Resin composition, method for producing laminate, and cured film

Abstract

To provide a resin composition capable of forming a cured film with excellent heat resistance and peelability when separating a laminate from a support, and a method for manufacturing a laminate.SOLUTION: In a method for manufacturing a semiconductor device, a cured film 2 of a resin composition containing a polyimide precursor is formed on a support 1, a laminate is further fabricated on the cured film 2, the cured film 2 is transformed by irradiating it with an active energy ray X, and then a semiconductor device 100 is formed by separating the laminate from the support 1.SELECTED DRAWING: Figure 3

Description

[Technical field]

[0001] The present disclosure relates to a resin composition, a method for producing a laminate, and a cured film. [Background technology]

[0002] In recent years, there has been an increasing demand for smaller, lighter, and more functional electronic devices. In response to these demands, semiconductor devices constituting the electronic devices are also required to be smaller, thinner, and more densely packed (for example, see Non-Patent Document 1).

[0003] Examples of semiconductor packages that can be made smaller and thinner include fan-out wafer level packages and multi-die wafer level packages that have been proposed in the past.

[0004] A process called RDL (Redistribution Layer) First has been proposed as one of the manufacturing processes for semiconductor devices with a thin and high-density wiring structure, such as fan-out wafer-level packages. In this process, a thin-film wiring layer is formed on a temporary fixing layer formed on a support, and then a semiconductor element is connected to the wiring layer, and the semiconductor element is sealed with a sealant to produce a semiconductor device. The semiconductor device is then peeled off from the support.

[0005] The temporary fixing layer used in the above steps is required to have resistance such that peeling does not occur between the support and the wiring layer even when various processes are performed when manufacturing a semiconductor device. Specifically, it is required that peeling does not occur between the support and the wiring layer in each process such as sputtering, CVD (chemical vapor deposition), PVD (physical vapor deposition), lithography, plating, wet etching, cleaning, hardening of interlayer insulating film, CMP (chemical mechanical polishing), die bonding, mounting, annealing, packaging, etc.

[0006] Known examples of such temporary fixing layer technology include that described in Patent Document 1. That is, Patent Document 1 discloses that a separation layer and an adhesive layer, which are temporary fixing layers, are formed on the support side, a semiconductor device is formed thereon, and then laser light is irradiated from the support side to alter the separation layer and reduce the adhesive force, thereby peeling off the semiconductor device.

[0007] Furthermore, Patent Document 2 discloses a method in which a temporary fixing sheet containing a resin composition containing an acrylic material is laminated on a light-transmitting support, a semiconductor chip is temporarily fixed on the temporary fixing sheet, the semiconductor chip is covered with an encapsulant, the encapsulant is ground, and wiring is formed on the surface of the semiconductor chip in this order, and then radiant energy is irradiated onto the temporary fixing sheet from the light-transmitting support side to decompose the resin composition and peel off the temporary fixing sheet from the semiconductor device. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Patent Publication No. 2018-93021 [Patent Document 2] Patent Publication No. 2017-98481 [Non-patent literature]

[0009] [Non-Patent Document 1] "Semiconductor Technology Yearbook 2013 Packaging / Mounting Edition", Nikkei BP, p41-p50. Summary of the Invention [Problem to be solved by the invention]

[0010] When manufacturing multiple semiconductor electronic components on a carrier substrate, such as in a fan-out wafer-level package, the aforementioned RDL first process can be used to form fine wiring layers and the like on the carrier substrate with reduced warping, making it possible to further reduce the size and thickness of semiconductor devices.

[0011] However, in the method described in Patent Document 1, the temporary fixing layer is made up of two layers, an adhesive layer and a release layer, and therefore the steps for producing the temporary fixing layer are complicated.

[0012] In the method described in Patent Document 2, a resin composition containing an acrylic material is used to prepare a temporary fixing sheet, and therefore the heat resistance of the temporary fixing sheet is about 150° C. Therefore, if an object is heat-treated at 200° C. or higher during the manufacture of a semiconductor device, voids or the like may be generated in the temporary fixing sheet due to decomposition of the acrylic material, which may cause peeling between the temporary fixing sheet and the semiconductor chip or the light-transmitting support.

[0013] In addition, when separating a laminate such as a semiconductor device temporarily fixed to a support via a temporary fixing layer formed by curing a resin composition, it is desirable for the laminate to have excellent peelability in order to suppress damage to the laminate.

[0014] The present disclosure has been made in view of the above, and aims to provide a resin composition capable of forming a cured film that has excellent heat resistance and peelability when the laminate is separated from a support, a method for producing a laminate using the resin composition, and a cured film obtained by curing the resin composition. [Means for solving the problem]

[0015] Specific means for achieving the above object are as follows. <1> A resin composition containing a polyimide precursor and used in the following treatments (a) to (c). (a) A cured film of the resin composition is formed on a support. (b) A laminate is formed on the cured film. (c) Separating the laminate from the support. <2> The composition further contains a solvent, and the content of the solvent is 50 parts by mass to 10,000 parts by mass per 100 parts by mass of the resin component. <1> The resin composition according to claim 1. <3> The solvent includes at least one selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, γ-butyrolactone, cyclopentanone, dimethylsulfoxide, dimethylimidazolidinone, and N-formylpiperidine. <2> The resin composition according to claim 1. <4> The cured film is not altered after being heat-treated at 100°C to 400°C for 4 hours or less. <1> ~ <3> 10. The resin composition according to claim 9 . <5> The polyimide precursor contains a compound having a structural unit represented by the following general formula (1): <1> ~ <4> 10. The resin composition according to claim 9 .

[0016] [ka]

[0017] In the general formula (1), X represents a tetravalent organic group, and Y represents a divalent organic group. 6 and R 7 each independently represents a hydrogen atom or a monovalent organic group. <6> The monovalent organic group includes a group represented by the following general formula (2): <5> The resin composition according to claim 1.

[0018] [ka]

[0019] In general formula (2), R 8 ~R 10 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms; R x represents a divalent linking group. <7> Further containing a polymerizable monomer and a thermal polymerization initiator <1> ~ <6> 10. The resin composition according to claim 9 . <8> Used for the processing of (d) below <1> ~ <7> 10. The resin composition according to claim 9 . (d) Removing the residue of the cured film remaining on the laminate after separation from the support. <9> In the step (d), the residue of the cured film remaining on the laminate can be removed by a solvent treatment. <8> The resin composition according to claim 1.

[0020] <10> <1> ~ <9> A step of preparing a resin composition according to any one of the above items; forming a cured film of the resin composition on a support; preparing a laminate on the cured film; Separating the laminate from the support; A method for producing a laminate comprising the steps of: <11> The thermal expansion coefficient of the support at 25°C to 300°C is 3 ppm / K to 15 ppm / K. <10> A method for producing the laminate described in claim 1. <12> The thickness of the support is 100 μm to 10,000 μm, and the transmittance of light with a wavelength of 355 nm is 90% or more. <10> or <11> A method for producing the laminate described in claim 1. <13> The cured film is irradiated with active energy rays to modify the cured film, and then the laminate is separated from the support. <10> ~ <12> 13. A method for producing the laminate according to claim 12. <14> The method further includes a step of removing residue of the cured film remaining on the laminate after separation from the support. <10> ~ <13> 13. A method for producing the laminate according to claim 12. <15> The heating temperature when forming the cured film is 100° C. to 450° C. <10> ~ <14> 13. A method for producing the laminate according to claim 12. <16> The average thickness of the cured film formed on the support is 0.1 μm or more. <10> ~ <15> 13. A method for producing the laminate according to claim 12. <17> the laminate is a semiconductor device including a wiring layer, an insulating layer, and a semiconductor chip, The step of producing the laminate includes a step of forming the wiring layer on the cured film, a step of forming the insulating layer that at least insulates the wiring layers, and a step of arranging the semiconductor chip on the insulating layer and connecting the semiconductor chip to the wiring layer. <10> ~ <16> 13. A method for producing the laminate according to claim 12. <18> the laminate further includes a sealing material that seals the semiconductor chip; The step of producing the laminate further includes a step of sealing the semiconductor chip connected to the wiring layer. <17> A method for producing the laminate described in claim 1. <19> <1> ~ <9> 2. A cured film obtained by curing the resin composition according to claim 1. Effect of the Invention

[0021] According to the present disclosure, it is possible to provide a resin composition capable of forming a cured film having excellent heat resistance and peelability when the laminate is separated from a support, a method for producing a laminate using the resin composition, and a cured film obtained by curing the resin composition. [Brief description of the drawings]

[0022] [Figure 1] 1 is a diagram showing steps of a method for manufacturing a semiconductor device according to an embodiment of the present disclosure. [Diagram 2] 1 is a diagram showing steps of a method for manufacturing a semiconductor device according to an embodiment of the present disclosure. [Diagram 3] 1 is a diagram showing steps of a method for manufacturing a semiconductor device according to an embodiment of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] Hereinafter, the embodiments for carrying out the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, the components (including element steps, etc.) are not essential unless otherwise specified. The same applies to the numerical values ​​and their ranges, and do not limit the present disclosure.

[0024] In the present disclosure, "A or B" may include either A or B, or may include both. In the present disclosure, the term "step" includes not only a step that is independent of other steps, but also a step that cannot be clearly distinguished from other steps as long as the purpose of the step is achieved. In the present disclosure, a numerical range indicated using "~" includes the numerical values ​​before and after "~" as the minimum and maximum values, respectively. In the numerical ranges described in the present disclosure in stages, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. In addition, in the numerical ranges described in the present disclosure, the upper or lower limit value of the numerical range may be replaced with a value shown in the examples. In the present disclosure, each component may contain multiple types of corresponding substances. When multiple types of substances corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple substances present in the composition, unless otherwise specified. In the present disclosure, the terms "layer" and "film" include cases where the layer or film is formed over the entire area when the area in which the layer or film is present is observed, as well as cases where the layer or film is formed over only a portion of the area. In the present disclosure, the average thickness of a layer or film is defined as the arithmetic mean value of thicknesses measured at five points on the layer or film of interest. The thickness of the layer or film can be measured using a micrometer or the like. In the present disclosure, when the thickness of the layer or film can be measured directly, it is measured using a micrometer. On the other hand, when the thickness of one layer or the total thickness of multiple layers is measured, it may be measured by observing the cross section of the measurement target using an electron microscope. In the present disclosure, the term "(meth)acrylic group" means an "acrylic group" and a "methacrylic group". When an embodiment of the present disclosure is described with reference to the drawings, the configuration of the embodiment is not limited to the configuration shown in the drawings. In addition, the size of the members in each drawing is conceptual, and the relative relationship between the sizes of the members is not limited to this.

[0025] <Resin composition> The resin composition of the present disclosure contains a polyimide precursor and is used in the following treatments (a) to (c). (a) A cured film of the resin composition is formed on a support. (b) A laminate is formed on the cured film. (c) Separating the laminate from the support.

[0026] The resin composition of the present disclosure can form a cured film having excellent heat resistance and peelability when the laminate is separated from the support. The reason for this is presumed to be that the resin composition contains a polyimide precursor, so that the cured film of the resin composition prepared on the support has excellent heat resistance, and further, when the cured film is irradiated with active energy rays such as laser light, or when the cured film is subjected to a heat treatment, the cured film is altered, so that the laminate has excellent peelability when separated from the support. Furthermore, the cured film obtained by curing the resin composition of the present disclosure functions as both an adhesive layer that bonds the laminate to the support, and a peel layer that can be separated from the support by altering the properties. Therefore, when the resin composition of the present disclosure is used in a method for producing a laminate, it is not necessary to form both an adhesive layer and a peel layer, and the manufacturing process of the laminate can be simplified.

[0027] The polyimide precursor may contain a polyimide precursor having a polymerizable unsaturated bond. This tends to improve the properties (e.g., thermal properties) of the cured film when the resin composition contains at least one of a polymerizable monomer and a thermal polymerization initiator described later, preferably both a polymerizable monomer and a thermal polymerization initiator. The polymerizable unsaturated bond may be a carbon-carbon double bond.

[0028] It is preferable that the cured film obtained by curing the resin composition of the present disclosure does not undergo any deterioration after being heat-treated for 4 hours or less at 100° C. to 400° C. More specifically, examples of the deterioration of the cured film include thermal decomposition, peeling, and changes in removability.

[0029] The resin composition of the present disclosure is preferably used in the following treatment (d). (d) Removing the residue of the cured film remaining on the laminate after separation from the support. For example, when the cured film is irradiated with active energy rays such as laser light, or when the cured film is subjected to a heat treatment, the cured film may be altered, and when the laminate is separated from the support, residues of the cured film may remain on the laminate after separation from the support. Therefore, it is preferable to remove the residues of the cured film remaining on the laminate by the above-mentioned treatment (d).

[0030] When removing the residue of the cured film remaining on the laminate by the above-mentioned treatment (d), it is preferable that the residue of the cured film remaining on the laminate can be removed by a solvent treatment. For example, the polyimide precursor has a structural unit represented by the general formula (1) described below, and R 6 and R 7 When at least one of the above groups contains a compound in which the compound is a monovalent organic group, the residue of the cured film remaining on the laminate tends to be easily removed with a solvent.

[0031] The polyimide precursor may be a compound having a structural unit represented by the following general formula (1).

[0032] [ka]

[0033] In the general formula (1), X represents a tetravalent organic group, and Y represents a divalent organic group. 6 and R 7 each independently represents a hydrogen atom or a monovalent organic group. The polyimide precursor may have a plurality of structural units represented by the following general formula (1), and X, Y, and R in the plurality of structural units 6 and R 7 may be the same or different.

[0034] In general formula (1), the tetravalent organic group represented by X preferably has 4 to 25 carbon atoms, more preferably 4 to 13 carbon atoms, and even more preferably 6 to 12 carbon atoms. The tetravalent organic group represented by X may contain an aromatic ring. When the tetravalent organic group represented by X contains an aromatic ring, examples of the aromatic ring include a benzene ring, a naphthalene ring, and a phenanthrene ring. Among these, a benzene ring is preferred from the viewpoint of improving the light transmittance of the polyimide precursor in the ultraviolet region. When the tetravalent organic group represented by X contains an aromatic ring, each aromatic ring may have a substituent or may be unsubstituted. Examples of the substituent of the aromatic ring include an alkyl group, a fluorine atom, a halogenated alkyl group, a hydroxyl group, and an amino group. When the tetravalent organic group represented by X contains a benzene ring, the tetravalent organic group represented by X preferably contains one to four benzene rings, more preferably contains one to three benzene rings, and even more preferably contains one or two benzene rings. When the tetravalent organic group represented by X contains two or more benzene rings, the benzene rings may be linked by a single bond or by an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a silylene bond (-Si(R A )2-;R Aeach independently represents a hydrogen atom, an alkyl group, or a phenyl group), a siloxane bond (-O-(Si(R B )2-O-) n ;R B each independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more.) or a composite linking group combining at least two of these linking groups. In addition, two benzene rings may be linked at two positions by at least one of a single bond and a linking group to form a 5- or 6-membered ring containing a linking group between the two benzene rings.

[0035] In the general formula (1), -COOR 6 The -CONH- and -COOR- groups are in the ortho position relative to each other. 7 The group and the -CO- group are preferably in the ortho position relative to each other.

[0036] Specific examples of the tetravalent organic group represented by X include groups represented by the following formulae (A) to (E). The present disclosure is not limited to the following specific examples.

[0037] [ka]

[0038] In formula (D), A and B each independently represent a single bond, a methylene group, a halogenated methylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-) or a silylene bond (-Si(R A )2-;R A each independently represents a hydrogen atom, an alkyl group, or a phenyl group, and A and B cannot both be single bonds.

[0039] In formula (E), C is a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a silylene bond (-Si(R A )2-;R Aeach independently represents a hydrogen atom, an alkyl group, or a phenyl group), a siloxane bond (-O-(Si(R B )2-O-) n ;R B each independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more.) or a divalent group combining at least two of these. C may be a structure represented by the following formula (C1).

[0040] [ka]

[0041] The alkylene group represented by C in formula (E) is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably an alkylene group having 1 or 2 carbon atoms. Specific examples of the alkylene group represented by C in formula (E) include linear alkylene groups such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group; a methylmethylene group, a methylethylene group, an ethylmethylene group, a dimethylmethylene group, a 1,1-dimethylethylene group, a 1-methyltrimethylene group, a 2-methyltrimethylene group, an ethylethylene group, a 1-methyltetramethylene group, a 2-methyltetramethylene group, a 1-ethyltrimethylene group, a 2-ethyltrimethylene group, a 1,1-dimethylethylene group, branched alkylene groups such as ethyltrimethylene group, 1,2-dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, 1-ethyltetramethylene group, 2-ethyltetramethylene group, 1,1-dimethyltetramethylene group, 1,2-dimethyltetramethylene group, 2,2-dimethyltetramethylene group, 1,3-dimethyltetramethylene group, 2,3-dimethyltetramethylene group, and 1,4-dimethyltetramethylene group; and the like. Among these, the methylene group is preferred.

[0042] The halogenated alkylene group represented by C in formula (E) is preferably a halogenated alkylene group having 1 to 10 carbon atoms, more preferably a halogenated alkylene group having 1 to 5 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 3 carbon atoms. Specific examples of the halogenated alkylene group represented by C in formula (E) include alkylene groups in which at least one hydrogen atom contained in the alkylene group represented by C in the above formula (E) is substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, a fluoromethylene group, a difluoromethylene group, a hexafluorodimethylmethylene group, etc. are preferred.

[0043] R contained in the silylene bond or siloxane bond A or R B The alkyl group represented by the formula (I) is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and further preferably an alkyl group having 1 or 2 carbon atoms. A or R B Specific examples of the alkyl group represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.

[0044] The combination of A and B in formula (D) is not particularly limited, and a combination of a methylene group and an ether bond, a combination of a methylene group and a sulfide bond, a combination of a carbonyl group and an ether bond, and the like are preferred. In formula (E), C is preferably a single bond, an ether bond, a carbonyl group, or the like.

[0045] In formula (1), the divalent organic group represented by Y preferably has 6 to 25 carbon atoms, more preferably 6 to 14 carbon atoms, and even more preferably 12 to 14 carbon atoms. The divalent organic group represented by Y may be a divalent aliphatic group or a divalent aromatic group. From the viewpoint of heat resistance, the divalent organic group represented by Y is preferably a divalent aromatic group.

[0046] Specific examples of the divalent aromatic group represented by Y include groups represented by the following general formula (F) and the following general formula (G).

[0047] [ka]

[0048] In general formula (F) or general formula (G), R each independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, or a phenyl group, and n each independently represents an integer of 0 to 4. In the general formula (G), D is a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a silylene bond (-Si(R A )2-;R A each independently represents a hydrogen atom, an alkyl group, or a phenyl group), a siloxane bond (-O-(Si(R B )2-O-) n ;R B Each independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more.) or a divalent group combining at least two of them. D may be a structure represented by the above formula (C1). Specific examples of D in general formula (G) are the same as specific examples of C in formula (E). As D in general formula (G), a single bond is preferable.

[0049] The alkyl group represented by R in general formula (F) or (G) is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and further preferably an alkyl group having 1 or 2 carbon atoms. Specific examples of the alkyl group represented by R in general formula (F) or general formula (G) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a s-butyl group, and a t-butyl group.

[0050] The alkoxy group represented by R in general formula (F) or (G) is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, and even more preferably an alkoxy group having 1 or 2 carbon atoms. Specific examples of the alkoxy group represented by R in general formula (F) or general formula (G) include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, an s-butoxy group, and a t-butoxy group.

[0051] The halogenated alkyl group represented by R in general formula (F) or (G) is preferably a halogenated alkyl group having 1 to 5 carbon atoms, more preferably a halogenated alkyl group having 1 to 3 carbon atoms, and further preferably a halogenated alkyl group having 1 or 2 carbon atoms. Specific examples of the halogenated alkyl group represented by R in general formula (F) or (G) include alkyl groups in which at least one hydrogen atom contained in the alkyl group represented by R in general formula (F) or (G) is substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, etc. are preferred.

[0052] In general formula (F) or general formula (G), n is preferably 0 to 2, more preferably 0 or 1, and further preferably 0.

[0053] Specific examples of the divalent aliphatic group represented by Y include a linear or branched alkylene group, a cycloalkylene group, a divalent group having a polyalkylene oxide structure, and a divalent group having a polysiloxane structure.

[0054] The linear or branched alkylene group represented by Y is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 15 carbon atoms, and even more preferably an alkylene group having 1 to 10 carbon atoms. Specific examples of the alkylene group represented by Y include a tetramethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, a 2-methylpentamethylene group, a 2-methylhexamethylene group, a 2-methylheptamethylene group, a 2-methyloctamethylene group, a 2-methylnonamethylene group, and a 2-methyldecamethylene group.

[0055] The cycloalkylene group represented by Y is preferably a cycloalkylene group having 3 to 10 carbon atoms, and more preferably a cycloalkylene group having 3 to 6 carbon atoms. Specific examples of the cycloalkylene group represented by Y include a cyclopropylene group, a cyclohexylene group, and the like.

[0056] The unit structure contained in the divalent group having a polyalkylene oxide structure represented by Y is preferably an alkylene oxide structure having 1 to 10 carbon atoms, more preferably an alkylene oxide structure having 1 to 8 carbon atoms, and even more preferably an alkylene oxide structure having 1 to 4 carbon atoms. Among them, the polyalkylene oxide structure is preferably a polyethylene oxide structure or a polypropylene oxide structure. The alkylene group in the alkylene oxide structure may be linear or branched. The unit structure in the polyalkylene oxide structure may be one type or two or more types.

[0057] Examples of the divalent group having a polysiloxane structure represented by Y include divalent groups having a polysiloxane structure in which a silicon atom in the polysiloxane structure is bonded to a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms. Specific examples of the alkyl group having 1 to 20 carbon atoms bonded to a silicon atom in the polysiloxane structure include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-octyl group, a 2-ethylhexyl group, an n-dodecyl group, etc. Among these, a methyl group is preferable. The aryl group having 6 to 18 carbon atoms bonded to the silicon atom in the polysiloxane structure may be unsubstituted or substituted with a substituent. Specific examples of the substituent when the aryl group has a substituent include a halogen atom, an alkoxy group, and a hydroxy group. Specific examples of the aryl group having 6 to 18 carbon atoms include a phenyl group, a naphthyl group, and a benzyl group. Among these, a phenyl group is preferred. The alkyl group having 1 to 20 carbon atoms or the aryl group having 6 to 18 carbon atoms in the polysiloxane structure may be of one type or of two or more types. The silicon atom constituting the divalent group having a polysiloxane structure represented by Y may be bonded to the NH group in general formula (1) via an alkylene group such as a methylene group or an ethylene group, or an arylene group such as a phenylene group.

[0058] In the general formula (1), the combination of the tetravalent organic group represented by X and the divalent organic group represented by Y is not particularly limited. Examples of the combination of the tetravalent organic group represented by X and the divalent organic group represented by Y include a combination of X being a group represented by formula (A) and a group represented by formula (E), and Y being a group represented by formula (G); a combination of X being a group represented by formula (D) and a group represented by formula (E), and Y being a group represented by formula (G), and the like. By using a group represented by formula (A) and a group represented by formula (E) in combination as X and a group represented by general formula (G) as Y, the elastic modulus of the obtained polyimide resin tends to be further improved even when the heat treatment is performed at a relatively low temperature of 300° C. or less. When X is a combination of a group represented by formula (A) and a group represented by formula (E), the ratio by number of the group XA represented by formula (A) to the group XE represented by formula (E) (XA / XE) is preferably in the range of 1 / 99 to 99 / 1, more preferably in the range of 50 / 50 to 90 / 10, and further preferably in the range of 70 / 30 to 90 / 10.

[0059] R 6 and R 7 each independently represents a hydrogen atom or a monovalent organic group, and R 6 and R 7 At least one of the groups is preferably a monovalent organic group. The monovalent organic group preferably contains an aliphatic hydrocarbon group having 1 to 4 carbon atoms or an organic group having an unsaturated double bond, more preferably contains an aliphatic hydrocarbon group having 1 or 2 carbon atoms or a group represented by the following general formula (2), and further preferably contains a group represented by the following general formula (2). In particular, when the monovalent organic group contains an organic group having an unsaturated double bond, preferably a group represented by the following general formula (2), the i-ray transmittance is high, and a good cured film tends to be formed even when cured at a low temperature of 300°C or less. Specific examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.

[0060] [ka]

[0061] In general formula (2), R 8 ~R 10 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms; R x represents a divalent linking group.

[0062] R in general formula (2) 8 ~R 10 The aliphatic hydrocarbon group represented by the formula (I) has 1 to 3 carbon atoms, and preferably 1 or 2. 8 ~R10 Specific examples of the aliphatic hydrocarbon group represented by the formula include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, etc., with a methyl group being preferred.

[0063] R in general formula (2) 8 ~R 10 The combination of R 8 and R 9 is a hydrogen atom, and R 10 is preferably a hydrogen atom or a methyl group.

[0064] R in general formula (2) x is a divalent linking group, and is preferably a hydrocarbon group having 1 to 10 carbon atoms. Examples of the hydrocarbon group having 1 to 10 carbon atoms include linear or branched alkylene groups. R x The number of carbon atoms in is preferably 1 to 10, more preferably 2 to 5, and further preferably 2 or 3.

[0065] In the general formula (1), R 6 and R 7 At least one of R is preferably a group represented by the general formula (2). 6 and R 7 It is more preferable that both of the above are a group represented by the general formula (2).

[0066] When the polyimide precursor contains a compound having a structural unit represented by the above-mentioned general formula (1), R 6 and R 7 R which is a group represented by general formula (2) 6 and R 7 The proportion is preferably 50 mol % or more, more preferably 80 mol % or more, and even more preferably 90 mol % or more. There is no particular upper limit, and it may be 100 mol %. The above ratio may be 0 mol % or more and less than 50 mol %.

[0067] The group represented by general formula (2) is preferably a group represented by the following general formula (3).

[0068] [ka]

[0069] In general formula (3), R 8 ~R 10 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms; and q represents an integer of 1 to 10.

[0070] In formula (3), q is preferably an integer of 1 to 10, more preferably an integer of 2 to 5, and even more preferably 2 or 3.

[0071] The polyimide precursor may be synthesized using a tetracarboxylic dianhydride and a diamine compound. In this case, in the general formula (1), X corresponds to a residue derived from the tetracarboxylic dianhydride, and Y corresponds to a residue derived from the diamine compound. The polyimide precursor may be synthesized using a tetracarboxylic acid instead of the tetracarboxylic dianhydride.

[0072] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, m-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, p-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(3, 4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis{4'-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 1,1,1,3,3,3-hexaphenyl Examples of suitable fluoro-2,2-bis{4'-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride include 1,1,1,3,3,3-hexafluoro-2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 4,4'-oxydiphthalic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, and 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride. The tetracarboxylic dianhydrides may be used alone or in combination of two or more kinds.

[0073] Specific examples of the diamine compound include 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 1,5-diaminonaphthalene, benzidine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, aminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 2,4'-diaminodiphenyl sulfone, 2,2'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 2,4'-diaminodiphenyl sulfide, 2,2'-diaminodiphenyl sulfide, o-tolidine, o-tolidine sulfone, 4,4'-methylenebis(2,6-diethylaniline), 4,4'-methylenebis(2, 6-diisopropylaniline), 2,4-diaminomesitylene, 1,5-diaminonaphthalene, 4,4'-benzophenonediamine, bis-{4-(4'-aminophenoxy)phenyl}sulfone, 2,2-bis{4-(4'-aminophenoxy)phenyl}propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis{4-(3'-aminophenoxy)phenyl}sulfone, 2,2-bis(4-aminophenyl)propane, 9,9-bis(4-amino phenyl)fluorene, 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 2-methyl-1,5-diaminopentane, 2-methyl-1,6-diaminohexane, 2-methyl-1,7-diaminoheptane, 2-methyl-1,8-diaminooctane, 2-methyl-1,9-diaminononane, 2-methyl-1,10-diaminodecane, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, diaminopolysiloxane, etc. The diamine compounds may be used alone or in combination of two or more kinds.

[0074] Having a structural unit represented by general formula (1), and R 6 and R 7 The compound in which at least one of the above is a monovalent organic group can be obtained, for example, by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a compound represented by R-OH in a solvent such as N-methyl-2-pyrrolidone or 3-methoxy-N,N-dimethylpropanamide to obtain a diester derivative, and then subjecting the diester derivative to a condensation reaction with a diamine compound represented by H2N-Y-NH2; or by reacting a tetracarboxylic dianhydride with a diamine compound represented by H2N-Y-NH2 in a solvent to obtain a polyamic acid, adding a compound represented by R-OH, and reacting the resulting mixture in the solvent to introduce an ester group. The solvent used in the reaction may be a solvent that can be contained in the resin composition of the present disclosure, which will be described later. In the diamine compound represented by H2N-Y-NH2, Y is the same as Y in the general formula (1), and specific examples and preferred examples are also the same. In the compound represented by R-OH, R represents a monovalent organic group, and specific examples and preferred examples are the same as R in the general formula (1). 6 and R 7 The same is true for The tetracarboxylic dianhydride represented by the general formula (8), the diamine compound represented by H2N-Y-NH2, and the compound represented by R-OH may each be used alone or in combination of two or more. The above-mentioned compound contained in the polyimide precursor can be obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a compound represented by R-OH to form a diester derivative, then reacting the diester with a chlorinating agent such as thionyl chloride to convert it into an acid chloride, and then reacting a diamine compound represented by HN-Y-NH with the acid chloride. Furthermore, the above-mentioned compound contained in the polyimide precursor can be obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a compound represented by R-OH to form a diester derivative, and then reacting the diamine compound represented by H2N-Y-NH2 with the diester derivative in the presence of a carbodiimide compound. Furthermore, the above-mentioned compound contained in the polyimide precursor can be obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a diamine compound represented by H2N-Y-NH2 to form a polyamic acid, then isoimidizing the polyamic acid in the presence of trifluoroacetic anhydride, and then reacting with a compound represented by R-OH. Alternatively, a compound represented by R-OH may be reacted in advance with a part of the tetracarboxylic dianhydride to react the partially esterified tetracarboxylic dianhydride with the diamine compound represented by H2N-Y-NH2.

[0075] [ka]

[0076] In the general formula (8), X is the same as X in the general formula (1), and specific examples and preferred examples are also the same.

[0077] The compound represented by R-OH used in the synthesis of the above-mentioned compound contained in the polyimide precursor is preferably methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, etc., and more preferably 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate.

[0078] There is no particular limitation on the molecular weight of the polyimide precursor, and for example, the weight average molecular weight is preferably 10,000 to 200,000. The weight average molecular weight can be measured, for example, by gel permeation chromatography, and can be calculated using a standard polystyrene calibration curve.

[0079] The resin composition of the present disclosure may contain a resin component other than the polyimide precursor. For example, from the viewpoint of heat resistance, the resin composition of the present disclosure may contain other resins such as polyimide resin, novolac resin, acrylic resin, polyether nitrile resin, polyether sulfone resin, epoxy resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polyvinyl chloride resin, etc. The other resins may be used alone or in combination of two or more.

[0080] In the resin composition of the present disclosure, the content of the polyimide precursor relative to the total amount of resin components is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and even more preferably 90% by mass to 100% by mass.

[0081] (solvent) The resin composition of the present disclosure preferably further contains a solvent. The solvent is not particularly limited, and examples thereof include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylacetamide, cyclopentanone, dimethyl sulfoxide, 3-methoxy-N,N-dimethylpropanamide, N,N,2-trimethylpropionamide, dimethylimidazolidinone, N-formylpiperidine, N-dimethylmorpholine, and propylene glycol 1-monomethyl ether-2-acetate. Among them, the solvent is preferably N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, γ-butyrolactone, cyclopentanone, dimethyl sulfoxide, dimethylimidazolidinone, and N-formylpiperidine. The solvent may be used alone or in combination of two or more.

[0082] When the resin composition of the present disclosure contains a solvent, the content of the solvent is preferably 50 parts by mass to 10,000 parts by mass, and more preferably 100 parts by mass to 10,000 parts by mass, per 100 parts by mass of the resin component.

[0083] (Polymerizable monomer) The resin composition of the present disclosure preferably further contains a polymerizable monomer from the viewpoint of improving the physical properties of the cured film. The polymerizable monomer preferably has at least one group containing a polymerizable unsaturated double bond, and more preferably has at least one (meth)acrylic group from the viewpoint of being polymerizable by a coupling agent or the like. From the viewpoint of improving the crosslink density and improving the photosensitivity, it is preferable that the polymerizable monomer has two to four groups containing a polymerizable unsaturated double bond, and more preferably has two groups from the viewpoint of removability of the residue of the cured film attached to the laminate after peeling it off from the support. The polymerizable monomers may be used alone or in combination of two or more.

[0084] The polymerizable monomer having a (meth)acrylic group is not particularly limited, and examples thereof include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane triacrylate, and trimethylolpropane diacrylate. Examples of the polymerizable monomer include diethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated isocyanuric acid triacrylate, ethoxylated isocyanuric acid trimethacrylate, acryloyloxyethyl isocyanurate, and methacryloyloxyethyl isocyanurate. Among them, the polymerizable monomer is preferably diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and tetraethylene glycol dimethacrylate.

[0085] The polymerizable monomer other than the polymerizable monomer having a (meth)acrylic group is not particularly limited, and examples thereof include styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, methylenebisacrylamide, N,N-dimethylacrylamide, and N-methylolacrylamide.

[0086] When the resin composition of the present disclosure contains a polymerizable monomer, the content of the polymerizable monomer is not particularly limited, and is preferably 1 part by mass to 50 parts by mass relative to 100 parts by mass of the polyimide precursor, and from the viewpoint of the thermal properties of the cured film, is more preferably 5 parts by mass to 50 parts by mass, and even more preferably 5 parts by mass to 40 parts by mass.

[0087] When the resin composition of the present disclosure contains a polymerizable monomer, the proportion of the polymerizable monomer having a (meth)acrylic group in the total amount of polymerizable monomers is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and even more preferably 90% by mass to 100% by mass, from the viewpoint of the physical properties of the cured film.

[0088] (Thermal polymerization initiator) From the viewpoint of improving the physical properties of the cured film, the resin composition of the present disclosure preferably further contains a thermal polymerization initiator. In addition, the resin composition of the present disclosure more preferably contains both the above-mentioned polymerizable monomer and the thermal polymerization initiator.

[0089] The thermal polymerization initiator is not particularly limited, and examples thereof include ketone peroxides such as methyl ethyl ketone peroxide, peroxyketals such as 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, and 1,1-di(t-butylperoxy)cyclohexane, hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, and p-menthane hydroperoxide, dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide, Examples of the thermal polymerization initiator include diacyl peroxides such as dilauroyl peroxide and dibenzoyl peroxide, peroxydicarbonates such as di(4-t-butylcyclohexyl)peroxydicarbonate and di(2-ethylhexyl)peroxydicarbonate, peroxyesters such as t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxybenzoate and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, and bis(1-phenyl-1-methylethyl)peroxide. The thermal polymerization initiator may be used alone or in combination of two or more.

[0090] When the resin composition of the present disclosure contains a thermal polymerization initiator, the content of the thermal polymerization initiator may be 0.1 parts by mass to 20 parts by mass, 1 part by mass to 15 parts by mass, or 5 parts by mass to 10 parts by mass relative to 100 parts by mass of the polyimide precursor.

[0091] (Light absorber) The resin composition of the present disclosure may further contain a light absorber from the viewpoint of suppressing the transmittance of light of a specific wavelength, for example, the transmittance of light of 355 nm. The light absorbing agent may be used alone or in combination of two or more kinds.

[0092] Specific examples of the light absorbing agent include: Benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone and other benzophenone derivatives; Acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexyl phenyl ketone; Thioxanthone, thioxanthone derivatives such as 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzil, benzil dimethyl ketal, benzil-β-methoxyethyl acetal and other benzil derivatives; Benzoin, benzoin derivatives such as benzoin methyl ether; Examples of the oxime include 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime), and oxime esters.

[0093] Specific examples of the light absorbing agent are not limited to the above-mentioned compounds. Other specific examples of the light absorber include organic light absorbers such as benzotriazole-based light absorbers, hydroxyphenyltriazine-based light absorbers, benzophenone-based light absorbers, salicylic acid-based light absorbers, radiation-sensitive radical polymerization initiators, and photosensitive acid generators; Novolac resins such as phenol novolac and naphthol novolac; Black pigments (e.g. carbon black) such as CI Pigment Black 7, CI Pigment Black 31, CI Pigment Black 32, CI Pigment Black 35; Non-black pigments such as CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Yellow 139, CI Pigment Red 242, CI Pigment Red 245, CI Pigment Red 254; Examples of dyes include CI Bat Blue 4, CI Acid Blue 40, CI Direct Green 28, CI Direct Green 59, CI Acid Yellow 11, CI Direct Yellow 12, CI Reactive Yellow 2, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, and CI Direct Red 83.

[0094] When the resin composition of the present disclosure contains a light absorbent, the content of the light absorbent may be 0.1 to 1.0 part by mass, or 0.2 to 0.8 parts by mass, relative to 100 parts by mass of the polyimide precursor.

[0095] (Coupling Agent) The resin composition of the present disclosure may further contain a coupling agent. The coupling agent reacts with the polyimide precursor to crosslink or the coupling agent itself polymerizes during heat treatment. This tends to further improve the adhesion between the obtained cured film and the support.

[0096] Specific examples of the coupling agent are not particularly limited. Examples of the coupling agent include 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthala. Examples of the suitable adhesives include silane coupling agents such as amido acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamido)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, and N-phenylaminopropyltrimethoxysilane; and aluminum-based adhesion promoters such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0097] The coupling agents may be used alone or in combination of two or more.

[0098] When the resin composition of the present disclosure contains a coupling agent, the content of the coupling agent is preferably 0.1 parts by mass to 20 parts by mass, more preferably 0.3 parts by mass to 10 parts by mass, and even more preferably 1 part by mass to 10 parts by mass, relative to 100 parts by mass of the polyimide precursor.

[0099] (Surfactants and leveling agents) The resin composition of the present disclosure may contain at least one of a surfactant and a leveling agent. When the resin composition contains at least one of a surfactant and a leveling agent, the coating property (for example, suppression of striation (unevenness in film thickness)) can be improved.

[0100] Examples of the surfactant or leveling agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenol ether.

[0101] The surfactant and leveling agent may be used alone or in combination of two or more kinds.

[0102] When the resin composition of the present disclosure contains at least one of a surfactant and a leveling agent, the total content of the surfactant and the leveling agent is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.05 to 3 parts by mass, per 100 parts by mass of the polyimide precursor.

[0103] (Polymerization inhibitor) The resin composition of the present disclosure may contain a polymerization inhibitor in order to ensure good storage stability. Examples of the polymerization inhibitor include a radical polymerization inhibitor and a radical polymerization suppressor.

[0104] Specific examples of the polymerization inhibitor include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, N-phenyl-2-naphthylamine, cupferron, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosamines, etc. The polymerization inhibitor may be used alone or in combination of two or more kinds.

[0105] When the resin composition of the present disclosure contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 30 parts by mass, more preferably 0.01 to 10 parts by mass, and even more preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the polyimide precursor, from the viewpoints of the storage stability of the resin composition and the heat resistance of the obtained cured film.

[0106] The resin composition of the present disclosure contains a polyimide precursor, and may further contain, as optional components, a solvent, a polymerizable monomer, a thermal polymerization initiator, a light absorber, a coupling agent, a surfactant, a leveling agent, a polymerization inhibitor, and the like, and may also contain other components and unavoidable impurities within a range that does not impair the effects of the present disclosure. For example, 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, or 100% by mass of the resin composition of the present disclosure is Polyimide precursor, A polyimide precursor and a solvent, A polyimide precursor, a solvent, and at least one of a polymerizable monomer and a thermal polymerization initiator; a polyimide precursor, a solvent, and at least one optional component selected from the group consisting of a polymerizable monomer, a thermal polymerization initiator, a light absorber, a coupling agent, a surfactant, a leveling agent, and a polymerization inhibitor; Polyimide precursor, solvent, polymerizable monomer, thermal polymerization initiator and light absorber or a polyimide precursor, a solvent, a polymerizable monomer, a thermal polymerization initiator, a light absorber, and at least one optional component selected from the group consisting of a coupling agent, a surfactant, a leveling agent, and a polymerization inhibitor; It may consist of.

[0107] <Cured film> The cured film of the present disclosure is obtained by curing the resin composition of the present disclosure. The cured film of the present disclosure is prepared on a support using the resin composition of the present disclosure, and is used in a method for obtaining a laminate by preparing a laminate on the cured film and then separating the laminate from the support.

[0108] Next, the method for producing the cured film will be described. The above-mentioned method for producing the cured film includes, for example, (α) a method including a step of applying and drying a resin composition on a support to form a resin film, and a step of heat-treating the resin film, and (β) a method including a step of forming a film with a constant thickness using the resin composition on a film that has been subjected to a release treatment, transferring the resin film to a support by a lamination method, and a step of heat-treating the resin film formed on the support after transfer. From the viewpoint of flatness, the method (α) is preferred. This method makes it easy to obtain a flat cured film, and is highly reliable when a laminate is formed on the cured film.

[0109] Examples of the method for applying the resin composition include a spin coating method, an inkjet method, and a slit coating method.

[0110] The material of the support is preferably a material that maintains the laminate in a flat state and is not damaged during the process of preparing the laminate or during transport, and is preferably a material that has sufficient rigidity from the viewpoint of suppressing warping of the laminate during the process of preparing the laminate. Examples of the support include an acrylic plate, a glass substrate, a semiconductor substrate such as a silicon wafer, a metal oxide insulating substrate such as a TiO2 substrate or a SiO2 substrate, a silicon nitride substrate, a copper substrate, and a copper alloy substrate.

[0111] In the case where the cured film is irradiated with active energy rays such as laser light from the support side to alter the properties of the cured film and separate the laminate from the support, the support is preferably one that can transmit active energy rays. For example, an acrylic plate or a glass substrate is preferable, and a glass substrate is preferable from the viewpoint of heat resistance.

[0112] From the viewpoint of preventing peeling of the cured film and the support in the process of producing the laminate and from the viewpoint of preventing warping during sealing, which is a subsequent process, the thermal expansion coefficient of the support at 25° C. to 300° C. is preferably 3 ppm / K to 15 ppm / K, and more preferably 5 ppm / K to 15 ppm / K.

[0113] The shape, size, etc. of the support are not limited and may be appropriately selected depending on the shape, size, etc. of the laminate to be produced, and may be in the form of a wafer, a panel (for example, a square), etc.

[0114] The thickness of the support is preferably from 100 μm to 10,000 μm, and more preferably from 100 μm to 2,000 μm, from the viewpoint of suppressing warping of the laminate in the process of producing the laminate and from the viewpoint of productivity of the laminate. From the viewpoint of irradiating the cured film with laser light from the support side to alter the properties of the cured film and suitably separating the laminate from the support, the support preferably has a transmittance of light with a wavelength of 355 nm of 90% or more.

[0115] In the spin coating method, the resin composition may be spin-coated under conditions of, for example, a rotation speed of 300 rpm (revolutions per minute) to 3,500 rpm, preferably 500 rpm to 1,500 rpm, an acceleration rate of 500 rpm / sec to 15,000 rpm / sec, and a rotation time of 30 seconds to 300 seconds.

[0116] A drying step may be included after the resin composition is applied to a support, film, or the like. Drying may be performed using a hot plate, an oven, or the like. The drying temperature is preferably 75° C. to 130° C., and more preferably 90° C. to 120° C. from the viewpoint of improving the flatness of the cured film. The drying time is preferably 30 seconds to 5 minutes. The drying may be carried out two or more times, whereby a resin film in which the above-mentioned resin composition is formed into a film shape can be obtained.

[0117] In addition, in the slit coating method, the resin composition may be slit coated under conditions such as a chemical discharge speed of 10 μL / sec to 400 μL / sec, a chemical discharge part height of 0.1 μm to 1.0 μm, a stage speed (or a chemical discharge part speed) of 1.0 mm / sec to 50.0 mm / sec, a stage acceleration of 10 mm / sec to 1000 mm / sec, an ultimate vacuum during reduced pressure drying of 10 Pa to 100 Pa, a reduced pressure drying time of 30 seconds to 600 seconds, a drying temperature of 60° C. to 150° C., and a drying time of 30 to 300 seconds.

[0118] The formed resin film may be subjected to a heat treatment. The heating temperature is preferably 100° C. to 450° C., more preferably 150° C. to 400° C., and more preferably 250° C. to 380° C. By keeping the heating temperature within the above range, damage to the support is suppressed, and energy saving in the process is realized, while a cured film can be suitably produced.

[0119] The heating time is preferably 5 hours or less, and more preferably 30 minutes to 3 hours. By keeping the heating time within the above range, the crosslinking reaction or the dehydration ring-closing reaction can proceed sufficiently. The heat treatment may be performed in air or in an inert atmosphere such as nitrogen, but is preferably performed in a nitrogen atmosphere from the viewpoint of preventing oxidation of the resin film.

[0120] Examples of equipment used for the heat treatment include a quartz tube furnace, a hot plate, a rapid thermal annealer, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, and a microwave curing furnace.

[0121] The average thickness of the cured film formed on the support is preferably 0.1 μm or more, more preferably 0.5 μm to 10 μm, and even more preferably 0.5 μm to 5 μm.

[0122] <Method of manufacturing laminate> Hereinafter, a method for producing a laminate of the present disclosure using the resin composition of the present disclosure will be described. The method for producing a laminate of the present disclosure includes a step of preparing the resin composition of the present disclosure, a step of forming a cured film of the resin composition on a support, a step of producing a laminate on the cured film, and a step of separating the laminate from the support.

[0123] The method for producing the laminate of the present disclosure includes a step of preparing the resin composition of the present disclosure. For example, the resin composition of the present disclosure may be prepared by synthesizing a polyimide precursor as described above, and mixing the synthesized polyimide precursor with optional components such as a solvent, a polymerizable monomer, a thermal polymerization initiator, a light absorber, a coupling agent, a surfactant, a leveling agent, and a polymerization inhibitor as necessary.

[0124] The method for producing a laminate according to the present disclosure includes a step of forming a cured film of a resin composition on a support. The step of forming the cured film is the same as the above-mentioned method for forming a cured film.

[0125] The method for producing a laminate of the present disclosure includes a step of preparing a laminate on a cured film. Examples of the laminate include semiconductor devices, more specifically, semiconductor devices including wiring layers, insulating layers, and semiconductor chips. The semiconductor device may also include a semiconductor wafer, a semiconductor chip, a glass substrate, a resin substrate, a metal substrate, a metal foil, or other metal films, a polishing pad, a resin coating film such as an insulating layer, a wiring layer, a sealant, and the like, as necessary. The semiconductor wafer and the semiconductor chip may have at least one selected from bumps, wiring, through-holes, through-hole vias, insulating films, and various elements formed thereon, or various elements may be formed or mounted thereon. Examples of the resin coating include layers containing an organic component as a main component; specifically, a photosensitive resin layer formed from a photosensitive resin, an insulating resin layer formed from an insulating material, and a photosensitive insulating resin layer formed from a photosensitive insulating resin material.

[0126] Hereinafter, a method for manufacturing a semiconductor device including a wiring layer, an insulating layer, and a semiconductor chip as a laminate will be described. At this time, the process for manufacturing the laminate preferably includes a process for forming a wiring layer on a cured film, a process for forming an insulating layer that at least insulates between the wiring layers, and a process for arranging a semiconductor chip on the insulating layer and connecting the semiconductor chip to the wiring layer.

[0127] First, a metal film may be formed on the cured film. Methods for forming the metal film include sputtering. In addition, components contained in the metal film include metals such as copper, gold, silver, platinum, lead, tin, nickel, cobalt, indium, rhodium, chromium, tungsten, and ruthenium, alloys consisting of two or more of these, and nitrides thereof. The metal, alloy, and nitride that can be contained in the metal film may each be one type or two or more types.

[0128] The average thickness of the metal film is not particularly limited, and is preferably, for example, 10 nm to 1000 nm.

[0129] Next, a patterned resist layer may be formed on the metal film, and then a wiring layer may be formed on the metal film. A liquid containing a resist may be applied onto the metal film. A film-like resist material may also be used, and a resist layer may be formed on the metal film by lamination or the like. The resist may be either positive or negative, and may be appropriately selected depending on the process.

[0130] The method for applying the liquid material containing the resist is not particularly limited, and examples of the method include coating methods such as spin coating, dipping, roller blade, doctor blade, spray, slit nozzle, inkjet, etc. After the liquid material containing the resist is applied, heating or the like may be performed.

[0131] After the resist layer is formed, a resist patterning step is performed. In the resist patterning step, the resist layer is exposed to light in a desired pattern and then developed by immersing the resist layer in a developer. These treatments preferably include a step of heating the resist layer before or after the resist layer is exposed to light.

[0132] After the patterned resist layer is formed, a wiring layer is formed on the metal film. In the wiring layer forming step, it is preferable to form the wiring layer by a method such as sputtering so as to connect with the metal film. Materials used to form the wiring layer include metals such as gold, silver, copper, and aluminum, and conductive resins. After the wiring layer is formed, the patterned resist layer is removed.

[0133] Also, a plating step may be performed after the wiring layer forming step. In the plating step, a plating layer is formed on the upper part of the wiring layer by electroless plating or electrolytic plating. In the plating step, a plating layer is formed on the upper part of the wiring layer by immersing an object in a predetermined plating tank. Examples of materials used to form the plating layer include chemical solutions used for solder plating, copper plating, gold plating, nickel plating, silver-tin plating, etc. Note that if a wiring layer of sufficient thickness can be formed by a technique such as sputtering, the plating step may be omitted.

[0134] Next, an insulating layer that at least insulates between the wiring layers is formed. The material used to form the insulating layer is not particularly limited as long as it is an insulating material having insulating properties, and examples thereof include resin materials such as polyimide, polybenzoxazole, benzocyclobutene, phenolic resin, and acrylic resin. The insulating material may be used alone or in combination of two or more. In the insulating layer forming step, for example, a liquid liquid containing an insulating material may be applied between the wiring layers and on the wiring layer. The method for applying the liquid liquid containing an insulating material is not particularly limited, and examples thereof include coating methods such as spin coating, dipping, roller blade method, doctor blade method, spray method, slit nozzle method, and inkjet method. As an example, the liquid liquid containing an insulating material may be applied between the wiring layers and on the wiring layer by discharging the liquid liquid containing an insulating material from the slit nozzle while moving the stage and the slit nozzle relatively while holding the support on the stage. In addition, after applying the liquid liquid containing an insulating material, it may be dried by heating or the like.

[0135] Next, vias are formed in the insulating layer to connect between layers. Methods for forming vias include a method of forming vias by patterning using a photosensitive resin, a method of processing a non-photosensitive resin, and the like. When using a photosensitive resin, the photosensitive resin layer may be exposed to light in an arbitrary pattern, and then developed by immersing in a developer. In these treatments, it is preferable to include a step of heating the photosensitive resin layer before or after exposing the photosensitive resin layer to light.

[0136] In the step of heating the photosensitive resin layer, from the viewpoint of reliability, the heating may be performed in the range of 100° C. to 400° C., preferably in the range of 150° C. to 400° C., and more preferably in the range of 180° C. to 380° C. In addition, in the present disclosure, the heat resistance temperature of the cured film is high, and even if the cured film is heated at, for example, 280° C. to 350° C., deterioration of the cured film is suppressed, and the reliability of the manufactured semiconductor device can be improved.

[0137] When the photosensitive resin layer is patterned, examples of the active energy rays to be irradiated include broadband light (wavelength 350 nm to 450 nm), ultraviolet rays such as i-rays, visible light, and radiation, among which i-rays are preferable. As the exposure device, a parallel exposure machine, a projection exposure machine, a stepper, a scanner exposure machine, a proximity exposure machine, etc. may be used.

[0138] When a non-photosensitive resin is used, the method for forming vias is not particularly limited. A resist layer may be formed on a non-photosensitive resin layer and processed, or laser vias, dry etching, or the like may be used.

[0139] Furthermore, if an insulating layer of sufficient thickness can be formed by deposition, CVD, sputtering, or the like, the insulating layer may be used to form the vias.

[0140] Next, a semiconductor chip is disposed on the insulating layer, and the semiconductor chip is connected to the wiring layer. At this time, the semiconductor chip and the wiring layer may be connected via connection terminals.

[0141] A connection terminal for connecting the semiconductor chip and the wiring layer may be formed in the same manner as the method for forming the wiring layer described above. Examples of metals used for the connection terminal include metals such as copper, gold, silver, platinum, lead, tin, nickel, cobalt, indium, rhodium, chromium, tungsten, and ruthenium, alloys of two or more of these metals, and nitrides of these metals. The semiconductor chip and the wiring layer may be connected by flip-chip mounting, or a semiconductor chip having bumps may be connected to the wiring layer via the connection terminal using a flip-chip bonder. In addition, an underfill material may be supplied between the semiconductor chip and the connection terminal in order to improve the reliability between them.

[0142] The step of preparing the laminate may further include a step of sealing the semiconductor chip connected to the wiring layer. The method of sealing the semiconductor chip using the sealing material is not particularly limited, and may be, for example, a compression molding method or a transfer molding method. In addition, the sealing material may be heat-treated after sealing the semiconductor chip with the sealing material.

[0143] From the viewpoint of suppressing warpage of the semiconductor device after encapsulation, it is preferable that the thermal expansion coefficient of the support is 3 ppm / K to 15 ppm / K at 25° C. to 300° C., and the thermal expansion coefficient of the encapsulant is 4 ppm / K to 8 ppm / K (CTE1: CTE less than the glass transition temperature (Tg)) at 25° C. to 300° C. Adjusting the thermal expansion coefficients of the support and encapsulant suppresses warpage of the semiconductor device after encapsulation, thereby making it possible to suppress damage to the semiconductor chip, suppress a decrease in yield, and the like.

[0144] The method for producing the laminate of the present disclosure includes a step of separating the laminate from the support. For example, in this step, the laminate may be separated from the support after the cured film is altered by heating, or the laminate may be separated from the support after the cured film is altered by irradiating the cured film with active energy rays. In the latter case, the cured film may be altered by irradiating the cured film with active energy rays such as laser light from the support side.

[0145] Irradiation of the cured film with active energy rays such as laser light alters the properties of the cured film, reducing the adhesive strength of the cured film, which allows the laminate to be easily separated from the support after irradiation with active energy rays.

[0146] The active energy rays are preferably light having a wavelength in the ultraviolet region, for example, ultraviolet rays having a wavelength of 10 nm to 400 nm are preferable, and ultraviolet rays having a wavelength of 300 nm to 400 nm are more preferable. Examples of the light source of the active energy rays include a low pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, an LED lamp, and a laser.

[0147] Examples of lasers include solid lasers such as YAG lasers, ruby ​​lasers, glass lasers, YVO4 lasers, LD lasers, and fiber lasers, liquid lasers such as dye lasers, gas lasers such as CO2 lasers, excimer lasers, Ar lasers, and He-Ne lasers, semiconductor lasers, and free electron lasers.

[0148] The type of active energy ray, the type of light source, the type of laser, etc. may be appropriately selected depending on the composition of the cured film.

[0149] It is preferable to separate the laminate from the support after the cured film is altered by irradiation with active energy rays or the like. At this time, the laminate is placed vertically below the object and the support is placed vertically above it, and the support is then lifted vertically upward, whereby the cured film is physically destroyed and the laminate can be separated from the support. The support may be lifted using a device that adsorbs and lifts the support, or the support may be lifted by an operator. At this time, it is preferable that the laminate is adsorbed to, for example, a stage or the like.

[0150] The method for producing a laminate according to the present disclosure preferably further includes a step of removing the residue of the cured film remaining on the laminate after separation from the support. In this step, the residue of the cured film remaining on the separated support may be removed.

[0151] Methods for removing the residue of the cured film include polishing, washing with a solvent, etc., and from the viewpoint of convenience, washing with a solvent, etc. is preferred.

[0152] The solvent used to remove the residue of the cured film is not particularly limited as long as it is a solvent that can remove the residue of the cured film without dissolving the materials contained in each component that the laminate may have, such as the wiring layer, the sealing resin, etc. The solvent may be supplied to the residue of the cured film by, for example, scanning a supply device such as a dispenser over the laminate, or by immersing the laminate in a tank that stores the solvent.

[0153] Examples of solvents for removing the residue of the cured film include water; hydrocarbon solvents such as pentane, hexane, decane, limonene, mesitylene, dipentene, pinene, bicyclohexyl, cyclododecene, 1-t-butyl-3,5-dimethylbenzene, butylcyclohexane, cyclooctane, cycloheptane, cyclohexane, and methylcyclohexane; and alcohols such as anisole, propylene glycol monomethyl ether, dipropylene glycol methyl ether, diethylene glycol monoethyl ether, and diglyme. or ether solvents; ester solvents or lactone solvents such as ethylene carbonate, ethyl acetate, N-butyl acetate, ethyl lactate, ethyl 3-ethoxypropionate, methoxypropyl acetate, 2-(2-ethoxyethoxy)ethyl acetate, propylene carbonate, γ-butyrolactone, etc.; ketone solvents such as cyclopentanone, cyclohexanone, methyl isobutyl ketone, 2-heptanone, etc.; amide or lactam solvents such as N-methyl-2-pyrrolidinone, 3-methoxy-N,N-dimethylpropionamide, etc. The above-mentioned solvents may be used alone or in combination of two or more.

[0154] The solvent for removing the residue of the cured film may contain a base. Specific examples of the base include: Inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate; Examples of the organic base include amines such as ethylamine, n-propylamine, diethylamine, ethanolamine, diethanolamine, triethanolamine, and triethylamine; ammonia; and ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide.

[0155] Residues of the cured film may be removed using a general resist stripping solution or the like.

[0156] The method for producing a laminate according to the present disclosure may include, after the step of removing the residue of the cured film, a step of etching the laminate, a step of dicing the laminate, etc. When the laminate is a semiconductor device including a semiconductor chip, dicing is performed within an area including the semiconductor chip to obtain an individual semiconductor device.

[0157] A method for manufacturing a semiconductor device according to an embodiment of the present disclosure will be described below with reference to Figures 1 to 3. In the description of the drawings, the same elements are denoted by the same reference numerals.

[0158] As shown in (a) of Fig. 1, a support 1 is prepared. Next, a resin composition containing a polyimide precursor is applied onto the support 1 and dried to form a resin film. The formed resin film is heat-treated to form a cured film 2 on the support 1 as shown in (b) of Fig. 1. 1(c), a metal film 3 is formed on the cured film 2. The metal film 3 may be formed by sputtering or the like.

[0159] Next, a liquid containing a resist is applied onto the metal film 3 to form a resist layer. After the resist layer is formed, it is exposed to light in a desired pattern, and then developed by immersing it in a developer. The resist layer may be heated before or after the resist layer is exposed to light. As a result, a patterned resist layer 4 is formed on the metal film 3, as shown in FIG. 1(d).

[0160] After the patterned resist layer 4 is formed, a wiring layer 5 such as copper wiring is formed between the patterns. The wiring layer 5 may be formed by sputtering or the like. In order to form a wiring layer 5 with a sufficient thickness, a plating step may be performed after the wiring layer formation step. As a result, the wiring layer 5 is formed on the metal film 3 as shown in FIG. 1(e).

[0161] Next, a liquid containing an insulating material is applied between the wiring layers 5 and on the wiring layer 5 by ejecting the liquid containing an insulating material from a slit nozzle, and the applied liquid is dried by heating. As a result, an insulating layer 6 is formed between the wiring layers 5 and on the wiring layer 5, as shown in FIG. 2(a).

[0162] As shown in (b) of Fig. 2, a via 7 is formed in the insulating layer 6. For example, the via 7 may be formed by processing the insulating layer 6 by laser via, dry etching, or the like. Thereafter, as shown in (c) of Fig. 2, a connection terminal 8 is formed in the via 7 by sputtering or the like.

[0163] Next, using a flip chip bonder, the semiconductor chip 10 having the bumps 11 is connected to the wiring layer 5 via the connection terminals 8. This results in a semiconductor device in which the semiconductor chip 10 and the wiring layer 5 are connected via the connection terminals 8, as shown in Fig. 2(d).

[0164] 3(a), the semiconductor chip 10 connected to the wiring layer 5 may be encapsulated using an encapsulant 20. After the semiconductor chip 10 is encapsulated, the encapsulant 20 may be subjected to a heat treatment.

[0165] Next, as shown in (b) of Fig. 3, active energy rays X may be irradiated onto the cured film 2 from the support 1 side to alter the properties of the cured film 2. After the cured film 2 is altered by irradiation with active energy rays X, the semiconductor device is separated from the support 1. This results in a semiconductor device 100 in which a residue 30 of the cured film 2 is attached to the metal film 3, as shown in (c) of Fig. 3.

[0166] Residues 30 remaining on the semiconductor device are removed by cleaning with a solvent. As a result, the semiconductor device 100 from which the residues 30 have been removed is obtained, as shown in Fig. 3(d). Furthermore, the metal film 3 is removed by etching or the like, thereby obtaining the semiconductor device 100 as shown in Fig. 3(e). EXAMPLES

[0167] The present disclosure will be described in more detail below with reference to examples and comparative examples. Note that the present disclosure is not limited to the following examples.

[0168] <Synthesis Example 1: Synthesis of pyromellitic acid-hydroxyethyl methacrylate diester> In a 0.5 liter plastic bottle, 43.5 g of pyromellitic dianhydride (hereinafter also referred to as PMDA) dried for 24 hours in a dryer at 160°C, 54.9 g of 2-hydroxyethyl methacrylate, and 0.220 g of hydroquinone were dissolved in 394 g of N-methyl-2-pyrrolidone, and a catalytic amount of 1,8-diazabicycloundecene was added to prepare a mixture. The mixture was stirred at room temperature (25°C) for 24 hours and esterified to obtain a pyromellitic acid-hydroxyethyl methacrylate diester solution. This solution is called the PMDA (HEMA) solution.

[0169] <Synthesis Example 2: Synthesis of 4,4'-oxydiphthalic acid diester> In a 0.5 liter plastic bottle, 15.5 g of 4,4'-oxydiphthalic anhydride (hereinafter also referred to as ODPA) that had been dried for 24 hours in a 160°C dryer, 14.1 g of 2-hydroxyethyl methacrylate, and 0.1 g of hydroquinone were dissolved in 118 g of N-methyl-2-pyrrolidone, and a catalytic amount of 1,8-diazabicycloundecene was added to prepare a mixed solution. The mixed solution was stirred at room temperature (25°C) for 48 hours and esterified to obtain a 4,4'-oxydiphthalic acid-hydroxyethyl methacrylate diester solution. This solution is called the ODPA (HEMA) solution.

[0170] <Synthesis Example 3: Synthesis of polyimide precursor (synthesis of A1)> In a 0.5-liter flask equipped with a stirrer and a thermometer, 493.2 g of the PMDA (HEMA) solution obtained in Synthesis Example 1 and 148.1 g of the ODPA (HEMA) solution obtained in Synthesis Example 2 were placed, and then 124.9 g of thionyl chloride was added dropwise using a dropping funnel while cooling with ice so that the temperature of the reaction solution was kept below 10°C. At this time, the molar ratio of PMDA (HEMA) to ODPA (HEMA) was 4:1. After the dropping of thionyl chloride was completed, the reaction was carried out under ice cooling for 2 hours to obtain a solution of acid chloride of PMDA (HEMA) and ODPA (HEMA). Next, using a dropping funnel, a solution in which 80 g of 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB), 83 g of pyridine, and 0.2 g of hydroquinone were dissolved in 227 g of N-methyl-2-pyrrolidone was dropped while being careful not to allow the temperature of the reaction solution to exceed 10°C under ice cooling. The reaction solution was dropped into distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyimide precursor, which is a polyamic acid ester. This is designated as A1. The weight average molecular weight of A1, calculated using gel permeation chromatography (GPC) in terms of standard polystyrene, was 40,000. 1 g of A1 was dissolved in 1.5 g of N-methyl-2-pyrrolidone, spin-coated on a glass substrate, and heated on a hot plate at 100°C for 180 seconds to volatilize the N-methyl-2-pyrrolidone, forming a coating film with a thickness of 20 μm. At this time, the i-line transmittance of the resulting coating film was 30%.

[0171] <Synthesis Example 4: Synthesis of polyimide precursor (synthesis of A2)> A polyimide precursor was obtained in the same manner as in the synthesis examples 1 to 3 described above, except that N-methyl-2-pyrrolidone was replaced with 3-methoxy-N,N-dimethylpropionamide. This is designated as A2. The weight average molecular weight of A2 was determined by gel permeation chromatography (GPC) using standard polystyrene and was 42,000. The esterification rate was 100 mol%.

[0172] <Synthesis Example 5: Synthesis of polyimide precursor (synthesis of A3)> A mixture was prepared by dropping a solution of 49.5g of 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB) dissolved in 100g of N-methyl-2-pyrrolidone into a solution of 30.20g of PMDA and 7.51g of ODPA, which had been dried in a 160°C dryer for 24 hours. The mixture was stirred at 30°C for 4 hours to obtain a reaction solution. This reaction solution was dropped into distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyimide precursor, which is a polyamic acid. This is called A3. The weight average molecular weight of A3, calculated using gel permeation chromatography (GPC) in terms of standard polystyrene, was 36,000.

[0173] <Synthesis Example 6: Synthesis of polyimide precursor (synthesis of A4)> A mixture was prepared by dissolving 7.07g of ODPA and 4.12g of DMAP in 30g of N-methyl-2-pyrrolidone (NMP). The mixture was stirred at 30°C for 4 hours, and then stirred overnight at room temperature to obtain a reaction solution containing polyamic acid. 9.45g of trifluoroacetic anhydride was added to the reaction solution, and the solution was stirred at 45°C for 2 to 3 hours. Next, 7.08g of 2-hydroxyethyl methacrylate (HEMA) was added to the stirred reaction solution, and the solution was stirred at 45°C for about 15 hours. This reaction solution was dropped into distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyimide precursor. This is referred to as A4. The weight average molecular weight of A4, calculated using standard polystyrene standards by gel permeation chromatography (GPC), was 20,000.

[0174] <Reference Example 1: Preparation of A5> As a polymer other than the polyimide precursor, a 4-hydroxystyrene polymer (weight average molecular weight=10,000, Maruzen Petrochemical Co., Ltd., product name "Marukalinker M") was prepared.

[0175] <Measurement of weight average molecular weight> The weight average molecular weights of A1 to A5 were measured as follows. Specifically, a solution in which 0.5 mg of A1 to A4 was dissolved in 1 mL of a solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1 / 1 (volume ratio)] and a solution in which 0.5 mg of A5 was dissolved in 1 mL of THF were used, and the measurement was performed under the following conditions. (Measurement conditions) Measurement equipment: Detector Hitachi Ltd. L4000UV Pump: Hitachi L6000 Shimadzu Corporation C-R4A Chromatopac Measurement conditions: Column Gelpack GL-S300MDT-5 x 2 Eluent: THF / DMF = 1 / 1 (volume ratio) for A1 to A4 A5 is THF LiBr(0.03mol / L), H3PO4(0.06mol / L) Flow rate: 1.0 mL / min, detector: UV 270 nm Standard polystyrene: A calibration curve was prepared using TSKgel standard polystyrene Types F-1, F-4, F-20, F-80, and A-2500 manufactured by Tosoh Corporation.

[0176] <Esterification rate> The esterification ratios of A1 and A4 (the ratio of ester groups reacted with HEMA to the total of ester groups reacted with HEMA and carboxy groups unreacted with HEMA for A1 and A4) were calculated by performing NMR measurements under the following conditions. The esterification ratios were 100 mol % for A1 and 80 mol % for A4 (the remaining 20 mol % being carboxy groups). (Measurement conditions) Measurement equipment: Bruker Biospin AV400M Magnetic field strength: 400MHz Reference material: Tetramethylsilane (TMS) Solvent: Dimethyl sulfoxide (DMSO)

[0177] <Examples 1 to 10 and Comparative Example 1> (Preparation of Resin Composition) Resin compositions of Examples 1 to 10 and Comparative Example 1 were prepared using the components and amounts shown in Table 1. The amounts shown in Table 1 are parts by mass of each component relative to 100 parts by mass of each polymer component. Also, blanks in Table 1 mean that the corresponding component was not included.

[0178] The components used in Examples 1 to 10 and Comparative Example 1 are as follows. (polymer) A1 to A5 above (solvent) B1: 3-Methoxy-N,N-dimethylpropionamide B2: N-methyl-2-pyrrolidone B3: Methyl lactate (Polymerizable monomer) C1: Triethylene glycol dimethacrylate (TEGDMA) C2: Ethoxylated pentaerythritol tetraacrylate C3: Hexakis(methoxymethyl)melamine (Thermal polymerization initiator) D1: Bis(1-phenyl-1-methylethyl) peroxide (Adhesive assistant) E1: 3-glycidoxypropyltrimethoxysilane E2: 3-Methacryloxypropyltrimethoxysilane E3: Triethoxysilylpropylethylcarbamate E4: 50% solution of 3-ureidopropyltriethoxysilane in methanol E5: A compound represented by the following formula (Y):

[0179] [ka]

[0180] <Removability evaluation> (Preparation of a sample for evaluating peelability) The resin compositions of Examples 1 to 10 and Comparative Example 1 were spin-coated onto a glass wafer (TEMPAX) as a support using an 8-inch spin coater coating device, and a drying step was carried out to form a resin film. The obtained resin film was heated at a prescribed temperature for 2 hours in a nitrogen atmosphere using a vertical diffusion furnace to obtain a cured film (thickness after curing: 2 μm to 5 μm). A 50 nm titanium layer and a 200 nm copper layer were deposited on the resulting cured film using a sputtering device. The film thickness was measured from the cross section using a SEM (scanning electron microscope). Next, the evaporated metal layer was subjected to electrolytic copper plating to form a copper layer of 20 μm, thereby producing a sample for evaluating peelability.

[0181] (Evaluation method and criteria) The above-mentioned peelability evaluation sample was irradiated with laser light from the glass wafer side over an area of ​​10 mm width and 100 mm length using a laser irradiation device 5331 (ESI) under conditions of a wavelength of 355 nm, a laser output of 0.4 W, a repetition frequency of 40 kHz, and a feed speed of 500 mm / s. After the laser beam was irradiated, a cutter knife was used to make a cut in the sample for evaluating peelability along the outer periphery of the area irradiated with the laser beam from the copper layer side, and the cutter knife was inserted between the cured film of the resin composition and the glass wafer in an area of ​​10 mm wide and 100 mm long to peel off the copper layer.

[0182] The peeled portion of the cured film was held with tweezers and pulled at a 90 degree angle to the glass wafer to evaluate whether the cured film and the metal layer on the cured film could be separated from the glass wafer. The evaluation criteria were as follows. The results are shown in Table 1. -Evaluation criteria- A: The cured film and the metal layer on the cured film were separated from the glass wafer without resistance. B The cured film and the metal layer on the cured film could be separated from the glass wafer, but resistance was encountered during separation. C The cured film and the metal layer on the cured film could not be separated from the glass wafer.

[0183] <Evaluation of Residue Removability> The resin compositions of Examples 1 to 10 and Comparative Example 1 were spin-coated onto a silicon wafer, which was a support, using an 8-inch spin coater coating device, and a drying step was carried out to form a resin film. The obtained resin film was heated at a prescribed temperature for 2 hours in a nitrogen atmosphere using a vertical diffusion furnace to obtain a cured film (thickness after curing: 2 μm to 5 μm). The obtained cured film on the silicon wafer was immersed for a predetermined time in a chemical solution (Dynastrip7700, Dynaloy Corporation) heated to a predetermined temperature. After cooling, the silicon wafer was washed with acetone and dried. After drying, the thickness of the cured film adhering to the silicon wafer was measured, and the rate of change in film thickness was calculated based on the following formula. Film thickness change rate (%) = 100 × [(film thickness before immersion in chemical solution) - (film thickness of patterned cured film after drying)] / film thickness before immersion in chemical solution

[0184] Using the film thickness change rate calculated as described above, the residue removability was evaluated according to the following criteria. The results are shown in Table 1. -Evaluation criteria- A The film thickness change rate is 100% to 90%. B: The rate of change in film thickness is more than 90% and is 50%. C The rate of change in film thickness is less than 50%.

[0185] <Evaluation of adhesion to metal layer> Each of the resin compositions of Examples 1 to 10 and Comparative Example 1 was spin-coated onto a silicon wafer using an 8-inch spin coater, and a drying step was carried out to form a resin film. The obtained resin film was heated at a prescribed temperature for 2 hours in a nitrogen atmosphere using a vertical diffusion furnace to obtain a cured film (thickness after curing: 2 μm to 5 μm). A 50 nm titanium layer and a 200 nm copper layer were deposited on the obtained cured film using a sputtering device. The film was then heated in a vertical diffusion furnace under a nitrogen atmosphere for 2 hours at the temperature shown in Table 1. The object was visually observed to see if there was any peeling between the cured film and the metal layer. The evaluation criteria were as follows. No peeling here means that the laminate, particularly the semiconductor device, can be produced without reducing the yield. The results are shown in Table 1. -Evaluation criteria- A No bubbles or peeling was observed between the cured film and the metal layer. B. Air bubbles or other peeling was observed between the cured film and the metal layer.

[0186] <Applicability evaluation when manufacturing laminates> The resin compositions of Examples 1 to 10 and Comparative Example 1 were spin-coated onto a 12-inch glass wafer (thickness: 800 μm) as a support using a 12-inch spin coater, and a drying step was carried out to form a resin film. The obtained resin film was heated at a prescribed temperature for 2 hours in a nitrogen atmosphere using an inert gas oven to obtain a substrate with a cured film (film thickness after curing: 2 μm to 5 μm). A 50 nm titanium layer and a 200 nm copper layer were deposited on the resulting substrate with the cured film using a sputtering device to obtain a substrate with a metal thin film layer. The film thickness was measured from the cross section using a SEM (scanning electron microscope).

[0187] Dry film resist RY5110 (Showa Denko Materials Co., Ltd.) was laminated onto the substrate with the metal thin film layer using a vacuum laminator under conditions of upper pressure bonding part temperature 110°C, lower pressure bonding part temperature 40°C, pressure 0.5 MPa, and pressure bonding time 90 seconds to obtain a substrate with a dry film resist and a metal thin film layer. Dry film resist - Metal thin film layer substrate, using a stepper type exposure machine, exposure dose 210mJ / cm 2 The circuit diagram was patterned on the dry film resist by exposure under the above conditions. The substrate on which the above-mentioned patterning was performed was developed using a developing machine within 1 to 3 hours after exposure to obtain a patterned substrate. The development was performed using a 1% aqueous solution of sodium bicarbonate as the developer under the conditions of a developer temperature of 30°C and a development time of 30 seconds.

[0188] The obtained patterned substrate was subjected to electrolytic copper plating to form copper wiring between the patterns, thereby obtaining a copper wiring-patterned substrate. The electrolytic copper plating process used a solution containing a copper sulfate aqueous solution and a specified amount of additive NSV series from Okuno Chemical Industries Co., Ltd. as the plating solution. The electrolytic copper plating was performed by adjusting the thickness of the copper wiring to 4.0 μm ± 1.0 μm in the wafer.

[0189] The dry film resist was removed from the obtained copper wiring-patterned substrate. The dry film resist was removed by immersing the copper wiring-patterned substrate in a liquid tank heated to 40°C and containing a resist stripping solution containing a predetermined amount of R100S (Mitsubishi Gas Chemical Co., Ltd.), R101 (Mitsubishi Gas Chemical Co., Ltd.), and pure water. This resulted in a substrate with copper wiring and a thin metal film.

[0190] Next, an insulating layer was formed on the obtained substrate with copper wiring and metal thin film. A negative photosensitive insulating photosensitive material was spin-coated on the substrate with copper wiring and metal thin film using a 12-inch spin coater, and then a drying process was carried out to obtain a substrate with a photosensitive insulating resin film having a thickness of 5 μm to 6 μm. This was then exposed to light at a dose of 250 mJ / cm using a stepper-type exposure machine. 2 A circuit pattern was formed on the photosensitive insulating resin film by exposure under the conditions of 1. Then, development was performed using a solvent developer, and the photosensitive insulating resin film was cured by heat treatment for 2 hours at 230°C or 280°C shown in Table 1 using an inert gas oven, thereby obtaining a substrate with an insulating layer and copper wiring.

[0191] A 50 nm titanium layer and a 200 nm copper layer were deposited on the obtained substrate with insulating layer-copper wiring using a sputtering device to obtain a substrate with a metal thin film layer 2. The film thickness was measured from a cross section using a SEM (scanning electron microscope).

[0192] Next, dry film resist RY5110 (Showa Denko Materials Co., Ltd.) was laminated onto the substrate 2 with the metal thin film layer using a vacuum laminator under conditions of upper pressure bonding part temperature 110°C, lower pressure bonding part temperature 40°C, pressure 0.5 MPa and pressure bonding time 90 seconds to obtain a substrate 2 with a dry film resist-metal thin film layer. For the dry film resist-metal thin film layer-attached substrate 2, a stepper-type exposure machine was used, and the exposure dose was 210 mJ / cm 2 The exposure was carried out under the above conditions to form a circuit pattern on the dry film resist. The substrate on which the above-mentioned patterning was performed was developed using a developer within 1 to 3 hours after exposure to obtain a patterned substrate 2. The development was performed using a 1% aqueous sodium bicarbonate developer solution as the developer under conditions of a developer temperature of 30° C. and a development time of 30 seconds.

[0193] The obtained patterned substrate 2 was subjected to electrolytic copper plating to form copper wiring between the patterns, thereby obtaining a copper wiring-patterned substrate 2. For the electrolytic copper plating, a solution containing a copper sulfate aqueous solution and a prescribed amount of additive NSV series from Okuno Pharmaceutical Co., Ltd. was used as the plating solution. In addition, the electrolytic copper plating was performed by adjusting the thickness of the copper wiring to 3.0 μm ± 1.0 μm.

[0194] The dry film resist was removed from the obtained copper wiring-patterned substrate 2. The dry film resist was removed by immersing the copper wiring-patterned substrate in a liquid tank heated to 40° C., which contained a resist stripping solution made by mixing a predetermined amount of R100S (Mitsubishi Gas Chemical Co., Inc.), R101 (Mitsubishi Gas Chemical Co., Inc.) and pure water. In this way, a substrate 2 with copper wiring and thin metal film was obtained.

[0195] Next, the metal thin film layer of the obtained copper wiring-metal thin film attached substrate 2 was etched to obtain a copper wiring-attached substrate 2. A prescribed amount of WLC-C2 (Mitsubishi Gas Chemical Co., Inc.) was used as an etching solution for the copper layer in the metal thin film layer of the copper wiring-metal thin film attached substrate 2, and a prescribed amount of WLC-T (Mitsubishi Gas Chemical Co., Inc.) was used as an etching solution for the titanium layer. By etching the metal thin film layer, the metal thin film between the copper wirings can be removed.

[0196] Subsequently, an insulating layer was formed on the obtained copper wiring-attached substrate 2. A negative photosensitive insulating photosensitive material was spin-coated on the copper wiring-attached substrate 2 using a 12-inch spin coater, and then a drying process was carried out to obtain a substrate 2 with a photosensitive insulating resin film having a thickness of 5 μm to 6 μm. This was then exposed to light at a dose of 250 mJ / cm using a stepper-type exposure machine. 2 A circuit pattern was formed on the photosensitive insulating resin film under the conditions of 1. Then, development was performed using a solvent developer, and the photosensitive insulating resin film was cured by heat treatment for 2 hours at 230° C. or 280° C. shown in Table 1 using an inert gas oven, thereby obtaining a substrate 2 with an insulating layer and copper wiring.

[0197] A 50 nm titanium layer and a 200 nm copper layer were deposited using a sputtering device on the obtained substrate 2 with insulating layer-copper wiring to obtain a substrate 3 with a metal thin film layer. The film thickness was measured from a cross section using a SEM (scanning electron microscope).

[0198] Next, dry film resist RY5110 (Showa Denko Materials Co., Ltd.) was laminated onto the substrate 3 with the metal thin film layer using a vacuum laminator under conditions of upper pressure bonding part temperature 110°C, lower pressure bonding part temperature 40°C, pressure 0.5 MPa and pressure bonding time 90 seconds to obtain a substrate 3 with a dry film resist-metal thin film layer. A stepper-type exposure machine was used to expose the dry film resist-metal thin film layer-coated substrate 3 to an exposure dose of 210 mJ / cm 2 The exposure was carried out under the above conditions to form a circuit pattern on the dry film resist. The substrate on which the above patterning was performed was developed using a developer within 1 to 3 hours after exposure to obtain a patterned substrate 3. The development was performed using a 1% aqueous sodium bicarbonate developer solution as the developer under the conditions of a developer temperature of 30° C. and a development time of 30 seconds.

[0199] The obtained patterned substrate 3 was subjected to electrolytic copper plating to form copper wiring between the patterns, thereby obtaining a copper wiring-patterned substrate 3. For the electrolytic copper plating, a solution containing a copper sulfate aqueous solution and a prescribed amount of an additive NSV series from Okuno Pharmaceutical Co., Ltd. was used as the plating solution. In addition, the electrolytic copper plating was performed by adjusting the thickness of the copper wiring to 2.0 μm ± 1.0 μm.

[0200] The dry film resist was removed from the obtained copper wiring-patterned substrate 3. The dry film resist was removed by immersing the copper wiring-patterned substrate 3 in a liquid tank heated to 40° C., which contained a resist stripping solution containing a predetermined amount of R100S (Mitsubishi Gas Chemical Co., Inc.), R101 (Mitsubishi Gas Chemical Co., Inc.) and pure water. As a result, a substrate 3 with copper wiring and thin metal film was obtained.

[0201] Next, the obtained copper wiring-metal thin film-attached substrate 3 was subjected to etching of the metal thin film layer to obtain a substrate with a rewiring layer. A prescribed amount of WLC-C2 (Mitsubishi Gas Chemical Co., Ltd.) was used as an etching solution for the copper layer in the metal thin film layer of the copper wiring-metal thin film-attached substrate 3, and a prescribed amount of WLC-T (Mitsubishi Gas Chemical Co., Ltd.) was used as an etching solution for the titanium layer. By etching the metal thin film layer, the metal thin film between the copper wirings can be removed.

[0202] A chip with wiring was bonded to the substrate with the rewiring layer described above. The Si side of the chip with wiring CC80-0101JY(SiN)_Model1 (Waltz Corporation; copper bump height 15μm, tin silver solder thickness 8μm) was thinned to a thickness of 200μm using a grinder, and then diced into 7.3mm squares using a blade dicing device. An NCF film (Showa Denko Materials Co., Ltd.) was then laminated onto the wiring side using a vacuum laminator to obtain a chip with NCF. The obtained chip with NCF was pressure-bonded onto the substrate with the rewiring layer using a flip chip bonder. Then, a heat treatment was performed to harden the NCF to obtain a substrate with a chip.

[0203] Next, the substrate with the chip was sealed with sealing resin W5MG (Showa Denko Materials Co., Ltd.) using a wafer-level compression molding device to obtain a resin-sealed substrate. This resin-sealed substrate was reflowed using a reflow device to connect the chip with wiring and the substrate with the rewiring layer, and then heat-treated at 150°C for 4 hours to fully harden the sealing resin, thereby obtaining a resin-sealed substrate. The resin sealing was performed at 150°C for 300 seconds, and the reflow was performed at a maximum temperature of 275°C.

[0204] Next, the resin-sealed substrate was separated from the support. Using a laser irradiation device 5331 (ESI), the entire resin-sealed substrate was irradiated with a laser from the support under the conditions of a wavelength of 355 nm, an arbitrary output depending on the sample, a repetition frequency of 40 kHz, and a feed rate of 500 mm / s. After irradiation, the support was separated by making a cut at the interface between the cured film and the metal thin film layer, and a resin wafer was obtained.

[0205] Next, the cured film remaining as a residue on the peeled surface of the obtained resin wafer was removed. The cured film residue was removed using a single-wafer spin cleaner and a cloth partially moistened with pure water. Next, the resin wafer was immersed for a predetermined time in a chemical solution (Dynastrip7700, Dynaloy Corporation) heated to a predetermined temperature. After cooling the resin wafer, it was washed with acetone and dried to remove the cured film residue on the metal thin film layer. If the cured film residue cannot be easily removed in this process, the connection terminal cannot be exposed, causing short circuits between wiring, poor connections, etc., leading to a decrease in yield.

[0206] Next, the metal thin film layer was etched on the resin wafer to obtain a laminated resin package. A specified amount of WLC-C2 (Mitsubishi Gas Chemical Co., Ltd.) was used as the etching solution for the copper layer of the resin wafer, and a specified amount of WLC-T (Mitsubishi Gas Chemical Co., Ltd.) was used as the etching solution for the titanium layer.

[0207] The process adaptability of the above-mentioned laminate fabrication was evaluated according to the following evaluation criteria. The laminate fabrication was also carried out at two curing temperatures for the insulating layer, 230°C and 280°C, to confirm the adaptability to the laminate fabrication process of the present disclosure. The results are shown in Table 1. -Evaluation criteria- A Throughout the production of the above-mentioned laminate, the metal thin film layer did not peel off, and the residue of the cured film could be removed, and each process could be carried out without any problems. B Although the metal thin film layer did not peel off, there was a problem with the removability of the cured film residue. C Peeling of the metal thin film layer occurred, and there was also a problem with the removability of the cured film residue.

[0208] [Table 1]

[0209] As shown in Table 1, the resin compositions of Examples 1 to 10 were superior in releasability from a support as compared with the resin composition of Comparative Example 1, and were also favorably evaluated for suitability in producing a laminate. Furthermore, the resin compositions of Examples 1 to 7 were excellent in the removability of the residue of the cured film obtained by curing the resin composition, and were also evaluated as being more suitable for producing a laminate.

[0210] <Conductivity evaluation of resin packages> For the obtained resin package, the cross sections and the electrical continuity of the copper wiring, insulating layer, etc. were checked to evaluate whether the copper wiring, insulating layer, etc. had deteriorated due to the heat caused by the separation process.

[0211] To confirm the cross section, the resin package was cut at an arbitrary location using a blade dicing device, and the cross section was polished with abrasive paper #2000 using a sample polishing device, and then the cross section was observed under an electron microscope. As a result, it was confirmed that there was no deterioration in the copper wiring and insulating layer in Examples 1 to 7. On the other hand, in Comparative Example 1, deterioration of a part of the insulating layer was confirmed.

[0212] In addition, a probe was used to check the electrical continuity of the resin package. In Examples 1 to 7, electrical continuity between the semiconductor chip and the rewiring was confirmed.

[0213] From the above, it was found that in Examples 1 to 7, a semiconductor package could be produced while suppressing abnormalities during the process, deterioration during peeling, and the like, regardless of the curing temperature of the insulating layer. [Explanation of symbols]

[0214] 1 Support 2 Cured film 3 Metal Film 4. Patterned resist layer 5 wiring layer 6 Insulating layer 7 Via 8 Connection terminal 10. Semiconductor Chips 11. Bump 20 Encapsulating material 30 Residue 100 Semiconductor device

Claims

1. Contains a polyimide precursor and a polymerizable monomer, The polymerizable monomer has two groups containing a polymerizable unsaturated double bond, and the resin composition is used in the following treatments (a) to (c). (a) A cured film of the resin composition is formed on a support. (b) A laminate is formed on the cured film. (c) Separating the laminate from the support.

2. 2. The resin composition according to claim 1, further comprising a solvent, the content of the solvent being 50 parts by mass to 10,000 parts by mass per 100 parts by mass of the resin component.

3. The resin composition according to claim 2, wherein the solvent comprises at least one selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, γ-butyrolactone, cyclopentanone, dimethylsulfoxide, dimethylimidazolidinone, and N-formylpiperidine.

4. The resin composition according to any one of claims 1 to 3, wherein the cured film does not change in quality after being heat-treated under conditions of 100°C to 400°C for 4 hours or less.

5. The resin composition according to any one of claims 1 to 4, wherein the polyimide precursor contains a compound having a structural unit represented by the following general formula (1): 【Chemistry 1】 (In general formula (1), X represents a tetravalent organic group, and Y represents a divalent organic group. R ６ and R ７ Each of R independently represents a hydrogen atom or a monovalent organic group. ６ and R ７ At least one of the groups is a monovalent organic group.

6. The resin composition according to claim 5 , wherein the monovalent organic group includes a group represented by the following general formula (2): 【Chemistry 2】 (In general formula (2), R ８ ~R １０ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms; R ｘ represents a divalent linking group.

7. A resin composition described in any one of claims 1 to 6, further containing a thermal polymerization initiator.

8. The resin composition according to any one of claims 1 to 7, which is used in the following treatment (d). (d) Removing the residue of the cured film remaining on the laminate after separation from the support.

9. The resin composition according to claim 8 , wherein in (d), a residue of the cured film remaining on the laminate can be removed by a solvent treatment.

10. A step of preparing a resin composition according to any one of claims 1 to 9; forming a cured film of the resin composition on a support; preparing a laminate on the cured film; Separating the laminate from the support; A method for producing a laminate comprising the steps of:

11. The method for producing a laminate according to claim 10, wherein the support has a thermal expansion coefficient of 3 ppm / K to 15 ppm / K at a temperature of 25° C. to 300° C.

12. The method for producing a laminate according to claim 10 or 11, wherein the support has a thickness of 100 μm to 10,000 μm and a transmittance of light with a wavelength of 355 nm of 90% or more.

13. The method for producing a laminate according to any one of claims 10 to 12, further comprising the steps of irradiating the cured film with active energy rays to alter the properties of the cured film, and then separating the laminate from the support.

14. The method for producing a laminate according to any one of claims 10 to 13, further comprising a step of removing a residue of the cured film remaining on the laminate after it has been separated from the support.

15. The method for producing a laminate according to any one of claims 10 to 14, wherein a heating temperature during formation of the cured film is 100°C to 450°C.

16. The method for producing a laminate according to any one of claims 10 to 15, wherein the cured film formed on the support has an average thickness of 0.1 µm or more.

17. the laminate is a semiconductor device including a wiring layer, an insulating layer, and a semiconductor chip, The method for producing a laminate according to any one of claims 10 to 16, wherein the step of producing the laminate includes the steps of forming the wiring layer on the cured film, forming the insulating layer that at least insulates between the wiring layers, and disposing the semiconductor chip on the insulating layer and connecting the semiconductor chip to the wiring layer.

18. the laminate further includes a sealing material that seals the semiconductor chip; The method for manufacturing a laminate according to claim 17 , wherein the step of fabricating the laminate further comprises a step of sealing the semiconductor chip connected to the wiring layer.

19. A cured film obtained by curing the resin composition according to any one of claims 1 to 9.

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