Laminate, method for manufacturing laminate, and method for forming pattern

Abstract

The present invention is a layered body that is obtained using a semiconductor substrate by forming a photosensitive resin layer on said semiconductor substrate, and is characterized in that the photosensitive resin layer includes a silicone backbone-including resin or an acrylic resin, the semiconductor substrate has a stepped surface on one side, a recessed section of the stepped surface is filled with a prewetting solution, and the photosensitive resin layer is formed thereon. Thus, the present invention provides a layered body wherein a photosensitive composition including a silicone backbone-including resin or an acrylic resin is used, a recessed section in a stepped surface of a stepped substrate is sufficiently filled in with said resin, and a level photosensitive resin film can be provided, and the present invention also provides a method for manufacturing said layered body with little material loss, and a method for forming a pattern wherein said layered body is used.

Description

Technical Field

[0001] The present invention relates to a laminate, a method for manufacturing the laminate, and a pattern forming method using the laminate.

Background Art

[0002] Among the demands for highly integrated semiconductor packages, in order to stack a plurality of semiconductor packages in one semiconductor package, silicon through electrodes (TSVs) that can penetrate a substrate or a die vertically and be electrically connected are used in 3D packages. When forming a wiring layer on a TSV, a SiO2 film is used as an insulating layer. This is formed by CVD, but it is difficult to form a flat film as the TSV becomes deeper. Furthermore, in order to achieve higher integration, since a polished thin wafer is used, a resin adhesive for bonding a support wafer for supporting it is required, and CVD needs to be performed at a low temperature of around 200°C.

[0003] Therefore, the formation of an insulating layer using a resin material has also been proposed. Examples of the formation method include a printing method, a spray method (Patent Document 1), an inkjet method (Patent Document 2), a spin coating method, a dip coating method, or a lamination method. Among them, there is also a method of embedding a TSV once using a photocurable resin and forming an insulating layer only on the side wall portion by opening a VIA by exposure. At this time, it is necessary to embed the resin in the TSV without gaps, and it is further necessary to form a film with a flat film thickness on the substrate.

[0004] This time, in particular, attention was paid to the spin coating method that is widely used. The spin coating method uses rotational centrifugal force and can form a flat coating film by dropping a coating material at the center of a wafer and then rotating it. However, generally, it is used on a flat substrate and is applied by rotation, so the amount of liquid actually remaining on the substrate is less than the amount of liquid dropped, and material loss is cited as an issue (Patent Document 3).

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0006] In view of the above circumstances, the present invention provides a laminate using a photosensitive composition containing a silicone skeleton-containing resin or an acrylic resin, in which the recesses on the stepped surface of the stepped substrate are sufficiently filled with the resin to provide a flat photosensitive resin film, a method for manufacturing a laminate capable of embedding a semiconductor substrate having a stepped surface on one side with a prewet solvent by spin coating and forming a flat photosensitive resin layer, and a method for forming a pattern using the laminate.

Means for Solving the Problems

[0007] In order to solve the above problems, the present invention provides a laminate including a semiconductor substrate and a photosensitive resin layer formed on the semiconductor substrate, wherein the photosensitive resin layer contains a silicone skeleton-containing resin or an acrylic resin, the semiconductor substrate has a stepped surface on one side, the recesses on the stepped surface are filled with a prewet solvent, and the photosensitive resin layer is formed thereon.

[0008] With such a laminate, a laminate can be obtained in which the recesses on the stepped surface of the stepped substrate are sufficiently filled with the resin using a photosensitive composition containing a silicone skeleton-containing resin or an acrylic resin to provide a flat photosensitive resin film.

[0009] At this time, it is preferable that the opening width of the stepped surface is 10 to 100 μm and the depth is 10 to 120 μm.

[0010] Even for a laminate having such a stepped surface, a laminate can be obtained in which the concave portions on the stepped surface of the stepped substrate can be sufficiently filled with the resin by using a photosensitive composition containing a silicone skeleton-containing resin or an acrylic resin.

[0011] At this time, it is preferable that the prewet solvent is a single solvent or a mixed solvent containing at least 30% by mass or more of a solvent having a boiling point of 130°C or higher.

[0012] For such a laminate, the concave portions on the stepped surface of the stepped substrate can be more sufficiently filled with the resin, and a more flat photosensitive resin film can be provided.

[0013] At this time, it is preferable that the photosensitive resin layer contains (A) a silicone skeleton-containing polymer, (B) a photoacid generator that decomposes by light of 190 to 500 nm to generate an acid, and (C) a solvent.

[0014] For such a laminate, the concave portions on the stepped surface of the semiconductor substrate can be finally filled well.

[0015] At this time, it is preferable that the (A) silicone skeleton-containing polymer contains a repeating unit represented by any one or more of the following formulas (a1) to (a4) and any one or more of (b1) to (b4). [Chemical formula] [In the formula, R 1 ~R 4 are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. m is an integer of 1 to 600. a 1 ~a 4 and b 1 ~b 4 are 0 ≦ a 1 < 1, 0 ≦ a 2 < 1, 0 ≦ a 3 < 1, 0 ≦ a 4 < 1, 0 ≦ b 1 < 1, 0 ≦ b 2 < 1, 0 ≦ b 3<1, 0 ≤ b 4 <1, 0 < a 1 +a 2 +a 3 +a 4 <1, 0 ≤ b 1 +b 2 +b 3 +b 4 <1, and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 = 1 satisfying number. X 1 X is a divalent group represented by the following formula (X1). 2 X is a divalent group represented by the following formula (X2). 3 X is a divalent group represented by the following formula (X3). 4 X is a divalent group represented by the following formula (X4).

Chemical formula

Chemical formula

[0016] With such a component (A), the recesses on the stepped surface of the semiconductor substrate can be finally filled better.

[0017] In addition, in the present invention, it is also preferable that the photosensitive resin layer contains (A') an acrylic polymer, (B') a photopolymerization initiator, and (C) a solvent.

[0018] Even with such components (A') and (B'), the recesses on the stepped surface of the semiconductor substrate can be finally filled well.

[0019] In the present invention, a first coating step of spin-coating a prewet solvent on a concave portion of a stepped surface of a semiconductor substrate having a stepped surface on one side to prewet and filling the concave portion of the stepped surface with the prewet solvent, a wiping step of removing excess prewet solvent when prewetting on the semiconductor substrate while spinning, and a second coating step of spin-coating a photosensitive resin composition containing a silicone skeleton-containing resin or an acrylic resin on the surface on the side where the prewet solvent is spin-coated and filled to form a photosensitive resin layer which is a coating film of the photosensitive resin composition are provided, which is a method for manufacturing a laminate.

[0020] With such a method for manufacturing a laminate, a substrate having a stepped surface on one side can be embedded with a prewet solvent by spin coating with less material loss using a photosensitive composition containing a silicone skeleton-containing resin or an acrylic resin, and a flat photosensitive resin layer can be formed.

[0021] At this time, it is preferable to perform the second coating step without stopping the rotation of the semiconductor substrate from the wiping step.

[0022] With such a method for manufacturing a laminate, the photosensitive resin composition can be dropped without the wafer surface drying, and the embedding of the semiconductor substrate having a stepped surface can be suitably performed.

[0023] At this time, as the prewet solvent used in the first coating step, it is preferable to use a single solvent or a mixed solvent containing at least 30% by mass or more of a solvent having a boiling point of 130°C or higher.

[0024] With such a method for manufacturing a laminate, by containing a solvent having a high boiling point, it is difficult for the surface of the semiconductor substrate to dry during prewetting or when dropping the photosensitive resin composition for forming the photosensitive resin layer, and it becomes easy to spread the coating.

[0025] In addition, in the present invention, in the laminate manufactured by the manufacturing method described above, a step of performing preliminary heating to cure the photosensitive resin layer to form a photosensitive resin film, a step of exposing the photosensitive resin film through a photomask, and after performing heat treatment after exposure, developing with a developer to dissolve and remove the unexposed portion to form a pattern are included, and a pattern forming method is provided.

[0026] In such a pattern forming method, since the step difference surface of the substrate can be well embedded with a photosensitive resin containing a silicone skeleton-containing resin or an acrylic resin to form a flat photosensitive resin film, an insulating layer can be well formed only on the side wall portion by opening a VIA by exposure (pattern formation).

Effects of the Invention

[0027] In the method for manufacturing a laminate of the present invention, by using a photosensitive resin composition containing a silicone skeleton-containing resin or an acrylic resin, the step difference on the semiconductor substrate can be cleanly filled with a high filling rate with a small amount of coating liquid, and further, the photosensitive resin layer on the semiconductor substrate can be formed flat.

Brief Description of the Drawings

[0028]

Figure 1

Figure 2

Figure 3

Embodiments for Carrying Out the Invention

[0029] As described above, there has been a demand for the development of a laminate, a method for manufacturing a laminate, and a pattern forming method capable of embedding a semiconductor substrate having a step difference surface on one side with a small material loss by spin coating using a photosensitive composition containing a silicone skeleton-containing resin or an acrylic resin and forming a flat film.

[0030] As a result of intensive studies to achieve the above object, the present inventors found that after performing a prewet on the concave portion of the stepped surface of a semiconductor substrate having a stepped surface on one side with a prewet solvent, and then applying a photosensitive resin composition containing a silicone skeleton-containing resin or an acrylic resin, it is possible to apply even a small amount of the photosensitive resin composition and to cleanly embed the concave portion of the stepped surface of the semiconductor substrate having a stepped surface on one side, and further found that the obtained laminate has the concave portion of the stepped surface embedded without gaps with the resin, and further that a flat film can be formed on the semiconductor substrate, thus arriving at the present invention.

[0031] That is, the present invention is a laminate comprising a semiconductor substrate and a photosensitive resin layer formed on the semiconductor substrate, wherein the photosensitive resin layer contains a silicone skeleton-containing resin or an acrylic resin, the semiconductor substrate has a stepped surface on one side, the concave portion of the stepped surface is filled with a prewet solvent, and the photosensitive resin layer is formed thereon.

[0032] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0033] [Laminate] The laminate of the present invention is a laminate comprising a semiconductor substrate and a photosensitive resin layer formed on the semiconductor substrate, wherein the photosensitive resin layer contains a silicone skeleton-containing resin or an acrylic resin, the semiconductor substrate has a stepped surface on one side, the concave portion of the stepped surface is filled with a prewet solvent, and the photosensitive resin layer is formed thereon.

[0034] As illustrated in FIG. 1, the laminate 10 of the present invention is a laminate comprising a semiconductor substrate 1 and a photosensitive resin layer 3 formed on the semiconductor substrate 1, wherein the semiconductor substrate 1 has a stepped surface on one side, the concave portion of the stepped surface is filled with a prewet solvent 2, and the photosensitive resin layer 3 is formed thereon.

[0035] At this time, the opening width of the stepped surface is preferably 10 to 100 μm, more preferably 50 to 80 μm, and the depth is preferably 10 to 120 μm, more preferably 50 to 100 μm.

[0036] [Method for manufacturing a laminate] As a method for manufacturing the laminate of the present invention, for example, a first coating step of spin-coating and prewetting a prewetting solvent in a concave portion of a stepped surface of a semiconductor substrate having a stepped surface on one side to fill the concave portion of the stepped surface with the prewetting solvent; a wiping step of removing excess prewetting solvent when prewetted on the semiconductor substrate while spinning; and a second coating step of spin-coating a photosensitive resin composition containing a silicone skeleton-containing resin or an acrylic resin on the surface on the side where the prewetting solvent is spin-coated and filled to form a photosensitive resin layer which is a coating film of the photosensitive resin composition. A method for manufacturing a laminate including these steps can be mentioned.

[0037] The method for manufacturing the laminate will be described below with reference to FIG. 2.

[0038] FIG. 2 is an example of the method for manufacturing the laminate of the present invention. First, a semiconductor substrate 1 having a stepped surface on one side is prepared (I in FIG. 2). Next, a first coating step is performed in which a prewetting solvent 2 is spin-coated and prewetted in a concave portion of the stepped surface of the semiconductor substrate 1 having a stepped surface on one side to fill the concave portion of the stepped surface with the prewetting solvent 2 (II in FIG. 2). Next, a wiping step is performed to wipe off the excess prewetting solvent 2 on the semiconductor substrate 1 while spinning (III in FIG. 2). Next, a second coating step is performed in which a photosensitive resin composition containing a silicone skeleton-containing resin or an acrylic resin is spin-coated on the surface on the side where the prewetting solvent 2 is spin-coated and filled to form a photosensitive resin layer 3 which is a coating film of the photosensitive resin composition, thereby obtaining the laminate 10 of the present invention (IV in FIG. 2). The obtained laminate 10 is further rotated so that the photosensitive resin layer 3 has a target film thickness. During this time, the prewetting solvent 2 is replaced with the photosensitive resin composition, so that the photosensitive resin composition is embedded in the semiconductor substrate 1 without gaps, and the laminate 10 of the present invention is obtained (V in FIG. 2). The details of each process will be described below.

[0039] (First Coating Process) Prewetting The first coating process is a process of spin-coating a prewetting solvent 2 into the concave portion of the step surface of the semiconductor substrate 1 having a step surface on one side to perform prewetting, and filling the concave portion of the step surface with the prewetting solvent 2. In the semiconductor substrate 1 having a step surface with unevenness on one side such as a TSV, if a photosensitive resin composition in a liquid state is usually applied as it is, the photosensitive resin composition does not enter the concave portion of the step surface, and it is difficult to embed. Therefore, by performing prewetting to fill the concave portion of the step surface with the prewetting solvent 2 first, the photosensitive resin composition to be applied next can easily enter and embedding becomes easy.

[0040] These prewetting solvents 2 are preferably organic solvents, and may be used alone or in combination of two or more kinds as a mixed solvent.

[0041] Examples of the prewetting solvent 2 include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-amyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol-mono-tert-butyl ether acetate, and γ-butyrolactone.

[0042] Among them, in this embodiment, the closer the polarity and solubility parameter are to those of the solvent (described later) used in the photosensitive resin composition to be applied later, the better the embedding will be.

[0043] When using a combination of two or more types, the organic solvent used as the prewet solvent preferably contains at least 30% by mass or more of a solvent having a boiling point of 130°C or higher, preferably 135°C or higher. Preferably, it contains 30 to 70 Mass % is good. In this case, the boiling point is preferably 130 to 160°C, more preferably 135 to 160°C. By containing a solvent with a high boiling point, it is difficult for the substrate surface to dry during prewetting or when dropping the photosensitive resin composition, and it becomes easier to spread.

[0044] Particularly, ethyl lactate, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, γ-butyrolactone, and a mixed solvent thereof, which have the best solubility of the photoacid generator, are preferred.

[0045] In prewetting, the rotation speed is preferably greater than 0 and up to 50 rpm, more preferably greater than 0 and up to 20 rpm. As a result, the prewet solvent 2 remains on the wafer, and at the same time, the prewet solvent 2 spreads over the entire concave portion of the step surface, so that the bubbles in the step disappear, and it is difficult for embedding defects to occur when the photosensitive resin composition is applied.

[0046] The time for holding the prewet solvent 2 on the semiconductor substrate 1 depends on the size of the step, but is preferably 1 to 30 minutes, more preferably 1 to 15 minutes.

[0047] Performing prewetting first makes it easier for the photosensitive resin composition to spread in the second coating step, leading to less liquid waste of the dropped liquid, and reducing material loss.

[0048] (Scrubbing process) The wiping process is a process of wiping the excess pre-wet solvent 2 on the semiconductor substrate 1 while spinning. The rotation speed is preferably 50 to 120 rpm, more preferably 80 to 100 rpm. Further, it is preferably spun for 1 to 20 seconds, more preferably 3 to 15 seconds. Thereby, since the excess pre-wet solvent 2 is removed without the wafer surface drying out, when the photosensitive resin composition is then dropped, it is easy to embed, and at the same time, it is possible to suppress a decrease in film thickness due to the coating liquid being diluted more than necessary by the pre-wet solvent and the viscosity decreasing.

[0049] (Second coating process) The second coating process is a process of spin-coating a photosensitive resin composition containing a silicone skeleton-containing resin or an acrylic resin on the surface of the side filled by spin-coating the pre-wet solvent 2 to form a photosensitive resin layer 3 which is a coating film of the photosensitive resin composition. After wiping the pre-wet solvent 2 in the wiping process, the photosensitive resin composition is dropped while rotating at a constant speed. After dropping, it is preferably spun for 1 to 20 seconds, more preferably 3 to 15 seconds. Thereby, due to the pre-wet solvent 2 on the wafer, even if the dropped liquid is small, it is easy to wet and spread on the wafer. Further, when accelerating to obtain the target film thickness, it is preferable to increase the speed step by step so that the pre-wet solvent 2 does not dry out and reach the maximum rotation speed.

[0050] In the second coating process, after pre-wetting in the first coating process, after rotating the substrate for the wiping process, the photosensitive resin composition for the second coating process may be dropped continuously at a constant speed without stopping the rotation, and then rotated at a constant speed for a certain time and then accelerated to form a flat coating film. By maintaining a constant rotation speed without changing the rotation speed in the process from wiping to dropping the photosensitive resin composition, the photosensitive resin composition can be dropped without the wafer surface drying out, and it becomes easy to embed a semiconductor substrate having a stepped surface.

[0051] Figure 3 is a graph showing the spin coating conditions for the first coating process, the wiping process, and the second coating process. The horizontal axis X represents the rotation time (seconds) in the coating process, and the vertical axis Y represents the rotation speed (rpm) of the semiconductor substrate in spin coating.

[0052] First, in the first coating process, a semiconductor substrate having a stepped surface on one side is prepared, and the rotation speed is increased from a stop state to S1. When S1 is reached, a prewet solvent is dropped, and spin coating is performed while maintaining the speed of S1 from T1 to T2. At this time, the required time from T1 to T2 varies depending on the size of the step. It is desirable to take a longer time for a larger step.

[0053] Subsequently, as the wiping process, the rotation speed is increased from S1 to S2 between T2 and T3, and the excess prewet solvent on the semiconductor substrate is wiped between T3 and T4.

[0054] Furthermore, as the second coating process, while maintaining the rotation speed of S2, a photosensitive resin composition is dropped at T4, and spin coating is performed at the same rotation speed as during wiping until T5.

[0055] Thereafter, the speed is gradually increased from T5 to T6 so as to reach the rotation speed S3 for the target film thickness. Here, a sudden increase in the rotation speed causes embedding defects. When the difference between the rotation speed S2 during wiping and the rotation speed S3 in the second coating process exceeds 1000 rpm, it is preferable to increase the rotation speed step by step. When the difference in the rotation speeds of S2 and S3 is less than 1000 rpm, it is preferable to accelerate to the rotation speed of S3 over 15 to 30 seconds.

[0056] Finally, the speed is decelerated from the rotation speed of S3 to 0 rpm between T7 and T8, and the embedding process ends.

[0057] In the laminate of the present invention, the photosensitive resin is in an uncured state, and the photosensitive resin composition has fluidity. Therefore, the two gradually mix at the interface between the pre-wet solvent and the photosensitive resin composition (photosensitive resin layer). In this process, a concentration gradient of the solvent will be present in the lamination direction, and such a mode is also included in the present invention. As the mixing at the interface further progresses and the two are uniformly mixed, the concave portion (step portion) of the stepped surface can be satisfactorily filled.

[0058] After the embedding process is completed, pre-baking is performed, and then by confirming that the steps in the wafer surface look uniform under an optical microscope, it can be confirmed that the photosensitive resin is embedded throughout the entire surface area.

[0059] (Photosensitive resin composition) The photosensitive resin layer is a coating film of the photosensitive resin composition, and the photosensitive resin composition contains a silicone skeleton-containing resin or an acrylic resin. When the photosensitive resin composition contains (A) a silicone skeleton-containing polymer as a base polymer, it preferably contains (B) a photoacid generator that decomposes by light of 190 to 500 nm to generate an acid, and (C) a solvent. In addition, when the photosensitive resin composition contains (A') an acrylic polymer as a base polymer, those containing (B') a photopolymerization initiator and (C) a solvent can also be used. In addition to the components (A), (B), (C) or (A'), (B'), (C), it can also contain (D) a crosslinking agent, (E) a quencher, (F) an antioxidant, etc. Hereinafter, each component will be described in detail.

[0060] [(A) Silicone skeleton-containing polymer] The silicone skeleton-containing polymer of the component (A) is not particularly limited, but it is preferably one containing any one or more of the repeating units represented by any one or more of the following formulas (a1) to (a4) and (b1) to (b4) (hereinafter, also referred to as repeating units a1 to a4 and b1 to b4, respectively).

Chemical formula

[0061] In formulas (a1) to (a4), R 1 ~R 4 are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. m is an integer of 1 to 600. When m is an integer of 2 or more, each R 3 may be the same as or different from each other, and each R 4 may be the same as or different from each other. In the repeating units a1 to a4, when there are two or more siloxane units, all the siloxane units may be the same or may contain two or more different siloxane units. When two or more different siloxane units are contained (that is, when m is an integer of 2 or more), the siloxane units may be randomly bonded, alternately bonded, or may contain a plurality of blocks of the same kind of siloxane units.

[0062] The monovalent hydrocarbon group may be linear, branched, or cyclic. Specific examples thereof include alkyl groups such as methyl group, ethyl group, propyl group, hexyl group, cyclohexyl group, and structural isomers thereof, and aryl groups such as phenyl group. Among these, the methyl group and the phenyl group are preferable in terms of easy availability of raw materials.

[0063] In the formula, m is an integer of 1 to 600, preferably an integer of 1 to 400, and more preferably an integer of 1 to 200.

[0064] In formula (X1), Z 1 is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group. R 11 and R 12 are each independently a hydrogen atom or a methyl group. R 13 and R 14 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. p 1 and p 2 are each independently an integer of 0 to 7. q 1 and q 2 are each independently an integer of 0 to 2.

[0065] The alkyl group may be linear, branched or cyclic, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and structural isomers thereof. The alkoxy group may be linear, branched or cyclic, and specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and structural isomers thereof.

[0066] In formula (X2), Z 2 is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group or a fluorene-9,9-diyl group. R 21 and R 22 are each independently a hydrogen atom or a methyl group. R 23 and R 24 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. r 1 and r 2 are each independently an integer from 0 to 7. s 1 and s 2 are each independently an integer from 0 to 2. The alkyl group and the alkoxy group are the same as those described above.

[0067] In formula (X3), R 31 and R 32 are each independently a hydrogen atom or a methyl group. t 1 and t 2 are each independently an integer from 0 to 7.

[0068] In formula (X4), R 41 and R 42 are each independently a hydrogen atom or a methyl group. R 43 and R 44 are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. u 1 and u 2is, independently, an integer from 0 to 7. v is an integer from 0 to 600, preferably an integer from 0 to 400, more preferably an integer from 0 to 200. Examples of the monovalent hydrocarbon group include those described in the description of R 1 ~R 4 . In the group represented by formula (X4), when v is an integer of 2 or more, the siloxane units indicated by the subscript v may be randomly bonded, alternately bonded, or may contain a plurality of blocks of the same kind of siloxane units.

[0069] The silicone skeleton-containing polymer of component (A) preferably has a weight average molecular weight (Mw) of 3,000 to 500,000, more preferably 5,000 to 200,000. In the present invention, Mw is a polystyrene-equivalent measurement value by gel permeation chromatography (GPC) using tetrahydrofuran as an elution solvent.

[0070] In formulas (a1) to (a4) and (b1) to (b4), a 1 ~a 4 and b 1 ~b 4 are numbers satisfying 0 ≦ a 1 < 1, 0 ≦ a 2 < 1, 0 ≦ a 3 < 1, 0 ≦ a 4 < 1, 0 ≦ b 1 < 1, 0 ≦ b 2 < 1, 0 ≦ b 3 < 1, 0 ≦ b 4 < 1, 0 < a 1 + a 2 + a 3 + a 4 < 1, 0 < b 1 + b 2 + b 3 + b 4 < 1, and a 1 + a 2 + a 3 + a 4 + b 1 + b 2 + b 3 + b 4 = 1, but 0 ≦ a 1 ≦ 0.8, 0 ≦ a2 ≤0.8, 0≤a 3 ≤0.8, 0≤a 4 ≤0.8, 0≤b 1 ≤0.95, 0≤b 2 ≤0.95, 0≤b 3 ≤0.95, 0≤b 4 ≤0.95, 0.05≤a 1 +a 2 +a 3 +a 4 ≤0.8, 0.2≤b 1 +b 2 +b 3 +b 4 ≤0.95, and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 Numbers satisfying = 1 are preferred, 0≤a 1 ≤0.7, 0≤a 2 ≤0.7, 0≤a 3 ≤0.7, 0≤a 4 ≤0.7, 0≤b 1 ≤0.9, 0≤b 2 ≤0.9, 0≤b 3 ≤0.9, 0≤b 4 ≤0.9, 0.1≤a 1 +a 2 +a 3 +a 4 ≤0.7, 0.3≤b 1 +b 2 +b 3 +b 4 ≤0.9, and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 Numbers satisfying = 1 are more preferred.

[0071] The silicone skeleton-containing polymer of component (A) preferably has a crosslinking group such as an epoxy group or a hydroxy group or a reaction point where a crosslinking reaction occurs in the molecule. That is, the polymer preferably contains at least one selected from repeating units a1 to a3 and at least one selected from repeating units b1 to b3. At this time, in formulas (a1) to (a4) and (b1) to (b4), a 1 ~a 4 and b 1 ~b 4 are numbers satisfying 0 ≦ a 1 < 1, 0 ≦ a 2 < 1, 0 ≦ a 3 < 1, 0 ≦ a 4 < 1, 0 ≦ b 1 < 1, 0 ≦ b 2 < 1, 0 ≦ b 3 < 1, 0 ≦ b 4 < 1, 0 < a 1 + a 2 + a 3 < 1, 0 < b 1 + b 2 + b 3 < 1, and a 1 + a 2 + a 3 + a 4 + b 1 + b 2 + b 3 + b 4 = 1, and preferably 0 ≦ a 1 ≦ 0.8, 0 ≦ a 2 ≦ 0.8, 0 ≦ a 3 ≦ 0.8, 0 ≦ a 4 ≦ 0.8, 0 ≦ b 1 ≦ 0.95, 0 ≦ b 2 ≦ 0.95, 0 ≦ b 3 ≦ 0.95, 0 ≦ b 4 ≦ 0.95, 0.05 ≦ a 1 + a 2 + a 3 ≦ 0.8, 0.2 ≦ b 1 + b 2 + b 3 ≦ 0.95, and a 1 + a 2 + a 3 + a 4 + b 1 + b 2 + b 3+b 4 A number satisfying = 1 is more preferred, where 0 ≦ a 1 ≦ 0.7, 0 ≦ a 2 ≦ 0.7, 0 ≦ a 3 ≦ 0.7, 0 ≦ a 4 ≦ 0.7, 0 ≦ b 1 ≦ 0.9, 0 ≦ b 2 ≦ 0.9, 0 ≦ b 3 ≦ 0.9, 0 ≦ b 4 ≦ 0.9, 0.1 ≦ a 1 +a 2 +a 3 ≦ 0.7, 0.3 ≦ b 1 +b 2 +b 3 ≦ 0.9, and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 A number satisfying = 1 is even more preferred.

[0072] In particular, the silicone skeleton-containing polymer of component (A) preferably contains repeating units a3 and b3. At this time, in formulas (a1) to (a4) and (b1) to (b4), a 1 ~a 4 and b 1 ~b 4 are such that 0 ≦ a 1 < 1, 0 ≦ a 2 < 1, 0 < a 3 < 1, 0 ≦ a 4 < 1, 0 ≦ b 1 < 1, 0 ≦ b 2 < 1, 0 < b 3 < 1, 0 ≦ b 4 < 1, 0 < a 1 +a 2 +a 3 +a 4 < 1, 0 < b 1 +b 2 +b 3 +b 4 < 1, and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3+b 4 Numbers satisfying = 1 are preferred, where 0 ≤ a 1 <0.8, 0 ≤ a 2 <0.8, 0 < a 3 ≤ 0.8, 0 ≤ a 4 <0.8, 0 ≤ b 1 <0.95, 0 ≤ b 2 <0.95, 0 < b 3 ≤ 0.95, 0 ≤ b 4 <0.95, 0.05 ≤ a 1 +a 2 +a 3 +a 4 ≤ 0.8, 0.2 ≤ b 1 +b 2 +b 3 +b 4 ≤ 0.95, and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 Numbers satisfying = 1 are more preferred, where 0 ≤ a 1 <0.7, 0 ≤ a 2 <0.7, 0 < a 3 ≤ 0.7, 0 ≤ a 4 <0.7, 0 ≤ b 1 <0.9, 0 ≤ b 2 <0.9, 0 < b 3 ≤ 0.9, 0 ≤ b 4 <0.9, 0.1 ≤ a 1 +a 2 +a 3 +a 4 ≤ 0.7, 0.3 ≤ b 1 +b 2 +b 3 +b 4 ≤ 0.9, and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 Numbers satisfying = 1 are even more preferred.

[0073] Each of the above-described repeating units may be randomly bonded or bonded as a block polymer. Further, the siloxane units in each repeating unit may be randomly bonded or may contain a plurality of blocks of the same kind of siloxane units. Further, in the silicone skeleton-containing polymer, the silicone (siloxane unit) content is preferably 30 to 80% by mass.

[0074] (A) The photosensitive resin layer using the silicone skeleton-containing polymer has good adhesion to a laminate, a semiconductor substrate, etc., good pattern forming ability, crack resistance, and heat resistance.

[0075] (A) The silicone skeleton-containing polymer of the component may be used alone or in combination of two or more.

[0076] [[Manufacturing method of (A) silicone skeleton-containing polymer]] The (A) silicone skeleton-containing polymer can be produced by subjecting at least one selected from a compound represented by the following formula (1) (hereinafter also referred to as compound (1)), a compound represented by the following formula (2) (hereinafter also referred to as compound (2)), a compound represented by the following formula (3) (hereinafter also referred to as compound (3)), a compound represented by the following formula (4) (hereinafter also referred to as compound (4)), a compound represented by the following formula (5) (hereinafter also referred to as compound (5)), and a compound represented by the following formula (6) (hereinafter also referred to as compound (6)) to addition polymerization in the presence of a metal catalyst.

[0077] [[Chemical formula]] (In the formula, R 1 ~R 4 and m are the same as above.)

[0078] [[Chemical formula]] (In the formula, R 11 ~R 14 , R 21 ~R 24 , R31 , R 32 , R 41 ~R 44 , Z 1 , Z 2 , p 1 , p 2 , q 1 , q 2 , r 1 , r 2 , s 1 , s 2 , t 1 , t 2 , u 1 , u 2 and v are the same as described above.)

[0079] Examples of the metal catalyst include single platinum group metals such as platinum (including platinum black), rhodium, and palladium; salts of platinum such as H2PtCl4·xH2O, H2PtCl6·xH2O, NaHPtCl6·xH2O, KHPtCl6·xH2O, Na2PtCl6·xH2O, K2PtCl4·xH2O, PtCl4·xH2O, PtCl2, Na2HPtCl4·xH2O (where x is preferably an integer from 0 to 6, particularly preferably 0 or 6), chloroplatinic acid, and chloroplatinate salts; alcohol-modified chloroplatinic acid (e.g., those described in U.S. Patent No. 3,220,972); complexes of chloroplatinic acid and olefins (e.g., those described in U.S. Patent No. 3,159,601, U.S. Patent No. 3,159,662, and U.S. Patent No. 3,775,452); those obtained by supporting platinum group metals such as platinum black and palladium on carriers such as alumina, silica, and carbon; rhodium-olefin complexes; chlorotris(triphenylphosphine)rhodium (so-called Wilkinson's catalyst); complexes of platinum chloride, chloroplatinic acid, or chloroplatinate salts with vinyl group-containing siloxanes (particularly vinyl group-containing cyclic siloxanes), etc. can be used.

[0080] The amount of the catalyst used is a catalytic amount, and usually, it is preferably 0.001 to 0.1 part by mass, more preferably 0.01 to 0.1 part by mass, based on 100 parts by mass in total of compounds (1) to (6).

[0081] In the addition polymerization reaction, a solvent may be used as necessary. As the solvent, hydrocarbon solvents such as toluene and xylene are preferred, for example.

[0082] From the viewpoint that the catalyst is not deactivated and the polymerization can be completed in a short time, the polymerization temperature is preferably 40 to 150°C, more preferably 60 to 120°C. The polymerization time depends on the type and amount of the resin to be obtained, but is preferably about 0.5 to 100 hours, more preferably 0.5 to 30 hours, in order to prevent the intrusion of moisture into the polymerization system. After the reaction is completed, when a solvent is used, the solvent can be distilled off to obtain the silicone skeleton-containing polymer of component (A).

[0083] The reaction method is not particularly limited. For example, first, at least one selected from compounds (3) to (6) is heated, then a metal catalyst is added thereto, and then compounds (1) and (2) are dropped over 0.1 to 5 hours.

[0084] Each raw material compound is preferably formulated such that the total amount of hydrosilyl groups of the compound represented by formula (1) and the compound represented by formula (2) is 0.67 to 1.67, more preferably 0.83 to 1.25, in terms of molar ratio, with respect to the total amount of alkenyl groups of at least one selected from compounds (3) to (6).

[0085] The Mw of the silicone skeleton-containing polymer can be controlled by using a monoallyl compound such as o-allylphenol or a monohydrosilane or monohydrosiloxane such as triethylhydrosilane as a molecular weight regulator.

[0086] [(A') Acrylic polymer] (A’) component acrylic polymer is not particularly limited as long as it is a polymer of (meth)acrylic acid ester. The weight average molecular weight Mw is not particularly limited either, but it is preferable to use a polymer with a molecular weight of 10,000 to 200,000, more preferably about 20,000 to 150,000. As the acrylic polymer, for example, ART CURE MAP-4050, ART CURE MAP-2801, ART CURE RA-3953 (manufactured by Negami Kogyo Co., Ltd.) and Foret ZAH-106, Foret ZAH-110 (manufactured by Soken Chemical & Engineering Co., Ltd.) are preferable. [[ID= 2]]

[0087] [[ID= 3]] [[ID= 4]][(B) Photoacid generator][[ID= 5]] [[ID= 6]](B) The photoacid generator as a component combined with the silicone skeleton-containing polymer of component (A) is not particularly limited as long as it decomposes upon light irradiation to generate an acid, but those that generate an acid upon irradiation with light having a wavelength of 190 to 500 nm are preferable. Since the composition used in the present invention has excellent compatibility with the photoacid generator, a wide range of photoacid generators can be used. [[ID= 7]] [[ID= 8]]

[0088] [[ID= 9]] [[ID= 10]](B) The photoacid generator is used as a curing catalyst. Examples of the photoacid generator include onium salts, diazomethane derivatives, glyoxime derivatives, β-ketosulfone derivatives, disulfone derivatives, nitrobenzyl sulfonate derivatives, sulfonic acid ester derivatives, imide-yl-sulfonate derivatives, oxime sulfonate derivatives, iminosulfonate derivatives, triazine derivatives, and the like. [[ID= 11]] [[ID= 12]]

[0089] [[ID= 13]] [[ID= 14]]Examples of the onium salt include sulfonium salts represented by the following formula (B1) or iodonium salts represented by the following formula (B2). [[ID= 15]] [[ID= 16]] [[ID= 17]][Chemical formula][[ID= 18]] [[ID= 19]] [[ID= 20]] [[ID= 21]] [[ID= 22]]

[0090] [[ID= 23]] [[ID= 24]]In formulas (B1) and (B2), R[[ID= 25]] 101 [[ID= 26]]~R[[ID= 27]] 105is, independently of each other, an alkyl group having 1 to 12 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, or an aralkyl group having 7 to 12 carbon atoms which may have a substituent. A - is a non-nucleophilic counter ion.

[0091] The alkyl group may be linear, branched or cyclic, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, an n-pentyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group and the like. Examples of the aryl group include a phenyl group, a naphthyl group, a biphenylyl group and the like. Examples of the aralkyl group include a benzyl group, a phenethyl group and the like.

[0092] Examples of the substituent include an oxo group, a linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 24 carbon atoms, an aralkyl group having 7 to 25 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, an arylthio group having 6 to 24 carbon atoms and the like.

[0093] R 101 ~R 105Examples of the group include an alkyl group which may have a substituent such as a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and a 2-oxocyclohexyl group; an aryl group which may have a substituent such as a phenyl group, a naphthyl group, a biphenylyl group, an o-, m- or p-methoxyphenyl group, an ethoxyphenyl group, an m- or p-tert-butoxyphenyl group, a 2-, 3- or 4-methylphenyl group, an ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, a dimethylphenyl group, a terphenylyl group, a biphenylyloxyphenyl group, and a biphenylylthiophenyl group; and an aralkyl group which may have a substituent such as a benzyl group and a phenethyl group. Among these, an aryl group which may have a substituent and an aralkyl group which may have a substituent are more preferable.

[0094] Examples of the non-nucleophilic counter ion include halide ions such as chloride ion and bromide ion; fluoroalkanesulfonate ions such as triflate ion, 1,1,1-trifluoroethanesulfonate ion, and nonafluorobutanesulfonate ion; arylsulfonate ions such as tosylate ion, benzenesulfonate ion, 4-fluorobenzenesulfonate ion, and 1,2,3,4,5-pentafluorobenzenesulfonate ion; alkanesulfonate ions such as mesylate ion and butanesulfonate ion; fluoroalkanesulfonimide ions such as trifluoromethanesulfonimide ion; fluoroalkanesulfonylmethide ions such as tris(trifluoromethylsulfonyl)methide ion; and borate ions such as tetrakisphenylborate ion and tetrakis(pentafluorophenyl)borate ion.

[0095] Examples of the diazomethane derivative include a compound represented by the following formula (B3).

Chemical formula

[0096] In formula (B3), R 111 and R112 is, independently of each other, an alkyl group or a halogenated alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, or an aralkyl group having 7 to 12 carbon atoms.

[0097] The alkyl group may be linear, branched or cyclic, and specific examples thereof include those exemplified in the description of R 101 ~R 105 The halogenated alkyl group includes a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, a nonafluorobutyl group, and the like.

[0098] Examples of the aryl group which may have a substituent include a phenyl group; alkoxyphenyl groups such as 2-, 3- or 4-methoxyphenyl group, 2-, 3- or 4-ethoxyphenyl group, 3- or 4-tert-butoxyphenyl group; alkylphenyl groups such as 2-, 3- or 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group, dimethylphenyl group; halogenated aryl groups such as fluorophenyl group, chlorophenyl group, 1,2,3,4,5-pentafluorophenyl group, and the like. Examples of the aralkyl group include a benzyl group, a phenethyl group, and the like.

[0099] Examples of the glyoxime derivative include a compound represented by the following formula (B4).

Chemical formula

[0100] In formula (B4), R 121 ~R 124 are, independently of each other, an alkyl group or a halogenated alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, or an aralkyl group having 7 to 12 carbon atoms. Further, R 123 and R 124 may be bonded to each other to form a ring together with the carbon atom to which they are bonded, and when forming a ring, R123 and R 124 The group formed by the combination of and R is a linear or branched alkylene group having 1 to 12 carbon atoms.

[0101] Examples of the alkyl group, alkyl halide group, aryl group which may have a substituent, and aralkyl group include those exemplified as R 111 and R 112 Similar ones to those exemplified as and R can be mentioned. Examples of the linear or branched alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and the like.

[0102] Specific examples of the onium salt include diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenyl iodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, (p-tert-butoxyphenyl)phenyl iodonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium p-toluenesulfonate, tris(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, diphenyl(4-thiophenoxyphenyl)sulfonium hexafluoroantimonate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium tris(trifluoromethanesulfonyl)methide, triphenylsulfonium tetrakis(fluorophenyl)borate, tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(fluorophenyl)borate,Triphenylsulfonium tetrakis(pentafluorophenyl)borate, tris[4-(4-acetylphenyl)phenyl]sulfonium tetrakis(pentafluorophenyl)borate, and the like can be mentioned.

[0103] Specific examples of the diazomethane derivative include bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(xylenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(cyclopentylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis(sec-butylsulfonyl)diazomethane, bis(n-propylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, bis(tert-butylsulfonyl)diazomethane, bis(n-pentylsulfonyl)diazomethane, bis(isopentylsulfonyl)diazomethane, bis(sec-pentylsulfonyl)diazomethane, bis(tert-pentylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-butylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-pentylsulfonyl)diazomethane, 1-tert-pentylsulfonyl-1-(tert-butylsulfonyl)diazomethane, and the like.

[0104] Specific examples of the glyoxime derivative include bis-o-(p-toluenesulfonyl)-α-dimethylglyoxime, bis-o-(p-toluenesulfonyl)-α-diphenylglyoxime, bis-o-(p-toluenesulfonyl)-α-dicyclohexylglyoxime, bis-o-(p-toluenesulfonyl)-2,3-pentanedione glyoxime, bis-(p-toluenesulfonyl)-2-methyl-3,4-pentanedione glyoxime, bis-o-(n-butanesulfonyl)-α-dimethylglyoxime, bis-o-(n-butanesulfonyl)-α-diphenylglyoxime, bis-o-(n-butanesulfonyl)-α-dicyclohexylglyoxime, bis-o-(n-butanesulfonyl)-2,3-pentanedione glyoxime, bis-o-(n-butanesulfonyl)-2-methyl-3,4-pentanedione glyoxime, bis-o-(methanesulfonyl)-α-dimethylglyoxime, bis-o-(trifluoromethanesulfonyl)-α-dimethylglyoxime, bis-o-(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime, bis-o-(tert-butanesulfonyl)-α-dimethylglyoxime, bis-o-(perfluorooctanesulfonyl)-α-dimethylglyoxime, bis-o-(cyclohexanesulfonyl)-α-dimethylglyoxime, bis-o-(benzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-fluorobenzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-tert-butylbenzenesulfonyl)-α-dimethylglyoxime, bis-o-(xylenesulfonyl)-α-dimethylglyoxime, bis-o-(camphorsulfonyl)-α-dimethylglyoxime, and the like.

[0105] Specific examples of the β-ketosulfone derivative include 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane, 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane, and the like.

[0106] Specific examples of the disulfone derivative include diphenyl disulfone, dicyclohexyl disulfone, and the like.

[0107] Specific examples of the nitrobenzyl sulfonate derivative include 2,6-dinitrobenzyl p-toluenesulfonate, 2,4-dinitrobenzyl p-toluenesulfonate, and the like.

[0108] Specific examples of the sulfonic acid ester derivative include 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, 1,2,3-tris(p-toluenesulfonyloxy)benzene, and the like.

[0109] Specific examples of the imide-yl-sulfonate derivative include phthalimide-yl-triflate, phthalimide-yl-tosylate, 5-norbornene-2,3-dicarboxyimide-yl-triflate, 5-norbornene-2,3-dicarboxyimide-yl-tosylate, 5-norbornene-2,3-dicarboxyimide-yl-n-butylsulfonate, n-trifluoromethylsulfonyloxynaphthylimide, and the like.

[0110] Specific examples of the oxime sulfonate derivative include α-(benzenesulfonium oxyimino)-4-methylphenylacetonitrile, and the like.

[0111] Specific examples of the iminosulfonate derivative include (5-(4-methylphenyl)sulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-(4-(4-methylphenylsulfonyloxy)phenyl)sulfonyloxyimino)-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, and the like.

[0112] Specific examples of the triazine derivative include 2-(methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, and the like.

[0113] In addition, 2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[(4-methylthio)phenyl]-1-propane and the like can also be preferably used.

[0114] As the photoacid generator of component (B), the onium salt is particularly preferred, and the sulfonium salt is more preferred.

[0115] From the viewpoint of photocurability, the content of component (B) is preferably 0.05 to 20 parts by mass, more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of component (A). If the content of component (B) is 0.05 parts by mass or more, it is preferable because there is no risk that the amount of acid generated is insufficient and the crosslinking reaction does not proceed sufficiently. Also, if it is 20 parts by mass or less, it is preferable because it is possible to suppress an increase in the absorbance of the photoacid generator itself and there is no risk of problems such as a decrease in transparency. Component (B) may be used alone or in combination of two or more.

[0116] [(B’) Photopolymerization initiator] As the photopolymerization initiator of component (B’) to be combined with the acrylic polymer of component (A’), known ones can be used and are not particularly limited. As the photopolymerization initiator, for example, Irgacure OXE01 (manufactured by BASF Japan Ltd.) and Irgacure OXE02 (manufactured by BASF Japan Ltd.) are preferable.

[0117] [(C) Solvent] The photosensitive resin composition used in the present invention may further contain (C) a solvent. The solvent is not particularly limited as long as it can dissolve the components (A), (A'), (B), (B') and various additives described below, but an organic solvent is preferred because it has excellent solubility in these components.

[0118] Examples of the organic solvent include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether (PGME), ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, and γ-butyrolactone. These organic solvents can be used alone or in combination of two or more. In particular, ethyl lactate, cyclohexanone, cyclopentanone, PGMEA, γ-butyrolactone, and a mixed solvent thereof, which have the most excellent solubility of the photoacid generator, are preferred.

[0119] From the viewpoints of the compatibility and viscosity of the photosensitive resin composition, the amount of the component (C) used is preferably 50 to 2,000 parts by mass, more preferably 50 to 1,000 parts by mass, and particularly preferably 50 to 100 parts by mass with respect to 100 parts by mass in total of the components (A) and (B).

[0120] [(D) Crosslinking agent] The photosensitive resin composition used in the present invention preferably further contains (D) a crosslinking agent. The crosslinking agent is the phenolic hydroxy group of the component (A) described above, or R13 , R 14 , R 23 or R 24 It is a component that can cause a condensation reaction with an alkoxy group represented by and can facilitate the formation of a pattern, and further increases the strength of the cured product.

[0121] As the crosslinking agent, a resin having an Mw of 150 to 10,000, particularly 200 to 3,000, is preferable. If the Mw is 150 or more, sufficient photocurability can be obtained, and if it is 10,000 or less, there is no risk of deteriorating the heat resistance after curing of the composition, which is preferable.

[0122] In addition, as the crosslinking agent, nitrogen-containing compounds such as melamine compounds, guanamine compounds, glycoluril compounds, and urea compounds containing an average of 2 or more methylol groups and / or alkoxymethyl groups in one molecule, formaldehyde, or amino condensates modified with formaldehyde-alcohol, phenol compounds having an average of 2 or more methylol groups or alkoxymethyl groups in one molecule, and epoxy compounds having an average of 2 or more epoxy groups in one molecule are also preferable.

[0123] Examples of the melamine compound include those represented by the following formula (D1).

Chemical formula

[0124] In formula (D1), R 201 ~R 206 are each independently a methylol group, an alkoxymethyl group having 2 to 5 carbon atoms, or a hydrogen atom, but at least one is a methylol group or an alkoxymethyl group. Examples of the alkoxymethyl group include a methoxymethyl group and an ethoxymethyl group.

[0125] Examples of the melamine compound represented by formula (D1) include trimethoxymethylmonomethylolmelamine, dimethoxymethylmonomethylolmelamine, trimethylolmelamine, hexamethylolmelamine, hexamethoxymethylmelamine, hexaethoxymethylmelamine, and the like.

[0126] The melamine compound represented by formula (D1) can be obtained, for example, by first methylolating a melamine monomer with formaldehyde according to a known method or by further alkoxylating it with an alcohol. The alcohol is preferably a lower alcohol, such as an alcohol having 1 to 4 carbon atoms.

[0127] Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, tetramethoxyethylguanamine, and the like.

[0128] Examples of the glycoluril compound include tetramethylolglycoluril, tetrakis(methoxymethyl)glycoluril, and the like.

[0129] Examples of the urea compound include tetramethylolurea, tetramethoxymethylurea, tetramethoxyethylurea, tetraethoxymethylurea, tetrapropoxymethylurea, and the like.

[0130] Examples of the amino condensate modified with formaldehyde or formaldehyde-alcohol include a melamine condensate modified with formaldehyde or formaldehyde-alcohol, a urea condensate modified with formaldehyde or formaldehyde-alcohol, and the like.

[0131] Examples of the modified melamine condensate include those obtained by addition-condensation polymerization of a compound represented by formula (D1) or its multimer (for example, oligomer such as dimer and trimer) and formaldehyde according to a conventional method until a desired molecular weight is reached.

[0132] Examples of the urea condensate modified with formaldehyde or formaldehyde-alcohol include methoxymethylated urea condensate, ethoxymethylated urea condensate, propoxymethylated urea condensate, and the like.

[0133] The modified urea condensate can be obtained, for example, by methylolating a urea condensate having a desired molecular weight with formaldehyde according to a known method, or by further alkoxylating it with alcohol.

[0134] Examples of the phenol compound having an average of two or more methylol groups or alkoxymethyl groups in one molecule include (2-hydroxy-5-methyl)-1,3-benzenedimethanol, 2,2’,6,6’-tetramethoxymethyl bisphenol A, and the like.

[0135] Examples of the epoxy compound having an average of two or more epoxy groups in one molecule include bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, novolak type epoxy resins such as phenol novolak type epoxy resin and cresol novolak type epoxy resin, triphenolalkane type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene-modified phenol novolak type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene ring-containing epoxy resin, glycidyl ester type epoxy resin, alicyclic epoxy resin, heterocyclic type epoxy resin, and the like.

[0136] When component (D) is included, its content is preferably 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass, based on 100 parts by mass of component (A). If it is 0.5 part by mass or more, sufficient curability can be obtained upon light irradiation, and if it is 50 parts by mass or less, the proportion of component (A) in the photosensitive resin composition does not decrease, so that the sufficient effects of the present invention can be exhibited in the cured product. The crosslinking agent for component (D) can be used alone or in combination of two or more.

[0137] [(E) Quencher] The photosensitive resin composition used in the present invention may further contain (E) a quencher. As the quencher, a compound capable of suppressing the diffusion rate when the acid generated from the photoacid generator diffuses in the photosensitive resin film in which the photosensitive resin layer is cured is suitable. By blending the quencher, the resolution can be improved, the change in sensitivity after exposure can be suppressed, the substrate dependence or environmental dependence can be reduced, and the exposure margin and pattern shape can be improved.

[0138] Examples of the quencher include ammonia, primary, secondary or tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, nitrogen-containing compounds having a sulfonyl group, nitrogen-containing compounds having a hydroxy group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives, imide derivatives, and the like.

[0139] Examples of the primary aliphatic amines include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert-pentylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine, and the like.

[0140] Examples of the secondary aliphatic amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N,N-dimethylmethylenediamine, N,N-dimethylethylenediamine, N,N-dimethyltetraethylenepentamine, and the like.

[0141] Examples of the tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N,N,N',N'-tetramethylmethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyltetraethylenepentamine, and the like.

[0142] Examples of the mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, benzyldimethylamine, and the like.

[0143] Examples of the aromatic amines and heterocyclic amines include aniline derivatives (e.g., aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N,N-dimethyltoluidine, etc.), diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (e.g., pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (e.g., oxazole, isoxazole, etc.), thiazole derivatives (e.g., thiazole, isothiazole, etc.), imidazole derivatives (e.g., imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazan derivatives, pyrroline derivatives (e.g., pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (e.g., pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methyl-2-pyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (e.g., pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4-(1-butylpentyl)pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridine, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (e.g., quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives, etc.

[0144] Examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (for example, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine, etc.).

[0145] Examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridinesulfonic acid, pyridinium p-toluenesulfonate, etc.

[0146] Examples of the nitrogen-containing compound having a hydroxy group, the nitrogen-containing compound having a hydroxyphenyl group, and the alcoholic nitrogen-containing compound include 2-hydroxypyridine, aminocresol, 2-quinolinediol, 3-indolemethanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N,N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 4-(2-hydroxyethyl)morpholine, 2-(2-hydroxyethyl)pyridine, 1-(2-hydroxyethyl)piperazine, 1-[2-(2-hydroxyethoxy)ethyl]piperazine, piperidineethanol, 1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)-2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyuridine, 3-quinuclidinol, 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N-(2-hydroxyethyl)phthalimide, N-(2-hydroxyethyl)isonicotinamide, etc.

[0147] Examples of the amide derivative include formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, benzamide, and the like.

[0148] Examples of the imide derivative include phthalimide, succinimide, maleimide, and the like.

[0149] As the quencher, the one represented by the following formula (E1) can also be used.

Chemical formula

[0150] In formula (E1), w is 1, 2, or 3. R 301 is any substituent selected from the substituents represented by the following formulas (E2) to (E4). R 302 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, which may contain an ether bond or a hydroxy group. Also, when there are two or more R 301 s, two R 301 s may be bonded to each other to form a ring together with the nitrogen atom to which they are bonded. Also, when there are two or more R 301 s, they may be the same or different, and when there are two or more R 302 s, they may be the same or different.

Chemical formula

[0151] In formulas (E2) to (E4), R 303 and R 305 and R 308 are each independently a linear or branched alkanediyl group having 1 to 4 carbon atoms. R 304 and R 307 are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, which may contain at least one selected from a hydroxy group, an ether bond, an ester bond, and a lactone ring. R306 is a single bond or a linear or branched alkanediyl group having 1 to 4 carbon atoms. R 309 is an alkyl group having 1 to 20 carbon atoms, and may contain at least one selected from a hydroxy group, an ether bond, an ester bond, and a lactone ring.

[0152] Examples of the compound represented by formula (E1) include tris[2-(methoxymethoxy)ethyl]amine, tris[2-(2-methoxyethoxy)ethyl]amine, tris[2-(2-methoxyethoxymethoxy)ethyl]amine, tris[2-(1-methoxyethoxy)ethyl]amine, tris[2-(1-ethoxyethoxy)ethyl]amine, tris[2-(1-ethoxypropoxy)ethyl]amine, tris[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane, 4,7,13,18-tetraoxa-1,10-diazabicyclo[8.5.5]eicosane, 1,4,10,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-6, tris(2-formyloxyethyl)amine, tris(2-acetoxyethyl)amine, tris(2-propionyloxyethyl)amine, tris(2-butyryloxyethyl)amine, tris(2-isobutyryloxyethyl)amine, tris(2-valeryloxyethyl)amine, tris(2-pivaloyloxyethyl)amine, N,N-bis(2-acetoxyethyl)2-(acetoxyacetoxy)ethylamine, tris(2-methoxycarbonyloxyethyl)amine, tris(2-tert-butoxycarbonyloxyethyl)amine, tris[2-(2-oxopropoxy)ethyl]amine, tris[2-(methoxycarbonylmethyl)oxyethyl]amine, tris[2-(tert-butoxycarbonylmethyloxy)ethyl]amine, tris[2-(cyclohexyloxycarbonylmethyl)oxyethyl]amine, tris(2-methoxycarbonylethyl)amine, tris(2-ethoxycarbonylethyl)amine, N,N-bis(2-hydroxyethyl)-2-(methoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(methoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-(ethoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(ethoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-(2-methoxyethoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(2-methoxyethoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-(2-hydroxyethoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(2-acetoxyethoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-[(methoxycarbonyl)methoxycarbonyl]ethylamine, N,N-bis(2-acetoxyethyl)-2-[(methoxycarbonyl)methoxycarbonyl]ethylamine, N,N-bis(2-hydroxyethyl)-2-(2-oxopropoxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(2-oxopropoxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-(tetrahydrofurfuryloxycarbonyl)ethylamine, N,N-bis(2-acetoxyethyl)-2-(tetrahydrofurfuryloxycarbonyl)ethylamine, N,N-bis(2-hydroxyethyl)-2-[(2-oxotetrahydrofuran-3-yl)oxycarbonyl]ethylamine, N,N-bis(2-acetoxyethyl)-2-[(2-oxotetrahydrofuran-3-yl)oxycarbonyl]ethylamine, N,N-bis(2-hydroxyethyl)-2-(4-hydroxybutoxycarbonyl)ethylamine, N,N-bis(2-formyloxyethyl)-2-(4-formyloxybutoxycarbonyl)ethylamine, N,N-bis(2-formyloxyethyl)-2-(2-formyloxyethoxycarbonyl)ethylamine, N,N-bis(2-methoxyethyl)-2-(methoxycarbonyl)ethylamine, N-(2-hydroxyethyl)bis[2-(methoxycarbonyl)ethyl]amine, N-(2-acetoxyethyl)bis[2-(methoxycarbonyl)ethyl]amine, N-(2-hydroxyethyl)bis[2-(ethoxycarbonyl)ethyl]amine, N-(2-acetoxyethyl)bis[2-(ethoxycarbonyl)ethyl]amine, N-(3-hydroxy-1-propyl)bis[2-(methoxycarbonyl)ethyl]amine, N-(3-acetoxy-1-propyl)bis[2-(methoxycarbonyl)ethyl]amine, N-(2-methoxyethyl)bis[2-(methoxycarbonyl)ethyl]amine, N-butylbis[2-(methoxycarbonyl)ethyl]amine, N-butylbis[2-(2-methoxyethoxycarbonyl)ethyl]amine, N-methylbis(2-acetoxyethyl)amine, N-ethylbis(2-acetoxyethyl)amine, N-methylbis(2-pivaloyloxyethyl)amine, N-ethylbis[2-(methoxycarbonyloxy)ethyl]amine, N-ethylbis[2-(tert-butoxycarbonyloxy)ethyl]amine, tris(methoxycarbonylmethyl)amine, tris(ethoxycarbonylmethyl)amine, N-butylbis(methoxycarbonylmethyl)amine, N-hexylbis(methoxycarbonylmethyl)amine, and β-(diethylamino)-δ-valerolactone, but are not limited thereto.,

[0153] (E) component content is 0 to 3 parts by mass with respect to 100 parts by mass of (A) component. When contained, from the viewpoint of sensitivity, 0.01 to 2 parts by mass is preferable, and 0.05 to 1 part by mass is more preferable. (E) component can be used alone or in combination of two or more kinds.,

[0154] [(F) Antioxidant] The photosensitive resin composition used in the present invention may further contain an antioxidant as component (F). By containing this (F) antioxidant, improvement in heat resistance and further ease of transparency of the photosensitive resin composition can be achieved. Examples of the antioxidant include hindered phenol compounds, ammonia, primary aliphatic amines, hindered amine compounds, and the like.

[0155] The hindered phenolic compound is not particularly limited, but the following are preferred. For example, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (trade name: IRGANOX 1330), 2,6-di-tert-butyl-4-methylphenol (trade name: Sumilizer BHT), 2,5-di-tert-butyl-hydroquinone (trade name: Nocrac NS-7), 2,6-di-tert-butyl-4-ethylphenol (trade name: Nocrac M-17), 2,5-di-tert-pentylhydroquinone (trade name: Nocrac DAH), 2,2’-methylenebis(4-methyl-6-tert-butylphenol) (trade name: Nocrac NS-6), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester (trade name: IRGANOX 1222), 4,4’-thiobis(3-methyl-6-tert-butylphenol) (trade name: Nocrac 300), 2,2’-methylenebis(4-ethyl-6-tert-butylphenol) (trade name: Nocrac NS-5), 4,4’-butylidenebis(3-methyl-6-tert-butylphenol) (trade name: Adeka Stab AO-40), 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM), 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate (trade name: Sumilizer GS), 2,2’-methylenebis[4-methyl-6-(α-methyl-cyclohexyl)phenol], 4,4’-methylenebis(2,6-di-tert-butylphenol) (trade name: Cyanox 226M), 4,6-bis(octylthiomethyl)-o-cresol (trade name: IRGANOX 1520L), 2,2’-ethylenebis(4,6-di-tert-butylphenol), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (trade name: IRGANOX 1076), 1,1,3-Tris-(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (trade name: Adeka Stab AO-30), tetrakis[methylene-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane (trade name: Adeka Stab AO-60), triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] (trade name: Irganox 245), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine (trade name: Irganox 565), N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide) (trade name: Irganox 1098), 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: Irganox 259), 2,2'-thio-diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: Irganox 1035), 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]1,1-dimethylethyl]2,4,8,10-tetraoxaspiro[5.5]undecane (trade name: Sumilizer GA-80), tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate (trade name: Irganox 3114), bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid ethyl)calcium / polyethylene wax mixture (50:50) (trade name: Irganox 1425WL), isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (trade name: Irganox 1135), 4,4'-thiobis(6-tert-butyl-3-methylphenol) (trade name: Sumilizer WX-R), 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenz[d,f][1,3,2]dioxaphosphepine (trade name: Sumilizer GP), etc. can be mentioned.,

[0156] Examples of the primary aliphatic amines include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert-pentylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine, etc.

[0157] The hindered amine compound is not particularly limited, but the following are preferred. For example, p,p'-dioctyldiphenylamine (trade name: IRGANOX 5057), phenyl-α-naphthylamine (trade name: Nocrac PA), poly(2,2,4-trimethyl-1,2-dihydroquinoline) (trade name: Nocrac 224, 224-S), 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline (trade name: Nocrac AW), N,N'-diphenyl-p-phenylenediamine (trade name: Nocrac DP), N,N'-di-β-naphthyl-p-phenylenediamine (trade name: Nocrac White), N-phenyl-N'-isopropyl-p-phenylenediamine (trade name: Nocrac 810NA), N,N'-diallyl-p-phenylenediamine (trade name: Nonflex TP), 4,4'-(α,α-dimethylbenzyl)diphenylamine (trade name: Nocrac CD), p,p-toluenesulfonylaminodiphenylamine (trade name: Nocrac TD), N-phenyl-N'-(3-methacryloyloxy-2-hydroxypropyl)-p-phenylenediamine (trade name: Nocrac G1), N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine (trade name: Ozonon 35), N,N'-di-sec-butyl-p-phenylenediamine (trade name: Sumilizer BPA), N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine (trade name: Antigene 6C), alkylated diphenylamine (trade name: Sumilizer 9A), dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate (trade name: Tinuvin 622LD), poly[[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]] (trade name: CHIMASSORB 944), N,N'-bis(3-aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-6-chloro-1,3,5 - Triazine condensate (trade name: CHIMASSORB 119FL), bis(1 - octyloxy - 2,2,6,6 - tetramethyl - 4 - piperidyl) sebacate (trade name: TINUVIN 123), bis(2,2,6,6 - tetramethyl - 4 - piperidyl) sebacate (trade name: TINUVIN 770), 2 - (3,5 - di - tert - butyl - 4 - hydroxybenzyl) - 2 - n - butylmalonic acid bis(1,2,2,6,6 - pentamethyl - 4 - piperidyl) (trade name: TINUVIN 144), bis(1,2,2,6,6 - pentamethyl - 4 - piperidyl) sebacate (trade name: TINUVIN 765), tetrakis(1,2,2,6,6 - pentamethyl - 4 - piperidyl) 1,2,3,4 - butanetetracarboxylate (trade name: LA - 57), tetrakis(2,2,6,6 - tetramethyl - 4 - piperidyl) 1,2,3,4 - butanetetracarboxylate (trade name: LA - 52), mixed esterification product of 1,2,3,4 - butanetetracarboxylic acid with 1,2,2,6,6 - pentamethyl - 4 - piperidinol and 1 - tridecanol (trade name: LA - 62), mixed esterification product of 1,2,3,4 - butanetetracarboxylic acid with 2,2,6,6 - tetramethyl - 4 - piperidinol and 1 - tridecanol (trade name: LA - 67), mixed esterification product of 1,2,3,4 - butanetetracarboxylic acid with 1,2,2,6,6 - pentamethyl - 4 - piperidinol and 3,9 - bis(2 - hydroxy - 1,1 - dimethylethyl) - 2,4,8,10 - tetraoxaspiro[5.5]undecane (trade name: LA - 63P), mixed esterification product of 1,2,3,4 - butanetetracarboxylic acid with 2,2,6,6 - tetramethyl - 4 - piperidinol and 3,9 - bis(2 - hydroxy - 1,1 - dimethylethyl) - 2,4,8,10 - tetraoxaspiro[5.5]undecane (trade name: LA - 68LD), (2,2,6,6 - tetramethylene - 4 - piperidyl) - 2 - propylene carboxylate (trade name: AdekaStab LA - 82), (1,2,2,6,6 - pentamethyl - 4 - piperidyl) - 2 - propylene carboxylate (trade name: AdekaStab LA - 87), etc.

[0158] (F) The content of the component is not particularly limited, but when it is contained, in the photosensitive resin layer used in the present invention, 0.01 to 1% by mass is preferable.

[0159] The photosensitive resin composition used in the present invention can be prepared by a conventional method. For example, the photosensitive resin composition used in the present invention can be prepared by stirring and mixing the above components and then filtering with a filter or the like as necessary. By applying this photosensitive resin composition, a photosensitive resin layer can be formed.

[0160] The photosensitive resin composition used in the present invention is preferably used, for example, as a protective film for semiconductor elements, a protective film for wirings, a coverlay film, a solder mask, a material for an insulating film for through electrodes (for TSV), and further as an adhesive between laminated substrates in three-dimensional lamination.

[0161] The viscosity of the photosensitive resin composition used in the present invention is preferably 50 mPa·s or more and 1500 mPa·s or less. Further, it is more preferably 150 mPa·s or more and 1000 mPa·s or less because the film flatness is good and a sufficient film thickness can be ensured on the step. In the present invention, the viscosity is a value measured at 25°C with a cone and plate type rotational viscometer.

[0162] Regarding the film thickness on the step, it can be applied at an arbitrary value by adjusting the amount of solvent in the photosensitive resin composition used in the present invention and the rotation speed during coating.

[0163] (Semiconductor substrate) The semiconductor substrate has a stepped surface on one side and is a semiconductor substrate with unevenness. For example, a semiconductor substrate having either one or both of grooves and holes with an opening width of 10 to 100 μm and a depth of 10 to 120 μm is preferable. The laminate formed with the photosensitive resin layer may have a gradient. It has excellent adhesion between the semiconductor substrate and the photosensitive resin layer and has high flatness. As described above, in the laminate of the present invention, by forming a photosensitive resin layer in a state where a pre-wetting solvent is previously applied on a semiconductor substrate, it is possible to obtain an inclined layer with a high solvent concentration on the semiconductor substrate side instead of a uniform dispersion between the pre-wetting solvent and the solvent in the photosensitive resin composition.

[0164] [Pattern Formation Method] The pattern formation method of the present invention is a pattern formation method including a step of preheating and curing the photosensitive resin layer to form a photosensitive resin film in the laminate manufactured by the manufacturing method described above, a step of exposing the photosensitive resin film through a photomask, and a step of developing with a developer after performing a heat treatment after exposure to dissolve and remove the unexposed portion to form a pattern.

[0165] The step of preheating and curing the photosensitive resin layer to form a photosensitive resin film is a step of forming a photosensitive resin film on a semiconductor substrate using a photosensitive resin composition. Examples of the semiconductor substrate include a silicon wafer, a silicon wafer for through electrodes, a silicon wafer thinned by back grinding, a plastic or ceramic substrate, and a substrate having a metal such as Ni or Au on the entire surface or a part of the substrate by an ion sputtering method or a plating method. A semiconductor substrate having either or both of grooves and holes with an opening width of 10 to 100 μm and a depth of 10 to 120 μm may be used. Note that the opening width and depth of the grooves or holes in the semiconductor substrate can be measured using a scanning electron microscope.

[0166] Examples of the method for forming the photosensitive resin film include a method of applying the photosensitive resin composition on the semiconductor substrate by a spin coating method and performing preheating (pre-bake: PB) as necessary to efficiently perform a photocuring reaction. The preheating can be performed, for example, at 40 to 140°C for about 1 minute to 1 hour.

[0167] The coating amount of the photosensitive resin composition can be appropriately selected according to the purpose, but an amount that results in a film thickness of 0.1 to 200 μm, preferably 1 to 150 μm, is preferred.

[0168] Next, the photosensitive resin film is exposed through a photomask. The exposure is preferably performed with light having a wavelength of 1 to 600 nm, more preferably with light having a wavelength of 10 to 600 nm, and even more preferably with light having a wavelength of 190 to 500 nm. Examples of light having such wavelengths include light of various wavelengths generated by a radiation generator, such as ultraviolet light such as g-line, h-line, i-line, and far ultraviolet light (248 nm, 193 nm). Among these, light having a wavelength of 248 to 436 nm is particularly preferred. The exposure dose is preferably 10 to 10,000 mJ / cm 2 is preferred.

[0169] The exposure may be performed through a photomask. The photomask may be, for example, one having a desired pattern drilled therethrough. The material of the photomask is not particularly limited, but preferably one that shields light having the above wavelength. For example, a photomask provided with chromium or the like as a light-shielding film is preferably used.

[0170] Furthermore, in order to enhance the development sensitivity, a post-exposure bake (PEB) may be performed. The PEB is preferably carried out at 40 to 150 °C for 0.5 to 10 minutes. By PEB, the exposed portion is crosslinked to form an insolubilized pattern that is insoluble in the solvent that is the developer.

[0171] After exposure or after PEB, development is carried out with a developer to dissolve and remove the unexposed portion to form a pattern. Examples of the developer include alcohols such as isopropyl alcohol (IPA), ketones such as cyclohexanone, and glycols such as PGME. However, the solvent used in the photosensitive resin composition can also be used. Examples of the development method include a normal method, such as a method of immersing the substrate on which the pattern is formed in the developer. Thereafter, washing, rinsing, drying, etc. are performed as necessary to obtain a photosensitive resin film having a desired pattern.

[0172] Furthermore, it is preferable to post-cure the film having the pattern formed thereon at 100 to 250°C, preferably 150 to 220°C, using an oven or a hot plate. When the post-curing temperature is in the range of 100 to 250°C, the crosslink density of the photosensitive resin film can be increased, and the remaining volatile components can be removed, which is more preferable from the viewpoints of adhesion to the substrate, heat resistance, strength, electrical properties, and further adhesion strength. The post-curing time is preferably 10 minutes to 10 hours, and more preferably 10 minutes to 3 hours. Even with a relatively low-temperature post-curing around 200°C, a film excellent in various film properties can be obtained with the photosensitive resin composition used in the present invention. The film thickness of the film (cured film) after post-curing is usually 1 to 200 μm, preferably 5 to 50 μm.

[0173] When it is not necessary to form a pattern, for example, when it is desired to form a merely uniform film, in the exposure step, film formation may be performed by exposing with light having an appropriate wavelength without using a photomask.

Examples

[0174] Hereinafter, the present invention will be described more specifically by showing synthesis examples, comparative synthesis examples, examples, and comparative examples, but the present invention is not limited to the following examples. In the following synthesis examples, the Mw of each resin was measured by GPC using TSKgel Super HZM-H (manufactured by Tosoh Corporation) as a column, with an analysis condition of a flow rate of 0.6 mL / min, an elution solvent of tetrahydrofuran, and a column temperature of 40°C, using monodisperse polystyrene as a standard.

[0175] The compounds (S-1) to (S-6) used in the following synthesis examples are as follows.

Chemical formula

[0176] [1] Synthesis of polymer containing silicone skeleton [Synthesis Example 1] Synthesis of silicone resin 1 To a 3 L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 117.6 g (0.28 mol) of compound (S-1), 79.5 g (0.3 mol) of compound (S-2), and 80.0 g (0.43 mol) of compound (S-3) were added. Then, 2,000 g of toluene was added and heated to 70 °C. Thereafter, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, and 67.9 g (0.35 mol) of compound (S-5) and compound (S-6) (y 1 =8) 399.8 g (0.65 mol) were added dropwise over 1 hour (total of hydrosilyl groups / total of alkenyl groups = 1.01 / 1.0 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100 °C and aged for 6 hours. Then, toluene was distilled off under reduced pressure from the reaction solution to obtain silicone resin 1. Silicone resin 1 was 1 confirmed by 1H-NMR (manufactured by Bruker) to contain repeating units a1, b1, a3, b3, a4, and b4. The Mw of silicone resin 1 was 28,000 and the silicone content was 64.4% by mass.

[0177] [Synthesis Example 2] Synthesis of silicone resin 2 To a 3 L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 90.1 g (0.34 mol) of compound (S-2), 223.6 g (0.52 mol) of compound (S-4), and 27.9 g (0.15 mol) of compound (S-3) were added. Then, 2,000 g of toluene was added and heated to 70 °C. Thereafter, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, and 38.8 g (0.2 mol) of compound (S-5) and compound (S-6) (y 1 =8) 492.μg (0.8 mol) were added dropwise over 1 hour (total of hydrosilyl groups / total of alkenyl groups = 1 / 1.01 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100 °C and aged for 6 hours. Then, toluene was distilled off under reduced pressure from the reaction solution to obtain silicone resin 2. Silicone resin 2 was 1 confirmed by 1H-NMR (manufactured by Bruker) to contain repeating units a2, b2, a3, b3, a4, and b4. The Mw of silicone resin 2 was 32,000 and the silicone content was 59.6% by mass.

[0178] [Synthesis Example 3] Synthesis of silicone resin 3 To a 3 L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 201.6 g (0.48 mol) of compound (S-1) and 227.9 g (0.53 mol) of compound (S-4) were added. Then, 2,000 g of toluene was added and heated to 70°C. Thereafter, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5% by mass) was added, and 155.2 g (0.80 mol) of compound (S-5) and compound (S-6) (y 1 = 38) 589.2 g (0.2 mol) were added dropwise over 1 hour (total of hydrosilyl groups / total of alkenyl groups = 1 / 1.01 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100°C and aged for 6 hours. Then, toluene was distilled off under reduced pressure from the reaction solution to obtain silicone resin 3. Silicone resin 3 1 was confirmed to contain repeating units a1, b1, a2, and b2 by 1H-NMR (manufactured by Bruker). The Mw of silicone resin 3 was 25,000, and the silicone content was 50.2% by mass.

[0179] [Synthesis Example 4] Synthesis of silicone resin 4 To a 3 L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 63.0 g (0.15 mol) of compound (S-1), 74.2 g (0.28 mol) of compound (S-2), 150.5 g (0.35 mol) of compound (S-4), and 42.8 g (0.23 mol) of compound (S-3) were added. Then, 2,000 g of toluene was added and heated to 70°C. Thereafter, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5% by mass) was added, and 58.2 g (0.3 mol) of compound (S-5) and compound (S-6) (y 1 = 8) 289.1 g (0.47 mol) were added dropwise over 1 hour (total of hydrosilyl groups / total of alkenyl groups = 1 / 1.01 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100°C and aged for 6 hours. Then, toluene was distilled off under reduced pressure from the reaction solution to obtain silicone resin 4. Silicone resin 4 1By 1H-NMR (manufactured by Bruker), it was confirmed that it contains repeating units a1, b1, a2, b2, a3, b3, a4 and b4. The Mw of silicone resin 4 was 23,000 and the silicone content was 50.0 mass%.

[0180] [3] Preparation of photosensitive resin composition [Compositions 1-1 to 1-7] According to the compounding amounts shown in Tables 1 and 2, each component was compounded, and then stirred, mixed, and dissolved at room temperature, followed by microfiltration with a 1.0 μm Teflon (registered trademark) filter to obtain photosensitive resin compositions 1-1 to 1-7.

[0181]

Table 1

[0182]

Table 2

[0183] The acrylic resins 1 to 3, photoacid generator PAG-1, photopolymerization initiator, crosslinking agents CL-1, CL-2, antioxidants F-1, F-2, and quencher AM-1 described in Tables 1 and 2 are as follows.

[0184] · Acrylic resin 1: ART CURE MAP-4050 (manufactured by Negami Kogyo Co., Ltd.) · Acrylic resin 2: ART CURE MAP-2801 (manufactured by Negami Kogyo Co., Ltd.) · Acrylic resin 3: Foret ZAH-106 (manufactured by Soken Chemical & Engineering Co., Ltd.)

[0185] · PAG-1

Chemical formula

[0186] · CL-1

Chemical formula

[0187] ·F-1: CHIMASSORB 119FL (manufactured by BASF) ·F-2: IRGANOX 3114 (manufactured by BASF)

[0188] ·AM-1

Chemical formula

[0189] [4] Evaluation of the embedding process In this example, three types of substrates, namely an Si substrate, a Ti / Cu substrate, and an SiO2 substrate, each having a step with an opening width of 70 μm and a depth of 80 μm, were prepared.

[0190] Next, a prewet solvent was dropped onto the stepped substrate over the entire surface for prewetting, and then 5 ml of each composition was dropped for embedding.

[0191] As spin coating conditions, referring to Figure 3, the rotation time is T1 to T2 = 300 seconds, T2 to T3 = 0.5 seconds, T4 to T5 = 8 seconds, T5 to T6 = 15 seconds, and the substrate rotation speed is S1 = 20 rpm, S2 = 100 rpm, S3 = 300 rpm.

[0192] After the embedding was completed, it was heated on a hot plate at 120 °C for 300 seconds to remove the solvent and dry it.

[0193] In this example, the target film thickness on the substrate after drying of the laminate was 20 μm.

[0194] Examples of embedding using Compositions 1-1 to 1-7 by the above method, and Comparative Examples of embedding under conditions without prewetting and without the rubbing step are shown in Tables 3 to 7. As the prewetting solvent, three types were examined: cyclopentanone, a mixed solution of cyclopentanone:PGMEA = 50:50, and a mixed solution of cyclopentanone:ethyl lactate = 50:50. The mixing ratio is by mass.

[0195] (1) Coating property The coating property of each composition on the wafer was evaluated when 5 ml of each composition was dropped. When the composition spread over one side of the wafer by the end of spin coating after dropping, it was marked as ○, and when it did not spread, it was marked as ×. The results are shown in Tables 3 to 7.

[0196] (2) Embedding property The cross-section of a step with an opening diameter of 70 μm and a depth of 80 μm of the laminate substrate fabricated in this embodiment was observed with a scanning electron microscope (SEM) to evaluate the embedding property. When the composition could be coated on the entire surface of the PB wafer after dropping and the composition was cleanly embedded to the bottom of the step without voids, it was marked as ○, and when it could not be embedded, it was marked as ×. The results are shown in Tables 3 to 7.

[0197] (3) Evaluation of flatness Using the above substrate, the film thickness of the composition on the substrate with a step and on the substrate without a formed step was measured with a scanning electron microscope (SEM). When the difference was within 20 ± 1 μm, it was marked as ○, when it was within 1 μm to 2 μm, it was marked as △, and when it was 2 μm or more, it was marked as ×. The results are shown in Tables 3 to 7.

[0198] (4) Evaluation of pattern formation property (2) On the substrate where the result was ○ in the evaluation, through a mask for forming a 60 μm Via leaving 5 μm on each of the left and right sidewalls within the step, exposure was performed using a contact aligner type exposure apparatus under exposure conditions of 365 nm. After exposure, PEB was performed at 140 °C for 5 minutes using a hot plate, cooled, and spray development was performed with PGMEA for 540 seconds to form a pattern.

[0199] The photosensitive resin film on the substrate on which the pattern was formed by the above method was post-cured at 180 °C for 2 hours using an oven while purging with nitrogen. Thereafter, cross-sectional observation of the formed 60-μm via pattern was performed using a scanning electron microscope (SEM). Further, from the obtained cross-sectional photographs, those with an opening up to the bottom in a vertical pattern were marked as ◎, those with an opening at the bottom in an inverted taper shape were marked as ○, those with scum observed at the bottom were marked as △, and those with defective openings were marked as ×. The results are shown in Tables 3 to 7.

[0200]

Table 3

[0201]

Table 4

[0202]

Table 5

[0203]

Table 6

[0204]

Table 7

[0205] As a result, as shown in Examples 1 to 35, a laminate comprising a semiconductor substrate and a photosensitive resin layer formed on the semiconductor substrate, wherein the photosensitive resin layer contains a silicone backbone-containing resin or an acrylic resin, the semiconductor substrate has a stepped surface on one side, the concave portion of the stepped surface is filled with a pre-wet solvent, and the photosensitive resin layer is formed thereon. It was found that when the laminate of the present invention is used, in a semiconductor substrate having a stepped surface, good embedding property and liquid saving can be achieved by pre-wetting, and a film with good flatness can be obtained.

[0206] On the other hand, Comparative Examples 1 to 3, 7 to 9, 13 to 15, 19 to 21, and 25 to 27, which did not undergo the scraping process, had poor flatness. Also, Comparative Examples 4 to 6, 10 to 12, 16 to 18, 22 to 24, and 28 to 30, which did not undergo prewetting, had poor coatability and embedability, and flatness and patternability could not be evaluated.

[0207] Note that the present invention is not limited to the above-described embodiments. The above-described embodiments are illustrative, and any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits the same operational effects is included in the technical scope of the present invention.

Claims

1. A laminate comprising a semiconductor substrate and a photosensitive resin layer formed on the semiconductor substrate, wherein the photosensitive resin layer contains a silicone skeleton-containing resin or an acrylic resin, the semiconductor substrate has a stepped surface on one side, and the recess of the stepped surface is filled with a prewet solvent, and the photosensitive resin layer is formed thereon, and the photosensitive resin layer in the recess has a concentration gradient of the prewet solvent in the stacking direction. A laminate characterized by that.

2. The laminate according to claim 1, wherein the opening width of the stepped surface is 10 to 100 μm and the depth is 10 to 120 μm.

3. The laminate according to claim 1 or claim 2, wherein the prewet solvent is a single solvent or a mixed solvent containing at least 30% by mass or more of a solvent having a boiling point of 130 ° C or higher.

4. The laminate according to any one of claims 1 to 3, wherein the photosensitive resin layer contains (A) a silicone skeleton-containing polymer, (B) a photoacid generator that decomposes by light of 190 to 500 nm to generate an acid, and (C) a solvent.

5. The laminate according to claim 4, wherein the (A) silicone skeleton-containing polymer contains a repeating unit represented by any one or more of the following formulas (a1) to (a4) and any one or more of (b1) to (b4). 【Chemical 1】 [wherein, R １ ~R ４ are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. m is an integer of 1 to 600. a １ ~a ４ and b １ ~b ４ are such that 0 ≤ a １ < 1, 0 ≤ a ２ < 1, 0 ≤ a ３ < 1, 0 ≤ a ４ < 1, 0 ≤ b １ < 1, 0 ≤ b ２ < 1, 0 ≤ b ３ < 1, 0 ≤ b ４ < 1, 0 < a １ + a ２ + a ３ + a ４ < 1, 0 < b １ + b ２ + b ３ + b ４ < 1, and a １ + a ２ + a ３ + a ４ + b １ + b ２ + b ３ + b ４ = 1. X １ is a divalent group represented by the following formula (X1). X ２ is a divalent group represented by the following formula (X2). X ３ is a divalent group represented by the following formula (X3). X ４ is a divalent group represented by the following formula (X4). 【Chemical 2】 (wherein Z １ is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group or a fluorene-9,9-diyl group. R １１ and R １２ are each independently a hydrogen atom or a methyl group. R １３ and R １４ are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. p １ and p ２ are each independently an integer of 0 to 7. q １ and q ２ are each independently an integer of 0 to 2.). [Chemical Formula 3] (In the formula, Z ２ is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group or a fluorene-9,9-diyl group. R ２１ and R ２２ are each independently a hydrogen atom or a methyl group. R ２３ and R ２４ are each independently an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. r １ and r ２ are each independently an integer of 0 to 7. s １ and s ２ are each independently an integer of 0 to 2.). 【Chemical Formula 4】 (wherein R ３１ and R ３２ are each independently a hydrogen atom or a methyl group. t １ and t ２ are each independently an integer from 0 to 7.) 【Chemical Formula 5】 (wherein R ４１ and R ４２ are each independently a hydrogen atom or a methyl group. R ４３ and R ４４ are each independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. u １ and u ２ are each independently an integer from 0 to 7. v is an integer from 0 to 600.) ]]

6. The laminate according to any one of claims 1 to 3, wherein the photosensitive resin layer contains (A') an acrylic polymer, (B') a photopolymerization initiator, and (C) a solvent.

7. A method for manufacturing a laminate, comprising: a first coating step of spin-coating a prewet solvent on a recess of a stepped surface of a semiconductor substrate having a stepped surface on one side to prewet and filling the recess of the stepped surface with the prewet solvent; a wiping step of removing excess prewet solvent when prewetting on the semiconductor substrate while spinning; and a second coating step of spin-coating a photosensitive resin composition containing a silicone skeleton-containing resin or an acrylic resin on the surface on which the prewet solvent is spin-coated and filled to form a photosensitive resin layer which is a coating film of the photosensitive resin composition.

8. The method for manufacturing a laminate according to claim 7, wherein the second coating step is performed without stopping the rotation of the semiconductor substrate from the wiping step.

9. The method for manufacturing a laminate according to claim 7 or claim 8, wherein as the pre-wet solvent used in the first coating step, a single solvent or a mixed solvent containing at least 30% by mass or more of a solvent having a boiling point of 130°C or higher is used.

10. In the laminate manufactured by the manufacturing method according to any one of claims 7 to 9, a step of performing preheating to cure the photosensitive resin layer to form a photosensitive resin film, a step of exposing the photosensitive resin film through a photomask, and after performing heat treatment after exposure, developing with a developer to dissolve and remove the unexposed portion to form a pattern. A pattern forming method characterized by including the steps.

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