoxy compounds; heterocyclic epoxy compounds; glycidyl ether type epoxy compounds; glycidylamine type epoxy compounds; etc. Among them, from the viewpoint of significantly obtaining the effects of the present invention, aromatic epoxy compounds are preferred, and among the aromatic epoxy compounds, naphthalene type epoxy compounds are preferred.

[0073] Specific examples of the aromatic epoxy compound include "HP4032", "HP4032D", "HP4032SS" (naphthalene-type epoxy compound) manufactured by DIC Corporation; "828US", "jER828EL", "825", "Epicoat 828EL" (bisphenol A-type epoxy compound) manufactured by Mitsubishi Chemical Corporation; "jER807", "1750" (bisphenol F-type epoxy compound) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolak-type epoxy compound) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (a mixture of bisphenol A-type epoxy compound and bisphenol F-type epoxy compound) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "HP4032H" (naphthalene-type epoxy compound) manufactured by DIC Corporation; "HP-4700", "HP-4710" (naphthalene-type tetrafunctional epoxy compound) manufactured by DIC Corporation; "N-690" (cresol novolak-type epoxy compound) manufactured by DIC Corporation; "N-695" (cresol novolak-type epoxy compound) manufactured by DIC Corporation; "EPPN-502H" (trisphenol-type epoxy compound) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolak-type epoxy compound) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl-type epoxy compound) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V" (naphthol-type epoxy compound) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN485" (naphthol novolak-type epoxy compound) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YL6121" (biphenyl-type epoxy compound) manufactured by Mitsubishi Chemical Corporation; "YX4000HK" (bixylenol-type epoxy compound) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene-type epoxy compound) manufactured by Mitsubishi Chemical Corporation; "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF-type epoxy compound) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene-type epoxy compound) manufactured by Mitsubishi Chemical Corporation; "jER1010" (solid bisphenol A-type epoxy compound) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane-type epoxy compound) manufactured by Mitsubishi Chemical Corporation, and the like.

[0074] The epoxy equivalent of a compound having two or more epoxy groups is preferably from 50 g / eq to 5000 g / eq, more preferably from 50 g / eq to 3000 g / eq, still more preferably from 80 g / eq to 2000 g / eq, and even more preferably from 110 g / eq to 1000 g / eq. By being within this range, the crosslink density of the cured product of the negative photosensitive resin composition becomes sufficient, and an insulating layer with a small surface roughness can be obtained. The epoxy equivalent is the mass of the resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0075] (F) The weight average molecular weight (Mw) of the component is preferably from 100 to 5000, more preferably from 250 to 3000, and still more preferably from 400 to 1500, from the viewpoint of significantly obtaining the desired effects of the present invention. The weight average molecular weight of the resin can be measured as a polystyrene equivalent value by gel permeation chromatography (GPC) method.

[0076] (F) The content of the component is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less, when the non-volatile components of the negative photosensitive resin composition are 100% by mass, from the viewpoints of limiting resolution and mechanical strength.

[0077] <(G) Solvent> The negative photosensitive resin composition may contain, as an optional component, (G) a solvent. The (G) solvent is a volatile component, and a solvent capable of uniformly dissolving at least any one of the components of (A) to (F) and (H) components can be used. Examples of such solvents include ether compounds having 2 to 9 carbon atoms such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; ketone compounds having 2 to 6 carbon atoms such as acetone and methyl ethyl ketone; saturated hydrocarbon compounds having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane, and decalin; aromatic hydrocarbon compounds having 6 to 10 carbon atoms such as benzene, toluene, xylene, mesitylene, and tetralin; ester compounds having 3 to 9 carbon atoms such as methyl acetate, ethyl acetate, γ-butyrolactone, and methyl benzoate; halogen-containing compounds having 1 to 10 carbon atoms such as chloroform, methylene chloride, and 1,2-dichloroethane; nitrogen-containing compounds having 2 to 10 carbon atoms such as acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; and sulfur-containing compounds such as dimethyl sulfoxide.

[0078] Further, examples of the (G) component include N-ethyl-2-pyrrolidone, tetrahydrofuran, N,N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, cyclopentanone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, anisole, ethyl acetate, ethyl lactate, and butyl lactate. The (G) component may be used alone or in combination of two or more.

[0079] (G) component content, when the total amount of the negative photosensitive resin composition is 100% by mass, is usually 1% by mass or more, preferably 150% by mass or more, more preferably 200% by mass or more, and 500% by mass or less, preferably 400% by mass or less, more preferably 300% by mass or less. By setting the content of the (G) component within such a range, the effects of the present invention can be significantly obtained.

[0080] <(H) Other Additives> The negative photosensitive resin composition may further contain (H) other additives to the extent that it does not inhibit the object of the present invention. Examples of the (H) other additives include surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, silicone-based surfactants; thermoplastic resins; phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black and other colorants; polymerization inhibitors such as hydroquinone, phenothiazine, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol; thickeners such as benton, montmorillonite; silicone-based, fluorine-based, vinyl resin-based defoamers; flame retardants such as epoxy resins, antimony compounds, phosphorus compounds, aromatic condensed phosphates, halogen-containing condensed phosphates; various additives such as phenolic curing agents, cyanate ester-based curing agents and other thermosetting resins can be added.

[0081] The negative photosensitive resin composition may contain a crosslinkable compound other than the (C) component and the (F) component. Examples of such crosslinkable compounds include nitrogen-containing compounds such as melamine compounds, guanamine compounds, glycoluril compounds, urea compounds containing two or more methylol groups and / or alkoxymethyl groups, or condensates thereof, and phenol compounds having two or more methylol groups or alkoxymethyl groups.

[0082] The negative photosensitive resin composition can be produced by mixing the above components (A) to (C) as essential components, appropriately mixing the above components (D) to (H) as optional components, and kneading or stirring as necessary by means of kneading such as a three-roll mill, ball mill, bead mill, sand mill, etc., or stirring means such as a super mixer, planetary mixer, etc.

[0083] <Physical properties and uses of negative photosensitive resin composition> The negative photosensitive resin composition exhibits the characteristic of excellent ultimate resolution. For example, exposure and development are performed using a mask for drawing round holes with an opening diameter of the exposure pattern of 10 μm, 15 μm, 20 μm, 25 μm, 30 μm. In this case, the ultimate resolution, which is the minimum size that can be opened, is preferably 25 μm or less, more preferably 20 μm or less, and even more preferably 15 μm or less. The evaluation of the ultimate resolution can be measured according to the method described in the examples below.

[0084] The negative photosensitive resin composition exhibits the characteristic of excellent remaining film property (film thickness reduction rate). For example, the film thickness of the negative photosensitive resin composition coated on a silicon wafer is measured, and the film thickness of the negative photosensitive resin composition after development is measured. In this case, when applied to the formula of film thickness reduction rate = film thickness after development / film thickness after coating × 100 (%), the film thickness reduction rate is preferably 70% or more, more preferably 90% or more. The remaining film property can be measured according to the method described in the examples below.

[0085] The cured product obtained by thermally curing the negative photosensitive resin composition at 200 °C for 2 hours exhibits the characteristic of a high elongation rate. This elongation rate represents the elongation rate until the cured product is pulled and broken, and the larger the value, the better the tensile strength. Due to this high elongation rate, the mechanical strength is high, and it is possible to obtain a cured product with high reliability for thermal cycle tests, drop impact tests, etc. The elongation rate is preferably 5% or more, more preferably 6% or more, and even more preferably 7% or more. The upper limit is not particularly limited, and it can be 20% or less, etc. The elongation rate can be measured according to the method described in the examples below.

[0086] The cured product obtained by thermally curing the negative photosensitive resin composition at 200°C for 2 hours exhibits the characteristic of having a low elastic modulus. This makes it possible to suppress the occurrence of warpage. The elastic modulus is preferably 20 GPa or less, more preferably 10 GPa or less, and even more preferably 6 GPa or less. The lower limit is not particularly limited, and it can be 0.1 GPa or more, etc. The elastic modulus can be measured according to the method described in the examples below.

[0087] The cured product obtained by thermally curing the negative photosensitive resin composition at 200°C for 2 hours exhibits the characteristic of having a low coefficient of thermal expansion (CTE). The coefficient of thermal expansion is preferably 35 ppm / °C or less, more preferably 30 ppm / °C or less, and even more preferably 25 ppm / °C or less. The lower limit is not particularly limited, and it can be 0.1 ppm / °C or more, etc. The coefficient of thermal expansion can be measured according to the method described in the examples below.

[0088] The cured product obtained by thermally curing the negative photosensitive resin composition at 200°C for 120 minutes exhibits the characteristic of having a small amount of warpage. The amount of warpage on an 8-inch silicon wafer is preferably 100 μm or less, more preferably 90 μm or less, and even more preferably 80 μm or less. The lower limit is not particularly limited, and it can be 0.1 μm or more, etc. The amount of warpage can be measured according to the method described in the examples below.

[0089] The cured product obtained by thermally curing the negative photosensitive resin composition at 200°C for 120 minutes exhibits the characteristic of having a low dielectric constant (Dk). The dielectric constant is preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less. The lower limit is not particularly limited, and it can be 0.01 or more, etc. The dielectric constant can be measured according to the method described in the examples below.

[0090] The cured product obtained by thermally curing the negative photosensitive resin composition at 200°C for 120 minutes exhibits the property of having a low dissipation factor (Df). The dissipation factor is preferably 0.03 or less, more preferably 0.02 or less, and even more preferably 0.01 or less. The lower limit is not particularly limited, and it can be 0.0005 or more, for example. The dissipation factor can be measured according to the method described in the examples below.

[0091] The uses of the negative photosensitive resin composition of the present invention are not particularly limited, but it can be used in a wide range of applications where negative photosensitive resin compositions are used, such as photosensitive films with a support, insulating resin sheets such as prepregs, silicon wafers, circuit boards (for multilayer boards, multilayer printed wiring boards, etc.), solder resists, buffer coat films, underfill materials, die bonding materials, semiconductor encapsulants, hole filling resins, component embedding resins, etc. Among them, it can be preferably used as a photosensitive resin composition for the insulating layer of a printed wiring board (a printed wiring board having a cured product of the negative photosensitive resin composition as the insulating layer), a photosensitive resin composition for the interlayer insulating layer (a printed wiring board having a cured product of the negative photosensitive resin composition as the interlayer insulating layer), a photosensitive resin composition for plating formation (a printed wiring board having a plating formed on the cured product of the negative photosensitive resin composition), a photosensitive resin composition for solder resist (a printed wiring board having a cured product of the negative photosensitive resin composition as the solder resist), a photosensitive resin composition for the redistribution layer formation of a wafer-level package (a wafer-level package having a cured product of the negative photosensitive resin composition as the redistribution layer), a photosensitive resin composition for the redistribution layer formation of a fan-out wafer-level package (a fan-out wafer-level package having a cured product of the negative photosensitive resin composition as the redistribution layer), a photosensitive resin composition for the redistribution layer formation of a fan-out panel-level package (a fan-out panel-level package having a cured product of the negative photosensitive resin composition as the redistribution layer), a photosensitive resin composition for buffer coat (a semiconductor device having a cured product of the negative photosensitive resin composition as the buffer coat), and a photosensitive resin composition for the insulating layer of a display (a display having a cured product of the negative photosensitive resin composition as the insulating layer).

[0092] [Semiconductor Package Substrate] The semiconductor package substrate of the present invention includes an insulating layer formed of a cured product of the negative photosensitive resin composition of the present invention. The insulating layer is preferably used as a rewiring formation layer, an interlayer insulating layer, a buffer coat film, or a solder resist.

[0093] Specifically, the semiconductor package substrate of the first embodiment of the present invention can be manufactured using the above-described negative photosensitive resin composition, and the cured product of the negative photosensitive resin composition is used as an insulating layer. Specifically, the method for manufacturing a semiconductor package substrate is as follows: (I) A step of forming a photosensitive resin composition layer containing the negative photosensitive resin composition of the present invention on a circuit board; (II) A step of irradiating the photosensitive resin composition layer with actinic rays; and (III) A step of developing the photosensitive resin composition layer in this order.

[0094] <Step (I)> As a method for forming the photosensitive resin composition layer, a method of directly applying a resin varnish containing a negative photosensitive resin composition onto a circuit board can be mentioned.

[0095] When directly applying a resin varnish containing a negative photosensitive resin composition onto a circuit board, a photosensitive resin composition layer is formed on the circuit board by drying and volatilizing the component (F).

[0096] Examples of the coating method of the resin varnish include, for example, gravure coating method, microgravure coating method, reverse coating method, kiss reverse coating method, die coating method, slot die method, lip coating method, comma coating method, blade coating method, roll coating method, knife coating method, curtain coating method, chamber gravure coating method, slot orifice method, spin coating method, slit coating method, spray coating method, dip coating method, hot melt coating method, bar coating method, applicator method, air knife coating method, curtain flow coating method, offset printing method, brush coating method, full surface printing method by screen printing method, etc.

[0097] The resin varnish may be applied in several portions, may be applied at once, or may be applied by combining a plurality of different methods. Among these, the die coating method, which is excellent in uniform coating properties, is preferable. Further, in order to avoid contamination with foreign matter, etc., it is preferable to carry out the coating process in an environment where foreign matter generation is small, such as a clean room.

[0098] After applying the resin varnish, drying is carried out using a hot air furnace or an infrared furnace, etc., as necessary. The drying conditions are preferably 80°C to 120°C for 3 minutes to 13 minutes. In this way, a photosensitive resin composition layer is formed on the circuit board.

[0099] Examples of the circuit board include a glass epoxy board, a metal board, a polyester board, a polyimide board, a BT resin board, a thermosetting polyphenylene ether board, etc. Here, the circuit board refers to a board in which a conductor layer (circuit) subjected to pattern processing is formed on one side or both sides of the support board as described above. Further, in a multilayer printed wiring board formed by alternately laminating a conductor layer and an insulating layer, a board in which one side or both sides of the outermost layer of the multilayer printed wiring board is a conductor layer (circuit) subjected to pattern processing is also included in the circuit board here. Note that the surface of the conductor layer may be previously roughened by blackening treatment, copper etching, etc.

[0100] <Step (II)> After a photosensitive resin composition layer is provided on the circuit board, an exposure process of irradiating a predetermined portion of the photosensitive resin composition layer with actinic rays through a mask pattern is then carried out. Examples of the actinic rays include ultraviolet rays, visible rays, electron beams, X-rays, etc., and ultraviolet rays are particularly preferable. The irradiation amount of ultraviolet rays is generally 10 mJ / cm 2 ~1000 mJ / cm 2 . As the exposure method, there are a contact exposure method in which the mask pattern is brought into close contact with the circuit board and a non-contact exposure method in which exposure is carried out using parallel rays without bringing them into close contact, and either method may be used.

[0101] In step (II), as the mask pattern, for example, via patterns such as round hole patterns can be used to form vias. The via diameter (aperture diameter) is preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 30 μm or less. The lower limit is not particularly limited and can be 0.1 μm or more, 0.5 μm or more, etc.

[0102] <Step (III)> After the exposure step, a pattern can be formed by performing a development step of removing the unexposed portions of the photosensitive resin composition layer with a developer. Development is usually performed by wet development.

[0103] In the case of the above wet development, as the developer, a developer that is safe, stable, and has good operability, such as an alkaline solution, an aqueous developer, or an organic solvent, is used. Among them, a development step using an alkaline solution such as an aqueous alkaline solution is preferred. Also, as the development method, known methods such as spraying, rocking immersion, brushing, and scraping are appropriately employed.

[0104] Examples of the aqueous alkaline solution used as the developer include aqueous solutions of alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; carbonates or bicarbonates such as sodium carbonate and sodium bicarbonate; alkali metal phosphates such as sodium phosphate and potassium phosphate; aqueous solutions of alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; and aqueous solutions of organic bases that do not contain metal ions such as tetraalkylammonium hydroxide. An aqueous solution of tetramethylammonium hydroxide (TMAH) is preferred in that it does not contain metal ions and does not affect the semiconductor chip.

[0105] These alkaline aqueous solutions can contain surfactants, antifoaming agents, etc. to improve the development effect. The pH of the above alkaline aqueous solution is preferably in the range of 8 to 12, more preferably in the range of 9 to 11. Also, the base concentration of the above alkaline aqueous solution is preferably 0.1% by mass to 10% by mass. The temperature of the above alkaline aqueous solution can be appropriately selected according to the developability of the photosensitive resin composition layer, but is preferably 20°C to 50°C.

[0106] Organic solvents used as developers include, for example, acetone, ethyl acetate, alkoxyethanol having an alkoxy group with 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, cyclopentanone, and cyclohexanone.

[0107] The concentration of such an organic solvent is preferably 2% by mass to 90% by mass with respect to the total amount of the developer. Also, the temperature of such an organic solvent can be adjusted according to the developability. Furthermore, such an organic solvent can be used alone or in combination of two or more. Examples of organic solvent-based developers used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone.

[0108] In pattern formation, two or more developing methods may be used in combination as necessary. Examples of developing methods include dip method, paddle method, spray method, high-pressure spray method, brushing, slapping, etc. The high-pressure spray method is suitable for improving resolution. When the spray method is adopted, the spray pressure is preferably 0.05 MPa to 0.3 MPa.

[0109] <Thermosetting (post-baking) process> After the completion of the above step (III), a thermal curing (post-bake) step is performed as necessary. In the above steps (I) to (III), the curing of the photosensitive resin composition layer may progress, but the thermal curing step can further progress the curing of the photosensitive resin composition to obtain an insulating layer with excellent mechanical strength. Examples of the post-bake step include a heating step using a clean oven. The atmosphere during thermal curing may be air or an inert gas atmosphere such as nitrogen. The heating conditions may be appropriately selected according to the type and content of the resin component in the negative photosensitive resin composition, but are preferably in the range of 150°C to 250°C for 20 minutes to 180 minutes, more preferably in the range of 160°C to 230°C for 30 minutes to 120 minutes.

[0110] <Other steps> The method for manufacturing a semiconductor package substrate may further include a drilling step and a desmear step after forming an insulating layer as the cured photosensitive resin composition layer. These steps may be carried out according to various methods known to those skilled in the art used for manufacturing a semiconductor package substrate.

[0111] After forming the insulating layer, if desired, a drilling step is performed on the insulating layer formed on the circuit board to form via holes and through holes. The drilling step can be carried out by known methods such as drill, laser, plasma, etc., and if necessary, these methods can be combined. However, a laser drilling step using a carbon dioxide laser, a YAG laser, etc. is preferred.

[0112] The desmear step is a step of performing a desmear treatment. Generally, resin residues (smear) adhere inside the openings formed in the drilling step. Since such smear may cause poor electrical connection, a treatment (desmear treatment) for removing the smear is carried out in this step.

[0113] The desmear treatment may be carried out by dry desmear treatment, wet desmear treatment, or a combination thereof.

[0114] Examples of dry desmear treatment include, for example, desmear treatment using plasma. The desmear treatment using plasma can be carried out using a commercially available plasma desmear treatment apparatus. Among commercially available plasma desmear treatment apparatuses, examples suitable for the production of semiconductor package substrates include a microwave plasma apparatus manufactured by Nissin Corporation and an atmospheric pressure plasma etching apparatus manufactured by Sekisui Chemical Co., Ltd.

[0115] Examples of wet desmear treatment include, for example, desmear treatment using an oxidizing agent solution. When performing desmear treatment using an oxidizing agent solution, it is preferable to perform swelling treatment with a swelling solution, oxidation treatment with an oxidizing agent solution, and neutralization treatment with a neutralizing solution in this order. Examples of the swelling solution include "Swelling Dip Security Gun P" and "Swelling Dip Security SBU" manufactured by Atotech Japan Co., Ltd. The swelling treatment is preferably carried out by immersing the substrate having vias or the like formed therein in a swelling solution heated to 60°C to 80°C for 5 minutes to 10 minutes. As the oxidizing agent solution, an alkaline permanganic acid aqueous solution is preferable, and examples thereof include a solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The oxidation treatment with the oxidizing agent solution is preferably carried out by immersing the substrate after the swelling treatment in an oxidizing agent solution heated to 60°C to 80°C for 10 minutes to 30 minutes. Commercially available products of the alkaline permanganic acid aqueous solution include, for example, "Concentrate Compact CP" and "Dosing Solution Security Gun P" manufactured by Atotech Japan Co., Ltd. The neutralization treatment with the neutralizing solution is preferably carried out by immersing the substrate after the oxidation treatment in a neutralizing solution at 30°C to 50°C for 3 minutes to 10 minutes. As the neutralizing solution, an acidic aqueous solution is preferable, and commercially available products thereof include, for example, "Reduction Solution Security Ant P" manufactured by Atotech Japan Co., Ltd.

[0116] When performing a combination of dry desmear treatment and wet desmear treatment, the dry desmear treatment may be carried out first, or the wet desmear treatment may be carried out first.

[0117] Regardless of whether the insulating layer is formed as a rewiring formation layer, an interlayer insulating layer, or a solder resist, after the thermosetting process, a drilling process and a desmear process may be performed. Further, in the method for manufacturing a semiconductor package substrate, a plating process may be further performed.

[0118] The plating process is a process of forming a conductor layer on the insulating layer. The conductor layer may be formed by sputtering after forming the insulating layer, may be formed by combining electroless plating and electroplating, or may form a plating resist having a pattern opposite to that of the conductor layer and form the conductor layer only by electroless plating. As a method of pattern formation thereafter, for example, a subtractive method, a semi-additive method, or the like known to those skilled in the art can be used.

[0119] The semiconductor package substrate according to the second embodiment of the present invention can be manufactured using the above-described negative photosensitive resin composition, and the cured product of the negative photosensitive resin composition is used as a rewiring formation layer. Specifically, the method for manufacturing a semiconductor package substrate is (A) A step of laminating a temporary fixing film on a base material, (B) A step of temporarily fixing a semiconductor chip on the temporary fixing film, (C) A step of forming a sealing layer on the semiconductor chip, (D) A step of peeling the base material and the temporary fixing film from the semiconductor chip, (E) A step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled, (F) A step of forming a rewiring layer as a conductor layer on the rewiring formation layer, and (G) A step of forming a solder resist layer on the rewiring layer, is included. Further, the method for manufacturing the semiconductor chip package is (H) A step of dicing and singulating a plurality of semiconductor chip packages into individual semiconductor chip packages may be included.

[0120] <Step (A)> Step (A) is a step of laminating a temporary fixing film on a base material. The lamination conditions between the base material and the temporary fixing film are not particularly limited. For example, the crimping temperature (lamination temperature) is preferably 70°C to 140°C, the crimping pressure is preferably 1 kgf / cm 2 ~11 kgf / cm 2 , the crimping time is preferably 5 seconds to 300 seconds, and it is preferable to laminate under reduced pressure with an air pressure of 20 mmHg or less. Also, the lamination process may be a batch type or a continuous type using rolls. The vacuum lamination method can be carried out using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include the Vacuum Applicator manufactured by Nichco Materials Co., Ltd., the Vacuum Pressure Laminator manufactured by Meiki Seisakusho Co., Ltd., the Roll Type Dry Coater manufactured by Hitachi Industries Co., Ltd., the Vacuum Laminator manufactured by Hitachi AIC Inc., etc.

[0121] Examples of the base material include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, cold-rolled steel sheets (SPCC); substrates impregnated with epoxy resins or the like in glass fibers and subjected to thermosetting treatment such as FR-4 substrates; substrates made of bismaleimide triazine resins such as BT resins; and the like.

[0122] The temporary fixing film can be peeled off from the semiconductor chip and any material that can temporarily fix the semiconductor chip can be used. Examples of commercially available products include "Revival Alpha" manufactured by Nitto Denko Corporation.

[0123] <Step (B)> Step (B) is a step of temporarily fixing a semiconductor chip on the temporary fixing film. The temporary fixing of the semiconductor chip can be performed using devices such as a flip chip bonder or a die bonder. The layout and the number of arrangements of the semiconductor chips can be appropriately set according to the shape and size of the temporary fixing film, the number of semiconductor packages to be produced, etc. For example, the semiconductor chips may be aligned and temporarily fixed in a matrix pattern with multiple rows and multiple columns.

[0124] <Step (C)> Step (C) is a step of forming a sealing layer on a semiconductor chip. Any insulating material can be used for the sealing layer, and the above-described negative photosensitive resin composition may also be used. The sealing layer is usually formed by a method including a step of forming a resin composition layer for sealing on the semiconductor chip and a step of thermally curing this resin composition layer to form the sealing layer.

[0125] The formation of the resin composition layer for sealing is preferably performed by a compression molding method. In the compression molding method, usually, the semiconductor chip and the resin composition for sealing are placed in a mold, and pressure and, if necessary, heat are applied to the resin composition for sealing in the mold to form a resin composition layer for sealing covering the semiconductor chip.

[0126] The specific operation of the compression molding method can be, for example, as follows. As a mold for compression molding, an upper mold and a lower mold are prepared. Also, a resin composition for sealing is applied to the semiconductor chip temporarily fixed on the temporary fixing film as described above. The semiconductor chip coated with the resin composition for sealing is attached to the lower mold together with the base material and the temporary fixing film. Then, the upper mold and the lower mold are clamped, and heat and pressure are applied to the resin composition for sealing to perform compression molding.

[0127] Also, the specific operation of the compression molding method may be, for example, as follows. As a mold for compression molding, an upper mold and a lower mold are prepared. The resin composition for sealing is placed on the lower mold. Also, the semiconductor chip is attached to the upper mold together with the base material and the temporary fixing film. Then, the upper mold and the lower mold are clamped so that the resin composition for sealing placed on the lower mold contacts the semiconductor chip attached to the upper mold, and heat and pressure are applied to perform compression molding.

[0128] The molding conditions vary depending on the composition of the resin composition for sealing, and appropriate conditions can be adopted to achieve good sealing. For example, the temperature of the mold during molding is preferably a temperature at which the resin composition for sealing can exhibit excellent compression moldability, preferably 80 °C or higher, more preferably 100 °C or higher, particularly preferably 120 °C or higher, and preferably 200 °C or lower, more preferably 170 °C or lower, particularly preferably 150 °C or lower. Also, the pressure applied during molding is preferably 1 MPa or higher, more preferably 3 MPa or higher, particularly preferably 5 MPa or higher, and preferably 50 MPa or lower, more preferably 30 MPa or lower, particularly preferably 20 MPa or lower. The cure time is preferably 1 minute or longer, more preferably 2 minutes or longer, particularly preferably 5 minutes or longer, and preferably 60 minutes or shorter, more preferably 30 minutes or shorter, particularly preferably 20 minutes or shorter. Usually, after the formation of the resin composition layer for sealing, the mold is removed. The removal of the mold may be performed before or after the thermosetting of the resin composition layer for sealing.

[0129] The compression molding method may be performed by discharging the resin composition for sealing filled in the cartridge onto the lower mold.

[0130] <Step (D)> Step (D) is a step of peeling the base material and the temporary fixing film from the semiconductor chip. It is desirable to adopt an appropriate method according to the material of the temporary fixing film for the peeling method. Examples of the peeling method include a method of peeling by heating, foaming, or expanding the temporary fixing film. Also, examples of the peeling method include a method of irradiating ultraviolet rays through the base material onto the temporary fixing film to reduce the adhesive force of the temporary fixing film and then peeling it.

[0131] In the method of peeling by heating, foaming, or expanding the temporary fixing film, the heating conditions are usually 100 °C to 250 °C for 1 second to 90 seconds or 5 minutes to 15 minutes. Also, in the method of irradiating ultraviolet rays to reduce the adhesive force of the temporary fixing film and then peeling it, the irradiation amount of ultraviolet rays is usually 10 mJ / cm 2 ~1000 mJ / cm 2 is.

[0132] <Engineering (E)> Engineering (E) is a process of forming a rewiring formation layer as an insulating layer on the surface from which the base material of the semiconductor chip and the temporary fixing film have been peeled off. The rewiring formation layer uses the negative photosensitive resin composition of the present invention. The method of forming the rewiring formation layer is the same as the method of forming the photosensitive resin composition layer in step (I) of the first embodiment.

[0133] When forming the rewiring formation layer, in order to connect the semiconductor chip and the rewiring layer in an interlayer manner, via holes may be formed in the rewiring formation layer.

[0134] Via holes can usually be formed by performing an exposure process of irradiating actinic rays through a mask pattern on the surface of the photosensitive resin composition layer for forming the rewiring formation layer, and a development process of removing the unexposed portion not irradiated with actinic rays with an alkaline aqueous solution. The irradiation amount and irradiation time of the actinic rays can be appropriately set according to the photosensitive resin composition layer. Examples of the exposure method include a contact exposure method in which a mask pattern is brought into close contact with the photosensitive resin composition layer for exposure, and a non-contact exposure method in which parallel light rays are used for exposure without bringing the mask pattern into close contact with the photosensitive resin composition layer. The actinic rays, the alkaline aqueous solution, and the exposure and development methods are as described above.

[0135] The shape of the via hole is not particularly limited, but is generally circular (substantially circular). The top diameter of the via hole is preferably 50 μm or less, more preferably 30 μm or less, still more preferably 20 μm or less, and preferably 0.1 μm or more, preferably 0.5 μm or more, more preferably 1.0 μm or more. Here, the top diameter of the via hole refers to the diameter of the opening of the via hole on the surface of the rewiring formation layer.

[0136] <Process (F)> Step (F) is a step of forming a rewiring layer as a conductor layer on a rewiring formation layer. The method of forming a rewiring layer on a rewiring formation layer may be the same as the method of forming a conductor layer on an insulating layer in the first embodiment. Also, steps (E) and (F) may be repeated to alternately stack (build up) the rewiring layers and the rewiring formation layers.

[0137] <Step (G)> Step (G) is a step of forming a solder resist layer on the rewiring layer. As the material of the solder resist layer, any insulating material can be used. Among them, a photosensitive resin and a thermosetting resin are preferable from the viewpoint of ease of manufacturing a semiconductor chip package. Also, the negative photosensitive resin composition of the present invention may be used.

[0138] Also, in step (G), if necessary, bumping processing for forming bumps may be performed. The bumping processing can be performed by methods such as solder balls and solder plating. Also, the formation of via holes in the bumping processing can be performed in the same manner as in step (E).

[0139] The method for manufacturing a semiconductor chip package may include step (H) in addition to steps (A) to (G). Step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and singulating them. The method for dicing a semiconductor chip package into individual semiconductor chip packages is not particularly limited.

[0140] [Semiconductor device] Examples of the semiconductor device in which the above-described semiconductor chip package is mounted include various semiconductor devices used in electric products (for example, computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical devices, and televisions, etc.) and vehicles (for example, motorcycles, automobiles, trains, ships, and airplanes, etc.).

Examples

[0141] Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "mass %", respectively, unless otherwise specified.

[0142] <Synthesis Example 1: Synthesis of Polyimide A-1> 45.2 g of p-phenylenebis(trimeric anhydride) (TAHQ) was placed in a 2 L separable flask, 500 mL of N-methyl-2-pyrrolidone was added, and the mixture was stirred at room temperature. Further, 6.32 g of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB) and 22.6 g of 5,5'-methylenebis(2-aminobenzoic acid) (MBAA) were added. At the same time, the reaction vessel was heated in an oil bath until the internal temperature reached 50 °C and polymerized for 20 hours. Next, 2.3 g of 3,5-dihydroxybenzoic acid and 185 g of toluene were added, and heating and stirring were carried out for 5 hours until the reflux of the solvent began in the oil bath. About 4.8 g of water was taken out from the reaction system by azeotropic dehydration with toluene, and an imidization reaction was carried out.

[0143] Next, the obtained reaction solution was dropped into 6 L of ultrapure water to precipitate the polymer, thereby generating the polymer. After filtering off the generated polymer, it was dried under heating at 80 °C in a vacuum dryer to obtain 71 g of polyimide A-1.

[0144] When the molecular weight of polyimide A-1 was measured by gel permeation chromatography (in terms of standard polystyrene conversion), the weight average molecular weight (Mw) was 55,000. Also, 1 As confirmed by 1H-NMR, polyimide A-1 is a copolymer having the following two structural units, and the copolymerization ratio is m:n = 20.5:79.5. Polyimide A-1:

Chemical formula

[0145] <Synthesis Example 2: Synthesis of Polyimide A-2> 45.2 g of p-phenylenebis(trimeric anhydride) (TAHQ) was placed in a 2 L separable flask, 500 mL of N-methyl-2-pyrrolidone was added, and the mixture was stirred at room temperature. Further, 8.84 g of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB) and 20.3 g of 5,5'-methylenebis(2-aminobenzoic acid) (MBAA) were added. At the same time, the reaction vessel was heated in an oil bath until the internal temperature reached 50 °C and polymerized for 20 hours. Next, 2.2 g of 3,5-dihydroxybenzoic acid and 185 g of toluene were added, and heating and stirring were carried out for 5 hours until the reflux of the solvent began in the oil bath. About 4.5 g of water was removed from the reaction system by toluene azeotropic dehydration, and an imidization reaction was carried out.

[0146] Next, the obtained reaction solution was dropped into 6 L of ultrapure water to precipitate the polymer, thereby producing the polymer. After filtering off the produced polymer, it was dried under heating at 80 °C in a vacuum to obtain 73 g of polyimide A-2.

[0147] When the molecular weight of polyimide A-1 was measured by gel permeation chromatography (in terms of standard polystyrene conversion), the weight average molecular weight (Mw) was 63,000. Also, 1 As confirmed by 1H-NMR, polyimide A-1 is a copolymer having the following two structural units, and the copolymerization ratio was m:n = 28.0:72.0. Polyimide A-2:

Chemical formula

[0148] <Synthesis Example 3: Synthesis of Polyimide A-3> 45.2 g of p-phenylenebis(trimellitate anhydride) (TAHQ) was placed in a 2 L separable flask, 500 mL of N-methyl-2-pyrrolidone was added, and the mixture was stirred at room temperature. Then, 5.05 g of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB) and 23.7 g of 5,5'-methylenebis(2-aminobenzoic acid) (MBAA) were added. At the same time, the reaction vessel was heated in an oil bath until the internal temperature reached 50 °C and polymerized for 20 hours. Next, 2.2 g of 3,5-dihydroxybenzoic acid and 185 g of toluene were added, and heating and stirring were carried out for 5 hours until the reflux of the solvent began in the oil bath. Approximately 4.3 g of water was removed from the reaction system by toluene azeotropic dehydration, and an imidization reaction was carried out.

[0149] Next, the obtained reaction solution was dropped into 6 L of ultrapure water to precipitate the polymer, thereby producing the polymer. After filtering off the produced polymer, it was dried under heating at 80 °C in a vacuum to obtain 71 g of polyimide A-3.

[0150] When the molecular weight of polyimide A-3 was measured by gel permeation chromatography (in terms of standard polystyrene conversion), the weight average molecular weight (Mw) was 38,000. Also, 1 As confirmed by 1H-NMR, polyimide A-1 is a copolymer having the following two structural units, and the copolymerization ratio was m:n = 13.7:86.3. Polyimide A-3:

Chemical formula

[0151] <Comparative Synthesis Example 1: Synthesis of Polymer A-4> 42.0 g of p-phenylenebis(trimellitate anhydride) (TAHQ) was placed in a 2 L separable flask, 550 mL of N-methyl-2-pyrrolidone was added, and the mixture was stirred at room temperature. Further, 6.13 g of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB) and 28.0 g of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) were added. At the same time, the reaction vessel was heated in an oil bath until the internal temperature reached 45 °C and polymerized for 20 hours. Next, 2.2 g of 3,5-dihydroxybenzoic acid and 185 g of toluene were added, and heating and stirring were carried out for 5 hours until the reflux of the solvent began in the oil bath. About 3.9 g of water was removed from the reaction system by toluene azeotropic dehydration, and an imidization reaction was carried out.

[0152] Next, the obtained reaction solution was dropped into 6 L of ultrapure water to precipitate the polymer, and Polymer A-4 was obtained by filtering the precipitated polymer and then drying it under heating at 80 °C in a vacuum to obtain 66 g of Polymer A-4.

[0153] When the molecular weight of Polymer A-4 was measured by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 74,000. Also, 1 The copolymerization ratio of the following structural formula A-4 confirmed by 1H-NMR was m:n = 19.4:80.6. Polymer A-4:

Chemical formula

[0154] <Comparative Synthesis Example 2: Synthesis of Polymer A-5> 39.3 g of ethylene ester of 1,2,4-benzenetricarboxylic acid 1,2-anhydride (TAEOL) was placed in a 2 L separable flask, 540 mL of N-methyl-2-pyrrolidone was added, and the mixture was stirred at room temperature. Further, 6.13 g of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB) and 28.0 g of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane were added. At the same time, the reaction vessel was heated in an oil bath until the internal temperature reached 45 °C and polymerized for 20 hours. Next, 2.2 g of 3,5-dihydroxybenzoic acid and 185 g of toluene were added, and heating and stirring were carried out for 5 hours until the reflux of the solvent began in the oil bath. About 4.1 g of water was removed from the reaction system by azeotropic dehydration with toluene, and an imidization reaction was carried out.

[0155] Next, the obtained reaction solution was dropped into 6 L of ultrapure water to precipitate the polymer. After the produced polymer was filtered off, it was dried under heating at 80 °C in vacuo to obtain 55 g of polymer A-5. When the molecular weight of polymer A-5 was measured by gel permeation chromatography (in terms of standard polystyrene conversion), the weight average molecular weight (Mw) was 59,000. Also, 1 The copolymerization ratio of the following structural formula A-5 confirmed by 1H-NMR was m:n = 21.8:78.2. Polymer A-5:

Chemical formula

[0156] <Examples 1 to 10 and Comparative Examples 1 to 2: Preparation of Negative-Type Photosensitive Compositions> The polyimides synthesized in Synthesis Examples 1 to 3, the polymers synthesized in Comparative Synthesis Examples 1 to 2, (B) a photo radical generator, (C) a compound having two or more ethylenically unsaturated bonds, (D) a sensitizer, (E) an adhesion aid, and (F) a compound having two or more epoxy groups were respectively blended as shown in the following table and dissolved in γ-butyrolactone to prepare a negative-type photosensitive composition.

[0157] In the following table, the contents of components (B) to (E) indicate the addition amounts (parts by mass) relative to 100 parts by mass of component (A). The usage amount of the solvent (γ-butyrolactone) was 280 parts by mass relative to 100 parts by mass of component (A) in each case.

[0158] [Table 1]

[0159] The abbreviations, etc. in the table are as follows. · Photoinitiator B-1: Irgacure OXE 02 (manufactured by BASF) · Photoinitiator B-2: Irgacure OXE 04 (manufactured by BASF) · Compound CL-2 having two or more ethylenically unsaturated bonds: A compound represented by the following structural formula [Chemical formula] · Compound CL-5 having two or more ethylenically unsaturated bonds: A compound represented by the following structural formula [Chemical formula] · Compound CL-7 having two or more ethylenically unsaturated bonds: A compound represented by the following structural formula [Chemical formula] · Sensitizer D-1: A compound represented by the following structural formula [Chemical formula] · Adhesion promoter E-1: A compound represented by the following structure (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403) [Chemical formula] · Adhesion promoter E-2: VD-5 (manufactured by Shikoku Kasei Co., Ltd.) · Compound F-1 having two or more epoxy groups: A compound represented by the following structural formula (HP-4032D, manufactured by DIC Corporation) [Chemical formula] Compound F-2 having two or more epoxy groups: A compound represented by the following structural formula [Chemical formula]

[0160] [Evaluation of limit resolution and residual film property (film thickness reduction during development)] Copper plating was laminated on a silicon wafer with a film thickness of 5 μm, and the negative photosensitive composition formulated in Examples and Comparative Examples was applied onto the substrate that had been roughened with a 1% hydrochloric acid aqueous solution for 10 seconds at a rotation speed suitable for a film thickness of 15 μm using a spin coater, and then heated on a hot plate at 120 °C for 5 minutes to prepare a photosensitive resin composition layer. This is referred to as a laminate.

[0161] The prepared laminate was exposed to ultraviolet light (wavelength 365 nm, intensity 40 mW / cm 2 ). The exposure dose was set to the optimum value in the range from 50 mJ / cm 2 to 1000 mJ / cm 2 . As the exposure pattern, a quartz glass mask for drawing round holes (vias) with opening diameters of 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, and 30 μm was used.

[0162] Next, a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 50 °C was sprayed onto the entire surface of the photosensitive resin composition layer of the laminate at a spray pressure of 0.1 MPa for an optimum time between 30 seconds and 600 seconds for spray development, and then water was sprayed for 30 seconds at a spray pressure of 0.1 MPa for spray rinsing. Further, heat treatment was performed at 200 °C for 120 minutes to cure the photosensitive resin composition layer.

[0163] The diameters of the bottoms of the vias with opening diameters of 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, and 30 μm in the exposure pattern were observed (magnification 1000 times) and measured by SEM. The minimum size that can be opened was defined as the limit resolution.

[0164] Furthermore, the film thickness after development was measured, and the remaining film property was calculated as the film thickness reduction rate by the following calculation method and evaluated according to the following criteria. Film thickness reduction rate = Film thickness after development / Film thickness after coating × 100 (%) ◎: Film thickness reduction rate is 90% or more 〇: Film thickness reduction rate is 70% or more and less than 90% ×: Film thickness reduction rate is less than 70%

[0165] <Measurement of elongation, elastic modulus, coefficient of linear thermal expansion, dielectric constant, and dielectric tangent> (1) Preparation of photosensitive resin composition film for physical property measurement The negative photosensitive compositions formulated in the examples and comparative examples were coated onto a peeled PET film (product name NS-80A: manufactured by Fujimori Kogyo Co., Ltd.) using a blade so that the film thickness became 140 μm. The solution on this PET film was heated at 80 °C for 20 minutes using a heating machine to obtain a photosensitive resin composition layer. The photosensitive resin composition layer was peeled from the PET film and attached to a metal frame using a heat-resistant tape, and cured at 200 °C for 2 hours to prepare a photosensitive resin composition film for physical property measurement.

[0166] (2) Measurement of elongation and elastic modulus The photosensitive resin composition film for physical property measurement was cut into dumbbell-shaped No. 1 specimens to obtain test pieces. Tensile strength measurement was performed on these test pieces using a tensile testing machine "RTC-1250A" manufactured by Orientec Co., Ltd., and the elongation and elastic modulus at 25 °C were determined. The measurement was carried out in accordance with JIS K7127. This operation was performed 3 times and the average value was shown in the table (unit: elongation = %; elastic modulus = GPa).

[0167] (3) Measurement of coefficient of linear thermal expansion (CTE) A photosensitive resin composition film for physical property measurement was cut into pieces with a width of 5 mm and a length of 15 mm to obtain test pieces. For these test pieces, thermomechanical analysis was performed by the tensile loading method using a thermomechanical analyzer (Thermo Plus TMA8310 manufactured by Rigaku Corporation). Specifically, after mounting the test pieces on the thermomechanical analyzer, two consecutive measurements were performed under the measurement conditions of a load of 1 g and a heating rate of 5 °C / min. Then, the linear thermal expansion coefficient (ppm / °C) in the planar direction in the range from 25 °C to 150 °C was calculated.

[0168] (4) Measurement of dielectric constant and dielectric loss tangent (dielectric properties) A test piece with a width of 2 mm and a length of 80 mm was cut from the photosensitive resin composition film for physical property measurement. For the cut test piece, the dielectric loss tangent was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 °C by the cavity resonance perturbation method using a measuring device "HP8362B" manufactured by Agilent Technologies.

[0169] <Warp evaluation> On an 8-inch silicon wafer, the photosensitive resin compositions formulated in the examples and comparative examples were applied using a spin coater at a rotation speed suitable for a film thickness of 25 μm, and then heated on a hot plate at 120 °C for 5 minutes. Further, a heat treatment at 200 °C for 120 minutes was performed to thermally cure the photosensitive resin composition layer. Thereby, a sample substrate including the silicon wafer and the cured product layer of the photosensitive resin composition was obtained. Using a shadow moire measuring device (Thermoire AXP manufactured by Akorometrix), the warp amount of the above sample substrate was measured at 25 °C. The measurement was performed in accordance with JEITA EDX-7311-24 of the Electronic Information Technology Industry Association standard. Specifically, taking the virtual plane calculated by the least squares method of all the data on the substrate surface in the measurement area as the reference plane, the difference between the minimum value and the maximum value in the vertical direction from the reference plane was determined as the warp amount (μm).

[0170]

Table 2

[0171] Examples 1 to 10 were able to obtain a cured product that was excellent in limit resolution and residual film properties during development, had a low coefficient of thermal expansion and modulus of elasticity, a high elongation rate, suppressed warpage amount, and furthermore excellent dielectric properties. On the other hand, Comparative Examples 1 to 2 had poor limit resolution and also poor residual film properties during development, and neither the mechanical strength nor the dielectric properties of the obtained cured products were satisfactory.

Claims

1. (A) A polyimide resin having a hydroxycarbonyl group in the molecule, (B) A photo radical generator, and (C) A compound having two or more ethylenically unsaturated bonds, and contains The component (A) is a negative photosensitive resin composition containing a polyimide resin having a structural unit represented by the following general formula (A-1) and a structural unit represented by the following general formula (A-2). 【Chemical Formula 1】 (In formula (A-1) and formula (A-2), X each independently represents a single bond, an oxygen atom, a sulfur atom, an ester bond, an alkylene group having 1 to 20 carbon atoms, an arylene group having 7 to 20 carbon atoms, or a divalent group consisting of a combination thereof, and Y1 and Y2 each independently represent a hydrogen atom, a halogen atom, a trimethylsilyl group, a trifluoromethyl group, a trimethylsilyloxy group, or a hydroxy group. m and n are any positive integers whose sum is 90 to 100.)

2. The negative photosensitive resin composition according to claim 1, wherein the component (A) contains a copolymer containing a structural unit represented by the general formula (A-1) and a structural unit represented by the general formula (A-2), and the copolymerization ratio of the structural unit represented by the general formula (A-1) and the structural unit represented by the general formula (A-2) (structural unit m represented by the general formula (A-1) / structural unit n represented by the general formula (A-2)) is 5 / 95 or more and 50 / 50 or less.

3. The negative photosensitive resin composition according to claim 1 or 2, wherein the component (A) contains a polyimide resin having a structural unit represented by the following general formula (A-3) and a structural unit represented by the following general formula (A-4). [Chemical Formula 2] (In formula (A-3) and (A-4), m1 and n1 are any positive integers whose sum is 90 to 100.)

4. The negative photosensitive resin composition according to claim 3, wherein the component (A) contains a copolymer containing a structural unit represented by the general formula (A-3) and a structural unit represented by the general formula (A-4), and the copolymerization ratio of the structural unit represented by the general formula (A-3) and the structural unit represented by the general formula (A-4) (structural unit m1 represented by the general formula (A-3) / structural unit n1 represented by the general formula (A-4)) is 5 / 95 or more and 50 / 50 or less.

5. The negative photosensitive resin composition according to any one of claims 1 to 4, which contains (D) a sensitizer.

6. The negative photosensitive resin composition according to any one of claims 1 to 5, wherein the component (C) is a compound represented by the following general formula (C-1). 【Chemical Formula 3】 (In formula (C-1), R １ each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, Z each independently represents a linear or branched alkylene group having 1 to 20 carbon atoms which may contain an oxygen atom, an arylene group which may contain an oxygen atom, or a propenylene group, and A represents a linear, cyclic or branched nc-valent hydrocarbon group having 1 to 10 carbon atoms, an nc-valent group derived from bisphenol, an nc-valent group derived from fluorene, an nc-valent group derived from tricyclodecane, or an nc-valent group derived from an isocyanuric group. nc represents a positive integer of 2 to 6.)

7. The negative photosensitive resin composition according to any one of claims 1 to 6, wherein the component (C) is a compound represented by the following general formula (C-2). 【Chemical 4】 (In formula (C-2), R １２ each independently represents a hydrogen atom or a methyl group.)

8. The negative photosensitive resin composition according to any one of claims 1 to 7, which contains an adhesion promoter (E).

9. The negative photosensitive resin composition according to any one of claims 1 to 8, which contains a compound having two or more epoxy groups (F).

10. A semiconductor package substrate including an insulating layer formed of a cured product of the negative photosensitive resin composition according to any one of claims 1 to 9.

11. A semiconductor device including the semiconductor package substrate according to claim 10.

12. A step of forming a photosensitive resin composition layer including the negative photosensitive resin composition according to any one of claims 1 to 9 on a circuit board; A step of irradiating the photosensitive resin composition layer with actinic rays; A method for manufacturing a semiconductor package substrate, which includes a step of developing the photosensitive resin composition layer.

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